Metasomatism

and

metasomatic rocks

1
 Metasomatism

and metasomatic rocks

ACADEMY OF SCIENCES OF RUSSIA, INSTUTE OF GEOLOGY OF ORE

DEPOSITS, PETROGRAPHY, MINERALOGY AND GEOCHEMISTRY SECTION
ON METASOMATISM AT THE COUNCIL ON MINERALIZATION AND
METALLOGENY

Responsible redactors:

[Link], academician
[Link], doctor in geological and mineralogical sciences

[Link], [Link], [Link],

[Link], [Link], [Link], [Link],
[Link], [Link],
[Link], Y.B. Shapovalov, M.S. Seredkin, V.A. Golovina

Translation from Russian : Jean Verkaeren and Jacques Duchesne

Technical assistance : Bernard Guy (guy@[Link])

First available on line : April 2015

2
Abstract

This book describes the main types of metasomatic processes and outlines the
theoretical bases of metasomatism in accordance with the theory of D. S.
Korzhinsky. Thermodynamics, dynamics and ideas concerning self-organisation
of metasomatic processes are developed according to the current theoretical
level. Results are given concerning technics of experimental study of
metasomatism. The relation of metasomatism to ore deposits is discussed, and
the new concept of formation of ore-concentrating dense salt melts and related
light metasomatic fluids is proposed. The significant part of the monograph
contains the characteristics of the main metasomatic families and rocks.
Detailled characteristics of geological setting, mineral composion, facies and
genetical considerations are given based on original and literature data.
This book may be interesting for petrologists, geologists studying ore deposits
and specialists in metasomatism. It can be used as a textbook of metasomatism
for graduate and postgraduate students.

22 tables, 127 figures, 462 bibliographic references.

English translation : Jean Verkaeren and Jacques Duchesne ; assisted by Bernard

Guy

Key-words : metasomatism ; metasomatic processes ; metasomatic rocks ;

Korzhinskii ; ore deposits ; self-organisation ; thermodynamics ; chemical
kinetics ; experimentation ; skarns ; greisens ; propylites ; secondary quartzites ;
beresites ; alkaline metasomatic rocks ; gumbeites ; argilisites

3
Foreword to the English translation

The text presented here was published in Russian in 1998 by World Scientific
Moscow under the aegis of the Russian Academy of Sciences (ISBN 5-891 176
-038- X). It was translated into English by Jean Verkaeren (Honorary Professor,
University of Louvain-la-Neuve, Belgium) and Jacques Duchesne (Honorary
Professor, University of Liège, Belgium) during the period 2000-2010, assisted
by Bernard Guy on some points (the English translation was prepared in parallel
with, and after, the first French translation). The edition of this file has been
made by Bernard Guy (Director of Research at the Ecole Nationale Supérieure
des Mines de Saint-Etienne) in 2014-2015. During a trip to Moscow in 2003,
Jean Verkaeren and Bernard Guy met the authors of the book, discussed some
technical issues, and received permission to develop this translation and make it
accessible to English- and French- speaking scientific communities. The
presentation has been simplified by grouping the figures at the end of each
chapter. All figure symbols have not been translated into French nor English: in
this English edition, symbols in Russian, or even French (as remains of the first
translation step) may be found. We temporarily leave things as they are, in order
to avoid further delay in the presentation of the book. Similarly the table of
contents is given with no indication of the page numbers. Corrections to the
translation and improvements of the presentation will be made in later versions.
Thank you to readers to report any problems they might identify in this edition
(guy@[Link]).

References: References appear in three groups: - the English translations of the

Russian references (alphabetic order following the Latin characters) ; - the
French translation of the Russian references, together with the original Russian
references (alphabetic order following the Latin characters); - the general
western (latin characters), non-Russian, references (mostly English).

Some articles published in Russian have been translated into English journals
such as Geochemistry International, Geological Review, etc., to which the
reader may refer.

4
Contents
Foreword ...........................................................................................................

Part I

THEORETICAL BASES OF METASOMATISM

Chapter 1. General presentation of metasomatism .......................................

1.1. Definition of metasomatism .......................................................................
1.2. Types of metasomatic processes, their links with
magmatism and metamorphism ...............................................................

Chapter 2. Thermodynamics of metasomatic systems ..................................

2.1. Local equilibrium and types of metasomatic systems ...............................
Equilibrium in metasomatic systems .........................................................
Thermodynamic types of metasomatic systems ........................................
2.2. Fluid-rock equilibrium in metasomatism ...................................................
Pressure of solution and mineral phases in the system ..............................
Crystallization pressure and surface tension in metasomatism .................
Particulars of solutions in microporous and microfissured surroundings .

Chapter 3. Dynamics of metasomatic processes .............................................

Dynamics of flows of solutions and matter in microporous environment .........
3.2. Causes and fundamental equations of metasomatism ................................
3.3. Metasomatic zoning of isotherm infiltration .............................................
Conclusion of the equation of zoning of isothermic infiltration ................
General properties of the isothermal infiltration metasomatic zoning ......
3.4. Diffusion metasomatic zoning ...................................................................
Conclusion of the equation of diffusion metasomatic zoning ...................
General properties of metasomatic diffusion zoning .................................
Bimetasomatic zoning .................................................................................
3.5. Complex types of metasomatic zoning ......................................................
Infiltration–diffusion metasomatic zoning .................................................
Metasomatic zoning in conditions of temperature gradients .....................
Other complex types of metasomatic zoning .............................................

Chapter 4. Kinetics of reactions and self-organization

of metasomatic systems ...............................................................
4.1. Mechanisms of metasomatic reactions ......................................................
4.2. Kinetics of metasomatic reactions .............................................................

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4.3. Self-organization and synergetics of metasomatic systems .......................

Chapter 5. Experimental modeling of metasomatism ...................................

5.1. Experimental methodology ........................................................................
5.2. Modelling of acid metasomatism of granites .............................................
Granite metasomatism under the action of acid chloridic solutions ..........
Metasomatism under the action of acid fluoridic solutions .......................
Metasomatism under the action of chlorinated and boric acid solutions ...
Metasomatism under the influence of chlorinated solutions containing CO2
and sulfur ....................................................................................................
5.3. Modeling of alkaline metasomatism of granites ........................................
Metasomatism of carbonates and sodium and potassium silicates under the
action of chloride solutions ........................................................................
Metasomatism under the action of alkaline fluorid solutions ....................
5.4. Dependence of facies of alkaline sodic metasomatism of granitoidic rocks
upon temperature and values of log(mNaCl/mNaOH) in the solution ......
5.5. Modeling of deposits of rare metals (W, Mo, Sn) in a greisenisation and
alkaline metasomatism of leucocratic granite
5.6. Conclusion...................................................................................................

Part II

METASOMATISM, MAGMATISM AND MINERAL FORMATION

Chapter 6. Theoretical aspects of the genetical link of

metasomatism, magmatism et mineral formation ....................

Chapter 7. Spatial and temporal correlations of metasomatites, ores and

magmatic formations ...................................................................

Chapter 8. Metasomatic zoning and ore zoning ...........................................

Chapter 9. Magmatism, metasomatism and massive sulfide mineralization

Chapter 10. Magmatism, metasomatism and rare metal mineralization ..

Chapter 11. Boron metasomatism, sodium metasomatism and gold

mineralisation .............................................................................

Chapter 12. Metasomatism and epithermal gold silver mineralization .....

6
 Part III

FORMATIONS OF METASOMATIC ROCKS

Chapter 13. Classifications of metasomatic rocks .......................................

Chapter 14. Physico-chemical systematization of metasomatic formations

Chapter 15. Metasomatites of alkaline ultrabasic and alkaline magmatic

complexes ....................................................................................
Fenites ........................................................................................................
Metasomatites of alkalino-ultrabasic carbonatite massifs .........................

Chapter 16. Skarns ..........................................................................................

16.1 Magnesian skarns ...............................................................................
16.2 Calcic skarns .......................................................................................

Chapter 17. Greisens .......................................................................................

Chapter 18. Propylites and propylitized rocks .............................................

Chapter 19. Secondary quartzites .................................................................

Chapter 20. Beresites et beresitized rocks ....................................................

Chapter 21. Alkaline metasomatites ..............................................................

21.1. Family of albitized granites.......................................................................
21.2. Family of sodic metasomatites of the contact zones of nephelinic-syenite
massifs
21.3. Aceites, a family of low-temperature sodic metasomatites

Chapter 22. Gumbeites ...................................................................................

Chapter 23. Argilisites and argilised rocks ...................................................

Chapter 24. Metasomatic rocks of shear zones and deep fracture zones ..

Succinct glossary of metasomatic terms and synonyms ...............................

References

7
Symbols of minerals

Ab – albite
Acm – acmite
Act – actinolite
Ad – adularia
Adr – andradite
Aeg – aegyrine
Ak – akermanite
Alun – alunite
Amph – amphibole
An – anorthite
Anc – analcime
Ank – ankerite
And – andalusite
Ap – apatite
Arf – arfvedsonite
Astr – astrophyllite
Bi – biotite
Brc – brucite
Brt – berthierite
Carb – carbonate
Cas – cassiterite
Cc – calcite
Ccn – cancrinite
Chl – chlorite
Chr – chromite
Chu – clinohumite
Cli – clintonite
Cor – cordierite
Cpx – clinopyroxene
Crn – corundum
Di – diopside
Dol – dolomite
Dsp – diaspore
En – enstatite
Ep – epidote

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Fa – fayalite
Fl – fluorite
Fll – fluellite
Fo – forsterite
Fsp – feldspar
Fspd – feldspathoid
Gel – gehlenite
Gib – gibbsite
Grs – grossularite
Grt – garnet
Hbl – hornblend
Hd – hedenbergite
Hem – hematite
H-Mel – hydromelilite (cyanite et cebollite)
H-Mic – hydromica
Ill – illite
Kln – kaolinite
Kfs – K-feldspar
Ky – cyanite
Lf – leucophyllite
Lib – liebenerite
Ln – larnite
Ls – leucoxene
Mc – microcline
Me – meionite
Mel – melinite
Er – merwinite
Mgs – magnesite
Mic – mica
Mic-Mnt– mica-montmorillonite
Mlb – molybdenite
Mln – melanite
Mnt – montmorillonite
Ms – muscovite
Mt – magnetite
Mtc – monticellite
Nar – narsasukite
Ne – nepheline
Ol – olivine
Olg – oligoclase

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Opx – orthopyroxene
Or – orthose
Per – periclase
Phl – phlogopite
Phn – phengite
Pl – plagioclase
Pmp – pumpellyite
Po – pyrrhotine
Prg – pargasite
Prh – prehnite
Prl – pyrophyllite
Prv – perovskite
Px – pyroxene
Py – pyrite
Qtz – quartz
Ran – rankinite
Rbk – riebeckite
Ru – rutile
Scp – scapolite
Sell – sellaite
Ser – sericite
Sil – sillimanite
Sod – sodalite
Spl – spinelle
Spn – sphene
Spur – spurrite
Srp – serpentine
TfBi – tetraferribiotite
Tfphl – tetraferriphlogopite
Ti-Mt – titanomagnetite
Tlc – talc
Toz – topaze
Tr – tremolite
Tu – tourmaline
Wes – vesuvianite
Wlf – wolframite
Wo – wollastonite
Zeol – zeolite
Zo – zoisite

10
 Foreword

D.S. Korzhinsky published more then 40 years ago “Essay on the

metasomatic processes”, in which he put forward, in a general and accessible
form, the main new ideas about metasomatism, outlining its links with
magmatism and metallogenesis, briefly characterizing the main types of
metasomatic processes and their mutual relations. Simply and intelligibly
written, the “Essay” in its foundation had profound theoretical elaborations of
the problems [Korzhinsky 19511,2, 19521,2, 19532] and detailed monographic
researches on metasomatites [Korzhinsky, 1947, 1948].
His “Essay on the metasomatic processes” greatly influenced in Russia
the development of research on that subject. Many articles were published and
the subject aroused great enthusiasm in international meetings of the Union, the
first one in 1963 [Metasomatic changes in lateral rocks and their role in
metallogenesis, 1966], the second in 1966 [Metasomatic problems, 1970], the
third in 1976 [Metasomatosis and Metallogenesis, 1974], the fourth in 1976
[Metasomatosis and Metallogenesis, 1978], the fifth in 1982 [Metasomatosis
and Metallogenesis, 1982]. The sixth [1987] dealt with metasomatic phenomena
in pre-cambrian rock masses [Pre-cambrian metasomatites and their ore-genesis,
1989; Metasomatic processes in pre-cambrian rock masses, 1991]. Regional
meetings took place in Ukraine, Kirgizstan, Ural and the Far East.
However, in the majority of articles published in proceedings of meetings
and pages of other journals, description and interpretation of metasomatosis
followed traditional presentations.
The main ideas developed between 1960 and 1990 were undoubtedly the
study of metasomatites with new methodical positions, i.e. [Link]’s
theory of metasomatic zoning.
Corresponding articles try to get more and more room in the proceedings
of conferences and in the pages of journals. Monographies appear where on the
example of various metasomatic formations [Link]’s theory of
metasomatism is given concrete expression and is developed. Among the most
brilliant are “Geology and metasomatic phenomena in the polymetallic skarn
deposits of western Karamazar” [[Link], 1959], the work of V.A
Zharikov and [Link], “Some problems in the study of the changes in
the embanking rocks in connection with metallogenic research”[1965] , “Skarn
deposits” by V.A Zharikov [1968], “Geological and physico-chemical
regularities of propyllytisation” by [Link] [1972], “Petrology and
geochemistry” by P.V. Koval’ [1975], “Metalliferous hydrothermal changes of
rocks” by [Link] [1978]. Other articles study the difference between
metasomatic formations, among them the theory of metasomatic zoning. For

11
instance [Link] and others “Greisens deposits” [1971], [Link]
“Conditions of formation at low temperatures of metalliferous metasomatites”
[1975],) [Link] “Argillization and mineralization, [Link]
“Metasomatosis in the crust”, “Baikal metalliferous metasomatites” [1972,
1979], [Link] “Precambrian alkaline metasomatites” [1972], and many
more.
Anyhow, by the end of the seventies all the main types of metasomatosis
were described, their mineralogical composition studied, as well as their
parageneseis, the structure of their deposit, and one or other degree their genetic
peculiarities had been elucidated. In other words the “formal” description of
metasomatosis had been nearly completed.
In the seventies, research on metasomatic processes was oriented in a new
direction: experimental modeling of metasomatic zoning by V.A. Zharikov, G.P.
Zaraisky and I.P. Ivanova. All the main types of metasomatosis were reproduced
in the past 20 and some years: alkaline metasomatites, lime and magnesian
skarns, greisens, andalusite and sulphurous quartzites, propyllites, berezites,
argillizites etc. For many metasomatic formations were determined the boundary
conditions of their formation ( in relation to P,T, activities of H2O, CO2, S, HCl,
KCl, NaCl and other components) were established the growth speeds of
diffusion columns and the necessary conditions to the flow of the infiltration
metasomatism. In particular, many important researches in experimenting
metasomatosis were carried out at the Institute of Experimental Mineralogy
(IME) in the laboratory of G.P. Zaraisky, in whose book “Zoning and formation
conditions of metasomatic rocks” (1989) is collected important original material
and is provided sufficient bibliography. The works on experimental modelings
of metasomatic displays have practically no counterparts in foreign researches.
Another new direction in the development of [Link]’s theory of
metasomatic zoning, is aiming at quantifying determination of the parameters of
the equilibrium phases in the locally equilibrated metasomatic
columns,reproduced on EVM. Possibilities of quantifying the dependence of
metasomatic parageneseis upon temperature, pressure and activity of the
components in the solution have appeared, thanks to important results in
theoretical and experimental researches. Firstly, there was provided a systematic
experimental study of the main rock-forming systems under conditions of a
perfectly mobile regime of H2O, CO2, HCl and NaCl [Zharikov et al. , 1972;
Ivanov, 1984; Hemley et al.1961; Frantz and Popp, 1979, 1980; Zharikov, 1991
and many others]. These researches have permitted not only to define the
stability field of the main parageneseis of metasomatic rocks, but also to obtain
from experimental data, the thermodynamic characteristics of minerals and their
components for high parameters. It was also important collectively to utilize the
known thermodynamic characteristics of the simplest minerals [Robie and
others, 1978; Naumov and others, 1971].

12
 Other researches played perhaps a decisive role in the calciculation of
metasomatic reactions. They consisted in elaborating methods to calciculate the
thermodynamic characteristics of components of aqueous solutions of
electrolytes for high parameters. Many researchers took part, but G. Helgeson’s
works played the leading role [Helgeson and Kirkham, 1974, 1982; Helgeson
and others, 1978; etc.].
Finally a direct step towards calciculation of metasomatic columns was
made by [Link] [1976], who elaborated a program of calciculation of the
composition in equilibrium in a multi-component hetero-phasic system (Gibbss
program). Further application of the equilibrium model in the diverse zones of
the metasomatic column ( method of successive reactors) yields an image of the
metasomatic zoning and its quantitative parameters. This Gibbss program
calciculation using approach of successive reactors has been successfully
employed to analyze various metasomatites, notably in peri-ore [Ivanov et al.,
1979; Ivanov and Borissov, 1980; Grichuk et al., 1982, 1984; Rizhenko et al.,
1977 etc.].
In the history of the development of metasomatic zoning theories are
outstanding several publications especially devoted to in-depth analysis of
equations of metasomatic zoning, their mathematic content, in search of a
possible quantitative solution, especially of the more complex cases of
metasomatism [Balashov, 1985, 1992; Demin and others, 1979; Zaraisky and
others, 1989; Frantz and Mao, 1976; Lichtner , 1991; Lichtner and Balashov,
1993; Guy, 1993; etc]. A new direction of research develops also in the
modeling of periodical zoning resulting from auto-organized metasomatic
systems [Roussinov and Zhoukov, 1994].
When research apparaising the domain of metasomatism, it is easy to see
that at the time of the last generalizations [Korzhinsky, 1953; Zharikov and
Omelianenko, 1965; Omelianenko, 1978], an enormous material has
accumulated either in the study of separate metasomatic formations or in the
theory of metasomatism. A new direction consisted in experimental and
computerized modeling of metasomatic processes. It has therefore appeared
essential and expedient to write a new collated book propounding the basis of
the contemporary metasomatic theory, a brief general characteristic of the main
types of metasomatism and showing the contemporary views about the ties
between metasomatism and magmatism, mineralization and other geological
phenomena.
The present book pursues these aims. Unlike earlier generalizations, the
present monograph was written by many authors under the direction of
[Link] and [Link]. The first, theoretical part is due to
[Link] (chapters 1-3), [Link], for paragraph “Crystallization
pressure “ in chapter 2 ), chapter 4 by [Link], chapter 5 by [Link].
Part II, dealing with interactions between metasomatism, magmatism and

13
metallogenesis, was written by [Link] using data from
[Link] (chapters 6, 9, 10) and [Link] (chapters 7, 8, 11). Part
III propounds principles of classification of metasomatic rocks; their systematic
is presented by B.I. Omelianenko in chapter 13 and in chapter 14. [Link]
presents the physico-chemical systematic of metasomatic formations. Then
chapter 15 by [Link] gives the main features of metasomatic formations and
types of metasomatic processes, the metasomatites of alkaline-ultrabasic
magmatic complexes and the phenites. Chapter 16 by [Link], N.N.
Pertsev, [Link] gives the skarns, chapter 17 by [Link], with
paragraphs by [Link], the greisens, chapter 18 by [Link] the
propyllities, chapter 19 by S.S. Abramov the secondary quartzites, chapter 20 by
O.V. Andreeva the beresites, chapter 21 by B.I. Omelianenko the alkaline
metasomatites, chapter 22 by V.L. Russinov with paragraphs by [Link],
chapter 23 by [Link] with one paragraph by [Link] the argillites,
and chapter 24 by Russinov with paragraphs by [Link] the crumpled
metasomatic zones and the abyssal fractures.
Recruiting so many collaborators had not only positive sides but also
definite difficulties. The positive element was obvious: each section was written
by a specialist who for many years had successfully worked with theses
problems. Each author’s individuality in turn made impossible a complete
uniformity in the designation of material when characterizing the various
metasomatic formations. However, the chief complication consisted in the
different treatment by the different authors of some complex genetic questions.
This does not touch the foundation of the theory of metasomatic zoning. Here
the authors were unanimous not only in admitting its essence (about which there
can be no doubt), but also its important methodslogical sognificance for the
comprehension of metasomatism. Disagreements occur about not particularl
demonstrated adjacent questions: the links between magmatism, metasomatism
and metallogenesis, or the origin of metalliferous solutions,the cause of mineral
precipitation. This remotely recalls the famous discussion in the twenties on the
role of an acid gas and an alkaline solution in metallogenesis (cf. [Link]
“Nature of the metallogenic fluid”). This question particularly concerns the
causes of evolution of the postmagmatic processes. It appeared more than once
even, after the mentioned discussion and after the hypothesis was uttered by
[Link] (1957) of acid hydrothermetal differentiations (see references in
the corresponding chapters). This, probably, objectively reflects not only the
complexity of the problem but also the multiplicity of possible mechanisms.
Elements of discussion of these and a few other genetic problems are not
to be considered as insufficiencies of the book. The existence of different
viewpoints (if sufficiently established) undoubtedly permit the essence of the
phenomena to be comprehended.

14
 We hope this book will rise interest and prove useful to large circles of
specialists.
V.A Zharikov [Link]

15
 Part I
Theoretical bases of metasomatism

Chapter 1

General presentation of metasomatism

1.1. Definition of metasomatism

Metasomatosis, metasomatism and metasomatic processes are practically
synonymous. Nevertheless some researchers mean by metasomatosis separate
metasomatic processes (potassic metasomatosis, sodic metasomatosis, etc.)
whereas by metasomatism they mean an aggregate of metasomatic changes as a
whole. There exist several definitions of metasomatism, but the most complete
appears to be the following, which in principle corresponds to the notion of
metasomatosis formulated by [Link] [1955].
Metasomatic processes: such processes develop in rocks and ores; they can
occur through substitution of minerals to others, entailing changes in the
chemical composition of rocks or ores; these changes are produced under
conservation of the solid state of rocks or ores as a whole, under the action of
fluids linked with inner endogenic processes in the earth.
This exhaustive definition singles out metasomatism amid other endogenic
processes. Above all is indicated the means or mechanism of realization of the
process: through replacement of a mineral by another.
This question will be addressed below in more detail, but it may already be
noted that liquefaction of minerals and simultaneous precipitation at this place
of another or several other newly formed minerals have a sharply predominant,
commanding significance.
For example pseudomorphoses may be observed as necessary presence in
metasomatites usually resulting from the formation of some minerals newly
formed on the pre-existing mineral. This peculiarity of the metasomatic process
is known as the “rule of constant volume in metasomatosis” long since
formulated by V. Lindgren [Lindgren, 1925]. It seems that another mechanism,
change of an ion into another, may be alleged in case of replacement of minerals

16
of proximate volume and structure. But [Link]’s curious experiments [Wyart
and Sabatier, 1956] with sodic solution enriched with 18O, have shown the
replacement of adulaire by albite to be due to a mechanism of liquefaction -
precipitation.
A second, very important definition of metasomatism as a process arising
with preservation of the solid state of the rock as a whole, is that the volume of
pores occupied by the solution is negligible compared to the volume of the
rocks, and that the whole matter in the pores is found in liquid condition. This
property of the metasomatic processes radically distinguishes them from
magmatic phenomena and from the filling up of voids or open fractures.
Crystallisation of melts or from fluids in a free volume (slopes, open fractures,
etc.) proceed along eutectic and eutonic principles contrary to the proper
tendency of metasomatism. We shall demonstrate below but may a already point
out that the characteristic feature of metasomatism development is a tendency
for the number of minerals to diminish and for monomineral rocks to appear in
the course of the process. On the contrary the eutectic-eutonic principles
augments the number of minerals in the course of crystallisation.
Metasomatism, as defined, entails variation in the chemical composition
of the initial rocks and the formation of new rocks, while is changed the content
of some petrogenetic (and ore) components. The formation of rocks in which
only water and carbonic acid are exchanged, i.e. in which reactions of hydration-
dehydration, carbonation-decarbonation occur, , is not a form of metasomatosis
but are traditionally related to metamorphism. Intrusion or removal of H 2O and
CO2 belongs to metamorphism. Intrusion or removal not only of H 2O and CO2
but also of other components belongs to metasomatism. Such is the generally
accepted boundary between metamorphism and metasomatism.
Other opinions exist however about the delimitation between
metamorphism and metasomatosis: V.S. Sobolev [Facies of metamorphism,
1970] alleges the high extension of metamorphic processes, with alkaline
content variations (usually in intrusion); considered possible to distinguish
between metamorphism, alkaline metamorphism and metasomatism. According
to other studies there correspondingly appear in the metamorphic processes
other content variations not only of alkaline but also of other components
[Krilova & al., 1972; Davidchenko, 1983; Glebovitsky & Bushmin, 1983].
Therefore metamorphic and metasomatic processes must be strictly delimited,
not according to variations of content but rather to the thermodynamic regime of
the components. To metamorphism are related processes in which H2O and CO2
are perfectly mobile; to metasomatism, those in which not only that occurs, but
in which the same in true for other petrogenetic components (the alkalines, CaO,
MgO etc. are perfectly mobile up to a regime of perfect mobility of all
components). Moreover, metamorphism is sometimes used in a broad sense
designating all the endogenous processes of transforming material in solid state.

17
 Metasomatic processes occur under the influence of fluids. All
peculiarities in composition and structure of the metasomatites depend on the
influence of fluids, of regimes insuring the differential mobility of components.
Respective paragraphs will show the physico-chemical part played by each
fluid. Their influence is immediately to be seen in geological observations.
Metasomatic changes are unequally distributed, their precise confinement in
zones of tectonic dislocation and fracturation, contacts, the enormous addition
and removal of materials unambiguously illumine the bond between
metasomatism and the influence of fluids. In evaluating the latters’ role in the
transport of matter in metamorphic processes, [Link] [Faif & al., 1962]
considered the alternative: either the temperatures of the metasomatic processes
may grow beyond 1200°C (the diffusion speed in solid state becomes then
geologically significant), or the transfer of matter occurs through fluids, proving
these to play an exclusive part.
The fluids apt to produce metasomatism generally appear as hydrothermal
solutions (or more rarely hydrothermal fluids), independent from the fact that
they are found in an essentially liquid or super-critical state. Moreover, it is
important to note that if we set aside the formations due to volcanic or
subvolcanic activity, no essential difference can be observed in metasomatites
between low, middle and high temperatures regarding their structure or
additions or removal of matters etc. (neglecting finally important information
about kinetic factors of the metasomatites in low temperature and at high scales
of high temperatures). This testifies that metasomatism shows similarities with
the properties of the liquids or “liquid-form” solutions. These solutions differ
from gases through their great density, by the great solubility of components and
noticeable their dissociation. On figure 1.1 a T-P diagram indicates the critical
point of water, of the NaCl solution, of the “critical isochores” and the plotting
of T-P parameters of gases-liquids, including from many hydrothermal ore
deposits, according to the data of Naumov & Touranov [1969]. Although
definition of the T-P parameters of the “gases-liquids” inclusions has notorious
errors one can already conclude that most points are disposed in domains
possessing properties of liquids.
New works have emerged in the last few years showing the possible role
of a gaseous phase in the transfer of matter.

1.2. Types of metasomatic processes, their links with

magmatism and metamorphism
Metasomatism arises under the influence of fluids: therefore for the
appearance of metasomatic processes, addition and removal of matter for the
peculiar structure of metasomatic bodies the manner of matter transfer into the
solutions is of decisive significance. Consequently D.S. Korzhinsky [1950] has
recognized two kinds, of metasomatism, diffusion and infiltration. To diffusion

18
metasomatic processes, are related those in which transport of components
occurs through diffusion in an aqueous liquid. In infiltration metasomatosis,
transport of matter occurs in the flow of liquid as a result of its infiltrating or
percolating though the rocks. Of course in natural conditions these extreme
cases of metasomatism occur rarely and we usually have to do with both
combined. However, the predominance of one or the other way of matter
transfer is precisely expressed in the scales and structure of the metasomatic
bodies. Essentially, the diffusion metasomatites, limited in their dimensions
(decimeter, meter, rarely more), which clearly coincide with the fissures and
contact surfaces, show gradual variations in the composition of their forming
minerals and rocks. On the contrary, infiltration metasomatism may occupy
significant masses of rocks with sharp changes in the composition of the
metasomatites. Similarity and differences in structure between diffusion and
infiltration metasomatites are examined further on.
To metasomatism proper are related processes linked with internal
endogenous forces of the earth. Such limitation is conditional but seems fully
well-grounded and this is why: replacement processes with variations in
chemical composition also appear habitually in zones of “hypergenesis”. Only,
factors such as low speed of reaction, kinetic parameters, influence of superficial
forces, replacement of living organic matter etc, which have no decisive
significance in endogenous metasomatism, assume essential significance.
Therefore, the corresponding processes are better called especially hypergenous
metasomatism. Even more conditional is the limit between endogenous
metasomatic processes since they occur in the crust and in the mantle. In this
case it is better specially to deal with mantle metasomatism since their main
peculiarity depends on the fact that under mantle conditions the influencing
environment proves to be the force of concentration of liquid brine very similar
to melts.
Metasomatic processes in the crust are undoubtedly linked with magmatic
manifestations. For some metasomatites this link is geologically evident: they
appear in zones of occurence of magmatic melts, contact zones or in very
intrusive massifs. The link of other metasomatites with magmatism is
established through geochemical symptoms and especially through the evolution
of hydrothermal solutions predetermined by their magmatogenous nature.
D.S. Korzhinsky [1955] as he underscored the link between
metasomatism and magmatism distinguished two great groups of metasomatic
processes: I. Those in magmatic stages, and II. Those in postmagmatic stage.
To the first group belong the metasomatites formed in the surrounding
rocks in periods of emergence and introduction of magmatic melts under the
influence of solutions distinguished from the liquid magmatic mass. On the
contrary, in the second group the processes occur after solidification and
crystallization of the intrusive massifs they have a spatial link with, also

19
transforming the intrusive rocks. These processes are influenced by residual
solutions issued from deeper magmatic chambers.
The post-magmatic metasomatic processes are in turn divided into three
subgroups: IIa, processes in early alkaline stage; IIb, processes in the acid
lixiviation stage and linked deposits; IIc processes in final hydrothermal stages.
An optimal subdivision of the post-magmatic metasomatic stages is based
on the surprising geochemical singularities of hydrothermal postmagmatic
processes. There are expressed in regular variations in the acid regime of the
magmatogenous fluids. The fluids’ acidity grows in these processes, reaches a
maximum and then decreases.
This particular evolution of the fluids, linked with their magmatic sources,
was first clearly formulated by [Link] [1955, 1957] as a hypothesis on
the acido-alkaline hydrothermal differentiation.
A few points should be underscored. First, should be remarked the
essential part played by the acid hydrothermal fluids and their reaction to rocks
(transfers and precipitation of metalliferous components) has long since and
constantly been described in geological literature. Possibly the most brilliant
difference of views appeared in the discussion in “Economic geology” at the end
of the thirties [Greyton, 1946]. Acid gas or and alkaline solution, the main
mineralizing fluids were always diversely interpreted, on the one side by K.
Fenner, N. Boous etc., on the other by L.G. Greyton, [Link], [Link],
summarized and diversely compromised by [Link] and [Link] et and others.
Secondly, extensive geological experiments have shown that there exists a
definite group of correlation between the various metasomatites, between them
and ores when these are related to one geological cycle. For instance
metasomatites of the skarn type always appear earlier than the greisens, or
mineralization in beresites and argillisites lags and appears a little later than
strictly perimetalliferous metasomatism. Many other examples of such
correlations might be adduced, which generally is explained through influence
of various fluids linked with their pulsating intrusions of different age and
separation from the hearth.
The prominent novelty of [Link]’s hypothesis of acido-alkaline
hydrothermal differentiation is that he succeeded in finding one main cause
determining all the main peculiarities of the postmagmatic processes. The main
factors appear to have been the regular change in the acidity of the very
hydrothermal fluids, from alkaline to acid and vice-versa. Namely, this internal
evolution of the fluids themselves brings about correlation in time and space
between different metasomatites and between metasomatites and ores, and
unites the acid and alkaline regimes of the solutions.
Other factors, namely temperature, depth, composition of the surrounding
rocks appear more particular, determining the concrete habit of metasomatites

20
and ores but are no important mechanism in the evolution of post-magmatic
fluids.
The theory of acido-basic evolution of magmatic fluids based on
[Link]’s hypothesis is now widely accepted and sufficiently
established from the physico-chemical viewpoint.
About their dependence upon the geological setting one can distinguish
between autometasomatism, contact metasomatism, periveinous and regional
metasomatism. They frequently succeed one another in time and space.
Autometasomatism (or simple metasomatism according to
[Link]) composes the apical parts and, near it, the veins which form in
the magmatic bodies. It usually appears as small changes in great masses of
magmatic bodies. Typical autometasomatic processes are, for instance,
albitisation of granitoid intrusions or serpentinisation of ultrabasic massifs. As
appears in the designation, these processes are linked with an early post-
magmatic stage.
Contact metasomatites are more diverse and specific. To begin with, the
different skarn formations developed in the early post-magmatic stage in
contacts of intrusions with carbonated rocks, or with enclosing aluminosilicated
and carbonated rocks, when they were setted in a zone of a hot intrusion area.
Skarn formations appear in contacts and in space, and in the genetic sense of the
term, as far as their development is linked with the emergence of fluids into the
zone of contact of a chemically unbalanced carbonated and aluminosilicated
surrounding and their mutual reactions. Skarns are contact infiltrations and in
this case, when the mutual reaction of two surroundings in unbalance has the
supreme significance, it is bimetasomatic.
To contacts are related mighty processes called “lixiviation around
contact” ([Link]), evolving in the acid stage and occupying parts of
contact intrusion and surrounding rocks.
The most brilliant example is given by the greisens and secondary
quartzites. The metasomatic contact processes develop in space through contact
lixiviation (towards the contact) and, in time, replace early stages of
autometasomatism.
To periveinous metasomatites is related the type of metasomatites,
propagated on long distances, linked with the formation of veins (and
stockwerks) of mineralization. Part of them is called metalliferous, although in
the conditions (an aluminosilicated surrounding) prevalent at the time of
formation they do not much outstrip the ore-deposit. Perimetalliferous
metasomatites develop in a large gamut of temperatures (from high to low
temperatures) but are always linked with the acid stage of the postmagmatic
process. However, morphologically, expressed metasomatism, such as the
periveinous one, may develop in an other stage of the hydrothermal process.

21
 Regional or areal metasomatism appears in various geological
environments. Regionally distributed is the alkaline (K,Na) metasomatism of
magmatic and the early post-magmatic stage in deep horizons of the crust. It
also appears at moderate and even at small depth, in external zones where take
place perimetalliferous processes such as greisenization, quartzo-sericitic
metasomatism, propyllitization and a few others. One should underscore well-
known correlations: zones of intense metasomatism as a rule are borded by
zones of small changes, having areal extension. Later on, they appear on their
turn within a deeper metamorphic area. As already pointed out, the difficulties to
distinguish external metasomatic zones from those of metamorphism have their
repercussion in defining alkaline metamorphism; one can add the problems of
distinguishing external zones of propyllitization and greenstone zones of
metamorphic modification of volcanic stratas. On the other hand, all this finally
reflects the close genetic link between metamorphism and metasomatism as a
result of the action of hydrothermal fluids of magmatic origin. “There exists an
indissoluble link between magmatic metamorphic, metasomatic and
hydrothermal metallogenetic processes” ([Link], 1955, p.363).

22
Fig.1.1. T - P curves of magmatic and metasomatic processes after data of research on
liquid inclusions.
Dotted lines of solidus in the system granite-water and curve of bi-phased gas-liquid
equilibrium in the H2O-NaCl system.
1- magmatic liquids; 2- postmagmatic fluids of granitoids and their metasomatites; 3-
hydrothermal solutions of ore deposits after data of numerous authors.

23
 Chapter 2

Thermodynamics of Metasomatic systems

2.1. Local equilibrium and types of metasomatic systems.

Equilibrium in metasomatic systems

The metasomatic variations of rocks and ores represent of course
irreversible processes. Only, the peculiarity of the evolution of endogenic
metasomatic processes consists in the fact that the variation of external
parameters that bring about metasomatic changes occurs much more slowly than
the processes of adaptation of the system to the varying parameters. It turns out,
in this way, that at each instant, in each portion of extension of the system,
equilibrium is completely reached with its determining parameters. This
condition is called local equilibrium, an appellation proposed in the fifties by
D.S. Korzhinsky [1950, 1957]. A little later appeared an analogue term, mosaic
equilibrium, in monographs and textbooks of thermodynamics [Bazarov, 1961].
It must be especially noted that the notion of local equilibrium directly
derives from the notion of thermodynamic equilibrium for the first time clearly
formulated by D.S. Korzhinsky [1949, 1957]. It is traditionally understood, in
thermodynamics, that a system is meant to be in equilibrium when its
thermodynamic potential is minimal (U = internal energy, F = free energy, G =
isobar potential, etc.), the state factors (the independent parameters) of the
system being constant and the intensive parameters being equal in the phases. In
such a system all the natural processes have taken place and the system stays
invariable, inactive for constant state factors whose number equals K+2 in a
simple thermodynamic system1. Such a representation is unwittingly linked with
the notion of equilibrium with perception of completeness of an exhausted,
”atrophied” system. This was dealt with not only by the thermodynamicists,
which gave rise to the notion of the “thermal death of the universe”
[Krichevcky, 1962].
This is however absolutely not the case and D.S. Korzhinsky was the first
in 1957, to underscore the fact that the notion of equilibrium unambiguously
defines the interdependence of the system’s parameters, but not at all their
1
Among simple thermodynamic systems there are some in which only thermal, mechanical or chemical
processes occur, and there is no electric, magnetic or others, which may besides also characterize similar
thermodynamic correlations. In this simple system, the number of independent intensive parameters (f in )and that
of extensive parameters (fex) is equal to: fin+fex=K+2.

24
behaviour. Somewhat changing Korzhinsky’s formulation it can be said that, the
system reaches its equilibrium when its thermodynamic potential is minimum,
whose status is entirely defined by K+2 independent parameters (state factors or
factors of equilibrium, another designation of independent parameters). With
that, it is indifferent whether these factors are constant, or are in process of
changing. It is important that, for each moment, the general state of the system
be defined by K+2 unknown parameters, so that the system’s thermodynamic
potential be minimal. In other words, the relaxation speed of the system must be
great compared to that of the state factors.
There exist rigorous proofs of complete equilibrium of the state of the
system. This is the rigorous dependence upon the phase rule and of the law of
distribution of the components between the phases in conformity to the equality
of the chemical potential components in the phases. Nernst’s equation of
distribution is a partial variant of these correlations. Obviously, the state of total
thermodynamic equilibrium possesses an absolute minimum of thermodynamic
potential, i.e. there is no other phase composition for a given chemical
composition of the system, which would have a smaller thermodynamic
potential.
In natural conditions, the total equilibrium is of course a limit case in
which are approached many particularly high temperature metasomatites. At the
same time, thorough research always also exhibits cases of rupture of the total
equilibrium, relicts of substituted minerals (breach of the law of phases), zonal
crystals (rupture of equality of chemical potentials), etc and a few other signs.
However, no evil without good, these deviations allow us to decipher the
mechanism of metasomatic replacements.
The systems are defined in total equilibrium, as we have underscored, by
means of K+2 independent parameters. For heterogeneous systems this is
possible only when the dependent intensive parameters are equal in all the
phases (the independent intensive parameters are equal for any system in
conditions of its task, or, as it is said, of its existence facing the external
medium). In the dependence of the metasomatic system upon the
thermodynamic type, these necessary imposed conditions may be different: in a
isotherm-isobar system such a condition is equality in the phases of the chemical
potentials of the components; in the isotherm-isochore systems, besides equality
of the chemical potentials, pressure must be the same for all phases.
Meanwhile, natural metasomatic processes, are noticeably characterized
by conditions in which pressure of the fluid phase, fulfilling a porous volume
and fractures in the rocks , is smaller than that exerted upon the solid rock
framework. In this case the system is not yet in perfect equilibrium, since an
independent parameter yet appears, the pressure of the fluid phase, and we find
K+3 independent parameters in the system. Only, such a system may be for any
long time stable if these Ps  Pf correlations are maintained as conditions to the

25
existence of the system and if the system possesses, in this state, a minimal
thermodynamic potential. We agree to naming this minimum, relative, reserving
the term “absolute” for a system entirely in equilibrium with K+2 state factors. It
is therefore more convenient to call “stable” any steady state with a number of
fin+fex > K+2 independent parameters (if they possess a relative minimum of
thermodynamic potential) leaving the definition “equilibrium or total
equilibrium” to a system with K+2 independent parameters and an absolute
minimum of thermodynamic potential.
Stable systems (with fin+fex > K+2), when in total equilibrium may find
themselves in local equilibrium if relaxation of internal dependent parameters of
the system can occur fairly more quickly than the variations of the K+3 (or any
fin+fex > K+2) external independent parameters. At every instant the system may
have a relative minimum of thermodynamic potential (i.e. a minimal value of the
state relatively to all the other phases for a given composition of the system and
the given K+3 (or f>K+2) independent parameters). We remark, looking
forward, that local equilibrium in a stable system with K+3 independent
parameters is the thermodynamic model prevailing in natural metasomatic
systems.2
Thermodynamic types of metasomatic systems
Natural systems are related to a particular type of thermodynamic systems
with perfectly mobile components (SPMC systems). A thermodynamic model of
natural systems was discovered by Korzhinsky [1963, 1940, 1950, and 1957]: it
was a marked contribution to natural sciences. The existence in nature of a
particular type of thermodynamic systems in reflected in a general geochemical
law called « principle of differential mobility of components ». This law has a
very general significance, governing matter transfer in whatever natural
processes, forming minerals, rocks and ores processes metamorphism,
metasomatism, magmatism and ore formation.
According to the principle of differential mobility of components, the
components taking part in whatever geochemical process behave qualitatively in
different manners: some behave inertly, with appearance of independent
extensive parameters (the mass of the components, their composition or quantity
in the system); others are perfectly mobile, with appearance of independent
intensive parameters (chemical potentials of the components, their activities,
concentrations, etc). This means that the equilibrium of minerals (and generally,
of phases) in the system and the phase modifications depend not only on
temperature and pressure, but also on the chemical potentials of the perfectly
mobile components, whereas the number of phases is determined by that of the

2
The term « non-thermodynamic » means « rapid ”: relaxation must occur much more quickly. As the limit
« much more rapid » would be equivalent to « instantaneous », but this does not exist in nature. « Rapid » means
that in all methods available to us we do not observe divergence with the equilibrium criteria, or we may neglect
a small divergence.

26
inert components (and other extensive parameters of the system such as in
volume, entropy).
The principle of differential mobility of components, notably in
metasomatic formations, is most striking and clear. The well-known regularity,
if you will, the general law of metasomatism is the reduction of the number of
minerals in the metasomatites in proportion to the growth of metasomatic
transformations, depending on the changes of thermodynamic regime of the
components, from inert state to perfect mobility. In chapter 3 we examine this
general law, lying at the basis of metasomatic zoning.
In the definition of metasomatism appears the constancy of the volume of
the system, more precisely its independence from the processes developing
inside the system. Therefore the most general type of metasomatic systems is
those with constant volume and temperature, with perfectly mobile components.
In the diffusion processes, where the moving force of matter transfer is the
difference in the chemical potentials of the components, the thermodynamic
potential is in the form:
Fm(dif) = f (T, V, ma…mi, j... k)
Fm = - pV + a ma... (Integral form) (2.1)
dFm(dif) = -SdT – pdV + a dma... - mj dj - Qi = 0 … (2.2)
(differential form)
where ma…mj are the masses of inert components, j... k the chemical
potentials of the perfectly mobile components, Qi the uncompensated heat, a
general expression of the system’s irreversible processes. Equilibrium
conditions in such systems is expressed by
Fm = min, dFm = 0 and d2Fm > 0 … (2.3)
The complementary necessary condition, equality in the phases of
dependent, intensive parameters:
pA = pB = ….. = pF
Aa = Ba = ..... = Fa (2.4.)
 =  = ..... = 
Ai Bi Fi

The law of phases in an isotherm-isochore system (SPMC):

nT,V,M = fin + fex- r = ki + 1 – r (2.5)
For metasomatic infiltration processes the matter transfer is brought about
by the flow of solution and fluid and that is why the independent parameters of
the perfectly mobile components appear through their concentration or activity
in the solution:
Fm(inf) = f (T, V, ma…mi, Cj... Ck)
Fm = - pV + a ma (integral form)
dFm(inf) = - SdT – pdV + a dma - j dCj - Qi = 0 (2.6)
(differential form)
or for a non-ideal solution:

27
 dFm(inf) = - SdT – pdV + a dma - j daj - Qi = 0 (2.7)
where a….i are the inert components, j….k the perfectly mobile ones. The
conditions of equilibrium, the same (2.3), aj is the activity of component j. But
we note that the components’ concentration do not appear in canonical
thermodynamic parameters: dm constrained with dC multiplied by RT/C.
The main difference between diffusion and infiltration metasomatism
consists in the fact that in diffusion the matter transfer can only occur towards
the smallest chemical potential of the components, whereas in infiltration
metasomatosis the matter transfer in the direction of the flow of matter is
unlimited (including introduction of matter in saturated solutions).
In metasomatic processes flowing with conservation of volume (more
precisely with independent volume) a situation is usually found when pressure
on the solid rock-frame is greater than the pressure of the liquid or fluid phase.
In such a case one finds, as told above, also K+3 independent parameters in the
system:
Fm(dif) = f (T, V, pF, ma…mi, j... k)
and
Fm(inf) = f (T, V, pF, ma…mi, Cj... Ck)
thus, accordingly:
dFm(dif) = - SdT – pSdVS + VFdpF + a dma - mj dj - Qi = 0 (2.8.)
and
dFm(inf) = - SdT – pSdVS + VFdpF + a dma - j dCj - Qi = 0 , (2.9.)
where S means solid phases, F means fluid solution.
Systems with unequal pressure in the solid phase and in solutions are very
wide-spread in nature; in particular, equilibrium processes and dynamic
processes in these systems are essential for comprehending metasomatic and
metallogenic processes.
Apart from the isotherm-isochore systems with SPMC, some metasomatic
processes occur in isotherm-isobar conditions. They develop in the external
zones of metasomatic aureoles, contiguous and transient to metamorphic
aureoles. They distinguish themselves by an insignificant introduction and
removal of matter, easily compensated by small changes of volume of the
altering rocks. Correspondingly, for the state factors and the thermodynamic
potentials:
Gm(dif) = f (T, p, ma…mi, j ... k)
Gm(inf) = f (T, p, ma…mi, Cj ... Ck)
Gm =  a ma (2.10)
dGm(dif) = - SdT + Vdp + a dma - j dmj - Qi = 0 (2.11.)
dGm(inf) = - SdT + Vdp + a dma - j dCj - Qi = 0 (2.12.)
2
The condition of the equilibrium Gm = min, dG = 0 and d Gm > 0 for a
heterogeneous system is carried out through equalizing the chemical potentials
of the inert components in the phases.

28
 Law of phases: nT,p,m = fin + fex - r = ki – r (2.13)
Isotherm-isobar conditions can be established when pressure on the solid
phase differs from that on the fluid one. For example, if the rocks are under
lithostatic pressure and the fluid phase under hydrostatic pressure, i.e. p F  0.37
pS, one member + VFdpF appears again in the equations 2.11 and 2.12 and the
system will be stable for K+3 given independent parameters. However, there is a
more suitable and general expression of the perfectly mobile state of a solution
through the chemical potentials (- mH2O dmH2O) or the activities (H2O RT dln
aH2O) of the aqueous phase in its components.

2.2. Fluid – rock equilibrium in metasomatism

Pressure of solution and mineral phases in the system

In natural conditions different relations appear between pressure on the
liquid phase (solution, fluid) and that on the solid phases, minerals (mineral’s
crystallization pressure). The latter usually means pressure exerted by the
mineral in its crystallization from the solution upon the environment (or, on the
contrary, by the solid milieu on mineral’s braising).
In the upper layers of the crust, are usually admitted lithostatic pressure of
the mining rocks and hydrostatic pressure of the aqueous solution. Let us take
the average density of the sedimentary and the weakly metamorphic rocks to be
about 2600mg/cm3 ; that of water 1000mg/cm3: then the relation between the
two is pF = 0.385pS. Hydrostatic pressure determined by that relation;
presupposes the existence of a continuous vertical column of solutions, but this
is rarely the case near the surface.
The relation pS > pF is the most general for large variation within the
limits pS  pF  0.385 pS depending on the depth, the source of the fluids, the
rock’s permeability and other physical parameters. The usual natural relations
are presented in fig. 2.1, a diagram showing depth (pS), pressure of the porous
solution (pF) after measurement of the pressure of the plastic water and the T-P
homogenization of the inclusions. Depth is estimated on geological data.
A limit case is when the pressure on the fluid phase is equal to that on the
solid phase, pF = pS. This condition is brought about by crystallization in the
presence of a free volume of water (in cavities and fissures) in superficial
reservoirs, or, on the contrary, for high T and P in an excess of solution when its
pressure ensures the equality of pressures on all the phases (for example, in an
instrument for high parameters under pressure of water vapor).
Situations known and discussed under the name of autoclave effect it
occurs when pressure of the fluid is higher than that of the surroundings.
However, one must consider, firstly, that for the system as a whole, this
metastable state is held up by a robust impenetrable envelope. Volcanic
explosions and ejections, geysers, etc. point out the system’s tendency towards a

29
stable state. Secondly, it is important to understand that, in violation of the
metastable state, pressure on the solid phase within the autoclave equals that on
the fluid phase.
The relation between pressure on the mineral and on the fluid phase is
directly linked with the components’ concentration in the solution. Let’s take for
simplicity’s sake a mineral K with one component, braised in a volume V. From
equation (2.8) we may conclude by means of cross differenciation:
(p / k)V = (mk / V) k
and, with passing to the complete derivative and the final increase (all
other parameters remaining constant), we get
dp = mk / V  dk = dkRT dln ak (2.14.)
and for an ideal solution
dp = dk RT dln Ck (2.15.)
k F
and integrating between the limits p and p and, correspondingly, CkC°k,
we get
pk – pF = dk RT ln Ck / C°k (2.16.)
F
where p is the pressure of the fluid phase in the free volume (more
exactly for pF = pS); C°k is the concentration saturation of the solution in
component K for a pressure of the solution (pF = pS); pk is the pressure on the
solid phase, Ck is the concentration of the component K corresponding to the
equilibrium with the mineral K at pressure pk, dk is the molar density of the
mineral.
From the obtained relations an important conclusion is that at high
pressure on the solid phase, when pF remains independent, i.e. pk > pF ,the
concentration of component K in the solution surpasses that of saturation (C°k,
when pk = pF). In other words, with correlations (pk > pF) usual for
metasomatism, the solution is supersaturated. This means that “metasomatizing”
solutions infiltrate the voids, the fissures (or rapidly soluble minerals), and they
immediately fill (or replace) them up to stability conditions pk > pF.
For the minerals with several components, summing up the right parts of
the equations, one gets:
dp=mk/Vdk=dk RTdlnaa…akdk RTdlnCa…Ck=dkRTdln (2.17)
where  is the solubility product. Integrating, we get:
pk – pF = dk  RT  ln / ° (2.18.)
From which it follows that we get these correlations: crystallization
pressure of a mineral depends on the degree of supersaturation of the solution by
the corresponding components and vice-versa. In general metasomatism (pk >
pF) the solutions are in equilibrium with the environing rocks and are
supersaturated if they are saturated, as we have determined, in the conditions pS
= pF. The influence by metasomatism of supersaturated solutions is amongst the
most important metasomatism processes; Lindgren'’s rule of constant volume is
by them defined in detail.

30
 Here is an instructive example of mineral formation when pressure on the
solid phase differs from that exerted on the fluid phase. Let some cavity of
volume V be partly filled with a fluid (pF) issued from the surrounding rocks
which are under a pressure (pS > pF) greater than in the cavity; enters a solution
with perfectly mobile components, j, h and k, for which we take the correlations
Ck/C°k > Ch/C°h > Cj/C°j. For simplicity’s sake, lot the perfectly mobile
components form their own minerals with one component, J, H, K. In a state of
equilibrium, F = -pV = min and et r = fex = 1, and the cavity must be filled with a
single mineral possessing the greatest crystallization pressure and built
components in a highly supersaturated solution (equation 2.16). However, the
process takes place in stages. We show it in more detail utilizing the diagram
fig.2.2: pressure (of crystallization and of the solution); volume (in its section,
naturally). On entering the free cavity, the solution is supersaturated regarding
all the components (j, h, k) and from the solution all the supersaturated minerals
will crystallize quantitatively (at the limit O/I) in proportion to their degree of
supersaturation K>H>J. Proportionately, part of the cavity, as shown on fig. 2.2)
or all the cavity will be filled with the minerals, pressure will exceed p I = dJ RT
lnCj as far as crystallization pressures pk and ph exert a higher influence on the
mineral J. The latter will be replaced by minerals H and K quantitatively in
proportion of the solution’s supersaturation. There results formation of zone II
built by of the minerals K and H at pressure pII, somewhat greater than pressure
pH as far as pK possesses a greater crystallization pressure than p H, but in that
zone lesser than full pK (zone III) owing to precipitation of component H
replacing component J. Finally, total replacement of mineral H occurs at the
limit II/III and the rear zone in equilibrium will be built only by mineral K,
developing a greater crystallization pressure pK – pF = dk  RT  in Ck/C°k. An
elevation of pH up to pII in zone II is linked also to the removal of component h
from zone III. Such peculiar filling of voids, of fissures through metasomatosis
occurs mostly for pS > pF.
Some important consequences:
Firstly, supersaturated solutions entirely preserve in metasomatism the
solid state of the rock as a whole (law of volume constancy): the cavities created
through dissolution, the fissures refill immediately with minerals and the
solution dries up.
Secondly, the cavities and fissures filled with the solution’s minerals are
submitted to “autometasomatism” in the sense that the precipitated minerals are
in turn replaced by another precipitated mineral developing a greater
crystallisation pressure, right up to monomineral formations of the most
supersaturated components of the solution.
Thirdly, the growth of big crystals favours reduction of the system’s free
energy. From F = - pV, where p = A / q pressure, the force A exerted by the

31
solution on the mineral’s surface (q), one immediately sees that bigger crystals
are thermodynamically preferred, the other conditions being equal3.
A more detailed discussion will require complementary data on surface
energy of crystals, its dependence on the grain dimension, an examination of the
link between the size of the crystals and the supersaturation concentration and
other kinetic parameters. Let us note here a notable natural peculiarity, the
growth of big crystals in the dissolution processes of mineral aggregates,
astounding druses of gems grow in the process of formation, when the solutions
are non-saturated enough relatively to the small crystals and slightly
supersaturated relatively to the big ones, of which the grains keep growing.

Crystallization pressure and surface tension in metasomatism.

Pressure capable of developing crystals on their own is an essential factor

in metasomatism. [Link] surmised that its cause was to be sought in
the monomineral “tendency” of metasomatic rocks. Pressure, as intensive
parameter, must develop in equilibrium in the whole system. Therefore in
isobaric systems crystallisation pressure must in principle be equal to the total
pressure for all minerals. Metasomatic processes often develop in constant
volume. If in such an isochore system is brought about a reaction in which the
volume of the newly formed minerals is less than the volume of the initial
mineral association, three different cases result.

1. Metasomatic contraction, or retreat under the influence of outer pressure

exerted by the enclosing rocks [Korzhinsky, 1993] as for example in the
formation of plagioclasites with corundum.
2. Growth of porosity, appearance of pockets.
3. The most usual case is the appearance of a supplementary mineral
refilling the liberated volume; for instance, calcite crystallisation replacing
phlogopite in the metasomatic bodies formed in phlogopite deposits. In all those
cases reduction of crystallisation pressure in the processes of mineral formation
is compensated either (1) by fracturation of surrounding rocks with transition to
an isobar process, or (2) by formation of voids, or (3) by deposition of a
supplementary mineral simultaneously with the liberated volume, and transition,
as in (1) to an isobar system.
If the volume of the products of the reaction exceeds the initial volume,
there develops a crystallisation pressure exceeding the external one. This is
linked with a rigid limitation of the system’s volume. The significance of
volume conservation, i.e. the isochore character of the system with development
of crystallisation pressure is tested for the water-ice system. In isobaric

3
N.B. There is here confusion between free energy F and force F!

32
conditions, water in open tanks coagulates under pressure of about 1 atm., equal
to crystallisation pressure. In isochore conditions, for instance in a filled pit
under a road carpet, at congealing ice a sufficient pressure develops to destroy
the carpet and swell the asphalt. In a solid recipient with water at –20°C ice
forms the colossal pressure of about 5 Kbar (a big earthquake occurs under
accumulated effort of only about 0.5 Kbar, i.e. in a lesser order of magnitude).
Either the recipient does not resist such pressure and breaks, or keeps its initial
volume with more compressed water and ice.
The full internal energy (U) develops in this simple system as total
thermic energy TS, mechanical energy (work) in the system (PV) and chemical
energy:
U = TS – PV + m, where T is absolute temperature, S the system’s
entropy, P pressure, V volume of the system,  the chemical potentials of the
components, m the molar quantities of the corresponding independent
components of the system.
Gibbs’s free energy (G) or isotherm-isobar potential constitutes only the
system’s “chemical” energy G = U – TS + PV = m, the most important
datum for our value, as notably G is tabulated in the reference works of Robie &
al. (1978). The isotherm-isochore potential or Helmoltz’s free energy is given by
F = U TS; or F – G = - PV; hence F = - PV + m
Further passing to the open system, i.e. to the system with inert and
perfectly mobile components we get precise expressions of Korzhinsky’s
isotherm-isochore potential F0:
F0 = F + ama +…+cmc ,
where a,....,c are the inert components i [Korzhinsky, 1977]. Thus,
introducing F into G = m, we get
F0 = – PVTB + fmf +….+kmk,
where f,…,k are the inert components. The physical sense of this
expansion in nature of the system consists in a limited volume of solid phases
through free infiltration of solutions through the limits of the volume, for
chemical potentials of perfectly mobile components outwardly fixed and equal
in all parts of the system (the chemical reaction advances more slowly than the
transfer of perfectly mobile components).
In conditions of equilibrium, the change of free energy dF0 = 0; this opens
the way to calciculation of pressure at a given temperature in an isochoric
system. Let us consider the concrete example of titanite formation in place of an
association of quartz and rutile, calcicium being perfectly mobile in the solution
infiltrated at 800K (526.8°C).
SiO2 + TiO2 + [CaO] = CaTiSiO5
G800 reaction = G800tit – G800qtz – G800rut = - 109.983 kJ/mol
[Robie et al., 1978]

33
 CaO = GCaO + RT lnaCaO = 0.0083143 kJ/mol; ln(aCaO) is the natural
logarithm of chemical activity of CaO. If for convenience we express natural
logarithm in decimal, then
CaOnCaO = 0 + 0.0083143 r800 lgaCaO = lgaCaO kJ/mol 0.4343
VTB = Vtit – Vqtz – Vrut = 5.565 – 2.2688 – 1.882 = 1.4142 kJ/mol
Thus, p = GCaO - 1CaO = (- 109.983 – 15.315aCaO) kJ/mol = 107.207 –
1.4142 kJ/mol
For a 1 bar pressure the activity in equilibrium of the CaO is 10 -7.18. For a
slightly higher activity, say 10-7, crystallization pressure of titanite in an isochore
system is gigantic, 1.963 kbar. A model for such a system can be represented,
for instance, by a quartzite mass traversed by a porous fluid, where the CaO
activity is 10-7, not sufficient for the formation of a calcicium-constraining
silicate (for instance, wollastonite for T = 800K and 1 bar aCaO = 10-6), but higher
than necessary for the formation of anorthite in association with quartz +
sillimanite (aCaO = 10-8.61). Let there be in the quartzite a parcel of rutile
inclusions. The fluid, as it crosses this parcel (geochemical barrier) will
crystallize titanite with an enormous pressure of crystallization. This pressure
sharply increases the quartz’s and the rutile’s solubility, which will liberate
volume for titanite until total disappearance of one of them. Another scenario is
possible: the enclosing rock doesn’t resist an enormous pressure, it gets
fractured or moves, which can increase the system’s volume, in which runs a
reaction and pressure decreases. Also possible is a combined development of
both, fracturation and dissolution.
In isochoric metasomatic systems there easily occurs a dissolution of
minerals, steady but with less crystallization pressure, liberating volume for the
minerals with less crystallization pressure. This mechanism operates at the
formation of metasomatic zoning accompanied with a monomineral tendency in
the rear zone. In the closed systems where no chemical exchange occurs with the
milieu, the condition of constant volume doesn’t end up in a quantitative
decrease of the coexisting phases; for instance the metamorphogenic alpine
veins, filled with closed fissures, are born in the absence of an intense
movement of fluids and matter transfer.
In terms of crystallisation pressure, one can examine the formation of
many symplectites, grids and other regular or irregular crystal germinations.
Within the limited volume, rocks may begin crystallising a new mineral
according to external conditions of mineral variation. But the volume is already
full of pre-existing minerals. If this new mineral’s pressure exceeds that of one
of the preceding minerals, the latter will begin to be replaced by the newcomer,
no matter whether these minerals share components. This is frequently
observed: needle germination (for instance, sagenite rutile in quatrz, ludvigite
needles in calcite, amphibole needles in quartz, fibrolite filaments in quartz, etc).
The appearance of a germ of new mineral in the pores brings about a local strain

34
in the mineral-host, a local distribution of it, and a free volume for the new
mineral. Various crystal grains, in various conditions, have in principle a
somewhat distinctive pressure. The difference must however be sufficient to
”pierce” the grain of the crystal-host, with the appearance of a greater
crystallisation pressure in these cases of rapid growth. If a newly formed mineral
contains inert components lacking in the mineral-host and liberated by the
reaction due to the changing condition, such a replacement may be limited, with
conservation of the mineral-host (as in sagenite) in connection with the content
of inert components in the rock. With a common inert component, replacement
may be only partial if inert components in the mineral-host do not suffice for a
complete replacement.
In connection with crystallisation pressure there are the problems of the
influence of superficial tension. The latter, in solid substances, summons forces
of attraction of atoms in the crystalline net, which hinders the detaching of
atoms and their gathering at the crystal’s surface. In principle, superficial
tension  in the crystal in various grains may be a little different and depend
also on temperature. It is measured in J/cm2. For weak, easily soluble bindings,
for instance NaCl (grain 100) at 200°C, one has  = 1.510-5 J/cm2; for strong
bindings, such as diamond (grain 111), one has = 11410-5J/cm2. Most
minerals evidently occur in this interval. Surface tension has a physical sense of
energy dissipated in forming surface mineral. So, in order to break a halite
crystal one cm broad into cubes 0.1cm broad (surface 600 cm2) an energy of
(1.510-5594) J/cm2 is needed. But, if from those small crystals is formed a
primitive crystal, global energy decreases in that amount, i.e. a spontaneous
process of increase of crystals takes place with energy release. Superficial
tension may be expressed through abundant pressure (P) on a solid phase. For
instance, diamond grains of 1mkm undergo an extra pressure of 11410-50.001
= 114 bar compared to a crystal of centimetric dimension. If the crystallization
pressure for centimetric crystals equals the system’s external pressure, the small
crystals undergo pressure (P + P) so much higher as the mineral’s grains are
smaller. For micrometric grains P may be high enough, from one to 100 bars,
not to exert any substantial influence on the equilibrium. If big crystals in a
system in equilibrium are in equilibrium with the solution, small crystals are out
of balance with the extra pressure brought about by the surface tension. In a
closed system may therefore appear spontaneous “recrystallisation”, growth of
big crystals and dissolution of small ones. In an isochoric open system may
appear such a situation that big crystals have a greater crystallisation pressure
than necessary for equilibrium, whereas small crystals have a negative one, i.e.
they must dissolve. Moreover, removal of the dissolved matter may predominate
over precipitation of big crystals, i.e. growth in big crystals occurs on a
background of general matter removal. It is through such a mechanism that
[Link] has explained the growth in pegmatites of big crystals on the

35
walls of the dissolution cavity. That is apparently how arise veins full of calcite
and nests with gigantic crystals of phlogopite and diopside in rocks with
diopside and phlogopite [Pertsev & Koulakousky, 1988]. The increase of
crystals along the path of fluids, as well as metamorphic recrystallisaton
(differentiation) induce for the most part a difference of pressure on small and
big grains.

Particulars of solutions in microporous and microfissured

surroundings
Metasomatic processes, we repeat, are provoked by solutions that appear
in thin pores and fissures. General effective porosity and microjointing of
compact eruptive and metamorphic rocks ranges from 0.2 to 1.2, rarely 1.5%. It
is essential to evaluate the maximal and minimal dimensions of porous channels
“working” in metasomatic processes. Numerous measurements of permeability
of compact mining rocks [Shmonov et al., 1995; Shomonov & Vitovtova, 1992;
Experiments in resolution of current problems of geology, 1986; Zharikov et al,
1990, 1993 et al.] imply dimensions of effective porous channels of 100 to 1000
Å (on - n10 µm) and microfissures of 10 to 100000 Å (10 – 100 m). [Link]
and R. Knapp [Norton & Knapp, 1997] give similar dimensions, of so-called
first pores, second microfissures. Experiments to defining permeability at
increasing temperatures [Zaraisky & Balashov, 1995] show that on account of
the anisotropy of the rocks’ thermic plasticity their permeability increases on an
average in order (fig.2.3).
Another way of estimating the effective dimensions of porous channels
may be based on the dynamic equilibrium of the minerals’ precipitation from
supersaturated solutions owing to pS > pF and, the contrary direction of the
process of dissolution resulting from the high concentration of the solutions in
equilibrium with the surface dispersed in minute pieces. These relations are
defined by the equalities:
q  dG + mk  dk (2.19.)
and
- dG = mk/q  dk =   dk (2.20.)
where G is Gibbs’s adsorption coefficient, showing superabundance of moles in
the volume of the top layer. In a solution with many components the value  is,
naturally, relative.
The behavior of solutions in ultraporous surroundings, with pores ranging
in the order of µm demands a particular attention. As already remarked
[Zharikov, 1976, 1995] in those conditions the solutions and their components
behave otherwise than a free solution volume. Despite extreme actuality of this
problem about direct or indirect reasons for formation of minerals and ore-
deposits, experimental research was formerly isolated [Shmonov & al, 1984;
Bielonozhko & Shmulovitch, 1986, 1987; Balashov, 1992]. Fig. 2.4 shows on

36
experimental and calciculated data the distribution in molar values of carbonic
acid between ultraporous spaces and free volumes of the solution (VCO2). From
the equality of the components’ chemical potentials we get:
PCO2 = VCO2 (2.21)
 CO2   CO2 =  CO2   CO2
P P V V
(2.22)
and in the same way for water:
PH2O = VH2O (2.23)
 H2O   H2O =  H2O   H2O
P P V V
(2.24)
It is easily seen that for high pressures  CO2 >  CO2 and accordingly
V P

 H2O < PH2O ranging from 1.5 to 4 times ( depending on T,P and pore
V

dimensions). Owing to the significant dependence of PCO2 and PH2O for porous
solutions, the activities of the components, above all H2O and CO2, distributed
between the minerals in equilibrium, may be very different from the real
concentrations of these components in the finely porous surroundings. In the
example dealt with (which has a fundamental significance with high parameters)
when PCO2 > 1 > PH2O the water’s molar fraction in the finely porous solution
will be much higher and that of carbonic acid much lower than the values we
have established for the mineral equilibrium. Disdain “particular”
thermodynamic properties of solutions in finely porous surroundings has led, in
particular, to a wide diffusion of errors on “dry metamorphism” and “dry
fusion” for high parameters.

37
Fig.2.1. Correlation of lithostatic pressure and fluid pressure after data of inclusions (a)
and measures of strata waters (b).
After data 1 of [Litvin and Tereshchenko, 1976]; 2 [Naumov and Tugarinov, 1962]; 3
[Prokofiev and Zorina, 1994]; 4 [Nechaev et al., 1987]; 5 [Fertl, 1980].

38
Fig. 2.2. Mechanism of cavity filling and autometasomatism.
Vr, remaining free volume of the cavity, PF pressure of solution in free volume, PK, PH, PJ
crystallization pressure of minerals in oversaturated solution.

39
Fig. 2.3. CO2 concentration in pores XPCO2 and in free volume XVCO2 of solution H2O +
CO2 .
1. 1000 bar, 400 oC , pores measuring 0.25.102 µm in zeolites (experiment); 2 idem at 3000
bar, 600 oC (experiment); 3 calciculated data for pores 0.08.102 µm in quartz at 1000 bar and
800 oC.

40
Fig.2.4 Dependence of permeability coefficients (k, millidarcys) upon temperature for
various models of granites at various effective pressures.
Experimental data of [Link] and [Link] [1989] 1,3 – 200 bar, 2,4 – 500 bar, 5 –
800 bar.

41
 Chapter 3

Dynamics of Metasomatic processes

3.1. Dynamics of flows of solutions and matter in microporous

environment.

In the study of metasomatic processes the manner of matter transfers by

solutions, as already underscored, has a fundamental significance. We
distinguish diffusion metasomatism, in which the diffusion speed of components
(uinf) is greater than the solution’s infiltration speed, and consequently, the
matter transfer proceeds through the difference between the chemical potentials
of components in the solutions, naturally beside the smallest value of the
component’s chemical potentials:
k dif k
I a Ldif
a a
dif
I (3.1)
a a
where Idifa...k are the components’ flows, a...k are the gradients of the
chemical potentials, Ldifa...Ldifk are the linear coefficients of proportionality:
a 
Ldif Ia ,....Ldif  Ik
a k
k . (3.2)
It is natural to express the specific flows of components by means of the
transfer speed. Evidently, the speed of the general flow in case of diffusion in
the same direction will be:
uS=udif+uinf (3.3)
whereas in the case of contrary diffusion the general flow:
uS=udif+uinf (3.4)
dif inf
which only makes sense if u > u .
We demonstrate below the real significance of the speed and parameters
on the basis of experimental and calciculated data.
Diffusion usually proceeds individually for each component, consisting of
a cooperative complex movement almost always determined by diffusion of big
molecules.
In infiltration metasomatism are carried out many variants of matter
transfer amongst which it is possible to distinguish two main manners: a) The

42
simplest case, when components’ transfer occurs in the course of dissolution
simultaneously with it. b) The second, most general case when each filtrating
component has its own individual speed.
If we designate the filtration speed of the components from a to k through
a, ...,k, and the filtration speed of the dissolution through 0, we can obtain
i
the relation  i  (3.5)-which is the coefficient of filtration effect,
0
characterizing the filtration speed of the given component relatively to the
solvent.
The notion of filtration effect was introduced into geological literature by
[Link] (1947), who generalized the marked cases of limited
permeability of the rocks [McKay, 1946]. Nature and size of the filtration effect
and its role in hydrothermal and metallogenic processes present interesting
geochemical problems. Theoretical and experimental research in these directions
was performed, notably by the author and his collaborators [Zharikov, 1965,
1969; Zharikov & Alexin, 1971 a,b, 1973; Zharikov et al., 1973; Alexin et al.,
1982; Experimental problems of geology, 1986 ; Experiment in solving current
problems of geology, 1994].
The physico-chemical nature of the filtration effect will be examined in
more detail below, its decisive role in the evolution of endogenic postmagmatic
processes, including metallogenic ones. Here, without examining causes, we
emphasize the component’s relative speed through coefficient a of the filtration
effect and introduce a few main relations.
Suppose an isolated cross-section (q=1) through which whatever
component i infiltrates:
dmi=CiWidt=i0Cidt (3.6)
Differentiating both members according to distance and reorganizing
them we get
1 C i Ci Ci i 0 (3.7)is the filtration equation of the
Wi t x x
component i in the conditions of the varying filtration effect.
A few consequences:
a) Starting with Ci constant and Ci 0 , from (3.7) we get:
x
Ci 0Ci i (3.8)
t x
or ln Ci 0 i (3.9)
t x
from which it evidently follows that a diminution of the coefficient of the
filtration effect !!!( xi 0 ) brings about the component “i” concentration in the
solution flow’s that will be higher in proportion of the component’s initial
concentration (Ci), and a significant diminution of i.

43
 b) We may suppose that surrouding rock has a somewhat constant
coefficient of filtration effect, then will be reached the stationary state (
Ci 0 ), for which:
x
i
i Ci Ci 0 (3.10)
x x
(iCi)
or 0 andCiI=const. (3.11)
x
Equation (3.11) can be conveniently presented in the form:
CiWi=Ci00 (3.12)
where Ci is the concentration for i= 1 or for i= 0.
0

There follows from equations (3.11) and (3.12) that in environments with
different I,the component s’ distinct concentration is established in the solution,
which may exceed the saturation concentration, resulting in the corresponding
components’ precipitation from the solution.
Leaving aside other manifestations of the filtration effect, we underline
that i may be more than unity, reflecting possible variations of the
hydrothermal differentiation of postmagmatic solutions.
Filtration effect usually implies the components’ movement in a
homogeneous liquid or super-critical solution. This however is not without fail.
In general conditions the component’s displacement is foreseen in the general
flow of the fluid, which may be homogeneous and heterogeneous. The problem
of the relative role of transfer in gaseous or liquid phase, of the metallogenetic
significance of gaseous or liquid transfer, is being discussed by geologists and
geochimists, notably acutely between K. Fenner, N. Bowen, [Link], K.
Ross and others relatively to the role of a gaseous or liquid component in the
processes of hydrothermal ore formation.
Nowadays the problem attracts special attention again, with the
possibility of the components’ simultaneous differential transfer by the
heterogeneous gas-liquid fluids: this phenomenon’s physico-chemical
preconditions depend on the limited solubility in H2OCO2 and H2OCO2
chlorure systems by means of very simple examples of hydrothermal solutions,
or in the more complicated systems: : H2OCO2albite, H2OCO2 granite,
H2OCO2–NaCl–albite and others. One of those conditions is the problem of
simultaneous filtration of the heterogeneous mixture of a steam-liquid in
ultraporous rocks. Experimental data in that direction are isolated. S.M.
Koshenchuk [Koshentchuk, 1993] has made a series of tests on filtration of
water-gas mixtures: H2OCO2, H2OAr, H2OCO2Ar through various
ultraporous filters under various pressures; main conclusion: precise information
from the experiments regards the different displacement speeds in gaseous and
liquid phases depending on the permeability of the environment. For a high
permeability (k=3-10 millidarcys), the flow of the gas-water mixture proceeds in

44
“barbotage”; for k between 3.10-6 and 3.0 millidarcys there occurs a
homogeneous flow and finally for small permeability with k=n.10-6 to n.10-4
millidarcys, water dominates the flow of initial gas-water mixture. The outlined
dependence requires further theoretical and experimental research.
V.M. Shmonov, V.I. Vitovtova, A.V. Zharikov and others, [Vitovtova &
Shmonov, 1982; Shmonov et al., 1995; Vitovtova, 1989; Zharikov et al., 1993]
have undertaken experimental researches on permeability of various rocks
(limestone, marbles, granites, crystalline, schists, etc) at high temperatures. The
influence of the rocks’ thermal plasticity on their permeability has been
particularly studied [Balashov & Zaraysky, 1989; Zaraysky & Balashov, 1995].
As a result, it has been possible to distinguish various types of evolution
of porosity depending on temperature, general and effective pressure, on
mineralogical composition of the rocks and a few more parameters.
Calciculation of the evolution of the field of permeability has been attempted on
a few objects: the skarn deposits of Saiak I and Tactau; the deposits of Ak-
Chatau, some horizons of very deep bore holes of Kola [Vitovtova et al., 1983;
Zharikov et al., 1985, 1990]. Referring the reader to the interesting data of these
works we note some important regularities, illustrating them with diagrams
(fig.3.1), building upon the results of those works.
Note that a reheating (under pressure, naturally) brings about on the whole
compression and increase of permeability of the rocks. It develops in differences
in lengthening of various minerals in different crystallographic directions.
Naturally, this is especially marked on polymineral rocks (such as granites).
Note the complex influence of temperature and effective pressure. However, as
shown by experiments of [Link] and his team, each rock type has its
own gamut of non-permeability when permeability coefficients are at less than
10-5 millidarcys, which practically rules out a noticeable transfer of the
solution.41)
We have shown above some important particularities in the solutions’
behavior in ultraporous environments. As shown by more thorough research it
would seem that a simple process of flow of solutions in ultraporous
environments develops as a complex physico-chemical phenomenon. It can be
said that the conditions at the limits depend upon contrary parameters. 1) The
formation of oversaturated solutions (with PS > PF) brings about filling of voids,
great pores, microcracks. There follows formation of active pores of optimal
dimensions, whose size is offset by necessary concentration of coexisting fluids.
The processes contribute to the rocks’ thermal plasticity. 2) On the other hand,

1)
Remember that in thermodynamics effective pressure means difference between pressure on the rock and
pressure on the fluid Peff =Ps-PF where  is a coefficient that informs about general pressure on “depth”, for
the condition of the earth crust  nears 1. However, for permeability, or more precisely for the flow’s speed, the
fluid pressure’s gradient is extremely significant, as shown by Darcy’s law, v=(k/)(pf/x) , where v is the
filtration speed, k the coefficient of permeability and  the viscosity.

45
the relation between temperature and effective pressure shows that there exist
maximal dimensions of porosity, in the order of 10-5-10-6 millidarcys; for
smaller pores the solutions’ flow cannot happen; one can only invoke diffusion
processes, complicated by the influence of superficial minerals.
In conclusion, the amounts of permeability of metasomatic skarns (cf. fig.
3.1), greisens and others show that their remaining permeability is sufficiently
high (n10-4 millidarcys).

3.2. Causes and fundamental equations of metasomatism.

Metasomatism appears as a violation of the equilibrium between the
surrounding rocks and coexisting hydrothermal solutions. In nature two extreme
cases may be distinguished: simple and full metasomatism.
Simple metasomatism occurs when there is deviation from equilibrium
during gradual evolution of the coexisting solution due to a variation of
temperature (and of whatever component’s solubility), a variation of the
coefficient of the filtration effect (and of the corresponding concentration of any
component), or the variation of other isolated factors. In that case, at the limit,
variation of whatever factor results in an “isolated” act of metasomatism. Many
examples of it are widely known: microclinization or albitization of feldspars
through “autometasomatism” of granititoids and other rocks.
The second, extreme, case, complete metasomatism, occurs when the rock
penetrates a solution the composition of which is completely independent from
that of the surrouding rock. In this case the altered rocks undergo reiterated
reactions with the acting solutions, with formation of a series of zones built of
metasomatic minerals. The succession of zones is called metasomatic column,
the regular structure of which will be examined below.
We have so far mainly considered that formation of metasomatic bodies,
their structure, strength and other important peculiarities result from matter
transfer through solutions. We have distinguished, accordingly, diffusion and
infiltration metasomatism. The former proceeds as a rule in isothermal
conditions, since the size of microporosity coefficients is usually 1.5 to 2 times
higher than that of the diffusion coefficients. However, in diffusion metosomatic
formations are observed regressive metasomatic transformations due to lowering
temperature during the process. These changes are as a rule visible in the form
of separate simple parts of metasomatic transformations.
Much more complex is the influence of temperature on infiltration
metasomatic formations. These frequently seize great masses of rocks which
may settle in various temperature conditions. One of the widespread and
relatively simple situations occurs with the existence of a field of temperature
gradient, for instance, in contact zones or apical parts of an intrusive massif.
Other examples can be found of “extended” temperature fields. Also
characteristic of infiltration metasomatism is temperature variation in time; but

46
in most cases this appears in simple metasomatic replacement, partial or total, of
separate minerals; and considering the general regularity of metasomatism, these
“applications’ may be considered as additional complications.
As shown above, metasomatism occurs as a rule in local equilibrium, i.e.
when, as against global changes of defiant metasomatic parameters, stable
equilibrium occurs at each instant within whatever elementary part. However, in
some metasomatites, little deep and usually of low temperature, stable
equilibrium is not reached, witness the conservation of relicts of incompletely
replaced minerals, conservation of parts of the rocks untouched by
metasomatism and so on. In such cases, in order to examine the general structure
regularities of metasomatic bodies, it is necessary either to take into account
parameters linked with the kinetics of corresponding replacement reactions, or
artificially to separate from the general system its part in equilibrium. But “it is
an ill wind that blows nobody good”, if metasomatism always happened in total
equilibrium we never could succeed in observing the finenesses of the
replacement processes, the mechanism of the minerals’ reactions and so on.
In establishing a metasomatism model called theory of metasomatic
zoning the method of [Link] [Korzhinsky, 19511,2, 19521,2, 1953,
1969] has surely proved the most rational. This method consists in establishing
and researching the simplest models of metasomatism with ulterior introduction
of complements to more simple schemes reflecting more complex cases.
Besides, it is interesting to take the most general view of the problem in
order correctly to evaluate the importance and limits of manifestation or
predominance of some separate, constitutive, complex metasomatic processes.
This has partially been made as to the common development of infiltration and
diffusion metasomatism [Zharikov, 1965].
Let us examine the most general case. A solution of arbitrary composition
penetrates a rock however composed in a field with a temperature gradient. If
we examine any elementary volume containing rocks, the general matter
flowing through this volume will naturally sum up the flows produced by certain
applied forces. These flows may put together, i.e. appear as the sum of different
flows, if the expression of the acting forces is correctly selected. It can be
affirmed [Zharikov, 1961, 1976; see for more details the courses of irreversible
thermodynamics] that there will exist between the flows linear relations if the
acting forces are expressed in conformity with the equation of the growth speed
of the entropy (see below).
So, the general flow may be expressed as
IS=Iinf+Idif+IT+Ikin (3.13)
and for a component "i":
ISi=Iiinf+Iidif+IiT+Iikin (3.14)
 dmi S
where I i  ( ) (3.15)
dt

47
 Iiinf being the infiltration flow, Iidif the diffusion flow, IiT the flow due to
temperature variation, Iikin the one influenced by the kinetics (speed) of
reactions. Let us take, according to Onsager’s principle
Ii = Li Xi (3.16)
where Li is the transfer’s linear coefficient and XI the acting force, we get
the general relation
Ii=LiinfXiinf+LidifXidif+LiTXiT+LikinXikin (3.17)
or
( dm ) (dm)inf (dm)idif (dm)iT (dm)ikin
dt i dt i dt dt dt
(3.18)
The expression of the acting forces in general form is obtained from
the equation of the growth speed of the entropy (De Groot & Mazur, 1964;
Zharikov, 1965, 1976) :

dt
  
di S u 1 diU
T dt
dQ p
 1   dV   dma
T dt
k

T dt a T dt
a

(3.19)
di S u
where is the growth speed of the entropy in the irreversible process
dt
in the system U = f(S,V,ma...mk). One can be sure that a similar expression of
irreversible changes through the system’s thermodynamic potentials can be
obtained for any thermodynamic system, including those with perfectly mobile
components [Zharikov, 1976].
Then the general equation of the matter transfer (of the component i) for
the metasomatism may be expressed as
p dif i T 1 kin i
IiS Linf
i  L   Li  Li 
T i T T T
(3.20)
Note that Onsager’s principles, law of linear correlation and
reciprocating principle, establishing a correlation between different processes
simultaneously flowing in the system are correct only for a selection of flow and
acting forces which conforms to the equation of growth speed of the entropy in
the system (equation 3.19), as made in equation 3.20.
The general flow equation (3.20) is at the basis of the conclusion of
the equation of metasomatic zoning. However, the conclusion of the generalized
equation of metasomatic zoning is so important that it is certainly more
reasonable first to deduce an equation of the separate types of metasomatism and
then, remembering the corresponding selection of active forces, to add the real
flows. It is also useful, in order to simplify the operations, to consider that in the
framework of one dimension space. In order to underscore the important ideas
and conclusions we have omitted many indispensable calciculations, referring
the reader for details to specialized works.

48
 3.3. Metasomatic zoning of isothermic infiltration
Conclusion of the equation of zoning of isothermic infiltration
In equation (3.20), the infiltration flow through a single volume of
the component “i” is defined as
 
inf
Iiinf  dmi Linf
dt i 
P
T
(3.21)
In isothermic conditions we have Li  Linf
inf
i ; for a one-dimensional flow
T
through an isolated section, p changes into p , then:
x
dm
dt

i
inf
Linf
i 
 p 

 x 
(3.22)
In equation (3.22) Liinf expresses the unity quantity of component
“i” moving through the flow, and Liinf = iCi (3.23), where Ci is the
component’s concentration in the solution and I the coefficient of the filtration
effect. In accordance with the known equation of the hydrodynamic speed of
filtration one gets the equality:
p
v k 
 l
(3.24)
where  is the solution viscosity, k is the coefficient reflecting the
structure (permeability) of the surroundings, and 
l
p
is the “hydraulic gradient”,
none other than the pressure gradient for the one-dimensional flow equal to p .
dx
Then, designating the filtration speed of the given solution in the given
surroundings by 0, we get:
0    p and
k l
p
0 
x
(3.25)
Finally, the filtration equation of component “i” through a single
section is noted as

dmi = i  Ci  0  dt = i  Ci  dv (3.26)

where v is the volume of the infiltrating solution dv = 0  dt.

The equation (3.26) has been used by [Link] [1969] as a
conclusion to the equation of infiltrating isothermal metasomatic zoning.

49
 Admittedly, the rock’s composition is arbitrary, but homogeneous;
the solution’s composition is arbitrary, but constant, unchanging in time; the
system of pores is uniform, but insignificant, i.e. the rock’s volume remains
constant; so does the temperature as stipulated. The principle of local
equilibrium is observed.
Starting from equation (3.26) we derive according to distance x and
dv 
anticipatively reassemble the two members: dx
 
 dmi iCi 
, and as a result we
x
get the expression
 i i Ci
v x
(3.27)
which shows that by infiltration of an elementary volume of the solution
v into an elementary volume of solid rock (a volume delimited by a single
section shifting along the elementary distance x ), there occurs a linked change
in the component i’s content in the solid rock (i) and in the concentration (Ci)
of the same component in the infiltrated solution. The sign minus signifies the
inverted order of the difference from initial to final state, I; the coefficient of
the filtration effect is taken as constant; we neglect the content of component i in
the porous solution. If the later is important, the expression (3.27) takes the
form:
 i S i  
  i Ci (3.28)
 v v  x
 i S i 
Or  vV   C li Ci (3.28a)
 v  x
where  is the initial porosity (volume of pores) of the initial rock. Taking
the pores volume into account has meaning in particular cases; generally this
member may be neglected.
If the solution contains an arbitrary number of components “k”, it is
natural to have “k” equations like (3.27):
 a a Ca ,...;  i i Ci ;  k k Ck
v x v x v k
(3.29)
We recall the condition that the process must develop in local
equilibrium, i.e. each moment in each elementary volume defined by the size of
components’ content in the solid rock, corresponds a single concentration in
equilibrium of those components in the solution. Thus, there are in all equations
only two independent parameters, the direction x and the volume v of the
infiltrating solution. In this case, the variation of content of any component “i” is
identically expressed as:

50
  
di  i dv v dx
v x x v
 
(3.30)
and if one chooses any section with a constant content “i”, i.e. dI = 0,
equation (3.30) can take the form:
i
dx  v
 
dv i
x
 
(3.31)
Comparing (3.31) with (3.27) we easily obtain:
dx
dv
 Cx xi
i
i
i

(3.32)
where dx
dv
is the relative displacement speed of the section with constant
concentration “i” in dependence upon change of concentration and content of
component “i” along an elementary segment of the path of the infiltrating
solution.
Obviously, such an expression of relative speed can be obtained for
all the “k” components, and we have a system of “k” equations in the form of

dxdv   Cx ax

(3.32):
a
a

dxdv   Cx xi

a
i
i
i

dxdv   Cx kx

(3.33)
k
k
k
In the system (3.33) the two variables x and v can be replaced by
one variable x or dx u , expressing relative speed. In which case system (3.33)
v dv


may be replaced by one equation:
uinf  dx a dCa ...i dCi k dCk
dv a...k da di dk
(3.34)
that expresses the dependence of the transfer speed of the column’s
section upon the components’ concentration change in the solution and their
content in the rock.
Equation (3.34) also shows that if we have chosen a determined
section after any physical index for any component (constant content of

51
component “i”) the chosen section behaves in the same way for all other
dCi
components. If in this section there occurs a change for any component i
di
there will occur in this section a change in concentration and content of all other
components (another possible solution can only give an indetermination 0 ).
0
If in the chosen section final changes occur in content and
concentration of the components, equation (3.34) should be written in the form:
x C C C
u inf    a a  ...  i i   k k
v a i k
(3.35)
Equations (3.34) and (3.35) are called equations of isothermal
metasomatic infiltration zoning, or of isothermal metasomatic infiltration
column. Further consideration will demonstrate this denomination’s legitimacy.
Note that solving equations (3.34) and (3.35) has require some indispensable
mathematical subtleties; a discussion of these details as can be found in the
works of D.S. Korzhinsky [1969, 1973], P. Lichtner [Lichtner, 1991], and B.
Guy [Guy, 1993].
Let us now examine the properties of infiltration of metasomatic
zoning resulting from equations (3.33) and (3.34). Surprising is the concordance
between these particular properties and of composition and structure of natural
metasomatites and experimental metasomatic columns; it undoubtedly serves to
a direct demonstration of the validity of the conclusion adduced above.

General properties of the isothermal infiltration metasomatic

zoning
We propound this part somewhat differently from [Link]
(1951), though rigorously following his main principles.
1. The cause of arising of a section consists in the replacement of
minerals by one another (at the limit of one by another). In fact, C i in equations
(3.34) and (3.35) represents saturation concentration of a given component
according to a given determined mineralogical composition of the rock.
Saturation concentration is invariable for a constant composition of the rock,
because any compatible concentration variation occurs at the limit with an

Ci Ci 
infinite speed i  0   . That is why the only cause of appearance of a
section is the appearance of a replacement front with qualitative change of the
mineralogical composition, i.e. appearance of new minerals replacing the initial
association. Then equations (3.34) and (3.35) describe corresponding fronts of
exchange with minerals of constant composition, where:

52
 uinf  x a Ca ...i Ci k  Ck
v a i k
(3.35)
Ca and i…Ck, k point to variation of concentration and content of
the components in any such section or, better, at each replacement front. Thus,
evidently, the higher Ci the higher the corresponding displacement speed ( x )
i v
of such a section.
A few useful graphs will illustrate these relations. We take for

example a column with three replacement fronts v  v  v 

I II III
x x x
, then on the
diagram x – v (fig. 3.2a) one can observe three straight lines
dxdv  tg dxdv  tg dxdv  tg ,
I
11
II
2
III
3 representing relative transfer speed
corresponding to the replacement fronts. Figure 3.2b shows diagram Ci-i of
intrusion and removal of component “i”, where the slant lines characterize the
relation to the transfer speed of the section, but at a fixed point the content and
concentration of component “i” between the sections, i.e. in the metasomatic
zones.
2. The sharp replacement limits and the constant composition of the
minerals and the solution at the limits of the zones appear as the characteristic
graph of the isothermal infiltration metasomatosis. This conclusion is well
visible in metasomatites formed by minerals of constant composition. In fact, if
Ca…Ck are the saturation concentrations in equilibrium with associated minerals
of constant composition, they remain constant in the limits coexisting with this
association, i.e. the limits of the metasomatic zone. The zone’s mineral
composition also remains constant in so far as the saturation concentration does
not depend upon the quantity of minerals and, on the contrary, the variations in
quantitative correspondence would lead to variation of concentration of the
coexisting solution.
Variation Ca…Ck may be only linked with variation in the zone’s
mineralogical composition, or, as may be said, to the qualitative variation of the
mineralogical composition, which occurs with the formation of a replacement
front of some minerals by others. In local equilibrium this front will be sharp: to
the percolation of each elementary volume of solution corresponds elementary
replacement of some minerals by others, with corresponding variation of
concentration and content of the component which in local equilibrium occurs
much more rapidly than the solution’s infiltration.
If along the column with minerals of constant composition, this
regime replacement is sufficiently clear and no special demonstrations are
needed, except reducing ones; then not so evident is analogous constancy of

53
concentration and composition of the rock, with sharp replacing fronts for
metasomatic zones with minerals of variable composition. An elegant
demonstration of this has been made by [Link]. We summarize it,
referring for details to the original [[Link], 1969].
On fig. 3.3 is represented the diagram of concentration (Ci), (i)
content of component “i” , in which there is the components i’s content in
minerals of variable composition M(M1M2), N(N1N2) and P(P1P2) and the
curve of relation CiI for these minerals (remember that for minerals of variable
i
composition we always have 0 , hence Ci 0 ). Finally on the diagram
xi i

sections v  v  v 

I II III
x x x
are plotted the lines corresponding to , where
x i Ci itg
v i , on which occurs replacement of minerals with one another,
with intrusion of component “i” (line a) and its removal (line b) (i, naturally,
constant).
It can easily be seen that the lines of the replacement fronts coincide
only with definite constant compositions of minerals’ solid solutions. In case of
intrusion of component i , it is the combination M2N2P2 that traces, in Roman
figures, the replacement fronts. In case of removal it is the combination are
P1N1M1. These correlations clearly show that the minerals’ solids solutions in
the isothermal infiltration columns possess a constant composition and that only
in certain cases is possible a very limited change of composition; for the column
of removal there are the minerals N1 and M1, whose possible change of
composition is indicated on fig.3.3 by a vertical dotted line.
In this way and in that case, when metasomatites accumulate
minerals of variable composition, the composition of minerals and solutions at
zone limits remain constant and replacement occurs suddenly there. Thus, (cf.
fig. 3.3) such and such a mineral can be replaced with a sudden variation of its
composition: M1M2N2P2.
Thus, constancy of composition of minerals and solutions at zone
limits and sudden, jerky variation at those limits are characteristic features of
isothermal infiltration metasomatosis.
Another important feature is indicated on the diagram. There occurs
in infiltration metasomatosis in each zone a maximal concentration of intruding
and a minimal one of removal components from those possible, compatible with
the given mineral composition of the zone. This immediately follows from
Ci
equation (3.35) v i i
x . If i is constant, x is as much higher as
v
C
the difference of concentration Ci is greater. At the zones’ limits i = 0 and ii

54
= , i.e. the component’s concentration attains infinitely quickly maximal or
minimal values, compatible with the given mineral composition.
It also follows from equation (3.34) and (3.35) that the relative
distance between sections, in other words, the interval between metasomatic
zones,

     
l  x  x i  Ci  Ci 
v v x
I II

 i
I II

i 
(3.36)
depends upon the components’ variations in concentration and
composition at the limits of the zone of the replacement front.

dxdv   dCda ... dCdi  dCdk

3. Metasomatic column and the cause of metasomatic zoning.
a i k
Equation (3.34) a i k defines the limit
(replacement front) between two metasomatic zones. If each zone contains “k”
components the general number 2k of parameters will be linked by (k-1)
equations of the form (3.34) and the number of independent parameters for two
contiguous zones will be 2k-(k-1) = k+1. If the initial rock contains k
components, whose compositions naturally are independent parameters on
appearance of a front or, in other words, a metasomatic zone independent from
the rock’s initial composition but depending therefore upon the components’
concentration in the solution, there is only a single parameter. Expressed in
thermodynamic parameters, it can be said that if the initial rock is determined by
k contents of inert components, then on transition towards the first metasomatic
zone one of the parameters becomes intensive, depending upon the
concentration of the component in the influencing solution.
These constructions may be extended in keeping with the
subsequent replacement fronts. So, in transition from the first metasomatic zone
with (k-1) contents of inert components to a subsequent zone, one more
parameter, due to equation (3.34), remains intensive, depending on
concentration of this component in the solution, but (k-2) contents of
independent components in the initial rock will be determined, i.e. will behave
like inert components, etc. Provided in the general case the number of fronts is
equal to k, an equal number of components will successively pass to the
perfectly mobile state and the number of metasomatic zones will in the general
case be equal to Z = k + 1 (3.37). This cluster of simultaneously formal zones is
called metasomatic column.
D.S. Korzhinsky’s introduction of the notion of metasomatic
column into scientific usage was the chief novelty in the explanation of
metasomatic processes. We insist on this. The zonal structure of the
metasomatic aureole had long been known to geologists and zoning was always
considered as resulting from some metasomatites succeeding to others. This was

55
a natural interpretation of observations of metasomatites replacing one another
and was linked to variation in the composition of the active solution. There was
no attempt whatever at expressing these presentations in the form of a mutual
coordination model.
D.S. Korzhinsky’s physico-chemical model has shown that exactly
on the contrary, in the most general case, i.e. for an arbitrary independent
composition of the initial rocks and the influencing solution, a metasomatic
column must arise as aggregate of metasomatic strictly limited zones, formed
simultaneously.
The cause of metasomatic zoning is the components’ differential
mobility, i.e. their successive passage from inert state to perfect mobility, creates
replacement fronts that form a column of metasomatic zones of different mineral
composition.
It is well known that the number of minerals is defined by that of
the system’s extensive parameters, and in the case of metasomatosis
,V,  ki 1 , i.e. equals the number of inert components in plus the volume.
rTmax
The successive passage of components from the inert to the perfectly mobile
state produces a corresponding diminution of the number of minerals in the
zones of the metasomatic column up to the last monomineral rear zone, formed
under the perfectly mobile behavior of all components. The volume occupying
this zone is filled by a mineral in connection with the components the solution of
which is most saturated and which consequently develop the highest
crystallization pressure.
Decrease of the minerals’ number in the metasomatic zones through
increasing intensity of the process up to formation of monomineral zones is a
most characteristic, distinctive feature of metasomatic processes.
In order to understand a metasomatic column as aggregate of
simultaneously formed of zones, the question arises what “simultaneous” means
in the physical expression and what are the real dimensions of these initial zones
and columns. Computerized modeling has shown that the unstable state (when
equation (3.37) and (3.35) do not function and there is no local equilibrium),
represents a negligible small part of the initial time. So, experiments show
[Zaraisky, 1989] that in simple column (with few zones) for a column thickness
of 0.3 to 0.4 mm, all the zones are clearly seen under the microscope, the limits
are sharp, with no mineral relicts. The formation time of an experimental
column is always known; it depends upon the initial rock’s composition, upon
the solution’s composition and concentration and of course upon temperature.
Considering average numbers, at high temperatures (400-500°C) a column is 2.0
to 5 mm thick and requires 144 to 216 hours. In other words, the mobility speed
of the front of the constituted column is in round numbers 0.3 to 0.6 mm per day
or 108 to 216 mm per year. Taking porosity in natural environments to be
substantially smaller (20 to 30 times), we can take speeds of 3.6 to 10.8 mm per

56
year. The usual thicknesses of the zones of infiltration metasomatic changes are
at least a few meters to a decameter. In other words the “kinetic stage” lasts
thousandths and even ten-thousandths of the time of the column’s formation.
Note that the succession of mineralogical reactions in the “kinetic
zone” corresponds in principle to the replacement reaction in the column in local
equilibrium. This is explained by the fact that the acting forces determining the
replacement front’s transfer speed prove in principle the selfsame that determine
the speeds of replacement reactions. So, according to equations (3.34) and
(3.35) the propagation speed of the replacement front in the metasomatic column
is as much higher as the difference between the components’ concentration in
contiguous zones is greater. Speed of the chemical reaction also depends upon
the components’ concentration and, for the replacement reactions, is so much
higher as the difference of the components’ concentration is greater. That is why
the column, having arisen in the first instants as kinetic, reorganizes itself easily
and rapidly in local equilibrium.
The column having formed progressively as the solutions were
infiltrating undergoes only proportional increase as far as all the similar values
shown in parentheses,
    
x I  a Ca v and l I / II  x I  x II  a Ca  a Ca v
a  a
I II

a 


remain constant. Only the volume of the infiltrating solution is a variable

independent parameter.
If the metasomatic solution contains “k” components, among which
initially are all inert (ki), the number (r) of zones is generally equal to Z = ki + 1
(3.36), as we saw. Remember that f ex  rT ,V ,   k i  1 .
max

This zoning, conditioned by the components’ alternative passage

from inert to perfectly mobile state, is called fundamental (principal) zoning.
But the sequel, in which the components reach perfect mobility, has been called
degree of components’ differential mobility or more simply degree of
components’ mobility.
The equation of infiltration zoning clearly, expresses quantitatively the
causes of various differential mobility of the components. If the external
replacement front is characterized by passage to the perfectly mobile state of
component “a” and the following front arises owing to the change of regime of

Ca x
I
Cb 
II
component “b”, we evidently get: v a a  v b b . In other words, the
x

components’ mobility depends upon the variation of concentration and the

linked change of composition of the component when passing from one
metasomatic zone to another: the higher the variation of concentration of the
saturation at lesser change of content of the component, the more mobile will be
the given component. It follows that there cannot be an “absolute” scale of

57
mobility. The components’ mobility is defined by the composition and
concentration of the influencing solution, by the composition of the replaced
mining rocks. On the other hand we observe preferential inertia of ill soluble
components such as Al2O3 or TiO2 in many metasomatic processes.
If multizonal columns, with Z = Ki + 1 zones, present the most
general cases of metasomatism, another extreme case is observed when under
the action of definite causes a single component alters its regime or its
concentration becomes different from that of the solution in equilibrium. In this
case there appears only one replacement zone, without multizonal columns
forming. This is called simple metasomatosis, as we pointed out above. Widely
known examples are: postmagmatic microclinization, granite albitization and
many others. Of course in natural conditions we come across various
intermediary formations, from total multizonal to simple metasomatites.
Two further important features of isothermal infiltration columns
are worth mentioning. Considering the “stable inertia” of some components and
the diversity of composition of natural minerals, it can be surmised that, in
nature also cases are repeatedly met when, on removal (or addition) of an inert
component there occurs more than one reaction of the rock with the solution
with formation of reaction minerals distinguished mainly by the maintenance of
one inert component, for example in the scheme:
IV III II I
 A A AB A AB2 A AB2 C  where the arrows indicate components
 
B and C reaching the perfectly mobile state. Or the natural example of the
internal zones of a greisens column:
IV III II I
 quartz quartz + topaz  quartz + muskovite  quartz + muskovite + kalispat  
 
Al K

In both columns, zones II and III contain the same number of minerals
and, consequently of inert components: conditional component B in the first
position column; component A1 in the second greisen column. Only, the
maintenance of inert components in zones II and III is different, owing to the
possibility of appearance of reactions minerals, ensuring a minimum decrease of
free energy at the passage from zone to zone (see below). This type of zoning is
in expediency called complementary. As its distinctive sign serves the identical
number of minerals in the contiguous zones.
Another feature in the structure of infiltration metasomatic columns is the
fact that the external zones with feeble variation, often regionally extended are
, p, ki ), whereas the internal zones with
formed in isobaric conditions ( rTmax

58
strong transformations always appear in constant volume ( rT,V, ki 1 ).
max

There is usually in these columns Z = Ki in so far as in a change of isobaric

towards isochoric regime two components at once reach the perfectly mobile
state. Such correlations are particularly characteristic of the zones of
propyllitization, beresitisation and quartzo-sericitic metasomatism in the coarse
evolution of these processes of variations of eruptive rocks. The cause of change
of the “mechanical” regime of the process is rather simple: in the external zones,
where addition and removal of components are insignificant (3-4%), this is
easily compensated by an even more insignificant variation of volume at
formation of hydroxylate silicates, carbonates, etc. Through an intense removal
of components happening in the internal zones, occurring voids are immediately
filled with a deposit of a mineral of the most saturated solution. In
metasomatites linked to granitoids, such a mineral is quartz, and the change
from isobaric to isochoric regime proceeds by the silica passing to the perfectly
mobile state. In metasomatites on basic rocks the role of perfectly mobile
mineral is often played by a carbonate.
To illustrate the exposition and make it concrete we show on table
3.1 a beresitization column of acid eruptive rocks characteristic of the
polymetallic deposits of Karamazar. The extend zones (1, 2, 3) having a coarse
extension, differ by partial rock transformations and, for many researchers, are
not even linked to beresitization. This is surely false. Moreover these external
transformations are specific of each type of perimetalliferous changes and may
properly indicate periveinous variations. Starting from zone 4, there appear
significantly more intensively transformed rocks (feldspar dissolution etc.).
These transformations occur isochorically, in conditions of constant volume of
the rocks, and the role of perfectly mobile mineral, filling up the volume deficit,
is played by quartz. Characteristically and instructively, all reactions at the
limits of zones 3/4, 4/5, 5/6, 6/7 occur by addition of silica, and quartz even
replaces ankerite, pyrite, i.e. originally no maintenance of silica.

59
 Table 3.1. Metasomatic column of beresitization
Zone of Zone of mineral associations Reaction of replacements and components
column becoming perfectly mobile
1 Qtz+Or+Ser+Ab+Chl+Cc+Py Or→

2 Qtz+Ser+Ab+Chl+Cc+Py →Ab±Ser±Qtz
Chl+Cc→
3 Qtz+ Ser+Ab+Ank+Py →Ank+Ser(↓↑K)
Ab→
+ + + +
4 Qtz Ser Ab Ank Py →Ser+Qtz(↓↑Na)+(↓↑Si)
Ank→
+ +
5 Qtz Ser Py →Qtz(+↓↑Mg)
Py→
+
6 Qtz Ser →Qtz(+↓↑Fe)
Ser→
7 Qtz →Qtz

Increase of mobility→ Type of

Inert components Components perfectly mobile process
Al, Fe, Mg, Si, Na, Ca, K O2, S2, CO2, H2O

Al, Fe, Mg, Si, Na, Ca K, O2, S2, CO2, H2O P = const.

Al, Fe, Mg, Si, Na Ca, K, O2, S2, CO2, H2O

Al, Fe, Mg Si, Na, Ca, K, O2, S2, CO2, H2O

Al, Fe Mg, Si, Na, Ca, K, O2, S2, CO2, H2O V = const.

Al Fe, Mg, Si, Na, Ca, K, O2, S2, CO2, H2O

All components perfectly mobile

4. Main conclusions. Theoretical research and experimental

models, together with natural observations, show that isothermal infiltration
metasomatosis is characterized by the following important features:
a) Through infiltration of solutions whose composition is arbitrary
but determined, unchanging in time through the rock the compositions of which
is arbitrary but homogeneous and constant in space, is formed a column of
sharply limited zones, differing in their own mineral composition.
b) There occurs at the zone limits a sudden, jerky change in the
composition of the rock and of the solution; in the limits of the zones the
compositions of rocks and solutions remain constant.
c) Replacement processes appear only at the zone limits and are
expressed in exchange of minerals with minerals of another composition.

60
 d) As solutions infiltrate there occurs only a proportional increase
of the column’s zones, without variation of their composition or structure.
e) Metasomatic zoning produces differential mobility of
components: at each zone limit, as the infiltration process grows more intensive,
a successive passage occurs of the components from inert to perfectly mobile
state; this succession is called row of differential mobility of components.
f) The components’ mobility is determined by their concentration in
the solution and their composition in the replaced rocks; the greater the
concentration variation for a lesser variation in the component’s content at the
replacement front (zone limit), the higher is the mobility of the given
component.
g) Successive passage of components from inert to perfectly mobile
state decreases the number of minerals in metasomatic zones (at the limit on one
mineral at each zone limit) until monomineral rear zones are formed; decrease in
the minerals’ number as metasomatism intensifies and, correspondingly, the
intensity of the rocks’ chemical transformation remains a characteristic
distinctive peculiarity of metasomatites.
h) Fundamental zoning, produced by the components’ differential
mobility, may be complicated by complementary zoning with the possibility of
some beneficial thermodynamic reactions of rock and solution without regime
change of components.
i) Evidently there is in the external zones of feeble variation the
usual change from isobaric to isochoric conditions in intensive metasomatosis.
The mentioned peculiarities characterize the most important
properties of metasomatic infiltration zoning. They represent the general
idealized model of isothermal infiltration metasomatosis. Natural metasomatic
columns developing in concrete geological environment, corresponding to or
approaching the limit of the mentioned properties, may have their specific
peculiarities. For instance, the frontal progression of a metasomatic column
occurs in condition of homogenous porosity. The presence of zones of high
permeability and jointing produces, naturally, primary, outstripping
developments of metasomatites in these zones.
The model of infiltration metasomatism depends on the principle of local
equilibrium. However, in a series of cases, particularly among metasomatites of
lower temperature, owing to irregular permeability or feeble reaction speeds,
mineral relicts are preserved of preceding zones. They are easily discerned by
the replacement structure or by their irregular distribution. Of course, these
minerals must in theoretical analysis be connected to a preceding zone. But, on
the other hand, if there were no mineral relicts and if the principle of local
equilibrium were absolutely applied, we never could decipher the detail of the
replacement mechanism.

61
 Finally, in the zone of metasomatic transformation by the solution can be
perceived the differences with the initial rock’s composition. In principle two
extreme cases can here be distinguished.

In one of them, when the change of chemical composition (i.e. of the

content of inert components) is small, there occurs then a variation of
quantitative relations of the minerals, fixing the virtual inert components. In the
other case there occurs a radical change in the initial rock’s composition.
Metasomatites formed on them are to be considered as an independent column:
it has another structure. An instance of beresites and listvenites has been
scrupulously studied, but there will be situations where these limits will be
difficult to draw.

3.4. Diffusion metasomatic zoning

Conclusion of the equation of diffusion metasomatic zoning
Starting from the equation (3.20) of general matter flow for the
isothermal diffusion flow of component "i" we get the expression:
dif

J  dmi  Ldif

i
dif
i i
 dt 
(3.38)
where Ldif
i is the kinetic coefficient expressing the quantity of component
"i" percolating through a unitary section at a given temperature and a given
activity of force . For the one dimensional flow this expression may become:
i Ldif
mi Ldif   i RT C Di Ci
t i
x C x x
(3.39)
or
mi Di Ci
t x
(3.40)
Equation (3.40) expresses Fick’s first law, also designating the quantity of
component "i" percolating at each time unity through a unitary section under a
Ci
concentration gradient equal to . Comparing the members of equations
x
(3.39) and (3.40), it is not difficult to see how through a complex multifactorial
non-linear value it represents the well-known diffusion coefficient:
Di  i RT
dif
L
Ci
(3.41)

62
    
Taking the derivative from both members of the equation:
  mi   D Ci
x t x i x
(3.42)
and adopting, as above, the section as isolated, but D1 as independent of
distance, one gets the expression of Fick’s second law:

i    Di Ci
t x x

(3.43)
where i is the content variation of component "i” in a unity of volume
t
 
of rock, and x  Di x
Ci 
its concentration variation in the solution. In (3.43)
we neglect the rock’s porosity with component “i”’s content in the porous
solution since they are very small relatively to the general determination of the
metasomatism. But if they are important, equation (3.43) should be replaced by
another one:
i S  Ci   Ci
t
 Di
x x
 
(3.44)
where iS is the content of component “i” in the solid rock,  the porosity
(the volume of pores), Ci component “i”’s concentration in the porous solution.
Equations (3.43) and (3.44) are equivalent to the usual notation of
Fick’s second law:

Ci    Di Ci
t x x

(3.45)
The only difference is that in (3.45) Ci refers to component i’s
t
concentration variation in the solution’s unitary volume for diffusion in a
homogeneous environment. For our purpose, examination of diffusion
metasomatism, it is important to choose as particular symbol i , concentration
t
variation (content in the unitary volume) in the solid rock.
If the solution contains “k” components, it is clear that we have k
equations of the form (3.43), each characterizing each component’s independent
diffusion. Equations (3.43) to (3.45) are nonlinear and their solution for systems
with several components is a difficult problem.
They usually are restricted to partial solutions (with determined
limited conditions) and to allowed approximations.
Referring the reader to the original works for the necessary
discussion [Korzhinsky, 1968, 1982; Frantz & Mao, 1976; Diemin & al., 1979;

63
Balashov, 1985, 1992; Guy, 1993] we limit ourselves to Korzhinsky’s very
succinct conclusion for the simplest cases of periveinous and contact
metasomatism. This conclusion was made like the conclusion of the equation of
infiltration zoning.
Adopting as constant the diffusion coefficients of the components
we get k equations of the form:
i  Di  Ci
2

t x2
(3.46)
In local chemical equilibrium the number of degrees of the free
system is limited to the k equations of the thermodynamic link of the
component’s concentration and content.
Then in determined limited conditions, when the initial rock’s
composition is constant (a = a0…, k = k0 for x = 0, t > 0) and the solution’s
composition is defined ( Ca = Ca0…, Ck = Ck0 for x =0 and t > 0), the state of the
zone of diffusion interaction depends upon only two parameters, x and t.
Observing the section that keeps constant the composition of

   
component i, we get:
di i dt  i dx0
t x x t
(3.47)
and substituting i from (3.46) we get k equations of the form
t

dx
dt
 D
i
 C i
i
x

2

x 2
i

(3.48)
For constant limited conditions and zones of constant composition
the system of k equations in the form (3.48), through substitution of a variable
x W
, where W = udif , the section’s adduced transfer speed, may be
t
transformed into an equation of simple diffusion zoning:

 
dx
dt a...k
 2Ca a
x x
 2Ci i
Da é  ... Di 2  Dk
x x
 2Ck k

x2 x
(3.49)
an equation legitimate for all the introduced limitations and the constant
composition of the zones.

64
 General properties of metasomatic diffusion zoning
Analysis of the diffusion equations and diffusion zoning allows us to
reveal the main particularities and properties of diffusion metasomatism, of
which we propound the results, referring the reader for detailed substantiation to
the works of [Korzhinsky, 1969, 1982; Demin et al., 1969; Guy, 1993;
Zharikov, 1965; Balashov, 1992]. First of all we underscore the chief difference
between diffusion and infiltration metasomatic zoning. While in the columns of
infiltration metasomatism the components’ concentration in the metasomatic
zones remains constant, in the zones of diffusion metasomatism the
components’ concentration in the solution changes continually.
Analysis of the diffusion equation shows the following:
 2Ci
a) For the zones of removal of components Ct i 0 and x2 0 (3.50).
Accordingly, the curves Ci = f(t) for x = const and Ci = f(x) for t = const
are convex.
b) For zones of components’ addition, on the contrary, Ct i 0 and
 2Ci 0
x2 (3.51)
and the curves Ci = f(t), Ci = f(x) are concave (for x and t constant, in
conformity*).
c) Curves Ci = f(t) and Ci = f(x) are suddenly nonlinear for feeble
values of x and t and clearly strive to linear dependence as far as t and x grow. In
 2Ci
other words for t and x very great, x2 0 and C x
cte , and the diffusion

equation may be approximately in linear dependence of the concentration

gradient upon the distance.
 Ci 2

d) It is established that, t 2 0 , i.e. the variation speed of the

component’s concentration, in other words, the diffusion speed decreases in
 2 Ci 0
time. Similarly the absolute value x 2 .and the variation speed of the
concentration (diffusion speed) decreases with distance. For low t, the exact
dependence
xW t (3.52)

*
Note that in the complex cases of configuration of reacting environments, the relations Ci/t for various x
may be more complicated. For instance, in the case of component i’s diffusion from the body’s limit in
infinite space for feeble X, C0 at first increases then decreases, whereas for higher X we always have
Ci/t > 0 (X is the body’s distance from contact in an infinite environment).

65
 where W is the adduced; diffusion speed, (one often takes approximately
x 2Dt ). This correlation is well confirmed by experimental reproduction of
the metasomatic diffusion columns. On fig.3.4 can be seen a few relations x
=f(t) for the diffusion columns of acid lixiviation and bimetasomatic reciprocal
action [Zharikov & Zaraisky, 1973; Zharikov, 1985; Zaraisky, 1989]. It can
easily be seen that speed W of growth of the limits of zones varies in wide
intervals from 0.4 to 18 cm/year1/2 depending on the situation of the column’s
limit, the porosity, the composition and pH of the solution.
e) If there occurs in the diffusion zone a reaction of the solution with
the solid rock, it is only possible with replacement of one mineral by another,
i.e. it leads to appearance of a diffusion metasomatic zoning. In this case,
equation (3.49) has a final solution:

   Ca    Ck
dx Da x ....Dk x
 
dt a k
(3.53)
in which the members have a real significance for the components taking
part in the replacement reactions. On graph C-x, lines C on these replacement
x
limits undergo a fracture (positive or negative, depending on whether there is an
addition or a removal of the given component). On fig.3.5 can be seen diagrams
C-x and I-x for the simplest case of replacement of unicomponent mineral A by
unicomponent mineral F with perifractural metasomatism, when initial
concentrations at the source (fracture) and in semi-infinite space (surrounding
rocks with one side of the fracture) are constant, Cf, Ca and C 0f , Ca0 , respectively.
A case is presented in which t is sufficient for concentration gradients to be
linear. It is easily seen that at the limit where A is replaced by F: A + (f)  F +
   
(a) (which usually manifests itself as FA)  Cxa < 0, but  Cxa > 0, i.e.
the concentration gradient of the reacting components is changing, which is
graphically expressed by discontinuity of curve Cx
. On fig.3.6 is represented
the general case of replacement by one component mineral F of the bimineral
rock A+B (also composed of one component minerals). Conditions at the limits
are similar only in the considered example: Cf , Ca , Cb is constant for x=0 and
x=, and thereby Cf is great compared with Ca and Cb for x=0 and, on the
contrary, Ca > Cb, much greater than Cf for x = . Time t is sufficient for the
linear dependence in the concentration gradients. Owing to the difference of the
components’ concentration gradients and diffusion coefficients in the zone of
reciprocal action on the initial rock A+B, there develops a column of
II I 0
metasomatic zones F F  A A B . For component f, at each limit (II/I and

66
  C f 
I/0),  x  < 0, which corresponds to an addition of component f and
 
replacement of B by F (limit I/0) and A by F (limit II/I). Accordingly, curve
C has two concave discontinuities. Mineral B at limit I/0 is replaced by
x
mineral F and component b is eliminated. Accordingly, for component b,
 
  > 0 and the line of the concentration gradient undergoes a convex
 x 
discontinuity. For component a, equation (3.50) at limit I/0 has no solution
Ca
because at that limit gradient x does not change and, consequently, does
 C f 
not produce elimination or admission of component a. At limit II/I,  x  > 0
 
and mineral A is replaced by mineral F with removal of component a, addition
of component f and, accordingly, the curves of the concentration gradient are
sharply concave (for component a), and convex (for component f). Especially
interesting is zone I, in which can change the content of components f and a and
consequently that of minerals F and A. Without loosing ourselves in discussing
this complex situation, we may note that this problem possesses, evidently, only
partial alternative solutions, the essence of which is reduced to the following. If
molar density of minerals F and A is different, then, for maintaining the linear
dependence of the components’ concentration gradients at the limits of zone I, a
variation is possible of the quantitative correlations of the minerals (cf. fig.3.6).
On the contrary, for proximate molar densities the composition of the zones will
remain constant, since the components’ dissolution or precipitation could lead to
breaking the linear dependence of their concentration gradient.

f) The main difference of diffusion metasomatic columns consists in the

behavior of the minerals, the solid solutions at the limits of metasomatic
zones. Since gradient of concentration of components at the zone limits
continuously varies, correspondingly the diffusion components’ content also
varies in the minerals of variable composition. The composition variation of
the minerals, solid solutions at the zone limits, is a characteristic sign of
diffusion metasomatic zoning (differing from infiltration).
g) The columns of metasomatic diffusion, as well as those of infiltration arise
under the influence of the components’ differential mobility and are therefore
characterized by reduction of the number of minerals in the zones as far as
intensity of the initial rocks’ metasomatic transformation increases. Apart from
this fundamental zoning, for diffusion metasomatic columns, a complementary
zoning is usually observed, which sometimes predominates and is formed by
reaction minerals for whose appearance conditions are favorable in which there
is uninterrupted, continuous variation of concentration of the added and

67
removed components. Complementary zoning, as we have mentioned, is
distinguished by an equal number of minerals in contiguous zones.

Bimetasomatic zoning
Bimetasomatic zoning is of special interest amidst diffusion
metasomatic formations, arising during slow penetration of solutions in the
contact zone between two environments in chemical unbalance. Owing to the
difference of concentrations (more exactly of chemical potentials) of the
components, there is observed in contact regions diffusion of components,
accompanied by formation in the diffusion zone of a few metasomatic zones
composed of reaction minerals ( if of course formation is possible of minerals
composed of diffusing components).
For clarity’s sake we consider two more simple cases of
bimetasomatic reciprocal action between one component minerals A and B,
forming reaction minerals composed of components a and b. On figure 3.7 are
given diagrams of concentration/distance (C-x) and of content/distance (i-x) in
the cases when components a and b produce reaction minerals of constant
composition. The diagram is established for a kind of time t>t0 when as a result
of reciprocal reaction action of components a and b a bimetasomatic column is
formed in the zone of oncoming diffusion:
 A A3B A2B AB2 AB3 B 
As far as reaction minerals have a constant composition, the content
of components in the zones constantly and jerkily varies from zone to zone. The
components’ concentration gradients continually vary, and at the zone limits,
curve Ca,b = f(x) presents a discontinuity in answer to the final solution  C  ,
 x 
positive in case of a component’s removal (convex fracture) and negative in case
of addition (concave fracture). In course of time the zones increase without
change of the column’s structure. Growth speed diminishes according to
 
equation (3.52) W  x  .
 t
On figure 3.8 can be seen the column’s structure and diagrams of
concentration (Ca,b) /distance (x) and contents of components (a,b)/distance(x) in
case of bimetasomatic reciprocal action of minerals with one component A and
B, with formation of reaction zones composed of minerals of variable
composition corresponding to the content of components a and b . Comparing
the column of figures 3.7 and 3.8 it can easily be seen that in the last case, at the
limits of zones composed of mineral-solid solution, a variation in their
composition takes place:

68
0.0 4 3 2 1 0
 A  from A9B1 to A8B2  from A7B3 to A6B4  from A4B6 to A3B7  from A2B8 to A1B9  B 

And then, adopting a limited miscibility of components a and b (in

the limits indicated above) in relation to which a zoning is formed, with ultimate
change of composition and the gradient of the components’ concentration at the
zone limits. If AB were characterized by complete miscibility of the
components, there might arise, between A and B removals, a unique zone of the
mineral AB:  AABB . The column introduced above ([Link].3.8) grows
without structure change, with slowing down in time according to equation
(3.52).
The considered examples of bimetasomatic zoning are obviously of
the most simple. In more complicated cases, for example with some diffusing
components and minerals with several components, of content either constant or
variable, the column’s structure is more complex and one may vary in time
according to the value of diffusion coefficients of the components and their
concentration gradients (gradients of activity) in the reacting environments and
the influence of the varying solution upon the composition’s activity. These
situations demand each time their concrete solutions.
However, even in the simplest cases the essential changes in the
structure of the columns are established for contact conditions not plane, but
curved contact of the reacting environments. Without devilling on a theoretical
analysis of these cases [Korzhinsky, 1969, 1982; Zharikov & Vlassova, 1961]
we examine by way of concrete illustration the influence of contact forms upon
the structure of bimetasomatic columns.
On figure 3.9 for zoning with reaction minerals of constant
composition (cf. fig.3.7), is shown the correlation of thickness of different zones
for a convex (I) and a concave (II) contact (relative to environment A). The
diagram is constructed with calciculation of the balance of components a and b,
necessary for the formation of reaction zones in the same relations as in the case
of plane contact considered above (cf. fig 3.7).
It can be easily seen that in the environment limited by a curved contact
there arises a progressive growth of the zones, linked to the fact that the volume
of replacing rocks decreases in course of time. This is very neatly expressed for
the most external limit ( A3BA  on fig. 3.9, I  AB3B  on fig. 3.9, II).
After a certain time t the initial rocks A or B may be totally replaced, conditions
at the limits being essentially different, as well as the speed and even the
direction of displacement of the limits (limit A2BAB2). On the side of the
convex contact the limits’ displacement speed will slow down not only
corresponding to xW t but also on the strength of the volume increase of
replaced rock (contact surface always grows, especially for the most external

69
front). Finally for a certain time t progress of the external zone may stop, and the
following zone will progressively replace the external one.
In general conclusion, when contacts are incurved, sharp
asymmetric bimetasomatic columns appear. This is particularly important in
case of bimetasomatic columns of skarns linked with selective replacement of
determined zones by superposed mineralization.

3.5. Complex types of metasomatic zoning

The equations and properties of infiltration and diffusion

metasomatic columns examined above obviously represent extreme types of
metasomatic zoning. But it is impossible not to note that even these extreme
approximations will suffice to unravel the structure peculiarities of many natural
metasomatic formations. Besides, in the general case, natural metasomatic
processes are complex phenomena, whose dependence upon main parameters
has been expressed above in generalised equations of matter flows (3.13) to
(3.20). Meanwhile a complete open solution of the general flow equation is for a
present lacking. Partial solutions have been obtained and researched for the
process combinations most widely spread in nature for associated processes of
infiltration and diffusion [Zharikov, 1965, Zharikov & Vlassova, 1961;
Balashov, 1985; Guy, 1993], for diffusion processes complicated by kinetic
reaction [Balashov & Lebedeva, 1989; Balashov & Lebedeva, 1991], for
infiltration in space with temperature gradient [Korzhinsky, 1953, 1969].
Without going into details of these complex theoretical models we give a
succinct account of the results.

Metasomatic zoning of infiltration – diffusion

Infiltration metasomatosis accompanied with diffusion is usual in
natural metasomatic processes. In reality, to such a type (with a more or less
great role of diffusion) belong most natural metasomatic columns. Only, in order
to determine the respective role of infiltration and diffusion in such or other
columns, a painstaking and labour-intensive study must be made of mineral-
solid solutions at all the zone limits, in so far as constancy (for infiltration) or
variableness (for diffusion) of their content are the only general and indubitable
criteria of difference. Such detailed researches are often inaccessible, therefore
are isolated examples of well studied complex columns of infiltration-diffusion
[Zharikov, 1968; Zharikov & Vlassova, 1961; Vlassova & Zharikov, 1975].

Let us briefly examine the structure peculiarities of infiltration–diffusion

columns. The summary flow of component "i"  i


 
 I S  dmi S 
dt  is composed of

70
  inf dmi
infiltration flow  Ii  dt

  inf
  dif
 and diffusion flow  Ii  dm
  dt
i
 
dif

 that can

be composed provided the acting forces are expressed according to the equation
of growth speed of entropy (3.19). Then
p dif i
IiS Iiinf  Iidif Linf
i X i  Li X i  Li
inf dif dif inf L
T i T
(3.54)
In isothermal conditions in a one-dimension space:
     
dt
S

dt
inf
dmi  dmi  dmi Linf
dt
dif
i
p Ldif
x
 i RT Ci
Ci x
(3.55)
Replacing kinetic coefficients by the usual filtration and diffusion
coefficient and putting the expression of the acting forces, as was done above for
a unitary section (q=1) we get:
dm
dt
i
  C  D C  C D C
S

x
i i
x
0 0
i
i i i
i

(3.56)
where, remember, i  i is the coefficient of filtration effect and  , 
0
0 I

are the speeds of filtration of the flow and component "i" (0 = i for i = 1).
Consequently, following the same path as at the conclusion of the
equation of infiltration zoning (cf. above but also [Korzhinsky, 1951a, 1969,
1982; Zharikov & Vlassova, 1961]) we further make the following
transformation. Taking from (3.56) the derivative on distance x and replacing
   
 dmi by  i where i is the component i’s content in the unitary volume,
x dt t
S

we get:
 
 i i Ci  Di 2
t
S

x
2Ci
x
(3.57)
Choosing a section where component i’s content is constant (i.e. di
= 0), for which:
  
di i dt i dx0
t x
(3.58)
in sum we get:
dxdt   Cx  x D xC  xi
S

i
i
i i
i
2

2
i

(3.59)

71
 an equation expressing the relative transfer speed of the determined
section (with constant composition of component i), as a result of the common
infiltration and diffusion transfer of the component.
Equation (3.59) may obviously take the form:
    
S
dx  dx  dx
dt i dt i dt i
inf dif

(3.60) or:
uiS uiinf uidif
(3.61)
dx
where u  dt
S
i   is the general speed
S
of the flow, equal to the
section’s transfer speed owing to infiltration:

dt
 
uiinf  dx iinf Ci  i
x x
(3.62)
and of the transfer speed of the section of matter diffusion:
u 
dif
i
dx  
dif

dt i
Di
2Ci i

x2 x
(3.63)
Equation (3.39) may also be expressed in dependence upon volume
of infiltrated solution since dv = 0 dt, and evidently:

 
dx i Ci  i Di  Ci  i
S

dv i x x
2

x2 x
(3.64)
For an “established” state of the process, i.e. if we adopt the limits
examined above, constancy of all coefficients and of conditions at the limits, and
constancy of concentrations gradient and others, then, in the system of k
equations of type (3.59) or (3.64), dependence between x and t or x and v is
established and the equations may be replaced by one adduced variable. Then
equation:
dxdt  dxdt  dxdt  ....dxdt 
S

a b k
(3.65)
or
dxdv  dxdv  dxdv  ....dxdv 
S

a 0 k
(3.66)

72
 will describe the zone limits in a complex column of infiltration-diffusion.
Equations (3.65) or (3.66) have a final solution for components taking part in a
replacement reaction of minerals with one another at the zone limits.
Let us consider in a most simple example the properties of
diffusion-infiltration zoning. Suppose, as a result of the solution’s infiltration,
through complicated diffusion of components, there will arise transfer of a one
component mineral A by another one component mineral F with formation of a
complementary zone of complex reaction mineral AF, that has a variable
composition. On fig.3.10 is represented as resulting from it the column  F | AF
| A , for which are constructed diagrams of concentration, (Ca, Cf), distance
(x), and components’ content in the zones (a, f) distance (x). It is easily seen that
each zone newly formed (F | AF) consists of two parts, a front one of diffusion
and a rear one of infiltration. At the limits of the diffusion parts there are
gradients of concentration of the diffused components and, at the limits of the
infiltration parts, the components’ concentration remains constant. Components’
content at the limits of the diffusion part of the zone, composed of a mineral of
variable composition, change and so does the composition of the mineral-solid
solution from to A3F (this is the composition adopted as limit for the
replacement of the initial mineral x) up to AF2 (this composition is adopted for
the zone’s infiltration part). At the limits of the diffusion part of zones F, its
composition remains constant, since F is a mineral of constant composition, in
the limits of the infiltration parts of the zone, their composition is constant, as is
that of the mineral - solid solution.
The relative thickness of the parts of diffusion and infiltration of the
zones depends upon the respective transfer speeds of the corresponding limits. It
is natural for the column’s diffusion part to exist if udif > uinf. In the contrary case
(uinf > udiff) it does not take place. These correlations are clearly illustrated in
graph x - t (fig. 3.11). The transfer speed of the infiltration limit is constant and
the transfer distance is xinf = uinf t, or xinf = w0 t if the reaction speed of the
diffusion at the limit is great (w0 is the speed of the solution filtration). The
speed of transfer of the diffusion limit is inversely proportional to t1/2 and xdif =
2D
udif  t1/2  (2Dt)1/2. It easily seen that xinf = xdif for t
w0 2 . The relations
x dif
0 or 2 D 1/ 2
0 i.e. if 2D is much smaller then w02 t , the diffusion part
xinf wt1/ 2
of the zones will be entirely pressed by infiltration flows.
Attempts have been made to evaluate the real relations of speeds
limiting the diffusion and infiltration processes [Zharikov & Zaraysky, 1973;
Vlassova & Zharikov, 1975; Zaraisky, 1989; Flecher & Hoffman, 1974; Guy,
1993]. From experimental data and informatic and analogical modelling it can
be with fair certainly deduced that diffusion speeds for high temperatures

73
amount to n·10-6 - n·10-4 cm2/sec, which determines transfer speeds of diffusion
limits in microporous rocks in order of n·10-6 - n·10-4 cm2/sec or 1.8-18
cm/year1/2. Consequently, filtration speed, being of a few decimetres a year,
which corresponds to permeability of about n·10-1 millidarcys , will practically
crush the zoning’s diffusion part and, on the contrary, for permeability lower
than 10-3 millidarcys the column’s structure will essentially be a diffusion
structure.
Note an important property of the diffusion-infiltration columns (cf. fig.
3.10): columns arise by diffusion (for feeble t); in course of time the infiltration
parts’ capacity increases and, for greater t the columns form essentially through
infiltration with complicated diffusion fronts of replacement.

Metasomatic zoning in conditions of temperature gradients

A temperature variation during a metasomatic process brings about

in definite conditions essential variations in the structure of metasomatic
columns. The equation of joint transfer for that case may be written:
I S I inf  I dif  I T
(3.67)
or
      
dt
S
dmi  dmi
dt
inf
 dmi
dt
dif
 dmi
dt
T
Linf
i 
p dif i T 1
L  Li 
T i T T
(3.68)
Meanwhile the latter’s general solution is lacking. Let us examine a
few partial real situations in natural procuresses. A first case concerns
components’ diffusion in a situation of thermal gradient. If there exists a
temperature gradient in space, it exerts practically no influence upon the
structure of diffusion metasomatic columns. Heat transfer in natural
metasomatic systems (up to 700°C) takes place substantially more quickly than
components’ diffusion [Korzhinsky, 1969, 1972]. Coefficients of thermal
conductibility are about n·10-4 - n·10-3cm2/sec, whereas the components’
diffusion coefficients, as noted above, vary from n·10-7 to n·10-5cm2/sec.
Abstractly such a case may of course occur when under whatever
external influence a substantial temperature gradient is maintained a long time in
the system. Then, due to the dependence of diffusion coefficients upon
temperature, the linear approximation to the solution of the equation of diffusion
is uncertain, and the structure of the diffusion column may vary in time. In this
case also, however, the system will tend to a stationary state when the thermo-
diffusion flow will be equilibrated by the usual one or, as it is called in these
cases, the flow of chemical diffusion (Idif + IT = 0).

74
 In conditions of temperature variation in time there occurs a
variation of the diffusion coefficients and of the zones’ growth speed. As far as
the diffusion coefficients dependence upon temperature, the different
components have the same sign, no structure variation of the columns must take
place. However, an important temperature decrease produces of course
regressive mineral reactions in the column.
Let us now consider the situations arising in infiltration
metasomatosis when there is a temperature gradient. In so far as the filtration
speeds are compared with the speeds of heat transfer through conduction and
surpass them, a real situation frequently occurs in nature when infiltration
metasomatosis develops in conditions of temperature gradient in space. Such
various processes of contact elimination are most neatly exemplified from which
arise greisenization and formation of secondary quartzites.
In case of infiltration metasomatism in conditions of spatial temperature
gradient, component i’s general flow will fold up from its own infiltration flow
and from the component’s flow due to temperature gradient (IS = Iinf + IT) or:
dmdt  dmdt  dmdt 
S inf T

(3.69)
It can be shown that the concentration gradient of saturation in space, as
function of temperature proves to be the component’s acting transfer force in a
field of thermal gradient. Then for the one dimensional flow of component “i
“we shall have:

dmi  iCi Li Ci w0dt
x

(3.70)
where  i is the coefficient of filtration effect, Li the proportionality
coefficient at the replacement of the acting forces ( it corresponds to a quantity
of the component transferred from the solution for a unitary gradient). Equation
(3.70) can take the form:
dmi iw0Ci Li w0 Ci
dt x ,
(3.71)
which answers equation (3.69).
Omitting the conclusion that was made of the perfectly analogous
conclusion of the equation of infiltration zoning, in sum we get the following
equation of infiltration metasomatosis in conditions of a field of thermal
gradient:
dx
dv

i
 C  i L C  i
x x
i
i
x x
i
i
2
2

(3.72)

75
 For k components we shall have a system of k equations of the form
(3.72).
In order to analyze this system of equations it is necessary to have
given (or determined from concrete conditions) limitations of condition and
dependence.
D.S. Korzhinsky has thoroughly studied the case in which through the
rock infiltrates a solution in equilibrium with it and, entering a contact zone with
a temperature gradient, begins to react with the surrounding rock. Such cases
correspond to conditions Iinf = 0, IS = IT or in equation (3.71) and (3.72),
dmdt  0 , then:
inf

dxdt  L xC xi

i
i
2 i
2

(3.73)
Since the components’ saturation concentration depends upon
temperature there will occur a quantitative variation in the mineral composition
of the surrounding rocks, up to the appearance of metasomatic zoning,
expressing the saturation concentration’s (Csat) dependence upon distance. As
far as Csat = f(T) and T = f(x) it is evident that Csat = f(x). The metasomatic
column, arising in course of time, will grow with the variation of the
quantitative correlation of the minerals that produce a structure change of the
column. The latter will be expressed in the disappearance of some zones and the
appearance of others.
As an example, fig.3.12 shows the somewhat changed diagram
[Korzhinsky, 1982] indicating rise and development of a metasomatic zoning for
a linear dependence of the saturation concentration (Csat) upon temperature
(which in turn is a linear function of the distance). The diagram on fig.3.12a
shows this dependence for components a, b, d, f and g. On fig.3.12b the
metasomatic zoning is schematically reproduced for columns composed of
minerals with a single component A, B, D, F and G.
At the linear dependence of saturation concentration Csat = kx + k, it
C sat 2C sat
is easily seen that x k and x2
0 . Then, in conformity with

equations (3.71), (3.72) and (for the examined case) dm

dt
 
inf
0 , we shall have

vi  k . This means that in proportion as the solution infiltrates for
components having a positive k, their content and that of the associated minerals
will decrease. In the examined case it is components b and d and minerals B and
D. On the contrary, for k negative, when the components’ saturation
concentrations (in other words their solubility) decreases, content of components

76
decreases in proportion of percolation and there occurs precipitation of the
corresponding minerals, components a ,f and g ([Link].3.12a). Moreover, for the
last two it is admitted that saturation concentration is reached in proportion of
the solution’s infiltration at T2 (for component f) and T4 (for component g).
The schematic diagram on fig 3.12b clearly shows the structure
change in time (v = w0 t) and distance (x) of the metasomatites. Owing to
percolation of solutions in virtue of the mentioned dependence of Csat upon T
and x in the initial mineral paragenesis A+B+D, there begin replacement
reactions of minerals B and D, which will dissolve through precipitating mineral
A (which is indicated by arrows:  dissolution,  precipitation). Except mineral
A, at limit x2 and temperature T2, saturation concentration of added mineral F
will be reached and then, further in the dissolving column, minerals B↑+ D↑ will
be replaced by the precipitating minerals F  and A . At limit x4 (isotherm T4)
saturation concentration of another added component g will be reached, and
dissolving minerals B and D, will be replaced by three minerals A, F, and G. It is
schematically shown how the metasomatic column will vary in proportion of the
solutions’ infiltration (i.e. in course of time) in whatever point x in the space
chosen by us of unidimensional thermal gradient (cf. fig.3.16). The diagram is
clear enough.
A few explanations will suffice. To construct the diagram the usual
conditions of metasomatism have been adopted, when there exist free volumes,
and, as shown above, pressure on the solid phase exceeds that of the fluid. In
these conditions the solution dries up, and the saturation concentration
corresponds to such conditions pS > pf. To construct the diagram it has been
admitted that for x from 0 to x3 CasatC sat
f , for x from x3 to x6 C f Ca , and for the
sat sat

f Cg . In consequence of these dependences, after v4 in

whole range of x Casat , C sat sat

zone x4 - x6 there begins dissolution of earlier precipitated G, but in zone x2 - x4

precipitation of mineral F. The final structure of the column for high v (v6) will
be  AF , and all remaining minerals will be replaced by those that develop
the greatest crystallization pressure in determined parts of the column.
Let us now consider, on an even more simple example, the general
case when the rock is penetrated by a solution in unbalance with it and forming
an infiltration zoning that develops in conditions of temperature gradient in
space (equation 3.71 and 3.72, where IS = Iinf + IT). Into the initial rock
composed by one component minerals A and B, let a solution penetrate,
oversaturated in a one component mineral F. For this, pF > pA > pB. In the
infiltration zone there is a temperature gradient defining a linear dependence of
C sat
S fl
saturation concentration (when p > p ) upon distance. Then k'  is
x
positive for component b and its solubility increases with distance; for
components f and a, k’ is negative; moreover, with whatever x, Casat becomes

77
 f . On fig.3.13 are represented diagrams C  x and - x, on which is
higher C sat sat

clearly seen that on a neat infiltration column  F  F + A  A + B (the double

line separates the initial rock) are superposed quantitative changes, of content of
precipitating (F,A) and dissolving (B) minerals, that finally produce a structure
change of the columns.
The simplest cases have been examined above, but as far as the
solubility’s dependence upon temperature (and distance) may be complicated,
the structure, correspondingly complicated and varying in time, will possess
metasomatic columns.
We have underscored above that infiltration columns with
temperature gradient are particularly characteristic of processes of elimination at
contact. Let us consider as illustration a typical column of endocontact
greisenization, where arrows accompanying the mineral symbols indicate
quantitative changes in minerals’ content taking place in the zones (c.f. fig.3.14,
structure of a column, taking no account of accessory components). Note that if
zones 1,2 and in some measure 3 have a coarse extension, then in the internal
zones 4 and 5 the variations are localized as veins and periveinous changes, and
their volumes are substantially smaller than those of the external zones (we
conventionally translate this into a conical graph).
Variation of temperature in time influences saturation
concentration, bringing about a concomitant variation in the growth speeds of
the zones and in quantitative correlation of the minerals. Most remarkable is the
fixation to retrograde replacements of the column’s initial minerals.

Other complex types of metasomatic zoning

In connection with the dependences reported above (equations 3.20,
3.29 and others) other complex types of metasomatic zoning are theoretically
possible and also occur in nature in determined conditions.
For instance, there is infiltration zoning, with variation (in space) of
the coefficient of filtration effect (i), for a substantially different value i of
the components, for example for the passage of a wave of acid components,
infiltration and diffusion zoning in conditions of substantial value of
replacement speed of the minerals and, more generally, of kinetic reactions.
Also possible are other complex combined influences of the factors of
equilibrium and dynamics of metasomatism upon content and peculiarities of
structure of the metasomatites.
Infiltration zoning through passage of a wave of acid components
was examined by [Link] (1982). He showed that soluability and
activity coefficients of the chief acid components depend upon the solution’s
general acidity. Consequently there occurs in the infiltration zone of the
solutions a “mineral” differentiation: in the zone of action of the acid wave

78
“basic” minerals will be eliminated and replaced by “acid” minerals. The real
forms of distribution of the minerals are defined by concrete dependences of
components’ solubility and activity coefficients upon the “structure” of the wave
of acid components.
Infiltration metasomatism has not been especially studied in
environments with different coefficients of the filtration effect. However,
utilizing researches on the filtration effect by Zharikov, 1969, Zharikov et al.
1973, one may propound two main cases. For an insignificant variation of i the
column structure remains unchanged; what does change (according to equation
3.34) is the transfer speed of the limits of the zones and the column as a whole.
For substantial changes, and especially those in various directions of i, the
column structure will be different and, owing to the concentration’s dependence
upon (c.f. equations 3.7, 3.10) it may vary in time with the appearance and
disappearance of separate zones.
Metasomatic zoning complicated by kinetic phenomena was not studied
by [Link], his theory of metasomatic zoning being founded on the
principle of total local chemical equilibrium. However, in many natural
metasomatic columns, a divergence is observed from the condition of
equilibrium: in many cases they are insignificant and negligible, but in a few
others they are essential. The problem of the role of kinetic parameters has been
examined by [Zharikov, 1971; Golubev, 1970; Rusinov, 1972; Balashov, 1985;
Balashov & Lebedeva, 1989; Zaraysky et al., 1989; Lichtner, 1991].
The inventory on principle of the role of the kinetic factor follows from
equations (3.14, 3.15, 3.20). In isothermal conditions
IiS Iiinf  Iidif  Iikin
(3.74)
or
       
dmi  dm
dt dt
S inf
 dm
dt
dif
 dm
dt
kin

(3.75)
Substituting the expression of the acting forces for isothermal
conditions we get:
 
dt
S
i p Li i  Li i
dmi Linf dif dif kin kin

(3.76)
The second member of equation (3.76) may be replaced in more
usual correlations by noting it, for example, through the chemical affinity (Ai)
and fullness of flow of reaction i [Khaaze, 1967; Prigogine & Defay, 1963]:
dmdt  L  A ddt
i
kin
kin
i i i
i

(3.77)

79
 or we may obtain a more complex expression through speeds of chemical
reactions. Combining Is = Iin f+ Ikin or Is = Idif + Ikin, one can essentially
characterize infiltration or diffusion metasomatism with kinetic phenomena.
Examining these questions in more detail, with abundant mathematical
computations (Balashov & Lebedeva, 1991) would go outside the frame of this
book; so, in order to characterize the main peculiarities of this kind of columns,
we shall consider a simple example (fig.3.15).
We have already examined the isothermal infiltration column,
formed of unicomponent minerals
2 1 0
 F  A + F  A + B 

At the zone limits develop replacement reactions at a final (observed) speed

comparable to the solution’s filtration speed. At limit I mineral B is replaced by
minerals F and A (with C sat f > Ca ); at limit II mineral A is replaced by mineral F
sat

(F  A). We thus agree that the replacement reactions are of the first order,
depending upon concentration (content) of the replaced component. So at limit I,
where occur parallel reactions of replacement of B by F and A:
df
k f b
dt
(3.78')
da k f b
dt
(3.78'')
And db dt
(k f ka)b
(3.78''')
where a, b, f are contents of unicomponent minerals A, B, F; let us
moreover take kf > ka . At limit II where mineral A is replaced by mineral F;
correspondingly
da ka2a
dt
(3.79')
df
and dt ka2a
(3.79'')
If the speed of replacement reaction is feeble (diverging from the
condition of local equilibrium) instead of sharp replacement fronts there appear
zones of gradual replacement, at limit I of zone 1 kin , where occurs the
replacement A+FB, and at limit II of zone 2kin with replacement FA. The
breadth of the “kinetic” zones depends upon time, the sine qua non condition for
total disappearance of the replaced mineral (respectively, B and A) and

80
consequently depends upon reaction speeds kf, ka, ka2 and the minerals A and B’s
contents in the initial rock and the infiltration part of the zone. Quantitative
correlations of minerals at the limits of the kinetic zones are determined by the
solution of kinetic equations (3.78 and 3.39) in the limits set by the content of
components (minerals) in the initial rock and by the number of infiltration
zones, which arouses no particular difficulties (Baguner, 1959; Benson, 1964;
Zharikov, 1971).
On fig. 3.15 is indicated the structure of the examined column, where the
breadth of “kinetic” zone parts is adopted for complete clarity. In nature kinetic
phenomena are only observed at low temperatures and in superficial conditions
and, characteristically, usually “kinetic zones” do not exist, as in the abstract
example of fig.3.15. The portions with mineral relicts not replaced to the end are
preserved in the form of separate spots in portions of uneasily circulating
solutions. We shall pursue in the following chapter examination of the kinetic
factors of metasomatism.

81
Fig. 3.1 Isopermeability depending on temperature and effective pressure for models of
granodiorites (I), marbles (II) and garnet (III) and wollastonite (IV) skarns.
Metric lines expressed in millidarcys (1 mdarc = 10-15 m2). The hatched parts are “non-
permeability” of rocks at given T-P . For these sections k < 10-5 millidarcys.

82
Fig. 3.2 Relative transfer speed of section (dx/dv) = tg α (a) and relative variation of
content (i) and concentration (Ci) of component i (b) within zones and at limits
(replacement fronts) at chosen correlations (dx/dv) I,II,III in cases of addition and removal
of components.

83
Fig. 3.3 Replacement reactions in columns with minerals of variable composition.
On the diagram are shown relations C1 - i for minerals of variable composition M (M1 – M2
), N (N1 – N2 ), P (P1 – P2 ) and relations x/v for fronts of addition (Ia , IIa , IIIa) and
removal (Ib , IIb , IIIb ) of component “i”.

84
 Fig.3.4. Growth speeds of periveinous diffusion (a) and bi-metasomatic columns
(b). On the graphs xW t designating mineral composition of corresponding zones and
speeds (W cm/year1/2 ) of displacement of the external limits of the zones.

85
Fig. 3.5 Variation of concentrations ( Ci ) and contents (i) of components in zone of
diffusion exchange of minerals of constant composition (mineral A replaced by mineral
F).
Reciprocal diffusion action of fissure with semi-infinite space (only part of which is shown,
by limited points) with stable concentration Cf and Ca for considerable t, when dC/dx
approaches linear dependence.

86
Fig.3.6 Variation of concentrations ( Ci ) and contents (i) of components in zones of
diffusion replacement of minerals of constant composition.
Initial rock A+B is replaced by mineral F with formation zonality F F+A | A+B → .
Reciprocal diffusion action of the source (fissure) with the semi-infinite space with constant
initial concentrations Cf, Ca, Cb and Cof, Coa, Cob for time t, when dC/dx approaches linear
dependence.

87
Fig.3.7 Diagrams of concentration of components (Ca, Cb) - distance (x) and content of
components (a,b) - distance (x) at a determined moment t >> to for a bimetasomatic
column with reacting minerals of constant composition.

88
Fig.3.8 Diagrams of concentration of components (Ca, Cb) - distance (x) and content of
components (a,b) - distance (x) at a determined moment t >> to for a bimetasomatic
column with reacting minerals with variable composition.

89
Fig.3.9 Correlation of thickness of bimetasomatic zones at curved contact surfaces.

90
Fig.3.10 Diagrams of concentration of components (Ca, Cb) - distance (x) and content
(a,b) - distance (x) for diffusion-infiltration column for any time t > to .
Minerals A, F of constant composition, mineral AF of variable content.

91
Fig.3.11 Diagram of distance (x) - time (t) for infiltration (xinf = wo t) and diffusion (xdif =
(2Dt)1/2 ).

92
Fig. 3.12 Structure of metasomatic infiltration columns, arising in conditions of
temperature gradient during continuous infiltration of solutions in equilibrium with the
rock.
Co is initial concentration; Csat is concentration of saturation; A,B,F are unicomponent
minerals, upward arrows are dissolution and removal; downward arrows, addition and
precipitation; v is volume of percolating solutions; x is distance; v1 – v2 is the structure of
column at determined time (v = wo t); x1 – x2 are variation of composition of rock in given
section as far as the solution percolates, i.e. with time.

93
Fig.3.13 Structure variation of metasomatic infiltration column as far as solution
percolates (v) owing to dependence of concentration of saturation upon distance (x) to
the axis of the column.
Conventional signs, cf. Fig.3.12.

94
Fig.3.14 Schematic structure of usual greisens column.
Upward arrows, dissolution of minerals; downward arrows, precipitation of minerals.

95
Fig.3.15 Infiltration column with kinetical transitions between zones.

96
 Chapter 4

Kinetics of reactions and self-organization of

metasomatic systems.

4.1. Mechanisms of metasomatic reactions

The mechanism of evolution of metasomatic reactions is defined by a

series of conditions, the most important of which is the aggregate state of the
substances taking part in the reactions of matters. According to this principle are
distinguished gaseous, solid and properly hydrothermal metasomatism. The first
two, although implying replacement of a mineral by another, are not all of them
typical manifestations of natural metasomatism.
Gaseous metasomatism is manifested, for instance, on contemporary
volcanoes, where they are observed on the walls of smoke-holes. Temperature
of the gas-jets reaches 300-400°C and under the atmospheric pressure liquid
water is absent in the jets. However, a reaction crust of neo formations in the
hole-wall is a few millimeter thick. Moreover, while the gases diffuse into the
rock, the walls of reciprocal action of theses gases with the rock rapidly decrease
their temperature and condense the water. Therefore nearly at once a liquid
aqueous solution is assisted by saturation of the surrounding rocks by superficial
waters. It can even provoke a further transformation of the rock. In rare cases
can purely gaseous metasomatism be observed. Hydrogen sulfide being chased
by vaporization through a burning ferruginous splinter, the latter can be replaced
by iron sulfides, but the geological significance of such a process is negligible.
That gaseous metasomatism occurs on a small scale is accounted for by the
feeble reciprocal action of the gases with the surface of minerals, their sorption
being minimal. Therefore the superficial energy of the mineral grains
constituting the rock does not perceptibly diminish in the reciprocal action with
the gas and is a high energetic barrier on the way of gas-rock chemical reactions.
Within the rock the gas can only penetrate the porous system, but its diffusion at
the intergranular limits is impeded by the fact that the gas does not moisten the
grains’ surface and there is thus no capillary effect. All that strongly diminishes

97
dissolution of the minerals in the gas, and there appears only a substitution
through diffusion within the solid phase, a very slow process, limited in space.
Replacement reactions of minerals in the solid phase are also of limited
significance. They are polymorphous transformation conversions, isomorphous
substitutions and decomposition of solid solutions.
Polymorphous conversions are in themselves pseudomorphous
replacements of an initial mineral by a newly formed one, without change in
the chemical content, but with variation of the symmetry of the crystalline net.
Conversion of high temperature  quartz to  quartz at lowering of
temperature to less than 573°C may serve as an example. The external shape
of  quartz crystals is preserved, but the system changes from rhombohedric
to trigonal. Experimental data about the transformation of  quartz into 
quartz show that the process occurs at a mobile limit within the crystal that
completely preserves its solid crystalline state. Before the replacement front
there develop a series of thin twin-lamellas as preparatory stage to a complete
transition to another polymorphous modification. On the strength of that,
conversion occurs through a regrouping of atoms in the crystalline net in solid
state; such reactions are energetically active and require a strong cooling
down. That is why many polymorphous modifications of silica appear as a
metastable formation far beyond the limits of their fields of stability. For
instance trydimite and crystobalite appear as products of habitual low
temperature neoformations in concretions of opal and silica, etc. on solfatara
fields in actively volcanic regions.
Transformation conversions arise with change in the crystalline structure of
the initial mineral or with variation of its content. This term was introduced to
wide usage by V.A. Frank & Kamenetsky [1978] concerning phyllosilicates
and the gradual change of a foliated silicate into another, neglecting the
dissolution stage, but preserving the main or characteristic structure motive of
the crystalline net. The mechanism is based on diffusion in solid phase inside
the grain. An example of transformation can be seen in the initial stage of the
biotite’s vermiculitization, a formation of hydrated biotite. V.A. Frank &
Kamenetsky and collaborators think there occurs, through this mechanism, a
replacement of the minerals of the kaolinite group by hydromica and
muscovite, and of smectite by muscovite [Frank – Kamenetsky et al., 1978].
In experiments made by them at 500-700°C and 1Kb from kaolinite
(unifoliated structure, triclinic system, modification 1Tk) they have obtained
only the unifoliated sheet 1M. The bifoliated sheet of modification 2M can
only be obtained, according to the authors, from bifoliated modification of
minerals of the kaolinite group, i.e. from dickite. Correspondingly,
trioctahedric mica (biotite) or chlorite may only be obtained from
trioctahedric smectite and not from the dioctahedric one. According to these
data, such conversion must be based on a succession of blocks or on the basis

98
 of the crystalline structure of the initial mineral, without its dissolution.
Endorsement of such wide distribution of the transformation mechanism in
nature is discussed. Kinetic experiments [Zotov & Mukhamet Galeev, 1987]
for low parameters (T up to 200°C, P=Psat of water) have shown the main
evolution of an alternative conversion mechanism of kaolinite to mica through
complete dissolution of the initial kaolinite. The transformation mechanism
may be considered rigorously proved only for a process of feeble hydratation
of the phyllosilicates, for instance for the formation of hydrobiotite on biotite.
Isomorphous replacement is a process widely spread in nature, in which,
by means of exchanges with the solution, the mineral’s content changes with
regard to parts of its components, with preservation of its structure frame at the
solid state. Supposedly, isomorphous replacements occur with the help of
diffusion at the solid stage. However, J. Wyart and Sabatier [Wyart and Sabatier,
1956] have shown that the phenomena of rearrangement and general diffusion
of atom in the net of plagioclase takes place in the presence of water.
Hydroxylated ions penetrate from the solution into the structure of the mineral,
occupying the voids. In those places of the net there arise constraints, and the
interatomic linkages weaken, forming channels in which the atoms move.
Diffusion at the solid stage may play the main role in many isomorphous
replacements. Experiments show this, for example, in the opposite diffusion of
magnesium and iron through the granular limit of garnet and cordierite brought
into contact [Guerassimov, 1992]. In the bordering regions of crystals of both
minerals there appear diffusion zones, 8 to 15 m broad, with gradual change in
the iron and magnesium content. A zone’s breadth depends upon the diffusion
speed and the duration of the process. This dependence served as basis for the
development of a method to determine the speed of metamorphic reactions and
the duration of processes of metamorphism. If in the example treated the
diffusion exchange of components took place between phases, in another case,
in skarns with wollastonite – hedenbergite the late parts of the solutions, with
great manganese activity, penetrating to the grains’ limits of these minerals have
provoked manganese diffusion in both sides of the contact [Rusinov & al, 1994].
The diffusion zones were 5 to 20 microns broad. So, isomophous replacement
occupies only outside parts of the crystals and it is unlikely that they have a
geological scale.
Disintegration of solid solutions with formation of pseudomorphosis of
two, more rarely several, minerals newly formed from an initial mineral - solid
solution is the most characteristic instance of diffusion in solid phase. This
process’s originality consists in the fact that it can occur either as quasi-static (in
quasi-equilibrium) or in manifest unbalance (spinodal decomposition). In the
former case, there suddenly form germs (exsolutions) of the final stable phase,
which then grow without change of content. In the case of spinodal
decomposition, appear at first embryos of phases within unsharp limits and are

99
hardly distinguishable in content from the matrix. Gradually, inasmuch as
decomposition develops, the dimensions of the excretions grow and their
composition changes, moving away from the matrix and nearing the content of
the stable ultimate member of the isomorphous series. So does the process
gradually composition through un uninterrupted series of metastable states with
periodical ondulatory distribution of concentration of components in the crystal,
which testifies to appearance of self-organization in the system of solid solution
products of decomposition.
Proper hydrothermal metasomatism is a capital geologically significant
variety of metasomatism. Hydrothermal metasomatic reactions, occurring with
the necessary participation of a liquid aqueous solution, the role of which has
been often underscored by D.S. Korzhinsky, includes precipitation and
dissolution of minerals. In this reaction as well as in another, two phases at least
take part, a solid and a liquid one. In metasomatic reactions representing the sum
of dissolution and precipitation reactions, at least three phases take part: two
solid and one liquid. The liquid phase (as a rule an aqueous solution) is
undersaturated compared to one of the solid phases and oversaturated compared
to the other. That is why the first phase is dissolved and the second one
precipitates instead. Dissolution of the mineral – reagent takes place at the
moving limit of reagent – solution. The streak of solution between this limit and
the surface of the precipitated mineral – product is usually about a few half score
Å to a few half score µm thick, so that product precipitation occurs immediately
after the reagent’s dissolution, and at macroscopic scale, dissolution and
precipitation appear as simultaneous processes. This replacement mechanism
has been clearly enough demonstrated for instance in the sanidine’s
hydrothermal replacement by montmorillonite [Samotoin et al. , 1996].
Electronic microscope study of rhyolite submitted to hydrothermal
montmorillonitization with the remarkable method of vacuum-metallization with
gold has shown that replacement begins with dissolution of the sanidine crystals.
On photographs of the sanidine surface it can be seen (fig.4.1) that in the initial
stage holes are formed on the surface and then, from them channels and cavities,
breaking the crystal into blocks. Form and orientation of the holes and channels
depend upon the crystallographic indices of the grain’s surface. The blocks have
the distinct form of sanidine crystals and a fine graded relief of surface,
testifying to a pseudo-ribboned mechanism of dissolution. Dissolution has taken
place slowly in a feebly saturated solution; block construction can be seen on
photos in natural light (fig.4.1,v). At the same time with dissolution there
occurred precipitation of montmorillonite on the sanidine surface.
Montmorillonite is formed in different parts in the whole volume of sanidine,
where the dissolution voids have formed. Montmorillonite particles are oriented
along the sanidine’s crystallographic directions. The montmorillonite sheets

100
separate into fine details of relief and of the form of the surface of the blocks of
dissolution of sanidine.
In some places, dissolution of initial minerals may forestall precipitation,
and then are formed pores and granular cavities into which the minerals may be
deposited through a mechanism of growth in a free space. Then there may be
formed pseudomorphoses of minerals with no common component with the
dissolved crystal. For instance in the lavas of the solfatara fields of volcanoes
are usually present sulfur pseudomorphoses in phenocrystals of pyroxenes and
feldspars (“impregnation”, according to [Link]). In regions of active
volcanism, at the rocks’ hydrothermal modification, partial pseudomorphoses of
adular or albite in phenocrystals of magmatic plagioclase are equally typical.
Secondary adular (or albite) replaces a marginal zone of the phenocrystal, but
the central part remains empty (case of pseudomophoses). In many epithermal
deposits, the internal zones of the column of metalliferous metasomatites are
intensively silicified with formation of lixiviation voids which fill up with quartz
in the form of druse, or look as vein filling. In all instances cited above
metasomatic reaction includes two heterogeneous reactions (dissolution and
precipitation) and homogeneous ones in the solution, and it takes place with
unfailing participation of a liquid, essentially aqueous phase. Water, with its
molecules of bipolar structure, has a high dissolution capacity. Through
reciprocal action with the crystal’s surface, it strongly diminishes the minerals’
dissolution energy, weakening the atomic linkages, at the grain’s surface, with
the rest of the crystalline net.
Reciprocal reactions of dissolution and precipitation are a specific feature
of metasomatism. The degree of this dependence determines in particular that of
the succession of structural elements and of composition in the replacement
processes. Near the composition or structure of reagent and product occurs
replacement through the epitaxial mechanism and arise homoaxial
pseudomorphoses. In some cases, dissolution of the crystal, for example of
potassic feldspar, locally augments the porous solution’s alkalinity in the
forming cavity and precipitation of minerals, even in the absence of elements in
common with the initial crystal. So, in the rhyolites’ perimetalliferous
metasomatism in epithermal polymetallic argentiferous deposits, carbonate,
galenite and chlorite precipitate in places where orthoclase and plagioclase
phenocrystals dissolve. Pseudomorphoses occur in which filling up takes place
long after dissolution, and the products display no link with the initial mineral.
Such are the pseudomorphoses of sulfur in the phenocrysts of pyroxene and
plagioclase in rocks on active volcans, in silica on vegetal remnants (for instance
silicified trees) and other pseudomorphoses.
Consequently the mechanism of hydrothermal metasomatic reactions
depends upon the physico-chemical conditions of the process and the relation

101
between reaction speeds of dissolution and precipitation, i.e., upon those
reactions’ chemical kinetics.

4.2 Kinetics of metasomatic reactions

One of the main differences between metasomatic and metamorphic

processes is the degree of equilibrium realization between rock and solution and
the influence of kinetic reaction of mineral formation upon the nature of the
mineral association forming there. Metamorphic processes are usually of long
duration, thus comparable to the geotectonic events (rising of mantellic plume,
riftogenesis, orogenesis, etc.) and are accompanied by relatively slow variations
of the metamorphism’s external parameters. Moreover, time fundamentally
succeeds in establishing equilibrium between solution and rock. That is why
researchers on metamorphic rocks deal principally with equilibrated associations
of minerals. The problem of kinetic reaction of mineral formation arises only in
some cases, during low temperature metamorphism, at formation of zonal grains
of minerals due to slowness of diffusion inside the crystals, but also at
appearance of coronarian and other structures, testifying to an incomplete local
recovery of balance of the rock-solution system during variations of the
metamorphism’s parameters. In most cases, the long duration of the
metamorphic processes and the slow variation of temperature and pressure allow
the rock to attain equilibrium with the metamorphic fluids.
Metasomatic processes are usually of less duration and are caused by the
solutions’ flows and, consequently, happen in conditions of high concentration
gradients, i.e. the processes are on the whole in strong unbalance. As shown by
[Link], one can choose in the study of metasomatic formations
domains to which one applies the principle of local or mosaic equilibrium. Such
domains are the internal parts of metasomatic zones in a column of metasomatic
zoning, where in each isolated point equilibrium is achieved between solution
and rock, but the equilibrium parameters vary from point to point. However, the
zone limits are characterized by an evident breach of equilibrium and
replacement reactions of minerals of external zones by minerals of internal
zones. It fairly often happens that amongst metasomatic rocks relicts are spread
of prior associations or intermediate, metastable products of reaction of mineral
formation. Diagnosis and analysis of these minerals’ associations in unbalance
require knowledge of kinetics of chemical reactions in general and metasomatic
ones in particular.
The role of chemical kinetics is expressed by the general equation of the
matter flow in metasomatism (cf. 3.13):
I S I inf  I dif  I T  I kin

102
 For a high speed of chemical reactions to the solution’s diffusion and
infiltration the last term of the equation may be neglected, but for a quick mass
exchange and slow reaction in isothermal conditions, the kinetics’ contribution
to the total flow may become dominant and determine the nature of the
minerals’ formation.
Formal chemical kinetics is based on the theory of absolute reaction speed
[Glesston & al., 1948] describing fairly well the simple homogeneous reactions
in the solution, the gas and other species of heterogeneous reactions.
Metasomatic reactions are distinguished by their particular complexity, because
they include as constituent parts at least 3 or 4 elementary reactions, of which
not less than 2 are heterogeneous (dissolution of the initial mineral and
precipitation of the new one).
Theory postulates that all reactions proceed through formation of an
“active complex” absorbing “activation” by formation of energy and later
dissolving into final products with energy secretion. Starting from these
energetic representations, the theory gives the dependence of reaction speed
upon the thermodynamic parameters of the active complex. Direct determination
of the reactions’ kinetic constants constitutes a very complex experimental
problem, because they depend upon the reaction’s path. The latter is very
sensitive to the slightest nuances in the conditions of the experiment’s
realization and is therefore difficult to reproduce. Naturally the number of
reactions of which we study the kinetics is limited, which compels to seek the
possibility of evaluating the kinetic reactions with the help of thermodynamic
values experimentally determined and calciculated.
The dependence of kinetic parameters upon thermodynamic properties of
initial and terminal stable products is not established from a general point of
view. Research about this relation are part of the general problem of the link
between dynamics and thermodynamics, a problem first raised by Boltsman in
his N-theorem. It was the first step to applying the entropy notion to
microsystems on the basis of kinetic equations, an idea further developed in its
application to the microscopic scale in the works of [Link] on
thermodynamics of irreversible processes.
Kinetic and thermodynamic parameters of a system are linked to the
equation of the second principle of thermodynamics. Combining the equation of
the system’s internal energy
dU = TdS – PdV + µdm with the expression of the heat process we get
dQ = dU + PdV  dW  Hdm , the balance of masses dm = dim + dem
and, considering that U=H-TS, [Link] [Khaaze ,1967] brings the equation
linking the thermodynamic variables and the kinetic parameters of the chemical
reaction:
TdS = dQ + T Sdn + dW + A d
(4.1)

103
 Here is introduced the notion of chemical affinity of a reaction A = µn (n
is the stoechiometric coefficient in the reaction, µ is the component’s chemical
potential) and  is the (incomplete) transfer degree of the reaction (0 <  < 1),
dW represents the dissipation of its own energy taking into account the work of
the friction forces, the electric forces and others. Equation (4.1) shows that an
entropy variation, being a function of the system’s state, depends upon the
energy exchange with the environment and upon the processes inside the
system, including the kinetics of chemical reactions. Entropy is here interesting
in that it serves as characteristic function in describing either equilibrium states
and quasi-static ones, or irreversible processes. It permits consequently to study
both these states within a unique thermodynamic approach. Equilibrium state is
defined by the entropy’s highest possible value, and entropy is the criterion of
stability of an equilibrium state. In irreversible processes with matter flow
through the system and a concentration gradient entropy is no criterion of
stability insofar as it varies in time. This variation is composed of the flow of
external energy and of entropy production in the reactions inside the system:
dS/dt = diS/dt + deS/dt
(4.2)
In relation to equation (4.1) the entropy flow is defined by

deS/dt = 1/T(dQ/dt) + (dn/dt)

(4.3)
but the entropy production by

diS/dt = 1/T(dW/dt) + 1/T Arwr

(4.4)
where w = dn/dt is the chemical reaction’s speed but dS/dt = P is the variation
speed (production) of the entropy. Contenting ourselves with the case of a
constant level of energy of dissipation, supported from outside (dw/dt = 0), we
get:
P = Arwr et dP/dt = 1/T d(Arwr)/dt.

In stationary state dP/dt =0, d(Arwr)/dt = 0; Ardw/dt + wrdAr/dt = 0, Ar:dwr =

-(dAr/dt):(dwr/dt).. Admitting that t is the only independent variable, we can
write Ar:wr = -dAr:dwr. In the case of a linear relation:

wr = aAr, dwr = adAr, dwr/dAr = -wr/Ar = a

(4.5)
where “a” is a phenomenological coefficient, signifying in this case “facility” of
initiating the corresponding chemical reaction: the greater “a” in absolute value,
the less necessary the affinity to attain the same speed and eliminate the
energetic barrier. For each reaction “a” is constant and a decrease of the reaction

104
speed brings about a proportional decrease of affinity. Since P possesses an
additive value and Pt = Pr = Arwr, it is then necessary in order to initiate in
parallel all possible reactions, to have higher affinity and speed and,
consequently, a higher entropy production than the consecutive movement of
these reactions. Consequently minimization of P requires a determined
succession of reactions.
Formation of a mineral from an aqueous solution occurs in several stages:
homogeneous reactions in the solution, formation of a crystal germ, growth of
the crystal.
At the germination stage, synthesis of an active complex requires extra
energy from an external source. Hence, the system’s potential energy increases,
accumulating in new interatomic linkages in the active complex, and entropy
accordingly decreases because a supplementary structure appears. In this
manner, at this stage, the system does not near equilibrium but moves away
from it. This divergence, provoking kinetic effects, is mathematically expressed
by violation of linear relations between chemical forces (reaction affinity) and
flows (reaction speed). Reaction speed and chemical affinity are functions of T,
P, Ci under the general form:

wr = f1(x1,x2,...,xn+1); Ar = f2(x1,x2,...,xn+1)
(4.6)
Eliminating variable xn+1 we obtain:

wr = f1(x1,x2,...,xn,Ar)
(4.7)
At equilibrium Ar = 0, wr = 0. Since Ar is a measure of the divergence
from equilibrium, we can put in row the expression of reaction speeds:

wr = (df1/dAr)Ar + (d2f1/dA2)A2 + ...

(4.8)
In close proximity of equilibrium (feeble value of A), limiting ourselves
to the first term of the resolution, we get to (4.5): wr = aAr, where a = (df/dA),
the phenomenological coefficient. In future we shall omit the index “r” in the
expression of the reaction’s speed and affinity. Between reaction speed and
affinity there is the relation:
w = wf [1-exp(-A/RT)]
(4.9)
where wf is the speed of direct reaction. In equilibrium w = 0 = wf :for a
divergence 0 < w < wf ,but for a sudden irreversible reaction w = wf > 0 .In the
following case, 1-exp(-A/RT) = 1; A/RT = , hence A = . Therefore owing to
the force of unbalenced processes, with a high value of A it is impossible to
neglect the second term the resolution of the speed:

105
 w = aA + (d2f/dA2)A2
(4.10)
which produces violation of linear relations between the speed of the reaction
and its affinity. For constant concentrations of reagents, reaction speed is
inversely proportional to the activation energy r = f(exp[-Ea]), and the
divergence from non-linearity in (4.10) is defined by Ea . Thus activity energy is
the cause and simultaneously the measure of the system’s divergence from
equilibrium, a measure of its non-linearity. It may be considered the leading
parameter, determining the process’s path and speed. A specific speed of
reaction (speed at unitary concentrations of reagents and products) is linked to
this parameter by Arrhenius’ correlation:

K = kT/[Link](-Ea/RT)
(4.11)
where A is the coefficient, K Boltzmann’s constant, h Planck’s constant, E a the
energy of activation.
As a result of the fact that the beginning of the reaction requires
elimination of the energetic barrier, in the system at the stage of the crystal’s
germination there arise supersaturation on the reacting components and,
consequently, at the limit of the reaction region, of the shading crystal with the
remaining solution there must exist flows of matter and energy. In connection
with the conditions examined above of a stationary state of the gradient system,
the processes for obtaining such a state must obey the law of minimal
production of entropy. Entropy production itself represents the speed of change
of entropy and that is why it is a function of the speed of corresponding
chemical reactions. Let us suppose for simplicity’s sake (for simple reactions of
the first order) that these values are linked to direct proportional dependence:

P = dS/dt = f(wr) = qwr = qkci

(4.12)
where q is the coefficient of proportionality. For unitary concentrations and for
k=1, q equals “standard” production of entropy (P’) and P = P'wr .Supposing the
components’ concentrations to be maintained constant by an external flow we
write:
P = P'k exp(-Ea/RT)
(4.13a)
In the stationary state, entropy production is minimal.
dP/dt = 0 and dP/dt = P'kd[exp(-Ea/RT)]/dt = 0
(4.13b)
After integration from t=0 to the moment of formation of the active complex we
get:

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 Ea/RT = lnC
(4.14)
If the process is non-stationary, P is not minimal and in correlation with
(4.13 a, b) the expression under exponent increases, i.e. the energy of activating
the reactions, occurring for a higher P, is greater. This distinction is expressed in
the various values of lnC. When examining the real processes it is more correct
to say that the states with a higher activation energy are characterized by a high
entropy production and to signify they are instable and less advantageous as to
energy. As we have shown above that formation of an active complex can be
considered in the frame of the model of a system with gradients and flows to
which Prigogine’s theorem is applicable; then of all possible reactions with least
activation energy it must not only start first but also occur in conditions nearest
to a stationary state.
From that view-point, Ostwald’ well-known rule is interpreted anew: if it
is possible that in successive reactions for the reagent to be transformed into a
final stable product, it is not a direct reaction that takes place but a formation of
intermediate metastable products of which the free energies differ less from
those of the reagent than do the free energies of the final product and reagents.
Comparing this rule to the conclusion reached above, we may say that, as a rule,
reactions with the least variation of free energy are characterized by the minimal
entropy production. This is exemplified by a successive series of crystallization
phases of silica from an oversaturated solution at low temperature; opal,
crystobalite, tridymite, quartz. Values of free energy for minerals of this series
equal accordingly (in Kcal/mol) -202,91; -204,17; -204,42; -204,[Link] can be
seen, energy value monotonously diminishes. Difference of energy is minimal
for the pair opal- crystobalite and maximal for the pair opal-quartz. Succession
in formation of silica phases, consequently, depends upon greater increase of the
phases’ free energy, although all precipitated phases, except quartz, are in low
temperature conditions thermodynamically unstable. The system’s option, by
gradual, non trivial way of evolution (unlike the direct solution-quartz way) may
be considered an element of auto-organization.
Usually, germ formation arises in the conditions of a non-stationary
process, since the initial deep concentration overcooling rapidly decreases while
the crystals start increasing and consequently conditions at the limit vary in
course of time. However, constant repetition of successive metastable
intermediate phases at formation of many minerals (silica form, polytypical
micas and chlorites, structural modifications of alkaline feldspars, etc.) testifies
to stability of the reactions’ kinetics, i.e. to approach of stationary state. On low
hydrothermal temperature synthesis of albite in experimentation and
propyllitisation processes is ,as a rule, formed, at the beginning, “high”
disordinate, albite, thermodynamically unstable at low temperature. Finally on it
can be converted into its ordinate, low temperature stable form. Calciculations

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carried out on replacement reactions of plagioclase by albite show that the
activation energy at the forming of metastable high albite constitutes 2.25
Kcal/mole at 1000°C, and that the stable ordinate form is 4.85Kcal/mole
[Rusinov, 1972]. Consequently, the difference between the plagioclase’ free
energy (N°50) and the inordinate albite’s is lower by a few Kcal than the
ordinate albite’s. Entropy increase is also smaller in the formation of inordinate
albite and production of entropy is smaller for the processes of plagioclase –
active complex – disordinate albite – ordinate albite, than in the row of
plagioclase – active complex – ordinate albite. This confirms the hypothesis that
the process tends to a stationary state, choosing a gradual path towards
equilibrium through metastable phases. Interestingly, with temperature
increasing, the degree of ordination of albite forming in natural processes
increases, and above 350°C perfectly ordinate albites are formed. Evidently with
temperature increase the energetic threshold decreases and so does the solution’s
saturation degree and it means that the reaction’s chemical affinity of inordinate
albite formation diminishes. Inasmuch as crystallization of ordinate albite
begins, the corresponding speed of synthesis of inordinate albite decreases.
Consequently we approximately observe the correlation of proportionality A =
ar, for which, as shown above, the principle of minimal entropy production is
justified. It means that the process nears a stationary state.
Analogous calciculations lead to a similar conclusion, and for the
formation of dioctahedric polytypes of bright micas in the synthesis of which, at
temperatures of 200-300°C metastable polytypical modification 1 M occurs first,
activation energy for their formation being lower than for stable modification
2M1[Mukhamed-Galeev & Zotov, 1989].
Kinetics of metasomatic reactions also exerts an influence on the
metasomatic zoning structure, now little significant, now essential. We examine
[Link]’s basic equation of infiltration metasomatic zoning. It is based
on the relation:
(dC/dx):(di/dv) = 1/f = K
Further on, he calls x and v a single variable, which tallies with an
accepted assumption about attainment of local equilibrium and invariance
therefore of spatio-temperal coordinates. If then we consider the speed of
chemical reactions as a non-instantaneous but final value (as happens in reality),
parameters x and v are found independent and cannot be replaced by one. Inside
each zone, where equilibrium exists between rock and solution, there is no
variation in the content of components in the rock and in the solution (dCi = di =
0). At the zone limits these changes have the final value (Ci/i)/(x/v) = K ,
where x is the distance from the section where the chemical reactions begins, v
the volume of the solution percolating through the section in course of time from
the initial to the given moment. Taking into account that CV = M ,i.e. the
component a’s variation of mass in the solution, and that M in the time unit

108
represents the reaction speed (M = r), then r/i = K/x. As far as, for a
constant temperature, one can adopt a reaction speed almost constant one can
write xi = K', i.e. with moving from the initial section towards direct
percolation of the solution, the component i’s content in the rock varies
according to a hyperbolic law (fig.4.2a) and the component’s distribution profile
in the rock in the three – zone – column must look (as shown on fig. 4.2b) (right
angles attenuated by diffusion).
If we fix the component’s content in the rock (i.e. the section’s position in
space), then Cv = K'' or (since v is function of time) Ct = K'''.
Concentration variation in course of time also follows a hyperbolic law.
Influence of speed of chemical reactions on the form of limits between
zones in the column of metasomatic zoning is in many cases insignificant. In
experiments with small zones and transverse section of the solution flow, it is
most often unobserved [Zaraisky, 1991]. However, in natural objects this
influence is frequently an important factor. In particular, in the systems with
participation of iron, manganese and other elements with valence changes, the
determined (critical) correlation of the speeds of chemical reactions (including
oxydo-reducing reactions in the solution), may result in stability loss of the
thermodynamic path of the zoning’s development. In such cases there appears in
the solution a dissipative structure, which is reflected in a rythmico – ribboned
zoning in the rock.
In low temperature processes reaction kinetics determines dissolution
sequence of the rock’s initial minerals and influences the forming of
associations of minerals and metasomatic zoning. In the hydrothermal changes
of recent volcanic thicknesses are formed rocks composed internally of mineral
associations in unbalance [Rusinov, 1972]. As a result a complex metasomatic
zoning has formed, including a zoning newly formed as a whole of minerals in
equilibrium with the solution’s composition, as well as relicts of magmatic
minerals. The latters’ dissolution follows a rigorous sequence, characteristic of
the determined interval of temperature and the hydrothermal type. On
propyllitisation olivine and hypersthene are dissolved in the most external zone;
near the internal ones have successively dissolved augite, plagioclase,
hornblende, magnetite. This succession, permanent with weak variations for
physico – chemical conditions determined in various geological environments
has been called “dissolubility row”. Unlike this row is one characterized by of
middle temperature processes, linked for instance with metamorphism of green
rock metamorphism. In these conditions, plagioclase and albite change places
with a row of solubilities: plagioclase dissolves totally and is replaced by albite
in a first stage, while augite remains unchanged even in intensely
metamorphosed rocks. Observations in regions of active volcanism have shown
that dissolution speed of plagioclase rapidly increases as temperature grows
from 100 to 300°C, while the speed of augite dissolution slowly grows.

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 Reaction speed for fixed concentrations of components and temperature is
k
defined by activation energy Aexp(E / RT)C i .
k
Supposing Ci , A and E constant after passing to logarithms and
differentiating we obtain dlnK=-(E/RT)1/dT. After integrating in the interval
from T1 to T2 (correspondingly from K1 to K2, making T2-T1=T) we get the
hyperbole equation [Russinov, 1972] (E+E)(ln[K2/K1]-E/RT)=-E/R . In the
coordinates T-ln[K2/K1], the hyperbole is situated in the second and fourth
quadrants (fig.4.3). The steep curve in the realm of low temperatures depends
upon the coefficient in the equation: the greater E/RT1 the quicker varies the
reaction’s specific speed with temperature increase.
In the example examined above, at low temperature the plagioclase’s
dissolution speed is smaller than the augite’s, but at higher temperature the
relation is inverted. Evidently this is provoked by a greater energy of dissolution
activation of the plagioclase compared to that of augite. The order of dissolution
of residual minerals determines in the solutions gradual dissolving of such and
such component and therefore influences the order of precipitation of the newly
formed minerals and the zoning of their distribution. This influence is observed
in the external zones of shallow propyllites [Rusinov, 1972]. Near the internal
zones, residual minerals undergo complete dissolution, and zoning approaches
the one theoretically expected. It is curious that the order of dissolubility treated
above (the order of increase of the minerals’ activation energy of dissolution) for
low temperature metasomatism tallies with the successive decrease value of
entropy and entalpy of these same minerals in standard conditions.
In this way kinetic relations may be used in interpreting mineralogical
associations, although great difficulties remain in creating general theories on
mineralogical associations in unbalance: there is a deficiency of experimentally
determined kinetic constants and the data’s fragmentariness about links between
kinetic and thermodynamic parameters. More promising is the use of the kinetic
approach, the study of auto-organized phenomena in systems in unbalance.

4.3. Self-organization and synergetics of metasomatic systems

A metasomatic system is an example of a complex dynamic system in
which side by side with progressive movements of aqueous solution flows
through a porous environment, a whole series of chemical reactions takes place
between solution and rock. A system difficult to modelize because in it a
dynamic flow is combined with chemical interactions, and side by side with
signs of equilibrium between rock and solution, in an infinitely small volume
there occurs a manifest unbalance at the limits of zones where replacement
reactions take place. Moreover, metasomatic zoning testifies to structuration
(structure condition) of a petrological system in which chemical reactions do not
take place in the whole volume of replaced rock but are concentrated on discrete

110
regions, at the replacement fronts. Naturally the zoning’s theoretical modeling
was made by way of approximation of the process through simpler physico-
chemical models based on the thermodynamics of locally stable states (cf.
Chap.2) or on kinetics of chemical reactions towards obtaining equilibrium
between rock and solution. However, such models have proved not capable to
interpret arising structures more complex than those in equilibrium, and
resulting from a system’s auto-organization [Klimontovich, 1995].
The most widely spread aspects of complex structures appearing in rocks
due to autoorganization phenomena, are rhythmical, ribboned structures (linear
and concentrically zonal), torch-like, globular structures and some others. Their
appearance is conditioned by Belousov-Zhabotinsky’s (dissipative structures)
either by oxido-reducing oscillating chemical reactions or by an autocatalytic
mechanism and the reaction’s evolution in a regime of exacerbation. General
conditions of appearance of auto-organization in a physico-chemical system are:
a strong unbalance, appearance of inverse linkages between elements of the
system, influence of chemical kinetics with which is linked the process’s non-
linearity. The basic tenets of the auto-organization theory are in conformity with
geological systems, and partly with mineralogical ones, and examples of such
systems are contained in the books of [Link] [1993] and [Link]
[1994]. A few partial models of metasomatic systems are examined in articles
by Russinov & Zhukov [ Russinov et al., 1994, Russinov & Zhukov, 1994].
In the basis of the theory of metasomatic systems and processes is
included the theory of metasomatic zoning. Its first mathematical model was
given by [Link], who considered metasomatic zoning as an
indispensable attribute and typical sign of metasomatic processes, distinguishing
them from magmatic and metamorphic ones. The mathematical models of
diffusion and infiltration zoning he has elaborated ([Link].3) are based on the
principle of local equilibrium and suppose formation of sharp, uninterrupted
limits between zones and between an external zone and the immutable rock. At
the limits (fronts) there occur chemical reactions with replacement (or
dissolution) of one of the minerals of the most external zone and a jump of
concentration or chemical potential of a corresponding component in the
solution. Models were initially applied to processes of skarn formation, then to
greisens and other objects and have shown a better correlation between them.
Later on the model of local equilibrium was confirmed by theoretical and
experimental researches [Zaraisky 1989, Balashov, 1985].
In low temperature processes a zoning’s formation is complicated by
kinetic effects owing to weak speed of chemical reactions. Studying these
effects, [Link] [1981] has obtained systems of dynamic and kinetic
equations, describing the components’ distribution in the solution flow and in
the rock with which it reacts, a distribution depending not only upon initial and
limit conditions, but also upon time. The obtained kinetic equations show the

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possibility of progressive variation of quantitative correlations of minerals in
the zones of the metasomatic column, in case of influence of chemical kinetics.
Further development of the theory of metasomatic zoning is linked to
study of strongly unbalanced processes, in which auto-organization is manifest.
Auto-organization can only arise in open systems [Prigogine, 1985] at an
exchange of energy and mass with the environment, i.e. under external
influence. For a weak value of the external influence, usually designated by the
term controlling parameter (which evokes variations in the system and its
passage from equilibrium to unbalance) fluctuations arising in the system
vanish, and it returns to equilibrium. When this parameter increases, fluctuations
are stabilized and may increase, but when it exceeds a critical value the system
passes to an auto-organization regime.
Schematically it can be shown on a bifurcation diagram that the model of
local chemical equilibrium tallies with the stable state for which the controling
parameter’s value is equal to zero. [Link]’s kinetic model encloses the
interval of the controlling parameter’s small values (the kinetic realm of the
linear correlations of forces and flows) but at the bifurcation point, is settled the
domain of synergetic effects (Fig. 4.4). [Link] [1980] has called synergetic
the directive, current among scientists, which analyses synchronic or
cooperative action of the system’s components resulting from auto-organization
and fractality (self-similarity) of the systems. Synergetic effects
(autoorganization) in metasomatic processes appear in 1) structure and dynamics
of the front of introduction of the metasomatizing solution into the rock,
instability of a flat front and appearance of clusters of percolation (penetration).
2) conditions of percolation of running waves of concentration and formation of
rhythmico-ribboned (periodical )zoning. 3) some fractal properties of
metasomatic zoning.
Autoorganization in the solution’s filtration flow appears at once at its
entering the rock. A metasomatic system is heterogeneous and strongly
unbalanced. It consists of a porous rock, an intergranular solution in equilibrium
with the rock, and an extraneous solution from outside into the porous space and
in unbalance with the rock and the inter-granular solution. The introduced
solution is generally characterized by physico-chemical parameters different
from those of the inter-granular solution. In particular, it has another density and
viscosity due to difference of temperature and salinity. Therefore both solutions
may be considered independent phases, at least in the zone of the foremost
metasomatic front. Their dynamic interaction determines to a large extent
morphology and some other features of developed zoning.
The normal succession of fronts, i.e. of interzonal limits is the skeleton of
metasomatic zoning. Some morphologic varieties of such reaction fronts for
simple cases of directional zoning are considered in the works of [Link]
[1994]. The most interesting case is that of a “trapping” front with precipitation

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of a “reactional” (Korzhinsky’s term) mineral , since it leads to formation of
metalliferous concentrations, for example uranium mineralisation at the
dissolution front of the initial rock (Fig. 4.5).
A plane continuous front of advance of a solution in a homogeneous
porous environment with dissolution or replacement of its minerals is stable
only for a relatively weak filtration speed. On its increase beyond the critical
value it loses the stability of the already relatively weak heterogeneities of the
rock at grain level. Consequently salients are formed in them that do not
disappear in course of time but stabilize themselves and tend to increase (Fig.
4.6). This phenomenon, known as fingering, is a typical example of
autoorganization [Ortoleva, 1994]: the solution retires to the salients’ basis from
the flow’s neighboring strips; the salient growth accelerates, but that of the
contiguous hollows slows down. On studying the calcite’s dissolution it
appeared that along the salient’s wall convective flows are formed, additionally
feeding the salient with fresh solution. In the growth process, depending upon
the relative filtration speeds, the salient’s structure may get complicate. It may
tend to ramify (Fig. 4.6).
The plane front’s instability is the basis of formation of clusters when the
solutions’ flow filtrates. The solution’s introduction takes place in a system of
pores along limits of the mineral grains. In the case of compact (volcanic,
intrusive or metamorphic) rocks the solution’s fundamental mass may be
considered as propagating at the inter-granular limits. Thickness of gap between
grains in arbitrary sections is infinitely less than the separating surface.
Therefore the solution’s movement may be approximate to the one in a bi-
dimensional space. Then, analysis of the conditions of introduction of the
metasomatizing solution in the rock comes down to a bi-dimensional problem of
displacement of one liquid phase by another from the intergranular space. The
solution of this problem from the general standpoint and from that of
mathematical modelizing for a different relation between the two phases’
viscosity [Panfilov & Panfilova, 1996] shows that introduction occurs along a
net of percolation clusters. On Fig. 4.7 can be seen an example of a tri-
dimensional computer model of percolation clusters. The latter s’ character is
defined by a relation between viscosity and speed of the infiltrating solution but
the shape is similar to a multi-ramified net of filaments or dendrites. The
dendritic clusters’ morphology varies depending upon correlation of viscosity of
the displacing and displaced phase and upon filtration speed. If the viscosity of
the displacing phase is smaller than that of the displaced one, for instance
because of high temperature and low salinity, there are formed jets of rupture
with small transversal branches. A continuous front is lacking. The whole
structure is lengthened towards the pressure difference. Consequently there
remains in the rock “enclaves” (unreplaced parts) and the front zone of the
metasomatic zoning is a system of more or less oriented veins. Such stockwerks

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composed of a net of ramified metasomatic subvertical veins, made up of
carbonates, quarts, epidote or biotite, are rather common in the aureoles of
deposits of some auriferous hydrothermal veins. If the displacing phase’s
viscosity exceeds that of the displaced one we are near such a situation, but at
the same time there forms behind the clusters a continuous substitution front. An
increased role of capillary forces furthers the clusters’ ramification and a more
complete filling up of the space with a cluster.
The described clusters are self-similar, i.e. the structure of part of a
cluster on whatever scale is similar to that of the whole. The degree of self-
similarity (fractality) valued by the fractal dimension, for clusters of
displacement of liquid by gas (calciculated for displacement of petrol by gas)
varies between 1.3 and 1.7 and is close to the universal value of the plane
clusters: 1.71 [Panfilov & Panfilova 1996]. Appearance of such a scale of
invariance is possible on condition there exists in the system a link of remote
order and reverse links between its parts. In that sense it can be said that
fractalization serves as sign of the system’s synergy, and the fractal dimension
as measure of its degree.
It was noted above that metasomatism takes place with the participation of
aqueous solution in unbalance with the rock. The solution infiltrates the rock
through a net of fractures and zones accompanying the solution. Admitting the
fractures’ breadth to be negligible compared to their expanse they may be
considered topologically a bi-dimensional, i.e. superficial object. In the direction
of the solution’s movement these channels align themselves in a definite
succession. In the first place the solution propagates through large fractures to
great length, from which it infiltrates in the form of percolation clusters in
smaller fractures, from which it spreads along the limits of heterogeneity within
the rock and further in intergranular limits and intragranular fractures. In space,
the aggregate of these channels forms a net of successive ramifications from a
main trunk resembling the crown of a tree (the development of a portion of the
solution is represented on Fig. 4.8). There is a more precise analogy with the
system of blood vessels of living beings, which distributes blood to each cell of
the whole organism. In this way the solution as a result of innumerable
ramifications invades each grain of the rock, filling up its whole volume. As a
result, the fracture system and the limit of heterogeneity in the rock, forming
superficial ramifications, fills up the volume, i.e. acquires the property of a tri-
dimensional object. This surface becomes fractal and possesses a fractal
dimension 2< Dfr < 3 [Mandelbrot, 1982], distinguished from the topological
(cartesian) dimension of the surface (Dt = 2), as well as from the tridimensional
objects (Dt = 3). One can calciculate the value of the dimension Dfr for each
concrete system, calciculate the number of ramifications at each step on a length
of several steps (generations of ramification) or calciculate the area of spatial

114
filling while changing the scale of count . For the surface’s projection
represented on the plane of the sketch on Fig. 4.8, Dfr = 2.58.
In [Link]’s [Wagner, 1997] experiments the liquid is displaced from
the space between two loosely pressed glass blades by means of blown air. The
clusters in this experiment look like bubbles united by microporous conductors.
Also possible is a full disengagement of these air bubbles from the feeding zone.
The bubbles distribution according to dimension in the experiment had a fractal
character, i.e. the dependence of the number of bubbles of a determined
dimension upon their diameter was gradual.
N = r -D, where D is the fractal number and, in case of plane clusters,
1<D<2. In case of formation of clusters with such a morphology (bubbles)
through a reciprocal chemical action of the solution’s forepart with the rock,
metasomatic nodules arise or ovoids of newly formed minerals, as if the
metasomatic fronts were not linked to those, complete, that follow them.
[Link] has described similar formations. These are linked, evidently, with
nest biotitization surrounding cupolas of continuous biotitization in the gold
deposits of Muruntay (Fig. 4.9). Fig. 4.10 shows a photo and a sketch of part of
the argentiferous epithermal veins of the Dukat deposit. A zone of continuous
bertierinization (chloritization) is bordered by one of rhythmical ribboning of an
adular-bertierite aggregate, and between them are settled zones of ovoids of the
same composition with an adular nucleus.
The formation mechanism of rhythmical ribboned skarns with
wollastonite-hedenbergite has been examined (Fig.4.11). The photo shows
fractalization of such a rhythm system. The succession of alternating finer and
coarser stripes changes from place to place in the zones, but in certain the
intervals the fractal dimension nears that of Kantor’s quantity, 0.45.
Consequently the given system is an example of auto-organization of a
hydrothermal metasomatic process, complicated by repeated changes of
trajectory in course of evolution. Models of rhythmic zoning in some particular
cases were earlier on examined by [Link] [Rusinov & Zhukov, 1994].
As the most general model, obtained as case of local equilibrium as well
as of processes of extreme unbalance, appears a model of metasomatic zoning of
isothermal filtration on a basis of running fronts and waves. Research of the
system of dynamic and kinetic equations and the character of their solutions
have shown that replacement fronts may vary at a constant speed, become sharp
and tally with [Link]’s model of local equilibrium. Frequently,
however, the replacement front is not a bi-dimensional surface but has a certain
thickness due to the final value of the speed of replacement reaction. Then
waves of concentration may appear. With the statements about running waves
according to a regular initial distribution of the component in the rock, we come
back to the model of running fronts and local equilibrium. In this case the rest
point of the system on the phase surface proves unattractive. It is an unstable

115
saddle with separate trajectories, therefore there can be here no oscillations. But
if distribution is heterogeneous, one or several waves may appear, but in this
case there is no stable oscillatory regime.
Most interesting is the case of oxydo-reducing reactions in the solution.
They notably serve as starting point of the system’s oscillatory regime of
functioning. Let us examine the system with ions of oxydo-reducing iron or
from a general point of view, of whatever element of variable valence
Mx + Y = X + Y
X  Y + ne-
X + Y = My + X,
where X is the reduced form, Y the oxydated one, M are the minerals. As a
result of research on the stability of resolution tallying with the equations of
reaction speeds were obtained phase portraits of the system for the considered
variants (Fig.4.12). From all these possible variants only an unstable focus can
initiate an evolution along a stable closed trajectory of a limited cycle type and
consequently arouse stable space oscillation of concentration. Observed
rhythmico-ribboned rock structure represents a copy of dissipative structure
developing in the solution. Fig. 4.13 shows the result of numerical modeling for
skarns with wollastonite-hedenbergite and it is visible that the development of
stripes of enriched minerals loses touch in course of time from the evolution of
dissipative structures in the solution.
Petrographic research has allowed to establish that rhythmic zoning has
appeared there as a result of a two-stage process. At first was formed on
limestone a wollastonite skarn with uniformly scattered grains of hedenbergite
with magnesium and aluminum, and later on there was dissolution of this early
hedenbergite and precipitation of much later hedenbergite highly rich in iron and
void of aluminum in the form of thin stripes within predominating wollastonite.
Dynamic and kinetic analysis of the system is based on equations of the main
reactions possible in it [Rusinov & Zhukov, 1994].
FeCaSi2O6 + Ca2+ = Ca2Si2O6 + Fe2+
(1)
(hedenbergite) (wollastonite)
FeCaSi2O6 + Ca = Ca2Si O6 + Fe3+
2+
+e-
(2)
Fe2+ = Fe3++e- (3)
Moreover, account has been taken of the existence, in the solution, of
mono- and poly-nuclear iron complexes. Analysis of the relation of speeds of
direct and inverse reactions in the system, with simultaneous analysis of the
dynamic equations of the solution’s filtration, has shown that the described
rhythmico-ribonned structure is formed in two stages. At first, dissipative
structure appears in the solution with an undulatory distribution of concentration
of bivalent and trivalent iron. Then it evolves and provokes dissolution and

116
peripheral deposits in form of stripes. This class of dissipative structures results
from oxydo-restoring reactions, both homogeneous in the solution and
heterogeneous between solution and minerals.
From the standpoint of the examined mechanism the conceptual
coincidence of periodical zoning usually occurs to a forward zone of the
metasomatic zoning as forming in the system’s most tense unbalanced regions.
We are thus not far from exhausting the reserve of the metasomatic zoning’s
synergetic properties, perspectives for further research.
In this way, autoorganization in its various forms of appearance is a
characteristic property of metasomatic and hydrothermal metalliferous systems,
and its research presents itself as of both theoretical and practical interest.

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Fig.4.1 Electronmicroscope photo of gold-pulverized sanidine crystals and its surface
replacement by montmorillonite according to [Samotoin et al., 1996]
a,b - photos of pulverized surface of sanidine; c - photos in parallel light (c, dissolved grain of
sanidine, d, newly formed montmorillonite), e, microdiffractogram of montmorillonite; f, its
spectrum of energy dispersion.

118
Fig.4.2 Dependence of component’s content in the rock upon distance (x) towards the
percolating solution (a) and also for the column (b) composed of three zones

119
Fig.4.3 Dependence of speed variation of activated energy of chemical reaction upon
increase of temperature, after [Rusinov, 1972].
K is constant of reaction , E is activation energy.

120
Fig.4.4 Bifurcation diagram.
X is propriety of the system (concentration, density etc.); λ simplifying parameter (λo -
equilibrium, λ1-unstable linear correlation, λc - critical point or point of bifurcation). Eq - area
of linear correlations, close to equilibrium; Dis - unbalanced area of non-linearity; Syn - open
area of synergetic effects.

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Fig. 4.5. Above: schema of structure of a forced front of precipitation of mineral B on
the front of dissolution of mineral A (the arrow indicate the direction of filtration of
solution). Below: schema of formation of uranium deposit in front of dissolution of
sandstone by a metalliferous solution [Ortoleva, 1994].
1 – sandstone; 2 – zone of pyrite dissemination; 3 – zone of intense pyritization; 4 – zone of
uranium ore; 5 – zone of calcite concretion; 6 – zone of argillisation; arrow indicates direction
of filtration of the solutions.

122
Fig. 4.6. Formation of plumes owing to unstable movement of flat fronts (left). Arrows
indicate direction of movement of solution and matter transfer. Right, complications of
structure of plume in the course of its growth.

123
Fig. 4.7. Result of numerical modelisation of percolating clusters after [Panfilov &
Panfilova, 1996].
Left, tridimentional model; right, bidimentional clusters of displacement of more and
less viscous liquid.

124
Fig. 4.8. Forms of solution arising from an open fissure in uniformly cracked and porous
lateral rock.
Arrows indicate direction of solution’s movement.

125
Fig. 4.9. Extent of metasomatic rocks in a section through part of ore-field of Muruntay
after [Rusinov & Rusinova, 1998].
1, 2 - zone of skarns association (1 - antinolite facies, 2 – pyroxeno-clinozoisite
facies); 3 – zone of “insular” biotites hornfels; 4 – zone of micahornfels; 5 – cupola of early
biotites; 6 – enclosing schists; 7 – area of granite injection; 8 – boundaries of facies; 9 -
boundaries of subfacies; 10 – boundaries of extent of ore mineralisation.

126
Fig. 4.10. Photo (a) and design (b) of sample from from quartz-ore vein from gold-silver
deposit of Dukat (Okhotsk – Chukotsk volcanic zone). Samples from collection of
[Link].
Digits indicate metosomatic zones; o.r. shows insular rhythmical bertierite-adular.
Length of sample 30 cm.

127
Fig. 4.11. Photo of sample of rhythmically banded wollastonite-hedenbergite skarn from
boron deposit of Dalnegorsk (Primorie).
Dark stripe, hedenbergite, digit stripe, wollastonite. Length of sample 18 cm.

128
Fig. 4.12. Phase portraits of solutions of systems of equations of oscillating fronts and
surface waves of phases (Cx, Cy) in dependence upon correlation of significant functions
f(Fxy = 0), g(Fxy + wx = 0), w(wx = 0).
Fxy is kinetics of oxydo-reducing reaction; wx, wy the kinetics of mass exchange
reaction of the solution with solid phases of components x, y. Continuous bold lines are
trajectories of solutions; arrows indicate their direction at a given point. C° is the component’s
solubility.
The phase portraits tally with various regions of dynamics of formation of
metasomatic zones: a, b - regime of unidirectional zonality in conditions of local equilibrium
in the zone (rest point, saddle point); c,d - regime of oscillating waves localized in rear limit
of given metasomatic zone (stable ans unstable focus); e, f - regime of oscillating waves
disseminated everywhere in the given metasomatic zone (limited cycles around instable knot);
a, b, e dextrogyre; b, d, f levogyre.

129
Fig. 4.13. Evolution of dissipative structure in solution (left) and evolution of the banded
structure in rock (right) as result of computerized modelization .
Y is concentration of component in solution; H, W are contents of minerals in rock (H
hedenbergite, W wollastonite), τ is extended time, r is distance in the direction of solution’s
filtration.

130
 Chapter 5

Experimental modeling of metasomatism

In the course of the last decade experimental modeling has permitted to

reproduce the main types of perimetalliferous metasomatic rocks and to appraise
the border conditions of their formation depending upon T, P, PCO , the solution’s
2

composition and concentration, pH , fO and other parameters [Zaraisky, 1989,

2

19931,2; Zharikov & Zaraisky, 1991]. In the present work, the results of these
researches have been used to interpret the physico – chemical conditions of
metasomatic processes in granitic systems, between which are distinguished
infiltration and diffusion (fig.5.1).

5.1. Experimental methodology

The basic volume of experiments was carried out by the method of

modeling of diffusion metasomatic zoning. The method’s main feature was D.S.
Korzhinsky’s modeling of an open system with perfectly mobile components.
The latters’ external activity in relation to the rock milieu was kept constant at
the expense of the great buffer volume of the solution, in which was placed a
small golden capsule open on one side (d=5mm, l=50mm) filled with
compressed rock powder with grains smaller than or equal to 0.1 mm. As initial
granitoidic rocks were used leucocratic granite, biotite granite and granodiorite
(table1). The capsule with rock powder was placed vertically in a hermetic
autoclave sheath of 150 cm³ prepared from an alloy of corrosion resisting
titanium (fig.5.2). The sheath was filled with the solution and of necessity were
introduced oxygen buffers and others, solid CO2, weight gauged, pulverized
quartz for the silicate solution’s saturation, metallic and other components
depending upon the experiments’ conditions. The flow/rock relation stood about
100/1.

131
Table 5.1. Chemical (% weight) and mineral (% volume) compositions of
granitic rocks utilized in experiments
Rocks
Leucogranite1 Biotitic granite Granodiorite3
SiO2 76,87 71,06 65,56
TiO2 0,30 0,20 0,72
Al2O3 12,56 14,59 15,52
Fe2O3 0,38 0,30 -
FeO - 1,75 3,64
MgO 0,10 1,20 2,19
CaO 0,50 1,74 3,98
Na2O 3,80 4,14 3,76
K2O 4,98 4,27 3,48
perte au feu 0,31 0,81 1,15
total 99,80 99,85 100,00
1
– KazCentral Kazakhstan, Akchatau : Qtz-35,0 ; Pl-34,0 ; Kfs-29,0 ; Bi-1,0 ; etc.-0,1
2
– Altaï (Kalbu), Belaïa Gora : Qtz-25,0 ; Pl-45,5 ; Kfs-19,0 ; Bi-9,5 , etc-1,0
3
– Tadjikistan, Maykhura : Qtz-23,5 ; Pl-45,5 ; Kfs-14,5 ; Bi-10,0 ; Amph-5,5 ; etc.-1,0

Use was made of solution of acids (HCl, HF), bases (NaOH, KOH) and
salts of rock-forming components: chlorides and fluorides of Na, K, Ca, Mg, Fe
as well as carbonates and metasilicates of Na and K in various combinations
depending upon the task of modeling. In many experiments the solution’s basis
were NaCl or KCl as the prevalent components of natural fluids that acidified
HCl or alkalified NaOH to obtain the indispensable amount of pH.
Concentration of liquids varied in broad limits from 10 -5 to 5moles/kg H2O, but
more often concentrations from 10-3 to1.0m were adopted. In the course of the
experiment the fluid remained motionless and reacted with the rock by the
components’ diffusion through the capsule’s open orifice. In opposite direction
occurred by diffusion the removal of the rock’s components. Owing to the
solution’s great volume, its composition did not much vary in the course of the
experiment, despite its reciprocal action with the granite. Granite got into
equilibrium with the external solution only in the hindmost zone at the capsule’s
open end, More deeply the rock remained in unbalance with the external
solution, but found itself, in each section, in a state near local equilibrium with
its porous solution. To this was included, naturally, modeling of an open system
with perfectly mobile components, whose activities, like pressure and
temperature, were determined outside in relation with the kind of milieu. In
experiments with fluorid solutions, instead of titanium sheaths smaller ones in
gold or platinum were used and smaller capsules. The experiments were made at
T = 250-600°C, P = 1 kbar and lasted one to four weeks.

132
 At the end there appeared in the capsule, instead of the initial
homogeneous rock, a zonal metasomatic column, frequently with sharp contact
zones. The greatest change took place in the rear zone at the capsule’s open end
and in direct contact with the influencing solution. The first zone (towards the
diffusion flow of the components) situated on the capsule’s closed end remained
in composition near the initial granite. The experimental columns were sealed
with an organic glue and cut lengthways by means of a diamond saw and
examined under the microprobe with the usual punctual method and the
scanning method with a narrow beam along transverse profiles in order to
determine the zones’ global chemical composition.
We consider experimental models only of those main types of
metasomatic rocks that form directly on granites, leaving aside another
metasomatic main group genetically linked to granites but usually localized in
intervening rocks (magnesium metasomatites of exocontact, propyllites,
berezites, quartz-sericite, quartz-adular-sericite metasomatites and others).
Taking into account the habitual close link of metasomatism with ore formation,
experimental modelling was also carried out of deposits of rare minerals,
synchronous with processes of acid and alkaline metasomatism of granite.

5.2. Modelling of acid metasomatism of granites.

The term acid metasomatism, or “acid leaching” [Korzhinsky, 1953], or

“hydrogenised metasomatism” [Hemley & Jones, 1964], used as generic for a
large group of metasomatic formations, is characterized by a common tendency
to remove basic chemical components (Fe, Mg, Ca) and alkalines (K, Na) with
increase of the rock’s general acidity. Formation of rear zones only composed
of siliceous and aluminous minerals or even only of quartz is the final result of
the most intensive display of acid metasomatism.

Granite metasomatism under the action of acid chloridic solutions.

Modelling of formation of secondary quartzites. Under the influence on

granite, granodiorite or quartz – diorite of aqueous solutions of HCl or
chloruried acid solutions with weak ratio mKCl/mHCl, mNaCl/mHCl,
mCaCl2/mHCl, quartz saturated, metasomatic columns are formed, the rear zone
of which is made up of quartz and of one of its alumino – silicated minerals:
kaolinite ( under 300°C), pyrophyllite (300-420°C) or andalousite (over 420°C)
depending upon temperature [Zaraisky et al., 1981]. As to mineral composition,
these experimental metasomatites may be compared to facies of secondary
quartzites with kaolinite, pyrophyllite and andalusite. They can be considered an
extreme case of acid leaching of a granite, when in the influencing acid solution

133
any other rock-forming components, except silica, are absent (or present in tiny
quantity).
Let us take as an example the structure of a metasomatic column obtained
as a result of the influence on a biotite granite ([Link] 5.1) of a solution of
0.1mHCl for T = 400°C (fig. 5.3). The minerals’ quantitative relations (%mol)
in the column’s zones were calciculated on data of determination of the gross
chemical composition with the microprobe scanning method with along a cross-
section (table 5.2). For simplicity’s sake we have not shown the part of porosity
forming in the different zones from 28 to 41 vol.%. We note that in table 5.2. the
porosities on hand refer to low values of the sum of chemical components, since
by means of analysis with microprobe scanning the content of the component is
determined in the smallest volume of porous environment. And only in the
absence of pores does the sum reach 100%. The data on table 5.2 show than in
the process of metasomatism FeO, MgO, CaO, Na2O and K2O undergo an
important removal, but that the content of SiO2, Al2O3 and TiO2 remains exactly
at the previous level, albeit silica always shows some leaching in rear zones 1
and 2.

Table 5.2. Chemical composition (% weight) of the metasomatic zones of the

experimental column, corresponding to the quartz –pyrophyllite facies of
secondary quartzites (cf. Fig. 5.3)
Zone
1 2 3 4 5 01
SiO2 48,4 45,7 49,9 53,2 50,7 49,7
TiO2 0,2 0,2 0,4 0,3 0,3 0,2
Al2O3 10,6 10,6 10,2 10,2 10,1 10,2
FeO* 0,1 0,6 2,3 1,4 1,3 1,4
MgO 0,0 0,0 1,0 0,7 0,7 0,9
CaO 0,1 0,3 1,0 1,0 0,9 1,2
Na2O 0,2 0,3 1,4 2,6 2,5 2,9
K2O 0,2 1,5 2,7 2,9 3,3 3,0
Somme 59,8 59,2 68,9 72,3 69,8 69,3
* All iron as FeO
1
0 – initial biotite granite, porosity=30 %

Temperature decrease to 300°C or less brings about formation, in the rear

zone, of kaolinite instead of pyrophyllite, whereas in the experiments at 500°C
andalusite is formed instead of pyrophyllite. Everywhere in the rear zones,
quartz is present as second phase. At all temperatures in the column’s central
zones muscovite develops. The succession of replacements, feldspar 
muscovite  pyrophyllite (kaolinite, andalousite) reflects the solution’s acidity
increase through movement in the column from fore zones towards rear

134
zones. The succession of replacements with temperature, in the rear zones of
the column of kaolinite by pyropyllite and andalusite tallies with the change of
temperature facies of secondary quartzes.

Modeling of quartz–muscovite greisens and quartz–potassic feldspar

metasomatites.
With increase of the ratio mKCl / mHCl in the active solution the
granite’s acid leaching decreases in intensity and in the rear zones of the
columns appear the micas, feldspars and other alumino-silicates (fig.5.4).
Experimental columns formed in these conditions may be compared with
the quartz – muscovite greisens and the quartz – feldspar metasomatites. So for
example, due to the influence on a biotite granite of the solution 1 mKCl + 0.05
mHCl + (quartz), pHinit=1.4, T=400°C, P=1kb, t=500 h, a column has been
obtained that approaches in composition and succession of zones the greisens of
quartz – muscovite facies (figures below indicate distance of zone limits from
the capsule’s open end).

Ms+Q Ms+Qtz+K Ms+Qtz+Kfs Ms+Qtz+Kfs+Pl Qtz+Kfs+Pl+ Bi-granit

tz fs +Bi +Bi Bi
0 2.8 6.1 33.7 43.7 48.7 mm

In similar experiments, but without quartz saturation of the column, the

rear zone is only composed of muscovite with strong porosity. Such columns
may be compared with the greisens of muscovite facies and of quartz –
muscovite, rarely present in nature.
Due to influence on a biotite granite of a strongly acid but highly
potassium – concentrated solution 3mKCl+0.1mHCl+[quartz], pH=0.8 for
T=500°C, P=1kb, t=240 h a metasomatism column with quartz-potassic feldspar
has been reproduced, in which granite was replaced at great depth by a quartz –
potassic feldspar aggregate:

Qtz+Kfs Qtz+Kfs+B Biotite granite

i
0 35.0 50.0 mm
And in this case the influence of solutions undersaturated in quartz
produces a monomineral rear zone of potassic feldspar.
At a temperature higher than 450°C quartz – muscovite greisens are
replaced, with increase of acidity (decrease of the ratio mKCl/mHCl), by the
quartz – andalusite facies of secondary quartzites or greisens, but under 300°C
by a quartz – kaolinite facies.

135
 Conditions at the limits of formation of secondary quartzites, quartz –
muscovite greisens and quartz – potassic feldspar metasomatites for a
temperature and value of the equilibrium ratio mKCl/mHCl in the solution may
be represented on the experimental diagram of phase relations in the granitic
system model Al2O3-SiO2-H2O-KCl-HCl (fig. 5.5).
This system tallies with the composition of the most modified rear zones of the
acid metasomatic columns, from which are removed all rock-forming
components, except Si, Al and K. Therefore the phase composition of the
diagram’s field tallies with the mineralogical composition of the rear zone
columns of corresponding metasomatic formations and facies. The upper
temperature limit of quartz – muscovite greisens is determined by thinning out
of the stability field of muscovite in association with quartz at 555°C. With a
PH2O increase it rises a little ( up to 590°C at 2 kbar), but with a decrease it
sinks (to 500°C at 0,5 kbar). Quartz feldspar metasomatites may exist in a very
wide range of temperature in conditions of increased potassic solutions. This
being so, with temperature decrease at constant HCl concentration it is necessary
to have the highest KCl concentration for an exchange of quartz – muscovite
and quartz – feldspar mineral association.
Modelling of quartz – albite metasomatism and propyllitization of
granitoidic rocks. Under the influence of sodic solutions, albitization stands as
the leading process of granite change. However, very acid Na containing
solutions of the type 1mNaCl + 0.1mHCl + [quartz]exert on granite nearly the
same influence as solutions of one HCl, i.e. bring about formation in rear zones
of columns of Qtz+Kln, Qtz+Prl or Qtz + And associations. Such columns tally
with the different facies of secondary quartzite formation. The cause of this is
neither presence nor absence of sodium in the solution, but high acidity. Under
influence of moderately acid, nearly neutral chloridic solutions with a different
sodium concentration (from 0.01 m to 5m NaCl) on a leucocratic granite (cf.
table 5.1), all the minerals of the initial rock, except quartz, are albitized, there
forms a metasomatic column of quartz albite type ((T=400°C, P=1kb, t=336 h,
solution 1m NaCl+[quartz], pHinit=5.8):

Ab+Qtz Ab+Qtz+Bi Ab+Qtz+Kfs+Bi Leucogranite

0 6.0 15.0 50.0 mm

Kfs at first, then biotite are replaced by albite. Relicts of initial oligoclase
are sometimes preserved. The rear zone is composed only of albite and quartz. A
certain increase in the solution’s acidity brings about muscovite in the transition
zones of the column in paragenesis with biotite, albite and quartz.
Influence of near neutral and weakly sodic solutions on granodiorite
([Link] 5.1) at T=300-500°C produces formation of column of the type albite
propyllites, the rear zone of which is made up of paragenesis of AB + Chl +

136
Amph + Zo (the solution SiO2– undersaturated). For T=500°C, P=1kb, t=336 h,
solution 1m NaCl + 0.0003m HCl, pHinit=3.7, we get the column:

Ab + Amph + Chl Qtz + Ab + Amph Qtz + Pl + Amph + Ganodiorite

+ Zo + Chm + Zo Bi + Chl + Zo
0 2.0 4.5 21.0 50
mm
As acidity increases from the composition of quadrimineral paragenesis of
the rear zone, successively disappear amphibole, zoisite and albite. Much more
stable is chlorite, which associates with paragonite in moderately acid sodic
solutions. In conditions of high acidity chlorite disappears, the column’s rear
zone is made up of Kln, Prl or And, to which quartz is added at the solution’s
silica saturation.

Metasomatism under the action of acid fluoridic solutions.

Modeling of granite’s greisenisation. Participation of acid fluoridic
solutions is the most characteristic of greisen formation processes, in particular
of formation of quartzous and quartz – topaz greisens with fluorite and F-
containing micas. By Io.B. Shapovalov [Shapovalov, 1988] were obtained the
first experimental data on topaz’s mineral equilibrium in the system Al 2O3 
SiO2  H2O  KF  HF (fig. 5.6).
It is established that topaz’s formation requires high enough
concentrations of HF and low KF in a solution in equilibrium (mHF>0.0025m,
mKF<0.006m pour T=400°C, P=1kb). This accounts for the limited expansion
of topaz greisens in nature. Depending on temperature the topaz’s low stability
limit is determined by equilibrium with andalousite, pyrophyllite or kaolinite.
The upper limit at all studied temperatures (300-600°C) is defined by
equilibrium with fluellite (AlF3.H20).
Greisens of quartz – topaz facies. The acid fluorid solution’s peculiarity
consists in the great solubility in them not only of silica but also of aluminium
[Zaraisky, 1999]. That is why to prevent granite dissolving in experiments with
a solution HF, crushed quartz and corundum have been added. Thus we
succeeded in obtaining for leucocratic granite (cf. table 5.1) a zoned column
tallying with the greisens’ quartz – topaz facies (T=500°C, P=1kb, t=336 h,
solution 1mHF + [quartz] + [Al2O3]):

Qtz + Toz + Qtz + Ms + Qtz + Ms + Qtz + Kfs + Qtz + Ab + Leucogranit

Fl Fl Kfs + Fl + Ab + Fl Kfs + Bi + e
(Ab) Fl
0 3.0 4.1 7.2 2.1 25 mm

137
 Quartz in rear zone predominates over topaz (fig.5.7). In the following
zones topaz is replaced by muscovite, even more deeply, stability of potassic
feldspar is retained and also, later on, that of albite of the initial leucocratic
granite. In all zones fluorite is present up to 1 to 3%.
Greisens of quartz-muscovite of facies. A weak increase of potassium
concentration in the solution (mKF > 0.006m) leads to replacement of topaz in
the rear zone by muscovite and increase in the quantity of potassic feldspar in
the remaining zones:

Qtz + Ms + Fl Qtz + Kfs + Qtz + Kfs + Qtz + Kfs + Leucogranite

Ms + Fl Ms + Bi + Fl Ab + Bi + Fl

Greisens in quartz facies. In chlorured solutions we did not succeed in

obtaining a column corresponding to quartz greisens, due to preservation of
alumine in the rear zone. However, alumina can be completely eliminated from
the rear zone due to reciprocal action of leucogranite with the quartz saturated
solution HF. In an experiment performed at T=900°C, P=1kb, t=336 h, the
solution 1mHF +[quartz] in excess produced a column with a practically
monoquartzic rear zone:

Qtz + Fl Qtz + Ms + Qtz + Kfs + Qtz + Kfs + Leucogranit

Fl Ms + Fl Ab + Bi + e
Fl
0 3.0 5.0 7.5 25 mm

To form the most complete column with a different quartz-topaz zone

between quartzic and quartz-muscovite zones a higher alumina activity is
needed in the solution (T=500°C P=1kbar, t=336h, solution 1m HF+0,17m
AlF3+[Qtz]).:
Such a lateral zoning is namely characteristic of symmetrically zoned
subvertical veined greisens bodies in the wolfram-molybdiferous deposits of
Akchatau in Central Kazakhstan [Zaraisky 1995].
The results of experimental modelling confirm the need of participation
of acid fluorid solutions in greisens forming processes. In fact, under influence
of fluorid solutions all types of fundamental facies of greisens can be obtained:
quartz-muscovite, muscovite, quartz-topaz and quartz, whereas chlorid solutions
can only bring about formation of quartz-muscovite and muscovite facies. The
example of greisens allows us to speak of secondary role of temperature as
compared with the solution’s composition. All types of greisen columns
characterized above were obtained in a wide range of temperature, from 300 to
600°C [Soboleva & al. 1988] and then the columns’ structure varied very

138
weakly with the temperature change, and it decidedly depended upon the
variation in the solution’ composition.

Metasomatism under the action of chlorinated and boric acid solutions.

In H3BO3 solutions without other components added, tourmalinisation has

not been reproduced. By adding NaCl tourmaline is formed only in the rear zone
of the metasomatic column on account of the dark-hued minerals of the rock. By
adding FeCl2, FeCl3 or MgCl2 tourmaline formation is much intensified in all the
column’s zones on account of dark-hued minerals as well as of feldpars. In
conditions of acid increase (pH = 1.5 to 4.0) it is necessary, in order to obtain
quartz-tourmaline greisens and other metasomatites with tourmaline, to have a
high concentration of H3BO3, from 0.5m at 600°C to 2.0m at 300°C. It is
established that tourmaline is always less ferriferous compared to the
equilibrated ferruginous solution and it shows a tendency for its ferruginosity to
increase as temperature decreases.

Metasomatism under the influence of chlorinated solutions

containing CO2 and sulfur.

The fundamental part of this series of experiments were carried out at a

moderately low temperature, from 250 to 400°C. In dependence on stability of
clayey minerals, sericite and potassic feldspar in the rear zone, the experimental
columns may be confronted with three groups of metasomatites: 1) argillisites,
2) beresites and metasomatites with quartz-sericite, 3) gumbeites and
metasomatites with quartz-potassic feldspar. Typomorphic minerals of beresites,
gumbeites and argillisites, except fixed aluminosilicates, are ankerite, calcite and
pyrite. On the diagrams in the coordinates T-P-XCO2-log(mK+/mH+) the field of
beresites occupies a central position (fig.5.8). With decrease of temperature and
value of ratio log(mK+/mH+), beresites are replaced by argillisites, but with
increase of those parameters, by gumbeites. Pressure variation acts in the
opposite direction. Remarkable is the rather narrow temperature range of
beresite formation (optimum T: 260 - 325°C) and their strong dependence upon
CO2 concentration in the fluid (XCO20.05). Decrease of XCO2 brings about
replacement of beresites by quartz-sericite metasomatites containing no ankerite
carbonate. Analogous correlations occur between ankerite-containing gumbeites
and quartz-potassic feldspar metasomatites without ankerites.

139
5.3. Modeling of alkaline metasomatism of granites

Metasomatism of carbonates and silicates of sodium and potassium

under the action of chloride solutions

Modeling of aegyrine albites and potassic feldpars. In conditions of sodic

alkaline metasomatism for an excess of quartz there is only an intense removal
of K2O from the granite and significant addition of Na2O [Zaraisky, 1989].
Feldspars are replaced by albite and biotite by aegyrine. As final result of the
change is found a rear zone of quartz-albite- aegyrine. (T=500°C, P=1kb, t=336
h, solution 1.0mNaCl+1mNaOH+[quartz], pHinit=12.8):

1 2 3 0
Qtz + Ab + Acm Qtz + Ab + Acm + Qtz + Pl + Kfs + Granite in biotite
(Bi) Acm + (Bi)
0 8.2 27.7 44.5 mm

On table 5.3 has been adduced the chemical composition of zones of this
column which it is interesting to compare with that of zones of acid leaching
columns (cf. table 2). Through acid leaching of the granite’s biotite, including in
acid solutions with high Na activity, an intense removal of all components
occurs from the rock, except alumina but including some removal of Na. In the
alkaline sodic metasomatism, from the granite, K2O is strongly leached (partly
also MgO) and much Na2O is added. The granite’s alumina concentrates in
albite, and through addition of Mg, Ca and Ti to the granite aegyrine is formed.
The action of sodic alkaline SiO2 undersaturated solutions brings about
the granite’s strong desilicatization. Instead of albite associated with aegirine are
formed in the rear zone feldspathoids, nerpheline, sodalite or cancrinite
depending on the anionic composition of the solution (OH-, Cl- or CO32-).
Evidently the condition of such high alkalinity is not typical of granitic massifs.
Potassic alkaline solutions bring about the granite’s potassic
metasomatism, expressed in intense potassic feldspathisation. The rear zone has
the mineral composition Qtz + Kfs + Bi. In the SiO2 undersaturated solutions,
the rear zone is made up of potassic feldspars. By very high alkalinity (solution
1.0m KOH) in the rear zone is formed, instead of Kfs, calcite associated with
tetraferribiotite. In the middle and forward zones of such columns calcite is
replaced by potassic feldspar, and on the biotite are formed aegyrine and
riebeckite.

140
Table 5.3. Chemical composition (% weight) of the metasomatic zones of the
experimental column, of alkaline, sodic metasomatism of biotite granite
(column of aegiritic albitites)
Zone
1 2 3 01
SiO2 49,7 49,9 51,8 49,7
TiO2 0,2 0,2 0,3 0,3
Al2O3 9,3 9,5 9,7 10,2
FeO* 1,2 1,1 1,5 1,4
MgO 0,5 0,3 0,5 0,9
CaO 1,0 1,1 1,2 1,1
Na2O 6,0 4,6 3,8 2,9
K2O 0,2 0,7 2,4 3,0
Total 68,1 67,4 71,2 69,5
* All iron as FeO
1
0 – initial biotite granite, porosity = 30 %

Metasomatism under the action of alkaline fluorid solutions

Modeling of alkaline albitites and “apogranites” with riebeckites and

aegyrines.
Presence of fluorite, cryolite, F-containing amphiboles and micas is usual
in many alkaline metasomatites developing in normal and alkaline granite. One
of the interesting problems is the possibility of formation of metasomatism of
granite with riebeckite and aegyrine, in the way of what we considered above
[Zaraisky & Zerianov, 1973].
In alkaline fluorid solutions the most intense granite transformation occurs
in absence of quartz saturation (T=500°C, P=1kb, t=95 h, solution 1.0 mNaF,
pHout=7.2):

Ab + Rbk Qtz + Ab + Rbk Qtz + Ab + Ksp + Biotitic granite

Rbk + (Bi)
0 1.0 12.0 40.0 mm

In the column’s rear zone is formed riebeckite albitite: quartz is

eliminated, potassic feldspar and plagioclase are completely albitized, but biotite
is replaced with alkaline amphibole. Meanwhile the column’s transition zone
tallies in composition with the typical riebeckitic granite. Temperature increases
up to 500 or 600°C brings about replacement of riebeckite by aegyrine.

141
 When the fluorid-sodic solutions are silica saturated, granite
transformation diminishes, quartz is preserved in the rear zone, while potassic
feldspar remains more stable. Increase of SiO2 activity furthers aegyrine
development instead of alkaline amphibole. However, the column’s transition
zone tallies even then with the ribekitic granite. This same paragenesis, of
typical riebeckite granites (Qtz + Ab + Kfs + Rbk) occurs in the transition zone
even under the influence upon biotitic granite of potassic alkaline fluorid
solutions instead of sodic ones (T=500°C, P=1kb, t=96h, solution 1.0m KF,
pHinit=7.3).

Kfs + Fe-Bi Kfs + Nar Qtz + Kfs + Qtz + Ab + Bi-granite

Rbk Kfs + Rbk +
(Bi)
0 1.5 14.0 35.0 40.0 mm

In this, buffering action of the rock is manifested, supplying Na to the

porous solution at the albite’s replacement by potassic feldspar. However,
depending upon the external solution’s cationic composition, the column’s rear
zone consists either of albite and riebeckite (NaF solution) or of potassic
feldspar and tetraferribiotite (KF solution). So is notably formed narsarsukite,
Na2(Ti,Fe)Si4O10(O,OH,F), in the column’s second zone, obtained in the KF
solution.

5.4. Dependence of facies of alkaline sodic metasomatism of granitoidic

rocks upon temperature and values of log(mNaCl/mNaOH) in the solution

In this series of experiments the initial rock was granodorite (cf. table 5.1)
and 1.0m NaCl was the solution’s basis. A change in alkalinity was obtained by
increasing NaOH from 0.0001 to 0.1m. The initial pH value increased from 7 to
12.8. The solutions were silica-undersaturated [Zaraisky et al., 1984].
As the solution’s alkalinity increased, the type of arising metasomatites
changed from albite propyllites in near neutrality to alkaline amphibole-
aegyrine-albitites and ultra-alkaline aegyrine-riebeckite-sodalite metasomatism
(fig. 5.9).
With temperature decrease from 400 to 350-300°C sodalite and albite are
replaced by analcime. An important limit between the fields of acid and alkaline
metasomatism is fixed by the replacement of actinolite amphibole in the
propyllites by alkaline amphibole in the albitites. In the P-T conditions of the
experiments this limit runs parallel to the line of neutral values of the pH T,P,
somewhat altered in the alkaline field. Analysis of solutions after experiments
reveals a sharp decrease (a hundred times) of removal from the rock of Fe, Mg
and Ca in alkaline, compared to acid conditions.

142
5.5. Modelling of deposits of rare metals (W, Mo, Sn) in the process of
greisenisation and alkaline metasomatism of leucocratic granite

In this series of experiments were used as source of W, Sn and Mo

swallowed wolframite, molybdenite and cassiterite crushed in a solution in a
separate bowl [Zaraisky & Stoyanovskaya, 1995]. As in other experiments,
condensed leucogranite powder was placed in an open golden capsule. Owing to
reciprocal action with the solution there appeared on the granite a metasomatic
column of diffusion with added quantities of W, Mo and Sn in the rear zones. As
means of “greisenizing” were utilized acid chlorured and fluorured solutions:
1m KCl + 0.5m HCl and 1m KF + 0.05m HF. For comparison’s sake we have
studied the influence of a nearly neutral solution of 1m NaCl, producing
leucogranite albitization, and of two alkaline solutions of 0.1m Na2SiO3 and
0.1m Na2SiF6, producing alkaline albitites on the granite. The obtained
metasomatic columns were cut up lengthwise and studied with microprobe, but
also, analysed, for ore components, by the method of quantitative spectral layer-
by-layer analysis, for which 6 or 7 trials were carried out on each line of the
column.
It was established that W, Mo and Sn may be transported in sufficient
quantities by solutions of varied composition, producing the granite’s
greisenization, albitization and alkaline metasomatism and be deposited
synchronously with the formation of these metasomatites, mainly in the rear
zones of the metasomatic columns (fig. 5.10). Instead of which, the mentioned
elements show an appreciable difference in their migratory capacity, to which
may be linked their frequent zonal distribution in the deposits.
We discover the marked dependence of rare metals’ addition and
precipitation upon the solution’s composition and acido-alkalinity (fig.5.11). So,
for example, W, Mo, and Sn are equally well transported by alkaline solutions.
At the same time, acid chlorured solutions are rather favourable to wolfram
transport and precipitation, but less so to molybdene transport. Tin migrates
farthest in solutions of Na2SiF6 and NaCl. Moderately acid fluorid solutions
worse than others deposit W and more easily Sn and Mo. Wolfram is best
introduced by very acid and very alkaline solutions and appreciably worse by
nearly neutral solutions. Molybdene is deposited in columns in much smaller
quantities than wolfram and tin and displays an inverse relation to the solution’s
acidity, showing the greatest accumulation in alkaline conditions. As a whole, at
a lower level of accumulation in the metasomatic zones and the distance of
migration to the column, the metals dispose themselves in the order W > Sn >
Mo. Thus, tin is most indifferent to the solution’s composition, but W and Mo
show a more pronounced selectivity.

143
5.6. Conclusion

The most intense metasomatic changes of granites usually coincide with

the peripheric intrusion zone, whereas in the granite’s internal core the changes
are usually weak and metalliferous mineralizations, as a rule, absent. Notably,
the peripheric and especially apical part of an intrusion is characterized by the
presence of local permeable structures (cracks, breach zones, compressed
cupolas, apophyses) provoking fluid flows. This phenomenon has a general
character and may be interpreted as the development in the intrusion’s contact
part of destructive thermoelastic tensions, conditioned by an irregular
temperature distribution during the granitic body’s crystallization and cooling
down. In the internal part of the intrusion, thermo-elastic tensions do not reach
destructive force, and cracks of thermal gradient are absent. Flow concentration
in local fluid conductors brings about formation in the lateral rocks, in contrast,
a marked diffusion of metasomatic zoning.
The type of metosomatic process depends on a combination of many
physico-chemical parameters and finds its most complete expression in a zonal
metasomatic column, a series of successive zones from unchanged granite to the
final product of its change. The method of experimental modelling produces
various types of metasomatic columns, nearly tallying with all natural
metasomatites (metasomatic formations) developed in granites.
For the formation of such and such a type of metasomatic column, most
significant is the composition of the rock and of the solution and its pH.
Temperature, pressure and other parameters are less important. So, for example,
for the formation of topaz greisens, action of acid fluorid solutions on the granite
is indispensable (>10-3m HF for 400°C and > 10-2m HF for 500°C) with high
alumina concentration (>5.10-4m Al) and a low potassium activity (<10-2m
KF). Albite propyllites determine the border field between acid and alkaline
metasomatism; they are formed in nearly neutral conditions. For the formation
of alkaline albitites with riebeckite-aegyrine, favourable are temperatures
between 350- 450°C and the action of essentially sodic alkaline solution with
pH > 6.6 to 8.5. Under the action on granite of chlorured solutions in conditions
of highest acidity (with low mKCl/mHCl ratio) arise metasomatic columns
tallying with secondary quartzites. Successive increase of the mKCl/mHCl ratio
at once brings about formation of columns of the quartz-muscovite greisens type
or quartz-sericite metasomatites, and afterwards of quartz-potassic feldspar
metasomatites (fig. 5.6). Many minerals of granitic metasomatites (quartz,
potassic feldspars, muscovite, albite, topaz, tourmaline, epidote, riebeckite,
aegyrine and others) are formed in a wide range of P-T conditions and cannot
serve as indicators of the metasomatism’s temperature or pressure, albeit their
presence allows us to judge the solution’s composition. The role of temperature
is determining in the replacement of quartz-kaolinite facies of secondary

144
quartzite by quartz-pyrophyllite and quartz-andalousite facies. Presence of
kaolinite in metasomatites indicate a temperature of the process not higher than
270-300°C, but of andalousite or coryndum, higher than 400°C. Pyrophyllite is
stable between 300 and 400°C. Corundum and diaspore are incompatible with
quartz and indicate undersaturated silica solutions.
Experimentally demonstrated is the possibility of ore deposits
immediately in the process of acid and basic metasomatism of granite. For
example W, Mo and Sn show a different migration capacity of metals and its
precise dependence upon composition and acidity of the corresponding
hydrothermal solution.

145
Fig. 5.1. Principal schemes of metasomatism manifestation in nature.
a – diffusion metasomatism; b – infiltration metasomatism; 1 - unaltered granite; 2 -
infiltration flow of fluids along a fracture or in zone of high permeability in granite; 3 -
diffusion flows of components in immobile pore solutions; 4 - symmetrical halo of diffusion
metosomatic wall-rock alteration; 5 - infiltration flow of solution through thickness of granite;
6 - halo of infiltration metasomatic alterations in granite.

146
Fig. 5.2. Scheme of experiment on modelisation of diffusive metasomatism.
a - loading of the autoclave before experiment: 1 - caping of the autoclave, 2 -
hermetic insert in titanium alloy, 3 - open gold capsule with granite powder filling, 4 -
solution, 5 - solid CO2, 6 - distilled water, 7 - capsule with oxygen buffer, 8 - open platinum
cup with powdered quartz, ore minerals or other solid substances.
b - capsule with granite after experiment: 1 - wall of the capsule, 2 - unaltered granite,
3 - column of diffusion metasomatic zones at closed end of capsule.

147
Fig. 5.3. Zonal pattern of experimental metasomatic column of acid metasomatism in
biotite granite, corresponding to the quartz-pyrophyllite facies of secondary quartzites
(T = 400°C, P = 1kb, t = 500h., solution 0,1mHCl +[Qtz], pHmax = 1,2).
Global chemical composition of zones, see Table 5.2.

148
Fig. 5.4. Variations of zoning of experimental columns of acid metasomatism of a
leucogranite in relation with values of ratio log (mKCl/mHCl) in the solution (T = 400°C,
P = 1 Kbar, t = 336h.)
SQ – secondary quartzites; G – greisens of quartz-muscovite facies ; QF – quartz-
feldspar metasomatites.

149
Fig. 5.5. Phase relations in the system Al2O3-SiO2-H2O-KCl-HCl for P = 1kbar and
excess of quartz [Zaraisky et al., 1981].
Digits indicate fields to which correspond in mineralogical composition inner zones of
the column of metasomatic facies: 1,2 and 3 quartz-andalusite, quartz-pyrophyllite and
quartz-kaolinite facies of secondary quartzites correspondingly; 4 quartz-muscovit facies of
greisens and quartz-sericite facies of secondary quartzites; 5 quartz-Kfeldspar metasomatites.

150
 Fig. 5.6. Fields of stability of topaz and other minerals in the system Al2O3-SiO2-
H2O-KF-HF in diagram log mHF – log mKF at T = 400°C, P = 1 kbar, quartz in excess
[Shapovalov, 1988].

151
Fig. 5.7. Structure of experimental metasomatic column of greisens of quartz-topaz
facies.

152
Fig. 5.8. Physico-chemical conditions of formation of beresites and other middle and low
temperature acid metasomatites after data of experimental modelisation.
Fields: A of argillites, B of beresites, G of gumbeites, QS of quartz-sericite
metasomatites.
Diagrams: a: T – log(mKCl/mH+) at XCO2=0,1; b: T-log(mKCl/mH+) for fields of
beresites at various values of molar fraction CO2 in H2O-CO2 fluid at (XCO2 = 0,01; 0,05; 0,1
and 0,2); c: XCO2 – log(mKCl/mH+) at T = 300°C; d: T-XCO2 at log(mKCl/mH+)=3,0; P H2O+CO2
everywhere equal to 1 kbar.

153
Fig. 5.9. Physico-chemical conditions of formation of alkaline sodic metasomatites after
experimental data [Zaraisky et al. 1984].
P=1Kbar, mNaCl = 1,0m = const, t = 336h; the solution quartz undersaturated, initial
rock: granodiorite. Symbols indicate position of runs in coordinates T = log(mNaCl/mNaOH). 1-
6: fields of formation of various types of alkaline sodic metasomatites for which are indicated
on the diagram typical parageneses of inner zones of experimental columns: 1- albite
propylites; 2- albite riebeckite metasomatites; 3 analcime-riebeckite metasomatites; 4-
analcime-riebeckite-aegirine metasomatites; 5- albite-riebeckite-aegirine metasomatites; 6-
sodalite-aegirine-riebeckite metasomatites.

154
Fig. 5.10. Depositions of W, Sn and Mo synchronous with experimental greisenization of
leucogranite at T=400°C, P = 1Kbar, t = 336h., solution 1mKCl + 0,05 mHCl +[Wlf,Cas,
Mlb and Qtz].

155
Fig. 5.11. Dependence of W, Sn and Mo content versus chemical composition and pH of
solution in experimental columns of greisenization and alkaline sodic metasomatism of
leugranite at T = 400°C, P = 1Kbar, t = 336 h., solution + [W, Cas, Mlb and Qtz]

156
 Part II
Metasomatism, magmatism and mineral
formation

Chapter 6

Theoretical aspects of the genetical link of

metasomatism, magmatism and mineral formation

The tight spacial link between products of metasomatism, magmatism and

mineralization has served as basis of the concept, now traditional, of so-called
hydrothermal mineralization, tightly linked with magmatism. According to this
concept, consolidation of intrusions, accompanied by concentration in residual
melts of ore metals, brings about a separation of metalliferous solutions enriched
with these metals, which solutions, penetrating the fissured zones of
consolidated parts of the intrusions and their enclosing rocks, form in them
metalliferous veins and metasomatic ore deposits surrounded by a
perimetalliferous aureole of altered enclosing rocks. In support of this concept
have been adduced data on general hydrothermal alteration (perimetalliferous
metasomatism) of country rocks containing ore veins, and on the zonal
disposition of metal ores with regard to ore-bearing intrusions, reflected in the
well-known scheme of ore-zoning of Emmons.

However, there were always doubts about the effectiveness of the simple
scheme proposed above. They are based on data about the low solubility of ores
in hydrothermal solutions. Already in the early twentieth century V. Lindgren,
notorious researcher in auriferous deposits, wrote that for the formation of the
Mother Lode (in USA), a vein very rich in gold reserve, it was necessary to have
a volume of solution almost equal to that of the Mediterranean sea. In order to
cancel this contradiction a few hypotheses have been proposed. It was alleged
that colloidal solutions may contain great concentrations of ore components and
massively deposit them at crystallization. But it remained unclear from whence

157
and how the colloidal solutions had drawn the metals. Besides, their extent is
limited, on the whole, to objects of near-superficial and subvolcanic facies of
depth. Even in these conditions most ores of collomorphe texture, considering
the result of crystallization of colloids, have in fact deposited from veritable
solutions. Another possibility of obtaining high concentration of metals is
included in the formation of organometallic complexes. Such complexes have
been synthesized in laboratory and observed in natural objects. Apparently, the
role of organic compounds in the extraction of metals and in their concentrated
transfer is considerable in the formation of stratified lead-zinc ores from brines
of the type of Cheleken (Turkmenistan) and the Mississippi valley (USA). In the
typical hydrothermal ore deposits is also observed the presence of organic
material filling up cavities and fissures in vein minerals and methane in fluid
inclusions. However, their quantity is in most cases not sufficient for the
formation of huge ore deposits.
Finally the model of recycling has recently become popular, i.e., the model
of repetitive convection of the solution. According to this model hydrothermal
ore deposits are formed in a zone of action of permanent circulation of
subterranean waters on the type of the “Benard cell” convections. Such cells are
formed on the roof of a magmatic chamber owing to a vertical gradient of
temperature. The heated subterranean waters remain aggressive and dissolve the
rocks’ components, including metals. Owing to difference of density with the
cold water, the hot ones rise to the top and cool down, precipitating an ore load,
and the cold jet settles down beneath. The repeated return of waters to the cell
gradually accumulates in the zone of cooling an ore mineralization, requiring no
supernatural volume of solutions. A similar model has been elaborated, for
instance, for the circulation of submarine waters in zones of oceanic rift, and
then extended to stratified sulfurous (pyrite) deposits and even to a few veinous
ones. The weak point of the hypothesis is that in the given mechanism the origin
of the metals is found exclusively in the rocks, in the immediately contiguous
deposit. Such an assumption is contradicted by the presence in the ores and
perimetalliferous metasomatites of elements clearly introduced from a deep
magmatic source and practically absent in the enclosing rocks. For instance,
some types of epithermal ore deposits of gold are characterized by tellurium,
selenium, vanadium and chrome, which do not exist in enclosing acid and
intermediate volcanic rocks. There is usually a high content of mercury in the
sulfide pyrites and veinous sulfide deposits. Analysis of paragenesis of
metasomatic minerals and of composition of fluid inclusions shows a high
fugacity of carbon dioxide in the zone of ore deposit, that cannot be explained
by the composition of underground waters. Finally, isotopic composition of
oxygen and hydrogen of metalliferous and metasomatic fluids in epithermal
deposits testifies to a significant part of magmatogene water in the fluid on deep
horizons. These facts, which do not deny the participation of convective

158
phenomena in the general process of formation of ore deposits, testify to an
addition of metals in the zone of ore deposition by a magmatic fluid. The
problem therefore of explaining the conditions of separation of metals from the
magma and their transfer by a magmatic fluid remains topical.
Lately, in connection with various experiments on the distribution of ore
metals in systems of the type of silicate melt-hydrothermal solution, there
appeared the possibility of an alternative hypothesis on the formation of an ore-
concentrating fluid, canceling many contradictions. These researches have
shown that in the most varied compositions of silicate melts and hydrothermal
solutions, ore metals concentrate preferably in silicate melts and are practically
not extracted from their aqueous solutions. Therefore separation of hydrothermal
solutions from residual melts is not accompanied by an ore-concentrating effect,
with which would possibly be linked the formation of huge ore deposits. In other
words, we encounter the same problem of “ocean of solutions” necessary to
extract from the magma a notable quantity of metals. To take such a quantity of
water from magmatic chambers is impossible, due to the limited solubility of
water in silicate melts, but production of water in magma from enclosing rocks
is a process thermodynamically impossible. The point is that water fugacity
increases with temperature. Therefore it is greater in silicate melt than in less
heated enclosing rocks, and in a contact zone arises a water withdrawal in the
direction of its decreasing fugacity, i.e. from magma into enclosing rock.
Theoretically possible is the absorption of water from enclosing rocks of “dry”
(containing no water) magma, but in nature, metalliferous granitic magmas are,
as a rule, water-saturated.

Experimental data show that in order to obtain effective ore extraction from silicate melts,
introduction into the system is necessary, of salt components (chloride, fluoride carbonate,
etc.) in sufficient quantity to isolate them in independent fluid-melting dense phases. These
dense phases also appear, in opposition to strictly hydrothermal veritable solutions, as
concentrators of ore metals, effectively extracting them from silicate melts. As an example
have been given on fig.6.1 and table 6.1 experimental data on the distribution of lead and
zinc amid granite melts, a dense chloride salt phase and an aqueous carbon dioxide
hydrothermal solution.
From the adduced data it can be seen that the dense salt phase in this
system serves as unique effective concentrator of ore minerals, and that with its
separation from the melt may be linked a process of formation of ore
concentrations. Analogous data have been obtained on fluoride melt phases,
extracting tungsten from residual granitic solutions (fig.6.2, table 6.2).

159
Table 6.1. Distribution of lead and zone between granite melt, salt and
hydrothermal phase of heterogeneous fluid(H2–CO2–NaCl) after
[Chevychelov, 1992]
Composition of Granite melt, Phase saline Hydrothermal
fluids, % mol. % weight % weight solution % weight
NaCl CO2 Pb Zn Pb Zn Pb Zn
53 - 0,07 0,12 1,20 1,60 - -
0,9 - 0,09 0,08 - - 0,23 0,18
32 - 0,03 0,03 0,42 0,25 - -
0,6 - 0,03 0,03 - - 0,10 0,04
52 10 0,03 0,04 1,00 0,80 - -
1,0 20 0,23 0,08 - - 0,35 0,10
47 18 0,02 0,06 1,20 1,35 - -
0,8 29 0,16 0,10 - - 0,19 0,17

Table 6.2. Initial (In) and medium composition (at % of metals) of phases I–
V of fluorid granitic systems with different salt additions

Salt Phase Si Al Fe Mg Ca Na K W
compositio
n
Initial 49.41 11.43 1.12 0.82 1.28 31.19 3.78 0.79
I 57.89 12.28 1.14 0.21 0.44 23.16 4.40 0.18
NaF II 57.30 12.01 1.61 0.07 0.43 24.18 4.31 0.09
III 2.39 9.43 0.17 10.06 23.10 43.09 5.54 6.22
IV 3.71 9.53 0.13 7.60 15.99 54.48 5.58 2.70
V 9.91 8.08 0.36 3.06 23.44 39.35 6.70 9.10
58.46 11.53 1.13 0.79 1.30 4.42 21.42 0.96
I 64.11 11.86 1.44 0.85 0.10 3.27 17.90 0.47
K2SiF6 II 62.88 11.96 1.31 0.31 0.16 3.80 19.09 0.49
III 2.01 11.07 0.44 8.37 17.45 21.25 33.43 5.98
IV 6.18 12.56 0.38 7.51 17.33 20.4 33.05 2.59
V 16.21 10.94 0.58 3.68 11.54 18.88 29.48 8.69
53.57 19.78 1.15 0.82 1.32 12.53 9.84 0.99
I 63.35 17.23 1.24 0.00 0.19 7.56 10.31 0.12
LiF+K2SiF II 59.33 7.10 1.19 0.45 0.69 9.94 10.87 0.43
6+ III 3.18 12.78 0.19 11.55 14.88 41.07 7.48 8.87
NaAlO2 IV 7.35 13.67 0.15 15.13 9.47 42.82 6.66 4.75
V 7.02 8.33 0.20 13.03 20.82 31.98 7.40 11.22

160
 62.35 13.30 1.32 0.92 1.49 5.05 14.51 1.09
I 67.68 13.20 1.93 0.20 0.07 2.45 14.30 0.17
LiF+ II 57.77 17.65 1.79 1.65 2.88 7.66 9.94 0.66
K2SiF6 III 4.51 16.75 0.47 6.39 13.90 23.04 30.01 4.93
IV 1.77 21.61 0.25 6.63 1.32 21.42 44.37 2.63
V 0.62 15.26 0.73 8.53 13.00 25.78 25.23 10.95
67.50 15.65 1.58 1.09 1.75 6.01 5.14 1.28
I 71.51 15.63 1.78 0.00 0.19 5.47 5.38 0.04
LiF II 70.00 16.30 1.82 0.23 0.33 6.00 5.27 0.07
III 5.27 4.01 0.37 10.07 39.03 11.36 0.65 29.24
IV 4.42 8.37 0.20 15.93 29.89 22.98 1.53 16.18
V 2.12 4.14 0.00 7.37 33.88 14.62 0.69 37.18

Those experimental data attest to the fact that fluids separate from residual
melts only in case of development in them of a heterogeneity, i.e. of their
dissociation in a salt phase and a hydrothermal solution, are they capable of
effective ore extraction. In that case the fluid’s heterogeneity determines two
independent lines of evolution in the formation of ore deposits: the line of
premetalliferous metasomatism and the line of formation of proper ore bodies,
superimposing themselves on the metasomatically alterated rocks. The usual
delay between ore emplacement and metasomatism is explained by a higher
mobility of hydrothermal solutions compared to more viscous dense phases rich
in metals and forming in the end a great variety of ore bodies. Melts departing
from them are formed in processes of development of liquid immiscibility in the
residual magmas. In determined conditions their metalliferous specialization
may form later on as a result of superimposition of metamagmatism on a
liquefying melt, i.e. change of composition of magma owing to filtration through
them of flows of transmagmatic fluids. This effect is most brilliantly manifested
in sulfurization of basic magmas and formation of copper-zinc and copper-
nickel magmatic deposits. An application of the hypothesis to ore deposits is
examined below on examples of deposits of pyrites, rare metals and veinous
gold.

161
Figure 6.1. Distribution of lead (1) and zinc (2) between granite melts, salt phase and
aqueous and CO2 hydrothermal solution, after data of table 1 [Chevichelov, 1992]

162
Fig. 6.2. Diagram of atomic percentage of metals, illustrating effectiveness of salt
extraction of tungsten relatively to hydrothermal solution.
Lower arrow illustrates crystallization accumulation in residual melt of silica and
tungsten at separation of minerals: biotite (Bi), anorthite (An), pyroxene (Px), albite (Ab) and
orthoclase (Or). 1, residual granite melt; 2-3, composition of melt phases, formed at its
separation (2 isolated analysis, 3 average analyses); I-II silicated phases, III-V salt melt
phases (tungsten concentrations).

163
 Chapter 7

Spatial and temporal correlations of

metasomatites, ores and magmatic
formations.
Metasomatism, magmatism and ore deposits usually are phenomena tightly
linked in space. In relation to magmatism one distinguishes between
metasomatism at magmatic (progressive) stage, accompanying magmatic
replacement of enclosing rocks; metasomatism at postmagmatic stage;
metasomatism the link of which with magmatism is non-evident or non-
existent. Of the greatest interest from the point of view of ore detection are
the products of postmagmatic metasomatism, and metasomatites at the
magmatic stage are not themselves metalliferous. A particular group of
metasomatites, revealing no clear links with magmatism, is represented by
low temperature argillilized rocks, for examples bentonites. Usually they
contain no mineralization of metals, but themselves serve as mineral
resources. However, examples are described, in the literature, of copper
(chalcopyrite) mineralization included in bentonites and having presumably a
hydrothermal origin.
Research on the correlation of metasomatism and ore deposits is one of
the main directions in the theory of metasomatic processes, owing to the general
interest for metasomatic rocks, thanks to the presence in them of ores of non-
ferrous and precious metals. This gives the problem an economic aspect and
some genetic uncertainty, because criteria of definition of an ore include
industrial conditions and technological possibilities, which vary in time. There
exist types of metasomatically altered rocks containing no mineralization,
known as “barren rocks”. They are products of subvolcanic argillization in the
solfatara fields on volcans and areas of unloading of thermal volcanic waters
resulting from halmyrolysis of basalts on the oceanic bottom, metasomatites at
magmatic stage, forming ahead the front of magmatic replacement of rocks
(except magnesian skarns, on which are superimposed postmagmatic
hydrothermal processes). Barren also are metasomatites formed in local matter

164
transfer in a process of regional metamorphism. In this case can only occur
either a dispersion or a redisposition of previous metal deposits.
A particular group of metasomatic rocks are those which present
themselves as mineral resources, such as for example some facies (zones) in
columns of metasomatic zoning. To them are related in argillized rocks and
secondary quartzites, agalmatolites (kaolinites), extracted as building stones;
alunites as raw materials for production of alums; corundum and alunite, for the
production of aluminum; bauxite in crusts of weathering; talc in contacts of
serpentinite massifs; apatite in massive alkaline and alkalino-ultrabasic rocks.
Metasomatic rocks presenting a potential ore aspect are subdivided,
concerning ore, into voluminous preore metasomatites, local protoore
metasomatites and periveinous synore metasomatites. Postore metasomatites are
uniform, usually presenting veinlets of calcite, quartz or zeolite, and yield little
information about ore-metasomatic processes. A detailed characterization of
metasomatites and the mineralization they contain is adduced in description of
the corresponding families, but in the present section are given the general
regular correlations between metasomatites and ore.
To preore metasomatites correspond products of hydrothermal
transformation of relatively great volumes of rocks (pervasive metasomatism)
without immediate link with ore deposits. Preore metasomatites, not being
themselves ore carrying, embody much later, generally acid metasomatites,
containing ore mineralization.
The most typical example of preore metasomatites is the familly of
propyllites. The peculiarity of propylitization consists in the fact that it begins
on the stage of introduction of magma and its replacement of enclosing rocks,
but it continues to a stage of cooling down of intrusion and separation from it of
postmagmatic hydrothermal solutions. Propyllitization occupies a volume of
rocks equal to the dimensions of the ore field. Mineralization, surrounded by
perimineralisation of altered rocks, is localized in propyllitized rocks in the form
of veins or of linear zones of veinous-disseminated mineralization, as, for
instance, in the gold-quartz deposit of Mnogovershinnoe in Low Priamour
(fig.7.1).
The most ancient potassium-argon age of biotite from the lower zone of
propyllites in this deposit is between 10 and 8 million years, but the age of
sericite, accompanying veins of ore-quartz, is between 72 and 75 million.
Examples of less wide-spread mineralization are dispersed in the volume of
propyllitized rocks. In those examples the age relations of propyllite and ore are
indistinct, but usually, one can observe replacement of chlorite and albite of
propyllites by sericite and signs of quartzification, i.e. signs of perimetalliferous
acid metasomatism superimposed on propylites.
Skarns are another example of pre-ore metasomatites. Their formation is
much less voluminous, their thickness does not exceed a few decameters, but

165
their extent, as a rule, is of several hectometers. Mineralization is usually
separated in time from skarnifaction processes by those of amphibolization (in
magnetite deposits) or more distinctly by the appearence of acid metasomatism
of beretization type (in polymetalic and gold deposits) and greisenization (in
tungsten deposits). Exceptional are magnetic ores in magnesium skarns at the
magmatic stage, synchronous with skarn formation. Some researchers [Ezhov,
1994] consider sulfide mineralization interspersed in skarns, to be synchronous
with skarn formation, for the reason that in some cases no signs are observed of
replacement by sulfides of the skarns’ pyroxenes and garnets. [Link]
corroborates that assumption by his own experiments [Ezhov & Zaraisky, 1995],
in which sulfides were deposited in a determined zone of the skarn column at the
time of the latter’s formation. These experiments show the possibility, in
principle, of sulfide deposits together with skarn minerals, if the skarnifying
solution contained a sufficient metal concentration and possessed a high enough
activity of sulfidic sulphur. In natural conditions, however, skarnifying solutions
have a clearly expressed chloridic character and a low concentration of sulphur
anions. Sulfur activity increases in a postskarn process at lower temperature,
when a great mass of sulfides precipitates. There is besides no sufficient reason
to isolate a disseminated mineralization from a distinctly postskarn vein
mineralization.
The protracted live of a hydrothermal system that is reflected in the
presence, besides directly perimetalliferous metasomatites, of preore ones,
including at magmatic stage, proves to be a compulsory feature of big deposits.
It is linked with the fact that in the long evolution process there occurs
“maturation” of the magmatic-hydrothermal system, which in the last stages of
evolution acquires the capacity concentratingly to deposit a great mass of ore
matter. “Maturation” includes a huge differentiation, in the magmatic chamber,
of a complete transformation of the system in its transfer from tendency to
eutectic to liquation with formation of ore-concentrated salt melts and
metasomatizing fluids of low density. Therefore, in particular, propylites,
although barren in themselves in most cases, are signs (together with the
presence of other metasomatites) pointing to ores of non-ferrous and precious
metals.
Protoore metasomatites are more varied than the preore ones. To them are
related periveinous beresites, listvenites, rocks with quartz-sericite and quartz-
chlorite sericite, argillised rocks, gumbeites, acites, greisens. Under the action of
acid solutions on silicic rocks (rhyolites, granites) arise secondary quartzites
containing scattered mineralization of molybdene (deposits of molybdene-
porphyry type). In the enumerated types of metasomatic rocks may appear
moreover products of specific processes, linked with an addition of
hydrothermal boron (tourmalinization), fluor (replacement of calcic plagioclase

166
by fluorite), vanadium and chrome (formation of roscoelite and fuchsite),
sodium (albitization), potassium (adularization).
Beresites border mineralized bodies of uranium, gold and polymetallic
deposits. Their potassium-argon age, as a rule, coincides, reserving errors of
method, with the age of ore, determined by inclusion of sericite in the sulfides or
segregation of adular in the ore vein. In the geological context, however, it is
established that perimetalliferous metasomatism occurred earlier than the ore
deposition. Beresitized rocks are cutted by a net net of quartz veinlets with ore
minerals,the last replacing carbonates and early pyrite of the beresites.
Moreover, ore minerals often appear together with berthierite (or ferriferous
chlorite), ferriferous magnesian carbonate or quartz, with which also are
replaced sericite and carbonates of beresites. Thus are formed protoore
metasomatites, although not much on the geological scale, but earlier than ore.
Quartz-sericite and quartz-sericite-chlorite perimetalliferous rocks in
pyrite deposits form under-ore metasomatic aureoles, nearly at the same time
with the deposition of massive sulfides. This is established by geological
correlations on recent deposits of Kuroko type and on example of
contemporaneous sulfide formation in the “black smokers” on oceanic bottom
(fig.7.2). In ancient pyrite deposits it is possible to distinguish the spatial
distribution of quartz-sericite metasomatites with regard to ore from their
reorientation in the process of metamorphism and folding. In the pyritaceous
polymetalic deposits of Metalliferous Altai, forming in the regional shear zones,
[Link] [1981], together with sub-ore metasomatic zones of acid
metasomatites, distinguishes over-ore zones of re-deposition taken out of sub-
ore zones of foundation (zones of chloritization, carbonatization, albitization). In
that case, mineralization constitute one of the zones of the metasomatic column.
In the molybdenum –bearing porphyric deposits protoore acid
metasomatism occupies a greater volume of rock in the endocontacts of granitic
porphyric intrusions. Volume variation is characteristic of preore metasomatism,
but in the given case the mineralization deposit is nearly contemporaneous with
silicification. As a result of metasomatism, essentially quartzitic rocks are
formed with dissemination of minerals rich in aluminium (corundum, andalusite,
diaspore, pyrophyllite). Above these rocks, in the fracturation zones, is
superimposed a streaky disseminated molybdenite mineralization accompanied
at places by sericite. In the deep parts of metasomatically transformed granites
extends a zone of quartz-orthoclase metasomatites, containing quartz-orthoclase
veinlets with molybdenite. Detection of high-aluminuous secondary quartzites is
not in itself a sufficient sign to confirm the presence of molybdene
mineralization. There exists a group of secondary quartzites that do not contain
ore mineralization. They differ by the presence in them of huge isolated high-
aluminous minerals (corundum, diaspore) that are on industrial scale and are
extracted as useful minerals. Furthermore, another difference consists in the fact

167
that secondary quartzites of porphyric deposits are formed under the action of
solutions with a much higher fluorine activity contributing to composition of
mica and fluorite, than high-aluminous “oreless” quartzites forming under the
influence of substantially chlorinated solutions.
In relation with more fundamental porphyric intrusions of alkali-
granodiorites or syeno-diorites are formed ores of the copper-porphyric type.
Protoore metasomatism in such deposits differ of the above characterized by a
much weaker degree of silicification. An important type of change is
sericitization up to formation of quartz-sericite rocks (“phyllites”). The
morphology of ore mineralization in them is analogous to that of molybdenum-
porphyric ores, but the time of ore deposition approaches that of sericitization.
Not only does sericite replace magmatic minerals in great volumes of rocks
(pervasive sericitization) but it directly accompanies segregation of copper
sulphides appearing as protoore as well as synore mineral.
Greisenisation of rocks occur either as periveinous alteration along veins
of quartz and greisens, or as volume alteration in cupolas of hypabyssal and
subvolcanic granitoids. Periveinuous greisenisation is protoore relatively to
inclusion in veins of mineralization of tin and tungsten, but it is almost
simultaneous with deposition of topaz and beryl in the veins. Volume
greisenisation (fig.7.3) in granite cupolas presents itself as preore alteration of
rocks.
Synore (ore-accompanying) metasomatism, differing from all types
described above, are mostly monomineral and consequently have no zonal
structure. They represent the result of reciprocal direct reactions of ore-fluids
with a varying surrounding, but their expansion is strictly limited by contacts of
grains or grain aggregates of ore minerals, contacts of ore veinlets and their lode
wall As examples may serve ore breccias in the gold-telluride deposits of
Kochbulak (Uzbekistan), in which fragments of surrounding rocks, cemented by
sulfide, cements are completely replaced by sericite or fringes of ferriferous
chlorite around thin veins of carbonate with native silver and silver arsenides in
the silver-arsenidic deposit of Aktepe (Uzbekistan) (fig.7.4). The strongly
limited extent of synore metasomatites within the boundaries of ore
mineralization and the absence, in most cases, of metasomatic zoning attests to
the specific properties of ore-carrying fluids, to their limited capacity, in
particular, to percolate through rocks. It may finally be linked to their great
viscosity compared to protoore solutions.
Synore metasomatites formed at high temperature may coincide in
composition with protoore metasomatites. For instance, in endocontacts of a
quartz-feldspar zone of contact metosomatism in molybdenum-porphyric
deposits molybdenite forms metasomatic veinlets together with feldspar and
quartz. More varied are synore metasomatites at middle or low temperature,
amongst which the most widely spread are those of amphibole, chlorite,

168
carbonate, potassic feldspar, albite, sericite and quartz. Feldspar metasomatites
are particularly interesting as they are accompanied by the most varied
mineralization and are formed in a wide range of temperature. In pegmatites,
albitization is accompanied by mineralization of rare metals (Ta, Nb, Be). The
process occurs in strict conditions of high alkalinity, in which even quartz is
replaced by albite. Quartz-feldspar metasomatites of molybdenum ores are
formed in a less alkaline surrounding and are accompanied by granite bleaching.
In mediothermal gold deposits veinlet metasomatic albitization is masked in
places by an increased concentration of metal, but in epithermal deposits
potassic feldspar is more significant: places of rock adularization and
development of adular in a quartz-ore vein usually coincide with ore pillars and
nests of rich ores of gold and silver.
Carbonates and chlorites of synore metasomatites are distinguished by
high (sometimes very high) ferruginous character and increased manganese
content. Greater manganese content of these minerals is particularly
characteristic of ores of galenite-sphalerite, silver-polymetal and gold-silver.
Apart from the composition, the distinctive peculiarity of minerals of synore
metasomatites is their metastable structural state. So, along with chlorite and
sometimes instead of it, there occurs berthierite in the metasomatites. This
mineral is, as to composition, identical with chlorite, but at the basis of its
structure lies a single-layer packet with interjointal distance of 7Å, whereas
chlorite is made up of double-layer packets with interjointal distance of 14Å.
Geological observations and experiments have shown that the structure of
berthierite is metastable and that under thermal influence or simply in course of
time it passes to the stable 14Å structure of chlorite. Sericite presents the
structural polytype 1M or 1M+2M mixture. The polytype 1M, as experimentally
established, is metastable and under thermal influence passes to a stable
modification. The development of metastable minerals in ore associations and
ore-accompanied associations expresses the strongly unbalanced character of the
process of ore deposition from oversaturated fluids. This also appears in the
appearance of autoorganization of a hydrothermal-ore system, bringing about
formation of rythmico-bandeded ores and synore metasomatites.

169
Fig. 7.1. Distribution of beresite facies on schematic geological sections across
manifestations of gold mineralization.
a, b – deposit of Mnogovershinnoe (Low Priamur) (a, contemporary situation of ore
veins, b, reconstruction at moment of ore formation; b, Angrensky gold ore region,
Kochbulak and Kairagach deposits in Central Asia. 1- post mineralization of granodiorite
porphyry; 2- protoore granodiorites, syenite-diorite porphyrite; 3- andesito-dacite volcanic
thickness; 4 terrigene rocks of basement; 5- quarts-ore veins. 6- biotite facies of propyllites; 7
– 9 facies of beresites (7- quartz-sericite, 8 quartz-calcite-sericite, 9 quartz-ankerite-sericite,
10- ore occurences and ores).

170
Fig. 7.2. Block-diagram and internal structure of hydrothermal spring depositing
sulfides on sea bottom after data of deep water drilling [Humphris et al., 1995]
Displays of distribution and numbers of bore holes. 1 - massive pyritic breccia; 2 -
pyrite-anhydrite breccia; 3 - pyrite-chert-anhydrite breccia; 4 - pyrit-chert breccia; 5 -
silicification of crushed enclosing rocks; 6 - chloritized brecciated basalts; 7 - basalts

171
Fig. 7.3. Generalizing scheme of vertical zoning in massive greisenization of granites
after [Shcherba et al. 1964].
1-3 altered granites; 1- microclinized, 2 - albitized, 3 - greisenized.

172
Fig. 7.4. Sketch model of ore vein with fringe of synore metasomatites from silver-
arsenide ores of Aktep (Kuraminskie mountains, Central Asia).
1 - carbonate vein; 2 - arsenides and native silver; 3 - chlorite; 4 - adular; 5 -
sericitized enclosing gabbro.

173
 CHAPTER 8

Metasomatic zoning and ore zoning

Ore mineralization, as a rule, is disposed in the central part of

metasomatic altered rocks, in the zone of their greatest transformation and of a
most intense hydrothermal process. In some types of metasomatites ores are
confined to definite mineral associations. For instance, in skarns, polymetallic
mineralizations selectively replaces various pyroxenes, which is linked with
greater solubility of hedenbergite in acid sulfide solutions, compared with garnet
and other skarn minerals.
It is quite complicated, although not less important, to explain the
correlation between vertical zoning of periore metasomatites and ores. Important
factors in the formation of vertical metasomatic zoning are temperature and
fugacity of oxygen [Rusinov, 1989]. At a different depth the relative influence
of these factors on mineralization is different. The role of oxygen rapidly
increases in the least deep formations, where intense aeration of subterranean
waters is possible. Here a change of zones (facies) is observed in the vertical
direction on small distance, reflecting not only temperature zoning, but also
sudden increase of oxidation degree of the forms of sulphur and iron in the
solution as the surface is approached. For instance, in the epithermal gold-silver
deposits may be observed upwards change of the zones: propylite with pyrite,
quartz-hydromica rocks with pyrite, quartz-kaolinite-alunite rocks with
hematite, monoquarzites in a vertical interval of 200 – 400 m.
More deeply, in subvolcanic and hypabyssal depth facies an important
role is played by the temperature gradient. It is reflected, for instance, in shift to
the surface of an epidote-chlorite facies of propylites by an albite-calcite or in
shift of calcite-sericite facies of beresites by ankerite-sericite facies ([Link].7.4).
In this figure is indicated the position of gold ore and silver-polymetallic

174
mineralization in aureole of metasomatic rocks in the ore region of Kochbulak-
Lashkerek. The deposits are distributed in the area of development of
beresitization of enclosing volcanic rocks, basically in the zone of ankerite-
sericite facies (Lashkerek, Kayragach) and a calcite-sericite facies on its limit
with the ankerite-sericitic one (Kochbulak). Further below, volcanic rocks
underwent metasomatism of the magmatic stage and keratisation, and in this
zone ore mineralization tapers out.
Other correlations of vertical metasomatic zoning and mineralization are
observed on the gold-quartz deposit at Mnogovershinnoe in low Amur (see
fig.7.1). Preore metasomatites are represented by propylites, in which zoning is
clearly manifested: the upper zone is composed of an epidote-chlorite facies
with parts of epidote-actinolite, and the lower one of a biotite facies. Abruptly
declining quartz-ore veins, surrounded by protoore berezitized rocks, cut
through propylites of an epidote-chlorite facies, and are deeply rooted in a
biotite facies. Gold mineralization is concentrated in the veins’ upper part,
dispersed among epidote-chlorite propylites, and rapidly tapers out in depth in
the biotite facies. Tin mineralization of quartz-cassiterite formation, coinciding
with the roof of subvolcanic granitoids, on the contrary, concentrate in a biotite
facies of propylites, in close contact with an intrusion. Ore bodies taper out in
contact-hornfelses.
These examples show that mineralization tends to localise in a determined
facies of metasomatites and tapers out in a region of facial limits. As lower limit
of extension in depth of gold and silver mineralization serves the biotite facies,
and for tin mineralization, contact hornfelses at higher temperature. In copper
porphyric deposits the lower limit of chalcopyrite mineralization coincides
approximately with the limit between sericite and a more deeply lying quartz-
feldspar facies, and in the molybdeno-porphyric the lower limit of extension of
industrial molybdenite lies in the zone of passage of quartz-feldspar
metasomatites with low altered granites.
While studying ore deposits it becomes necessary to distinguish deep
formation and degree of erosion of neighbouring deposits or even of ore bodies.
Such distinctions are sometimes too small and do not function according to
parageneses of non-metallic minerals, but are noticeable in associations of ore
minerals (mainly sulfides) more sensitive to variations of physico-chemical
parameters. [Link] [1940] drew attention to the fact that in conditions
of small depth the oxygen’s fugacity is a factor of equilibrium, which is
reflected in replacement of pyrothite by pyrite and of magnetite by hematite.
Later research has shown coincidence at small depths of sulfides containing
metals (arsenic, antimony, tellurium) in the highest positive valences. In these
conditions, oxidation conditions of mineral formations are determined by
oxygen fugacity, which in turn depends upon depth and degree of aeration of the
subterranean waters.

175
 The variations of oxygen fugacity, finally, are more strongly reflected in
the equilibrium of sulfides and metalloxides than in the stability of rock-forming
silicates and carbonates. Nonetheless, since this parameter clearly depends upon
the depth of the hydrothermal process, and upon temperature, we observe some
correlation between the vertical zoning of ore mineralization and metasomatic
ore deposition. It is clearly possible to see this correlation on the example of
correlation of extension of arsenic minerals and the acid metasomatites that
enclose them in depth (table 8.1). At the basis of this table is placed comparison
of two types of vertical zoning: zoning of acid periore metasomatites,
determined either by temperature, or by oxygen fugacity ( and, consequently,
depth) of the process; and zoning of ore minerals, conserving arsenic in various
valences, depending on

Table 8.1. Comparison of facies of depths of metasomatites and ores

Depth, km Facies of Facies of Types of Facies of ore on
lgf CO 
2
depth acid mineralisation degrees of
after metasomatites [Shikazono, oxidation
D.S. Korzhinsky 1985]
lgf CO 2
Superficial Kaolinite- Auripigment
(without epidotes) alunitic
Hydro-
Subvolcanic micaceous Au –Ag
1 (without Enargitic
(-2 ÷ 0) clinozoisites) (-2 ÷ 0)  
lgf O =-35÷-42
2
Ankerite- Faded ore without
sericitic enargite

Pb –Zn –Mn
(-1 ÷ +1)
Hypabyssal Calcite-sericitic Arsenopyritic
2
(0 ÷ +4)

Cu –Pb –Zn
(-0.5 ÷ +2)
(+2 ÷ +8)

176
oxygen fugacity. A geological factor, uniting these two types of zoning, is
depth; with the latter’s increase temperature augments and so does carbon
dioxide fugacity, and diminishes oxygen fugacity. The most oxidized forms of
arsenic are found in mineral superficial formations in contemporary volcans and
in zones of hypergene oxidation of ore accumulation (scorodite, orpiment) and
also in upper horizons of some ore deposits of epithermal and porphyric type
arising in subareal, well aerated stratas (enargite, luzonite). Passing to deeper
horizons, these phases are replaced by others, realgar and faded ores, with less
oxidized forms of arsenic. Enargite contains arsenic in highest valence (+5), but
are not characteristic of superficial formations, where in the presence of sulphur
the main form of arsenic manifestation is orpiment with a lower valence of
arsenic (+3). Enargite detections in solfatare fields of volcans are isolated. This
is explained by reciprocal electronic action of arsenic and copper: in enargite,
copper is found in valence (+1) since it takes part with sulphur to oxidation of
arsenic, having less affinity than arsenic with sulphur. As a result, the high
valence of arsenic in enargite is determined by external oxydizing conditions
and intramolacular electronic transfers. That is why enargite is formed in less
oxydizing conditions than orpiment, as obvious in the reaction equation:

0.5As2S3 + 3Cu2+ + e- + 2.5H2S = Cu3AsS4 + 5H+.

(orpiment) (enargite)

With increase of depth and decrease of oxygen fugacity is obtained

instead of orpiment a spreading of realgar ( AsS with arsenic valence +2), and in
environments with copper saturated solutions, enargite is replaced by tennantite
(with As+3). In an even more reducing milieu and at greater depth appear as
main phases of arsenic, arsenides, arsenopyrites, lôllingite, arsenious pyrite, i.e.
minerals in which arsenic plays the role of anion with negative valence. Native
arsenic is relatively rare in nature owing to its high affinity with sulphur. Its
deposition from volcanic gases is due to the reducing action of arsenic at the
expense of the sulphur oxidation.
Practically there exists a main vertical zoning of metasomatic rocks in the
scale of ore fields and even regions. For instance, the basic classical schema of
porphyric fluido-magmatic system of R. Sillitoy (fig.8.1), which develops from
the metallogenetic zoning of Emmons, in conformity to a given type of fluido-
magmatic systems, may serve as reliable guide in the searches of ore deposits in
regions of porphyric intrusions.

177
Fig. 8.1 Scheme of structure of hydrothermal magmatic systems producing Cu-Mo
porphyritic deposits [after R. Sillitoe, adduced by Smirnov, 1965].
1 - granodiorites; 2 - stock of granite porphyries; 3 - hydrothermal breccia pipes; 4 -
propyllitized rocks; 5 - sericitized rocks; 6 - orthoclase metasomatites.
Caption in Russian (vertical axis): maximum number of porphyry copper deposits

178
 CHAPTER 9

Magmatism, metasomatism and massive

sulfide mineralization

The genetic link of pyrite ore-formation with volcanism, established

through examining recent Japanese deposits (such as the so-called Kuroko ore)
in comparison with ancient Ural deposits, has been traced by A.N. Zavaritsky.
[Link] especially underscored the role of submarine volcanism,
accompanyed with accumulation of volcanic sedimentary deposits, to which are
subordinate stratiform massive sulfide deposits. Given the links with exhalation-
sedimentary processes, these deposits are usually characterized by a great range
of mineralization and a variety of metallic composition.
Copper-zinc sulfides occurences on oceanic bottom are closely linked
with magmatic chambers, which are situated according to geophysical data at
small depths under mid-oceanic ridges. These chambers are divided into lower,
ultrabasic, and upper basic parts. The basic one directly feeds the basaltic
eruptions of the mid-oceanic ridges. Basalts of this type are characterized by
high variation of the magnesium content (in inverse relation with content of
iron, titanium and vanadium) from 16% MgO in magnesian basalts to 3-4%
MgO in titanic ferrobasalts. Magmatism is characterized by a reducing regime
and relatively low fluid pressure. Crystallization temperature of the magma in
these conditions is relatively high, and crystallization occurs in the zone of
stability of pigeonite, which enters the composition of phenocrysts and of the
matrix (type of pigeonite basalt of K. Kuno). The diagram of differentiation of
magma (fig.9.1) includes fractional crystallization with formation of
ferrobasaltic melts, which then liquefy with separation of icelandites,
ferrodacites, alkaline liparites, pantellerites and comendites. A similar separation
of acid melts reflects immiscibility of pyroxene-quartz melt, characteristic only
of residual magmas, rich in iron and titanium. Roman digit I on fig.9.1 indicates
ferrobasaltic trends of crystallization differentiation, typical of rift magmatism
and conditioned by fractioning of pyroxene jointly with plagioclase. Evolution
culminates in separation of ferriferous melts with formation of small volumes of
rocks of average and acid composition. Exactly with this stage of evolution of

179
volcanic complexes, there arise, together with acid, extremely iron enriched
magmas, linked with pyritic mineralization. Ferriferous magmas under the
action of fluxes of transmagmatic fluids are slightly subjected to sulfurization
with enrichment of copper and chalcophile metals. Amongst rock-forming
minerals the plagioclase structure is the most favourable for receiving lead
replacing calcicium, which also determines accumulation of lead in the residual
melt and its absence in pyrite ores, linked with rift magamatism. On the
contrary, copper and zinc enrich residual melt. This sketch is confirmed by geo-
chemical data on the composition of porphyrites of the Sinantchin suite in
southern Sikhote-Aline [Filimonova, 1988]. Content of metals in these
porphyrites and their plagioclase phenocrists (digits in parentheses) consist in
g/t: Cu = 40 (20), Zn = 100 (10), Pb = 15 (30). Consequently, lead was chiefly
captured by phenocrysts of plagioclase, whereas copper and zinc accumulated in
the residual melt.
On fig.9.1 is distinguished, on principle, the differentiation trend II, linked
to crystallization and fractionation of olivine. This trend assists increase of water
pressure in the magmatic chamber, reducing, according to experimental data,
crystallization of plagioclaseand broadening the crystallization field of coloured
minerals, specially olivine. This trend may be called andesitic since olivine
fractioning brings about a rapid accumulation of silica in the residual melt and
replacement of basic by intermediate magmatism. It is characterized by
transition from a regime of extension to one of compression and magmatism of
orogenic type. Despite the difference, this trend is completed, like the
ferrobasaltic one, in the splitting of melts, but with formation of a great volume
of acid magma and of a relatively small one of iron rich melts, submitted to
sulfurization, which serves as basis of sulfides formation in the basalt-andesite
trend of evolution. In this trend, plagioclase fractioning was limited; therefore,
lead with zinc accumulated in the residual melts, determining a specific
character of pyritic ores, linked with that magmatism. An example of
development of the andesitic trend is the volcanic complex of Mutodjar (South
Ural) [Marakushev et al., 1993], but an example of more advanced evolution is
the rhyolito-basaltic formation in Ural.
The series of genetic types of pyritic deposits culminates in the pyritic
polymetallic deposits of Altai and Japan (Kuroko type), linked with products of
deepest differentiation of magmatic chambers and formation of a great volume
of acid magmas.
Perimetalliferous metasomatism in pyritic deposits, on the whole uniform
enough, brings about formation of quartz-hydromica perimetalliferous rocks. A
typical zoning of metasomatites is indicated on fig.9.2 for pyritic deposits of the
Kuroko type in Japan. In the zone of a channel of solution transfer takes position
the most altered silicified rocks with dissemination of pyrite and chalcopyrite.
They are surrounded by a zone of quartz-hydromica alteration with finely

180
disseminated pyrite, and still farther from the channel takes position argillized
rocks, composed of quartz, of mixed minerals of the mica-smectite and chlorite
type. These rocks gradually pass to slightly altered enclosing rhyolites. Pyritic
deposit is directly bordered by a thin little zone of magnesian chlorite; at the
periphery of the pyritic lens are displayed trains of thin-grained silico-hematite
rocks. Amongst rare minerals present in ores of Kuroko type [Geology of
Kuroko deposits, 1974], are recorded pyrophyllites, associated with diaspore in
the fine-grained black (polymetallic) ore, and kaolinite. Non-metalliferous
minerals in the ore bodies are gypsum and anhydrite, underlying a pyrite
deposit, and barite situated in a body merged with sulfides of black ore. On data
of isotope analysis of oxygen and hydrogen in metasomatic minerals, the isotope
composition of the water of the solution which has produced metasomatism
tallies with the composition of oceanic water with small admixture of magmatic
one. In the composition of ore minerals is found the presence of magmatogene
elements arising from the depth. So, in sphalerite is contained an increased
content of bismuth, cobalt and nickel, in galenite antimony, arsenic and
mercury, in pyrite bismuth, nickel and cobalt. These elements are not
characteristic of enclosing rocks and may come either from deep seated
chambers with ultra-basic and basic melts (nickel, cobalt), or from
transmagmatic fluids born in the mantle (mercury, arsenic, antimony).
In pyrito-polymetallic deposits of Altai type linked with sodico-potassic
magmatism, sericite metasomatites have a substantially potassic composition.
From the deposits of Kuroko type considered above differs the mineral
composition of these metasomatites by the presence of carbonates (calcite and
breunnerite) which coincide with the inner zone of perimetalliferous alteration.
Such perimetalliferous metasomatites are in mineralogical composition
analogous to beresites. [Link] [1981] propounds the following lateral
matasomatic zoning for the Tichono deposits from enclosing rocks to the axial
part of underore products of acid metasomatism: slightly altered porphyrite,
sericite + quartz + chlorite + calcite (+ pyrite + rutile), sericite + quartz +
breunnerite (+ pyrite + rutile), sericite + quartz (+ pyrite + rutile). Probably the
development of carbonates in this type of deposit is linked with the sufficient
depth of their formations in regional shear zones and, consequently, with
increasing fugacity of CO2 in the fluid. This permits to suppose a closer link of
formation of the given deposits with the manifestation of magmatism. There are
even data on participation of sulfide melts in ore formation [Starostin et al.,
1979]. The small role of sea-water, relatively to endogene, in ore formation is
here confirmed by data on the composition of a hydrothermal solution based on
the study of fluids enclosed in ores: the quantitative correlation of cations in the
solution (Mg > K > Na) differs from that in sea-water (Na > Mg > K).
In the Ural type periore metasomatites are subject to regional
metamorphism and represent a quartz-sericite-chlorite facies, in which are

181
distinguished rocks substantially silicated with pyrite, or quartz-sericitic with
pyrite, quartz-sericite-chlorite and quartz-sericite-chlorite-albite rocks transient
to enclosing porphyrites. Moreover, there exist essentially sericite and chlorite
rocks directly contiguous to massive-sulfide ores. Amongst uncharacteristic
minerals are noted paragonite, datolite and turmaline, and amongst rare ones
pyrophyllite, diaspore, corundum, andalusite, and in non-metamorphosed
deposits mixed-layered minerals of the mica-smectite type. Mentioned
aluminium minerals are described in the altered rocks of the Kaban ore field in
Central Ural [Loguinov, 1945] near contacts with granitoid massifs. Minerals of
boron are found in small quantity in silicified rocks. Basically that is turmaline,
but in some deposits in south Ural are found veins of pink datolite. Particularly
interesting are the occurrences of paragonite. Formerly this mineral was found in
shales and counted as product of regional metamorphism, as opposed to
potassium mica of periore altered rocks. Data have appeared about the content
of a sodium component in periore sericites [Loguinov et al., 1976], but they also
were linked with the superposition of regional metamorphism. However, the
works of [Link] showed the link of paragonite formation in quartz-
sericite rock with ore emplacement [Grabezhev et al., 1995]. The appearance of
sodium metasomatism, telescoping acid alteration, serves as confirmation of the
existence of sodium saline melts, metals extracted from the magma and then
taking root behind a mobile acid solution in enclosing vulcanites. According to
[Link], the sodium character of metasomatism with formation of
paragonite is inherited from the substantially sodic type of the siluro-devonian
magmatism in central Ural.
In small quantity is found chrome-containing potassic mica, fuchsite, in
periore quartz-sericite rocks. Its occurrences attest to addition in the zone of
pyrite formation, at least of part of elements from a deep source, since
immediately in the context of pyrite deposits are absent ultra-basic rocks that
could have been sources of chrome.
So, the composition of metasomatic periore rocks on pyrite deposits
distinctly reflects dependence upon the character of magmatism, signs of
activity of deep fluids and correlation with the composition of ores. The
supplied material corroborates the fundamental position of the hypothesis
propounded above of an “ore saline melt”, separating at a determined stage of
evolution of the magma under influence of transmagmatic fluids.

182
Fig. 9.1 Liquidus diagram of differentiation of residual ferruginous liquids in regime
of low (a) or high (b) fluid pressure.
I - ferrobasalts; II - ferroandesites (islandites) and ferro-rhyolites; III - basalts; IV -
andesites and rhyolites.

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Fig. 9.2 Scheme of metasomatic zoning (vertical section) in periore altered rocks of
Kuroko deposits. In lower left corner is indicated the presumed direction of the solutions
[Zotov & Rusinov, 1975]
1 - argillites; 2 - breccia and rhyolitic tufs; 3 - “white” rhyolites; 4 - massive sulfides;
5 - gypsum; 6 - chloritic rocks; 7-10 products of periore metasomatism (digits in parenthesis
designate number of zones); - 7 propyllitized rhyolites; 8 - argillized rocks; 9 – quartz-
hydromica rocks; 10 - quartz-pyrite rocks; 11 - lithological limits; 12 - limits of metasomatic
zones; 13 - fracture.

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 CHAPTER 10

Magmatism, metasomatism and rare metal

mineralization

Ores of tungsten and molybdenum are in general associated with

silicification and feldspar metasomatism. Tungsten deposits are linked with
granitoid magmatism and situated either directly in apical greisenized granitic
cupolas, or in skarns with superimposed greisens. Tungsteniferous granites are
characterized by an increase in iron and alumina and by fluor content and
belong to the reducing type [Abramov & Borizovski, 1996], i.e. crystallize at
diminished oxygen fugacity. These composition peculiarities of tungsteniferous
granites witness to the notable reciprocal action of fluid and magma in course of
evolution of the magma in conditions of open system (i.e. in a flow of
transmagmatic fluids). The action of fluids on crystallisation of granitoid melts
is attested by the high degree of microclinization and albitization of granites (cf.
fig. 7.3). In ascending direction, immutable granites are replaced by
microclinized, and even higher, by albitized ones. Starting from this zone of
albitization is observed a diffused rock greisenization, increasing upwards, to the
roof of the massif. A characteristic peculiarity of such massifs is the repetition
under albitized granites of a zone of microclinization, but under it, again of a
zone of albitization already directly in endocontact. Greisens with tungsten
mineralization coincide with this upper zone of albitisation, but quartz-tungsten
veins are also situated in rocks of the massif’s roof. The periodicity
(rythmicality) of structure of tungsten granite massifs is reflected not only in the
zoning of feldspars. In the apical part of such massifs are observed areas of
development of rhythmic-banded quartz-granites. An example of such situation
has been describded in granites of Central Kazakhstan (Povilaitis, 1966).
Tungsten-containing granite massifs with greisens are usually surrounded with
slightly keratinized enclosing rocks; moreover, intense greisenization and
maximal increase in tungsten content coincide with endocontact in apical part of
the massif. This shows that the apical part of the massif of crystallizing granite

185
was sealed above by slightly permeable enclosing rocks, usually shales, i.e.
itself constituting a relatively closed system, a snare for the rising
magmatogeneous fluids.
Interpreting interrelations between magmatic (silicatic) melts,
metasomatism and tungsten mineralization is possible on the basis of
experimental phase diagrams correspondence (cf. fig. 6.2). Lower arrows
indicate trends of homodromous change of composition of the melts,
conditioned by their crystallization differentiation. On all the extensive change
of composition of the melts it is possible for hydrothermal solutions to separate
from them; these solutions, judging from experimental data, cannot effectively
concentrate metals in themselves: their tungsten content is at the same level as in
the silicate melt from which they separate. A strong ore-concentration effect in
the studied systems is only attained with development in them of melt
heterogeneity, reflected in the separation of fluid salt-rich phases ( III, IV, V on
fig.6.2), where tungsten concentration may increase in one order of magnitude
compared with the melt. This effect determines the capacity of magmatic
systems to generate ores. This is linked to the degree of salt accumulation in the
track of magma heterogenizations, which requires a relative closing of the
system, so that transmagmatic fluids cannot wash away salt components.
An important peculiarity of salt ore concentration is its selectivity, which
determines the metallic composition of ore deposits. For instance, tin is
indifferent to relation with fluorids, which effectively extract tungsten, and tin
concentration in fluoridic salt melts does not exceed its concentration in a
hydrothermal solution. As tin concentrators serve chloride melts. It is interesting
that in fluoride melts, extremely poor in silica, alumina content in all the studied
systems (except these of granitic –LiF) remains high, close to its content in the
initial melt. This circumstance has been used in elaborating a liquation method
of extracting aluminium from non-bauxitic raw materials [Marakushev et al.,
1991]. By varying the salt composition it is possible to obtain another tendency
and modelise in magmatic systems processes that lead to simultaneous
accumulation of silica and metals, which finally culminates in the formation of
quartz-ore veins. The composition of these melts may be reduced to two
components: an alkaline silicate (Na2SiO3, Na4SiO4 etc.) and ore salt (MFn, MCln
etc.), which in lowering temperature may react reciprocally and form quartzitic
ore phases ( M+SiO2 ) and mobile halogenides, easily dissolved, of alkaline
metals: 1.5Na2SiO3 + MFn = M + 1.5SiO2 + (nNaF). In the same way can be
formed quartz nuclei in granite pegmatites and ore veins, whose transportation
accompanies separation of hydrothermal solutions that brings about periore
metasomatism. As confirmation of the reality of the propounded sketch is
displayed the detection, included in minerals of quartz-ore veins, of fluids, not
only of low density and low salinity, but also of highly dense solutions with
concentrations up to 20-30 and even 45% equ. NaCl.

186
 Granitic magmatism develops under the influence of flows of
transmagmatic fluids. Enormous masses of precambrian granites are formed in
conditions of an open system and flows of fluids wash away from the melt a salt
load, depositing it outside the limits of the system. That is why such granite
masses are oreless. A similar situation prevails in deep and in average horizons
of more recent granite batholiths formed at depths in the order of 5-10 km. The
fluid crosses these areas, encountering no obstacles. In the upper part of the
batholith fluids accumulate in structural tracks of granite apophyses in the roof
and assists salt accumulation. Under the screen, fluid pressure increases, the
vertical gradient of pressure diminishes, serving as motive power for the
ascending fluid. As a result, after a lapse of time, the flow of fluids slows down,
and suddenly begin the cooling down of the melt, its crystallisation and
heterogeneization. The forming heterophasic hydrothermal solutions penetrate
through cracks into the surrounding rocks and differentiate themselves into
hydrothermal low density solution and dense viscous salt-ore phase. The
solution rises in front, as more mobile phase, and brings about metasomatism,
but the salt part moves more slowly, penetrates later and deposits ore. If
conditions are not favourable to differentiation, phase separation does not occur,
and metasomatites are formed with a disseminated mineralization.

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 CHAPTER 11

Boron metasomatism, sodium meta-

somatism and gold mineralization

In the geological literature about ore bodies in gold, tin and some other
deposits mention is more than once made of metasomatic albitization. Its
appearance is linked with the sodic character of solutions transferring and
depositing gold and tin, and with decomposition of sodium-containing soluble
complexes of these metals. In these same deposits is carried out a development
of dispersed turmalinization accumulated in veinlets, which basically coincide
with on-ore or above-ore horizons. Turmalinization’s relative time is estimated
by various authors rather differently, from preore to synore. Research on
metasomatism and gold-ore veins and black shales deposits have shown that
both turmalinization, as well as, albitization in different quantitative correlations
are present in all these deposits. This might mean that both manifestations result
from one and the same process, the action of one and the same solution with
high activity of sodium and bore. However, with these suppositions do not
accord the opposite acido-basic characters of these elements. Moreover,
metasomatic turmaline and albite principally concentrate on different depth
levels of deposits or ore bodies and reveal signs of non-simultaneity. Turmalin
is observed in association with quartz, more rarely with sericite and pyrite, in
acid preore metasomatites in upper parts of deposits. Metasomatic albite
displays veinlets around ore bodies or inside them on average and deep
horizons, but in the course of time, it precipitates near the main ore associations
or simultaneously with them. In some places the albite veinlets themselves are
auriferous. Truly, albite and turmaline are not always spatially separate. For
instance, in ore field Muruntau in some parts of drill core MC-3, depth intervals
of turmalinization and albitization overlap and turmalin veinlets are surrounded
by fringes of metasomatic albite. In other parts of the core of the same drill,
turmalin and albite are observed separate (fig.11.1); moreover, albitization
coincides with ore intervals, but zones of the most intensive turmalinization are
displayed upwards. On the Sovietskoie deposit turmalinization is seen over

188
separate ore bodies. Over the upper ore bodies it is seen in the quarry, but in the
deep shaft horizons it is fixed over the other ore bodies. Similar correlations are
typical and are repeated in big streaks on many auriferous deposits.
In some deposits of epithermal and porphyric type turmalin is
concentrated in bodies of explosive breccias, which are formed with outbursts,
produced by massive degasing emission of magmatic melts. This witnesses
concentration of bore together with other volatile components in the residual
magmatic melts. About links of bore with other volatile components, in
particular with fluorine is corroborated with the increased content of the last in
the composition of turmaline of some of the investigated deposits. For example,
in turmaline from the Muruntau ore-field is contained up to 0.72% fluorine.
The geochemical link of sodium and bore in a hydrothermal process is
distinctly evidenced by analysis of data on the composition of waters in
geothermal areas of active volcanism. On a diagram constructed upon data of
[Link] [1987] (fig.11.2), is visible the straight interdependence between the
contents of these elements in thermal waters. In the same work is propounded,
as results of drilling in geothermal areas, the composition of deep “initial”
thermal waters and waters arising from bore-hole. Deep waters are substantially
impoverished in bore and sodium, compared with the latter, which shows the
differentiation and, possibly, stratification of solutions in the bore-hole at
sinking of pressure and temperature with upwards withdrawal of a less dense
phase, enriched with volatile matters, in particular with bore. In this way,
analysis of natural manifestations of turmalinization in ore fields and of bore
content in volcanic hydrotherms reveals a rather close link of bore and sodium,
but at the same time also shows a difference in their behaviour, occurring at a
determined stage of the solution’s evolution.
Concerning the source of boron in hydrothermal deposits there exist two
opinions: 1) supply from a magmatic deep source and 2) redeposition with
extraction from enclosing rocks. On the majority of deposits are visible aureoles
of boron diffusion, but no aureole of impoverishing (removal), therefore there is
no reason to suppose boron to have been borrowed directly in periore
metasomatism of enclosing rocks. Turmalin in those aureoles has an increased
fluorine content, a characteristic component of remaining deeply differentiated
granitic melts and of fluids accompanying them, but in parallel with
turmalinization there occurs sodic metasomatism in the form of albitization.
Comparison of these facts permits to suppose that in ore deposits boron basically
has come from magmatic fluids. Bore may fall into magma with different
properties: it may come from deep transmagmatic fluids or be borrowed from a
melt at the magmatic replacement of basement rocks. It is important to notice
that the main mass of boron in metasomatic ore fields has been brought by a
magmatic fluid.

189
 At cooling down and subliquidus crystallization of the granitoid magma,
the residual melt gets enriched in silica, alkalis and volatile components. Boron,
having a small ionic radius, near that of aluminum, isomorphically replaces
aluminum in the structure of the alumino-silicated melt and stays in the
remaining melt together with fluorine, whereas the other volatile components,
for instance chlorine, are distributed in fluid phase upon earlier stages of
crystallization. Increasing content of boron in the melt changes granite eutectic
toward albite(quartz + albite + potassic feldspar) enriched in sodium. In the
subliquidus area in the H2O-NaCl-NaAlSi3O8 system, there may exist silicate
and salt melts, and fluid. Moreover, sodium accumulated in eutectic melt is
accompanied by an increase of sodium content also in the coexisting salt melt.
At the final stage of magma crystallization boron separates from the melt owing
to crystallization of a significant part of the latter and thus, concluding portions
of the salt phase are enriched in sodium and boron. At sinking pressure and
temperature, insofar as this phase nears the surface, the fluid phase separates
from it, its volume increases and has its volatile components easily redistributed,
amongst them boron, while sodium remains in salt phase. The salt phase,
concentrating in itself ore components and sodium enrichment, is hardly mobile
and stays, but while moving to the surface from an easily mobile fluid phase,
having an anionic composition and being enriched, notably in boron. The salt
phase, according to the statements of [Link], deposits ore
mineralization, while the fluid phase brings about preore acid metasomatism,
including turmalinization. In this way, sodium and bore, closely linked with the
silicate and salt melts, separate at the splitting of the salt phase with secretion of
acid fluid.
Turmalinization does not always occur intensively; sometimes turmaline
is found in metasomatites in the form of accessory mineral. Apparently the
degree of development of turmalinization is determined not so much by the
quantity of bore in the magmatogene fluid as by the conditions of its
precipitation. For turmalinization it is advantageous, in order for acid
metasomatism to occur at high temperature, to have a relatively earlier stage of
evolution of a hydrothermal solution, such as takes place in copper-
molybdenum-porphyries, boron-bearing silicates skarn deposits and gold-
quartzitic deposits in black shales. But if acid metasomatism shifts to a low
temperature area, turmalinization occurs feebly. In these conditions magnesium
and aluminium associate in micaceous silicates (chlorites and clayey minerals),
while boron remains in the solution and is disseminated. Such a situation is
characteristic of some epithermal gold-silver deposits that are accompanied with
periore argilization, and gold-sulfidic deposits, included in black-shales series.

190
Fig. 11.1. Relations of zones of albitization and turmalinization of gold ore deposits.
a - extension of albite, turmaline and ore intervals in core of well MC-5 (ore field
Muruntau, West Uzbekistan); b - position of turmaline zones in a vertical section through
Soviet deposit. On plane section of ore zones II and III projected from ore zone of Quarry
area (I). 1 - ore zones; 2 - aureoles of turmalinization; 3 - dislocation faults; 4 - quarry
benches (schematically shown); 5 - subterranean galleries; 6 - bore holes.

191
Fig. 11.2. Relations between sodium and bore in waters of hydrothermal bore holes of
the world.
Digits of points indicate geothermal fields and their bore holes [Ellis, 1982].

192
 CHAPTER 12

Metasomatism and epithermal gold-silver

mineralization

The avalanche of researches and publications, in the middle of the 20 th

century, about periore metasomatism has, in the seventies, abated, due to a
certain disappointment in the effectiveness of these researches. The greatest
difficulties were clarified in the discrimination of ore-containing metasomatites
from the general mass, in which predominate, as to volume, oreless varieties.
Moreover, the mechanism was not studied, linked with ore deposits and periore
alteration of enclosing rocks, but that provoked uncertainty of the geologist in
applying empirically observed rules to search and prospecting. D.S. Korzhinsky’
statement about “forestalling wave of acid components” in precipitating ores
after stages of acid metasomatism in late alkali stage had a purely general, not
sufficiently concrete character. In many cases, other factors exert a
predominating influence on ore precipitation: temperature, fugacity of oxygen,
sulphur, etc.
A new impulsion to research of periore metasomatites came from the
appearance in the nineties of publications on epithermal gold metasomatites,
taking into account the latest data on isotopic composition of oxygen, hydrogen
and sulphur of hydrothermal fluids, either metalliferous or metasomatizing, as
well as data on cation-anioni composition of solutions, their oxydo-reducing,
acido-basic properties [White and Hedenquist, 1995]. In these and other works
was shown the possibility not only of distinguishing oreless metasomatites from
ore-bearing, but also of determining, after the character of periore
metasomatism, the type of ore mineralization for a given field of deposits.
Epithermal deposits are formed at small depth of the order of 1-2 km at a
temperature of 150-300°C with active participation of underground waters of
meteoric origin. That is why conditions of hydrothermal activity are in a large
measure determined by the paleogeographic and hydrogeological situation of the
region. The dependence upon these conditions of periore metasomatism and the

193
character of mineralization for massive sulfide type of deposits formed in
submarine volcanic series on one side and subaerial ones on the other has been
discussed by V.P. Loginov [1970]. Differences have been evidenced between
the two mentioned groups of sulfide ores. They are included in a high
development of albite, kaolinite and intense silicification (up to formation of
quartzites with diaspore and andalusite) in the “subaerial” type and significantly
lesser acidity and oxidation of the solutions formed in the “submarine” type of
deposits, in which the enclosing rocks have turned up preferentially sericitized.
Recently a similar distinction has been extended to epithermal gold-silver
deposits, formed in conditions of different aeration of underground waters
[Rusinov and Rusinova, 1977]. Only, these observations were not clearly
enough linked with differences in ore mineralization. It was only possible to
show that in the “sabaerial” type are found faded ores with a high degree of
oxidation of tellurium (goldfieldite).
The first two types of epithermal mineralizations, differing in character
from periore metasomatism, were divided into adular-sericitic and acido-sulfatic
types [Heald et al.,1987]. Recent studies of ore mineralogy, of physico-chemical
environment of ore deposits and isotopic light elements studies have led
[Link] and [Link] to precise and more fully formulate the principal
differences between these types of deposits, which were given the names of low
sulfidation (corresponding to adular-sericite) and high sulfidation
(corresponding to acid-sulfate) [White and Hedenquist, 1995]. The term high
sulfidation signifies that in ores of a given type participate parageneses of
sulfides with high oxidized states of metals (As5+, Sb5+, Te4+, Cu2+), for instance
enargite, luzonite, goldfieldite. In connection with high valence of the metal, the
sulfur/metal relation in these minerals is also high. On contrary, in the ores of
low sulfidation the metals’ valence is lowered (As+, Sb3+, Te2+, Cu+) and the
sulphur/metal relation in the corresponding minerals is low. Both treated types
of deposit are formed from fluids differing in chemical composition. The
deposing fluids of the low sulfidation type are analogous to hydrothermal
springs in the bore-holes on contemporary geothermal fields. They have an
acidity index near neutral and a relatively reducing character. High sulfidation
systems are associated with acid fluids formed in magmatic-hydrothermal
environment [White and Hedenquist, 1995] and having an oxydizing character.
Isotope researches have shown that in the environment of low sulfidation
in thermal springs predominates meteoric water, although presence of magmatic
water and magmatic gases (CO2, SO2, HCl) is also encountered [Hedenquist and
Lowenstern, 1994]. Fluids of this type in depth, in area of origin, were in
equilibrium with the enclosing rocks and therefore had the character of neutral
reducing hydrotherms, in which CO2, H2S and NaCl had important soluble
forms. On fluid arrival in regions of small depth and low pressure it emits a
gaseous phase, enriched in CO2 and H2S. Gas condenses on the surface in

194
subsoil waters; with that, H2S oxydates at the expense of atmospheric oxygen,
and there arise, steam heated, ultra-acid sulfate waters with pH = 2 – 3 at T =
100°C. Accordingly, in the zone of H2S oxidation arises an intense acid
metasomatism with silicification of the rocks and removal of all or nearly all
components, except silica and, partly, alumina. Gently pitching layers are
formed, or lenses of monoquartzites, quarzites with alunite and kaolinite, which
abruptly give way under quartz-sericite-adular metasomatites, forming steeply
Characteristic Types of deposit
properties.
Highsulfidation Lowsulfidation
Form of ore bodies Predominate: zones Predominate: veins and
of dissemination and stockwerk zones
metasomatic bodies
Quartz, barite
Vein kaolinite, pyrophyllite, adular,illite, sericite,
minerals diaspore, allunite calcite, calcicedonite
Ore Pyrite, sphalerite, galenite, chalcopyrite tetraedrite-
minerals tennantite

Enargite, luzonite, Arsenopyrite, electrum,

covellite tellurides, selenides
Examples of Goldfield(USA), Emperor(Fiji),
deposits Summitville(USA), Golden Cross(New
El(Chile), Zealand),
Rodalquilar(Spain), Porgera(New Zeland),
Lepanto(Philippine) Round Mountain(USA),
Karamken(Russia)
Table 12.1. Comparative description of low sulphidized and highsulphidized
epithermal deposits after [White and Hedenquist, 1995]

pitching zones. Precisely in the axial parts of such zones of metasomatism,

occurring in slightly acid milieu, are distributed ore bodies. That is why
detection of metasomatic zoning has significance for determining the position of
flow of fluids and, consequently, most probably that of ore mineralization.
Comparison of the environment of these two types is offered on fig.12.1 and
table 12.1.

Using the analogy of the described ore system with contemporary active
geothermal systems, in which are directly measured temperatures of formation
of mineral parageneses of altered rocks, it is possible to follow paleo-isotherms
in ore systems along parageneses of metasomatic minerals. Determining the

195
position of paleo-isotherms is important for evaluating the level of erosion level
of the epithermal system. Most epithermal ores are deposited in temperatures of
180 to 200°C, which implies a depth of 100 to 800-1500 m below the paleo-
level of underground waters [Hedenquist and Henley, 1985]. If in the discovered
ore manifestation a mineral formation occurs at a temperature above 200-250°C,
this means that the system is deeply eroded and therefore of small interest as ore
object. A low temperature of mineralization indicates weak erosion of
mineralization and possibility of ore detection in depth. The cited authors give
as good indicators of paleotemperatures clay minerals with variable inter-
layered spaces. With rising temperature smectite (whose stability in
hydrothermal natural conditions is limited to a temperature below 160°C) is
transformed into illite-smectite and even illite, which is stable at a temperature
over 220°C [Reyes, 1991]. Precisely such a succession is proper to periveinous
metasomatites insofar as nearing the ore vein in epithermal gold-silver deposits,
such as, for instance, Baleiskoie (Transbaïkal), Karamken ([Link]). Ore
veins contain adular and calcite, indicating less acid condition of ore formation
than in periveinous metasomatism. To temperature sensitive minerals are related
zeolites (T more than 200-220°C), epidote (more than 200-240°C), and also, at
even higher temperature, biotite and amphiboles, depositing in root parts of the
epithermal mineralisation.
In an environment of high sulfidation, fluids separate from a relatively
oxidized magmatic source [White and Hedenquist, 1995] and rise, slightly
reacting with enclosing rocks. Gases arising in the fluid composition may get
absorbed in underground waters with dismutation of sulfide gas:
SO2 + H2O + 1/2O2 = H2SO4 .
As a result there arise ultra-acid (pH=0-2), hot (200-300°C) oxidizing
solutions which, reacting with enclosing rocks, bring about acid metasomatism
with silicification and removal of most of the rock’s components. Presence of
hydrogen sulfide together with H2SO4 assists simultaneous precipitation of
sulfide metals in the form of dissemination and a set of thin veinlets. An ultra-
acid milieu of mineralization is reflected in the formation of such minerals as
kaolinite, alunite, pyrophylite, diaspore etc. Some of these minerals, moreover,
are sensitive to temperature. For instance the stability field of pyrophylite in the
presence of quartz is higher than 320-360°C, but that of zunyite and topaz is
higher than 260°C [Reyes, 1990]. In foreign literature the associations of
enumerated minerals are related to “advanced argillic alteration”, but in Russian
literature, to associations of secondary quartz. In these associations, i.e. in the
most acid metasomatites, are situated the zones of mineralization. This
constitutes yet another difference from the adular-sericite type, in which ore
mineralization coincides with the less acid metasomatites.
An essential moment in the comparison of the separate types of ore is that
alunite quartzite may be present in both, but they have moreover a different

196
nature: in the low sulfidation (adular-sericite) type they form in the zone of
hydrogen sulfur oxidation by superficial waters; but in the high sulfidation type
(acido-sulfate) they form directly in the zone of ore precipitation at a depth not
inferior to 0,5-1 km. It is therefore important to distinguish acid metasomatites
occurring 1) in a hydrothermal process the acidity of which is conditioned by
magmatic gases, 2) in superficial formation of acido-sulfatic waters, steam
heated, 3) in posthydrothermal weathering of sulfide minerals.

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Fig.12.1. Schema showing the difference between “high”- and “low” sulfidation
situations of epithermal gold deposits after [White & Hedenquist, 1995].

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 Part III

FORMATIONS OF
METASOMATIC ROCKS

Chapter 13

Classification of metasomatic rocks

The study of natural objects convincingly shows that the existing metalliferous
deposits are in close spatial connection with the different types of metasomatic
formations, with which they are variously related in age and genesis. Survey of
metasomatites and their utilization for metallogenic previsions requires that all
their variety be characterized by positing rigorously classified categories. This
implies a corresponding classification of the metasomatic rocks.

Such a classification may be accepted and successfully utilized if it objectively

reflects the rocks observed in nature and if precise criteria have been elaborated
allowing to place any rock, according to observed facts, into the classification.
Classifying metasomatites is a more complex problem than classifying other
types of rocks. For instance the magmatic rocks composition is roughly
determined by that of magmatic baths and their structure by the latter condition
of crytallisation. It is therefore in order to determine a magmatic rock, to know
its composition and its structure. Idem for sedimentary and metamorphic rocks.
But in the case of a metasomatic rock it is quite insufficient to know its
composition and its structure, because these depend upon the simultaneous
influence of the substituted rocks, of the degree of thoroughness of their
metasomatism and the properties of the solutions. Identical solutions arouse a
complex of metasomatites spatially and genetically linked, differring in

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composition and structure and which for cartography it is necessary nonetheless
to unite. On the other hand, owing to various hydrothermal and metasomatic
processes characterized by a distinct mineral specialization, there may form
metasomatites of similar composition and structure that must however be in the
cartography distinguished. In correctly determining metasomatites the criteria
characterizing petrogenetic processes as a whole and chiefly the solutions
properties are of fundamental importance.

State of the art. The first approaches to a classification of metasomatites result

in dividing them according to the character of the neoformed mineral [Lindgren,
1901, 1918, 1934-1935; Schwartz, 1939] or according to the composition of the
added chemical element [Goldschmidt, 1933; Eskola, 1920; Barth, Correw et
Eskola, 1939; Terner, 1951]. In the fifties the works of D.S. Korzhinski [1953],
N.I. Nakovnik [1954], V.A. Zharikov [1956, 1959] outline a "formation"
approach to the study and systematics of metasomatites. A "formation"
significance was attributed to the terms skarns, greisens, beresites, propylites,
secundary quartzites. Each term designated rocks linked to a rigorously defined
petrogenetic process. So, N.I. Nakovnik [1954] considered secundary quartzites
as a genetic, independant complex of enclosing metalliferous rocks,
characterized by typical geological, petrographic, mineralogical and
metalliferous tokens. The necessity of a "formation" approach of the systematics
of metasomatic processes was for the first time scientifically discussed by V.A.
Zharikov in 1956. He showed that the designations used with reference to a
newly formed mineral or an added chemical element are unsuitable for
classifying metasomatites because the entirety of the various mineral and
chemical modifications synchronically occuring in the various parts of the
geological body exposed to the influence of hydrothermal solutions prove to be
the essential feature of practically all metasomatic processes. Attempts to a more
thorough "formation" approach of the classification and cartography of
metasomatites were made by V.A. Zharikov et B.I. Omelianenko [1965, 1966,
1978, 1992], D.V. Rundqvist & [Link][1974], [Link] and
[Link] [1978], [Link] [1978], [Link] and [Link]
[1981], V.V. Zhdanov [1983], O.N. Gryaznov [1992]. The development of the
"formation" approach has been greatly influenced by the works of the six USSR
colloquies on perimetalliferous metasomatism in Leningrad from 1963 to 1987,
as weel as of the regional colloquies on the problem, especially about Ural
metasomatites. At present, the "formation" approach is adopted by all the
specialists in the CIS. At the same time, many disagreements have arisen about
the terms metasomatic formations and metasomatic facies, applied to different
types of metasomatites, to the nature of the link between metasomatites and
magmatic, particularly metamorphic processes, and the mutual relation of the
different types of metasomatites. Various approches have been made to

200
cartography metasomatic rocks and the use of its results for the search for
deposits. Many difficulties arise from the lack of a unique principle of
designation, cf. infra.

General features of metasomatic formations. The classification succinctly and

schematically reflects the main features of metasomatites. It is based on several
positions summarizing the study of metasomatic phenomena :
- under the action of solutions of such and such genetic type occur various
metasomatic rocks of which structure and composition are determined by the
solutions' properties, the composition and structure of the initial rocks and the
latters' degree of metamorphic transformation;
- any metasomatic body formed by the action of hydrothermal solutions of a
determined genetic type has a zonal structure characterized either as a
metasomatic column (if the metasomatic body is formed in homogeneous
surrounding) or metasomatic columns (in heterogeneous surrounding);
- composition of an internal (rear) zone characterizes a condition of equilibrium
attained between the rock and the initial solution and is roughly determined
by the solution's properties;
- composition of an external (front) zone characterizes a condition of
equilibrium attained between the rock and the exhausted solution and is
roughly determined by the composition of the rock submitted to a
substitution;
- in any process of hydrothermal metasomatism can be distinguished on one
side an early stage of rocks metasomatism, on the other terminal stages in
which are formed veins, cement of breaches and associated periveinous
modifications spuperposed on the metasomatites formed earlier on;
- rock transformations which are the most significant as to size and determine
the main typomorphic characters of metasomatites are linked to the early
stage of hydrothermal metasomatism;
- at the terminal stages the properties of the hydrothermal solutions are altered,
hence the development within the metasomatic body of later mineral
associations superposed to earlier formed;
- contrary to early stage metasomatism which occur on a continuous front,
those of the latter stages occur sporadically, tending to weigh upon veins and
fissility zones, complicating and somehow masking the metasomatic aureoles
of the early stage;
- apart from rare exceptions, metalliferous mineralization occurs at the terminal
stages of the processes of hydrothermal metasomatism;
- the terms used in classifying metasomatic rocks always refer to the early
stage; the others are characterized by a complementary term (for instance,
beresite with ensuing chloritization);
- five sorts of minerals contribute to the composition of metasomatites :

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 a) minerals formed at the early stage of hydrothermal metasomatism;
b) minerals of the initial rock remaining stable during metasomatism;
c) residual, non entirely substituted minerals which despite their stability
during metasomatism, but owing to causes preventing completion of
metasomatic reactions, have been kept in the metasomatized rocks;
d) minerals formed in the terminal stages and developing to the detriment of
earlier formed;
e) minerals contributing to the composition of veins, cement of breaches, that
have formed owing to filling up of free cavities.

Many points universally admitted only concern particular types of

metasomatism. No doubt has been uttered about the genetic link between some
of them and certain magmatic formations. However, such a link is difficult to
prove for other types of metasomatic rocks. We are far from having established
for all types of metasomatites, mutual relations in age and genesis. And this is
what makes open to criticism classifications made about the metasomatites
belonging to which types of magmatic rocks and which stages of the
hydrothermal process [Zharikov, 1956, 1966; Zharikov and Omelianenko, 1965,
1978]. Certainly less open to discussion is a classification in which metasomatite
associations observed in nature are distributed according to acidity-basicity and
temperature of the solutions [Zharikov, Omelianenko et Pertsev, 1992].
Unfortunately such a classification is more formal and does not reflect the
important genetic relations already established for some types of metasomatism.
This deficiency may be partly eliminated by introducing complementary
features into the classification (table 13.1). This has seemed to be the most
productive way to the proposed classification.

Basic principles of a classification of metasomatites. Every classification may

be expressed in a succession of therms such as brick - house - quarter - city, i.e.
it may contain elements relative to different levels of organization. If these
elements really occur in nature and are based on the current methods in geology,
such a classification may be admitted by the specialists. Concerning
metasomatic rocks, such elements are the following.

A. Zone of the metasomatic column representing a natural body formed by a

fixed paragenesis of minerals in equilibrium. This zone is the singular initial
term of the hierarchic scale of classification categories. Such zones may
have been determined by usual methods of geology using documentation and
microscopically studying thin plates.

B. Metasomatic column (facies) representing entirety of metasomatic zones,

disposed in a determined sequence and formed at the expense of rocks of a

202
 certain composition. To the designation of each facies is associated that of
the initial rock (for instance, apogranitic greisen, apocarbonatite, etc.). The
columns' constitution is based on the study of thin plates taken from all over
the metasomatic bodies. Although the diversity of facies is determined by
the constitution of the initial rocks, these facies may also in many cases
differ according to the variation of the intensif parameters (temperature,
pressure, pH, Eh, chemical potentials of the perfectly mobile components)
peculiar to such and such petrogenetic process. For instance there may have
occured for the propylites, according to temperature, a facies with actinolite-
epidote, epidote-chlorite or chlorite-carbonate.

C. Metasomatic familly representing an entirety of metasomatic facies formed

by solutions of a certain petrogenetic type. This formation is considered as a
chief element of classification. Owing to its exceptional importance it will
be especially explained below.

D. The group of metasomatic formations genetically acquainted, representing

metasomatites of consecutive elaboration belonging to various types of
formation but to the selfsame hydrothermal cycle. Such groups are
distinguished by their dependance upon the magmatism type and the latter's
depth of manifestation. For instance, in connection with magmatism of an
intrusive granitoid of a certain stage their may form silico-alcaline
metasomatites (products of granitisation), magnesium skarns, feldspathic
metasomatites, calcic skarns, greisens, constituting one group of associated
matasomatic formations. For cartography of metasomatites in the vast
regions in which occur various stages of magmatic elaboration, it may be
useful for the metallogenic prevision to distinguish between the associated
matasomatic formations. The volume of this kind of classification nearly
corresponds to the "formation of regional metasomatism" of E.V. Pliushchev
[1978] or to the "pneumato-hydrothermal (fluidogene) complex of A.E.
Shlyguine and V.D. Gukova [1981]. In most cases for the systematics of
metasomatites at this level the data are insufficient since the maps are partly
hypothetic.

Metasomatic formation as a basis of a classification of metasomatites.

Thorough investigation of formational analysis in geology has led to
systematizing and coordinating many data about magmatic and sedimentary
rocks and the metalliferous deposits. It is generally admitted that metallogenic
analysis is fundamental for metallogeny. Since metasomatic formation is a
particular case of geological formation, it must closely correspond to the
fundamental meaning of this term. Opportunities to use the term formation in
the study of the various geological series are given by N.S. Shatsky [1964]

203
definition according to which the formations are natural complexes or
associations of rocks in mutually close paragenetic connection in age and space.
If minerals are parageneses of elements and rocks parageneses of minerals,
geological formations are parageneses of rocks. There are many other
definitions of this term, betraying the objectice difficulty in clearly determining
the limits of a formation.

The specialists in formational analysis Y.A. Kuznetsov [1964], N.S. Shatsky

[1965], N.P. Kheraskov [1967] have underscored the need to support
formulation of any geological notion as elements that can be established with the
usual methods of geology. Hypothetic elements should be excluded from the
difinition of crucial notions such as "formation". Only elements that can be
observed and studied should intervene, or else every researcher will give his
own interpretation depending upon those petrological hypotheses that suit him
best. Admittedly, none of the formulations so far given of the notion of
"geological formation" wholly meets that requisite. Although formation
constitutes a group of really existing unities directly accessible to study and
cartography it seems hardly possible to define it unequivocally. This applies to
"metasomatic formation". It is therefore necessary to clear up its semantic
content.

"Formational" approach in the classification of metasomatosis rests on the well

established existence of groups of closely linked metasomatic rocks that
metodicaly occur in various regions in an initial geological surrounding. Every
such group is formed under the action of solutions of a determined genetic type.
Admittedly there exist in nature a limited number of genetic types of
hydrothermal solutions. The interaction of such a solution with rocks of diverse
constitution determines formation of a group of metasomatic rocks we unite
under the term "metasomatic formation".

Formulating the notion of "metasomatic formation" was first attempted by V.A.

Zharikov [1956, 1968]. He believed that a metasomatic formation can be
defined as a group of metasomatic facies elaborated in the course of one
petrogenetic process (or a geological process genetically unique).

This definition was later made more precise by Jarikov et Omelianenko [1978].
They proposed to call metasomatic formation a natural group of metamorphic
facies characterized by one determined mineral group and one determined
geological position. Unfortunately this needs a complementary explanation :
whar should be meant by one only petrogenetic (geological) process or by a
determined geological position ? Il fut proposé de désigner une formation
métasomatique comme un ensemble

204
D.V. Rundqvist et I.G. Pavlova [1974] consider a formation of hydrothermal
metasomatosis as a variety of geological formation. It can be defined as a group,
obeing a statistically stable norm, of metasomatic rocks linked by a general
structure. Hence the structure of a formation is perceived as a type of
spatiotemporal linkage reflecting the rocks' arrangement.

B.I. Omelianenko [1978] defined a metasomatic formation as a group of

metasomatic rocks characterized by a series of statistically stable features
continuously occuring within a metalliferous province and are repeated in other
regions in similar geological conditions. Among these features : the place
occupied in the region's geological evolution; the nature of relations with a
determined type of magmatism, the details of mineral and chemical
composition; metallogenic and geochemical specialization; conditions of
localisation; bormality of the metasomatites' structure.

These features not only characterize metasomatic rocks as such, but also
petrogenetic processes. Some may coincide in different types of formation, but
they in their entirety are a necessary and sufficient condition to decide belonging
to a "formation" of metasomatites [Omelianenko, 1975].

O.N. Griaznov [1992] proposes to call "metasomatic formations" a constant

association of metasomatic rocks resulting from a unique petrogenetic process in
time and space.

Typically all the authors just cited give the same meaning to the concept of
metasomatic formation, although realizing that no definition can be given of it
excluding any different interpretation.

Metasomatic facies proves to be a singular element of classification. According

to V.A. Zharikov [1956, 1959, 1968], it is a group of metasomatic rocks formed
in different zones of a unique metasomatic column, in fact, a complex of
modification linked to the action of a determined type of solution on rocks
initially identically composed in determined external conditions (temperature,
depth, degree of mobility, activity of perfectly mobile components). According
to B.I. Omelianenko [1978] the metasomatic facies is a group of metasomatic
rocks forming a determined metasomatic column. Obviously the former
definition is based on causal characteristics, whereas the latter is based on
derived, but directly observed characteristics. However, the two definitions are
equivalent. If each facies is described by a cluster of metamorphic zones, a
metasomatic formation is described by the entirety of facies composing it.

205
Hydrothermal cycle, its stages, its link with magmatism and mineralization.
There exist between the different types of formation of metasomatites diverse
mutual spatiotemporal and genetic relations. Some of them are successive
derivates of one postmagmatic activity, others belong to stages of different ages.
Il is by evidencing the relations between metasomatites of different types of
formation and magmatism that determines this successful use of the results of
cartography for metallogenic analysis, previsions and search for deposits. It is
very important for the solution of these questions that one comprehends the most
general laws of hydrothermal metasomatic processes.

Analysis of metasomatic development in the tectono-magmatic evolution of the

pleated regions has shown that to each stage of a tectono-magmatic cycle, as
understood Y.A. Bilibine [1955] et I.G. Magakian [1959] corresponds a finished
hydrothermal cycle [Zharikov and Omelianenko, 1965]. Hydrothermal cycle
means a finished period of hydrothermal activity characterized by evolution
according to certain laws of the contitution and properties of magmatic
solutions. Many confirmations hace been published [Skoroskelpine, 1974;
Velichkine and Volovikova, 1978]. The notion of hydrothermal cycle permits
not only to describe a natural group of hydrothermal metasomatic processes but
also to establish a parallel between a hydrothermal activity and other geological
processes, notably magmatism. Such a confrontation implies that a hydrothermal
activity may be linked to concrete magmatic massifs as well as a whole cluster
of magmatic manifestations of each definite stage of a tectono-magmatic cycle.

Most of the known types of metasomatites are characterized by their links with
such and such magmatic formations. In some cases the link is direct, genetic,
expressed in the coincidence of the metasomatites with magmatic bodies of a
determined composition or with their exocontacts. In other cases the
metasomatites can be very far from the magmatic bodies at the time of their
formation. A link is also observed between metasomatite type and the nature of
the formations nearest to them in age. In such cases we speak of paragenetic
links. There is no doubt about the noted interdependencies when are most
generally considered the details of the hydrothermal metasomatic formations
developed in regions with a magmatism of granitoid, alcalin, ultrabasic alcalin,
intrusive gabbroid or, for instance, in regions with an acid or basic vulcanism.

Terms used to designate metasomatic formations. The most appropriate are

those which as soon as they appeared, designated a cluster of rocks formal under
the influence of solutions of a determined type (for instance magnesium skarns,
gumbeites, lisites, fenites). Some have acquired a formational meaning, although
they initially designated a rock of determined constitution and outward aspect.
Such are for instance the names greisen, skarn, beresite. Their use in broad

206
formational sense is rightly objected by some researchers [Rundqvist et al.,
1971], who would prefer a term to keep its initial meaning and want to separate
the notions of greisen and formation with greisen, beresite and formation with
beresite, etc. This seems justified, for it avoid different interpretations of one
and the same concept. Only, if at the beginning of an article it has been stated
that the term is used in the formational sense and if the subject is constantly
formation, there is no need to repeat the word again and again.

Unfortunate seems the use of terms alluding to the most typical newly formed
mineral (albitised granites, metasomatites with chlorite-turmaline) or ton an
added chemical element (silico-alcaline or potassic metasomatites). Some of
these have traditionally been used in a formationale sense, others have acquired
this sense in the last few years. A great part has invaded geological literature to
such an extent that replacing them would bring confusion and rejection by most
researchers. In the proposed classification we have resorted to terms based on a
different principle. Admittedly this classification shows inevitable
insufficiencies. But its unity is preserved, since all the terms are given a
formational meaning.

Geological literature sometimes uses different terms for the same metasomatites.
We have used the most wide-spread and put the others in parentheses.

Metallogenic specialization of metasomatites. There may exist between the

processes of metasomatic transformation and the mineralized deposits the
following relations :
a) they may appear simultaneously, mineralization being located in determined
zones of the metasomatic column;
b) mineralization occurs a little later than the metasomatites as a result of a
common hydrothermal process (type of associated mineralization);
c) metasomatites and mineralization are not genetically linked, although the
former serve as a surrounding favorable to mineralization.

The classification thus distinguishes synchronous, associated and superposed

metalliferous elements. The synchronous type is characteristic of deposits with
rare metals, formed at high temperature; the superposed type is typical of the
skarns, which constitute a chemically active surrounding largely favoring
precipitation of metalliferous elements with superposition of acid lixivisation
processes; the associated type characterizes the overwhelming mass of deposits.

Associated metamorphic processes. Formation of metasomatites of one or the

other formational type results from processes of very long duration. This is
shown, in partucular, by the important aureoles of metasomatic tranformation

207
and, frequently, the complete achievement of observed metasomatic reactions. It
is easy to show that in order for metasomatic reactions to be achieved, a volume
of solution is needed that is many times greater than that of the rocks sumitted to
transformation. In the course of this long time the solutions' parameters are
constant enough and determine a rigorously determined sense of the
metasomatic reactions, ending up in forming a zonally structured metasomatic
body with a determined final composition. However, at the early stage of the
hydrothermal process the metasomatic transformations usually change
perceptibly. Although late associations usually develop less than the early ones,
they can nevertheless complicate the structure of the metasomatites, particularly
in the latter's central zones, replacing partly, or indeed completely in some
places, the associations formed earlier on. Thus it is not rare for an argilisation
to turn into hydromicatisation, shamositisation, carbonatisation and so on.
Notably, a metalliferous mineralisation is a rule closely associated with the late
mineral associations. Transformations linked to the final stages are usually
called periveinous or mineral escorting.

One particular of associated metasomatic processes is the preference for the

formation of one or, more rarely, two minerals, which is besides reflected in the
names of these processes. A great inequality of distribution is even usual in the
space of the newly formed minerals. They are clearly controled in the
fracturation and cataclasis zones superposed to the primary metasomatic
zonality. A large part of the associated mineralisation is constituted by veins,
microveins and cements of breaches. No metasomatic zonality is formed in a
process of associated metasomatosis. Most often associated mineral genesis
happens through filling up the free space due to the pores by means of a
determined mineral and replacement of minerals previously formed in the
coushing zones. Contrary to rule, the limits of the zones of primary zonality
cross the outlines of the development zones of the associated mineralisation. But
the zonal distribution of associated mineralization clearly shows its much later
formation compared to the metasomatites linked with the main stage of the
process.

Knowledge of associated metasomatic processes typical of each formation may

be very useful to that of metasomatic rocks and its applications. Unfortunately,
information on this point is very scanty; hence the correspondent column in the
classification requires important complements.

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209
210
211
 CHAPTER 14

Physico-chemical systematization of meta-

somatic formations

An assemblage of metasomatic rocks formed in a determined type of

geological processes (i.e. to metasomatic formations) is characterized by a
completely determined complex facies (association of metasomatic minerals),
which corresponds to characterized intervals of importance of the main
parameters of mineral formation. Attempts were therefore natural to classify
metasomatites according to the variation of these parameters, amongst which
temperature and regime of acido-alkalinity of the solutions exert the most
substantial influence. As example may serve the classification of [Link]
and [Link] [1991] in which the types of metasomatic rocks are classified
according to temperature and pH of the solutions. The authors disclaim the
efficiency of using the formation approach and operate with the terms “types of
rocks and facies”. This approach coincides with the position of American
geologists who generally do not employ the term “formation” for assemblages
of metasomatic rocks. In our opinion the notion of “metasomatic formation” is
informative to the extent that it gives a clear presentation of the whole complex
of geological and physico-chemical conditions of the formation process, of the
links of metasomatism with the other geological processes (magmatic, tectonic,
ore formative). For instance, it is quite understandable that greisens are formed
from highly fluoric fluids in connection with granite intrusive magmatism in
regions of orogenesis and tectono-magmatic activization. Although their facies
vary in mineral composition and initial replaced rocks, they naturally unite in a
distinctly marked single genetic group of rocks.
Unlike the formation, metasomatic rocks, as has been shown in the
preceding chapter, are distinguished in mineral composition: quartz-sericitic,
quartz-feldspathic, carbonate-chloritic, tourmaline-chloritic, quartz-alunitic, etc.
In most cases these designations correspond to metasomatic facies, i.e., families
of rocks formed in similar physico-chemical conditions and characterized
consequently, by similar parageneses of minerals. The facies of the
metasomatites are extraordinarily varied, since depending on many factors
(temperature, acidity-alkalinity, fugacity of oxygen & carbon dioxide,
composition of replaced rocks). In natural conditions, however, are found a

212
limited number of facies combinations formed jointly and steadily repeated in a
definite geological surrounding (i.e. metasomatic formations). Despite a marked
geological orientation to isolation of the formations, the latter are characterized
by the limits of the variations, proper to each of them, of the physico-chemical
parameters, above all, temperature and acidity of the solutions. These limits get
blurred, often the fields of neighbouring formations are partly cut off, but all, in
well-known approximation, may be approached by regions in the space of
physico-chemical parameters.
Enumeration of one universal genetic classification of such an extensive
& varied group of geological objects such as the metasomatic formations, is
doomed to failure. Systematization is possible on a limited number of
parameters with a definite purpose. We attempted systematization of formation
in the spirit of [Link]’s idea of the acid-alkaline evolution of hydro-
thermal solutions. As basis, take the principle of the diagrams from the work of
[Link] et al. [1983], [Link] and [Link] [1991]. In view of the fact
that metasomatic processes occur in very wide limits, variations of temperature
from less than 100ºC to the temperature of melting of rocks (700-1200ºC) in
comparing the formations as to acidity of formation of their mineral associations
with utilization of pH indicator there arise difficulties in the calciculation &
comparison of the pH value for the different temperatures. Therefore, we have
employed to construct the diagram (fig.14.1), as indicator of acidity-alkalinity,
the relation of gross activity of one-valenced or two-valenced bases in the
solution to the activity of the proton. In such an approach there is no need of a
quantitative scale of acidity and one may be content with a qualitative diagram.
In order approximately to characterize quantitatively the formation field, on the
abscissa axis are indicated benchmark pH values after data of [Link]
[1989].
Most boundaries of these fields present themselves as monovariant of
equilibrium of mineral phases in the presence of the solution. Part of them is
displayed on the experimental data existing in the literature; another part, on the
basis of interpretation of geological data and paragenetic relations of minerals. It
is well known that concentration of chemical components in the solution is
based on their equilibrium with corresponding minerals of the rock. The
obtained arrangement of the field on the diagram corresponds on the whole to
the interrelations of natural metasomatic formations. On the diagram are shown
four main groups of metasomatites, reflected basically in the variations of
acidity-alkalinity of the solutions: 1) the most acid (secondary quartzites), in
which from alumosilicates there is stable kaolinite, in which Al is contained
only in coordination 6; 2) less acid (beresites, greisens) with muscovites,
containing Al in two coordinations (4 and 6); 3) perineutral metasomatites, in
which there are stable framework silicates (feldspars and zeolites) with Al only
in coordination 4; 4) alkaline metasomatites with feldspathoids (Al coordination

213
= 4 and Al/Si ratio higher than in feldspars and zeolites). Rather clearly are
distinguished on the diagram the fields of high temperature metasomatites,
bordering on those of middle temperature on the level of about 400ºC. The
boundary between middle and low temperature metasomatites is established a
little above 200ºC. To those of high temperature are related argilizites, quartz-
kaolinitic facies of secondary quartzites, hydromicaceous facies of beresites,
calcite-albitic facies of propylites and partially gumbeites.
Evolution trends of parameters of fluids and the corresponding succession
of metasomatic formations in the course of development of magmatogene
hydrothermal systems, indicated on the diagram mark an increase of acidity of
the fluids in the course of time (arrows are directed from early to late
formations). In high temperature systems the trends are almost vertically
oriented, reflecting a great temperature gradient, but in low temperature systems
the position of the trend is nearly horizontal owing to the small gradient of
temperature. It is essential that a maximum of acidity of the fluids and solutions
should occur in various systems at various temperatures: 150-250ºC in
propylite-beresitovic and propyplite-argilizitic ranges, 300-400ºC in the range of
K-feldspar metasomatite- secondary quartzites, 400-500ºC for the successive
hornfels-skarn-greisens, 700-800ºC in metasomatites of alkalino-ultrabasic
magmatic complexes. At the end of the pointer-marked trends occurs an
inversion of alkalinity of fluids (late low temperature alkaline stage according to
[Link]), which has not been indicated lest the diagram would be
overloaded. The differences of the temperature inversion show that apart from
temperature, acidity of the solutions is limited to a certain undulatory function,
linking the solution’s acidity with the dynamics of its filtration through the rocks
and with the solution-rock interactions.
The proposed outline presents itself as an attempt at systematizing the
main metasomatic formations. It permits a detailed elaboration by means of
isolation of facies or new formations in the limits of marked fields. For instance,
in the field X of united formation of albitite zones of deep breaks and albitites,
there are peri-ore metasomatites in gold-ore deposits. Some specific groups of
metasomatites extend in the fields of the described formations. For example,
quartz-turmalinic in greisens, carbonate-orthoclasic, in gumbeitic and so on.

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Fig. 14.1. Phase diagram (T-pH) of important metasomatic families.
Continuous curves – field limits of families (I – XII) and limit rock-magma; stroke line –
limit between magmatic (above) and postmagmatic (below) metasomatic stages; - broken
lines – trends of metasomatic processes (1 – 9); shaded strike – approached location of neutral
and near-neutral solutions.
Family fields: I – fenites; II – magnesian skarns; III – calcic skarns; IV – greisens; V –
secondary quartzites; VI – propylites; VII – berezites; VIII – quartz-Kfeldspar metasomatites;
IX – gumbeites; X – alkaline metassomatites (aegyrine-albite, albitites, microclinites); XI –
aceites; XII – argillisites.
Evolution trends (1 – 9): 1 – “porphyry” (quartz-feldspars metasomatites – secondary
quartzites); 2 – greisens; 3 – skarn-greisen; 4 – skarn-berezite; 5 – skarn-propylite-berezite; 6
– propylite-gumbeite-berezite; 7 – propylite-argillisite (in epithermal deposits); 8 – propylite-
argillisite (in geothermal fields); 9 – alkali-feldspar.
Limits of univariant fields (10 – 20): 10 – Fsp + (K,Na)2O = Fspd; 11 – Aeg + H2O = Rbc; 12
– Cpx + (K,Na)2O = Aeg; 13 – Di + H2O + CO2 = Act + Chl; 14 – Ab + CaO = Pl; 15 – Ms +
K2O = Fsp; 16 – Kln + K2O = Ms; 17 – Ms + H2O = Ser; 18 – Dsp + Qtz + H2O = Kln; 19 –
Ab + H2O = An; 20 – Ank + Qtz + MgO = Cc + Chl + CO2.

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 CHAPTER 15

Metasomatites of alkaline ultrabasic and

alkaline magmatic complexes

15.1. Fenites

Definition. Fenites are high-temperature metasomatites associated with

magmatic rocks of annular complexes of an alkaline ultrabasic carbonatite
formation. They were first described in the Fen massif (Norway) [Brogger,
1921]. Annular alkaline ultrabasic complexes with carbonatites are confined to
cratons and their marginal parts.
In the last decades was determined yet another formation type of
carbonatites confined, differently from annular complexes, to deep, extended,
fracture zones of folded belts [Ginsburg & Samoilov, 1983]. Alkaline rocks
linked with carbonatites of that type are formed in deep parts of the earth crust,
and with them are also associated fenites and silico carbonate metasomatites
[Sobachenko & Gundobine, 1993].
To the fenites, [Link] [1985] and recently [Link] & [Link]
[1994] relate also metasomatites at the magmatic stage, formed with intrusion of
nepheline and alkaline syenites, on ultrabasic, alkaline-ultrabasic and alkaline
magmatic rocks of the preceding phases of intrusion, and also on alkaline
enclosing rocks. In this case all these metasomatites are considered as facies of
fenites on different replacing rocks: silicic, ultrabasic and alkaline, as well as
carbonate rocks.
If we hold on to the initial acception of this notion, the fenites are then
high-temperature alkaline metasomatites formed at the magmatic stage at the
time of intrusion of alkaline rocks into silicic rocks, granites and granito-
gneisses, enclosing alkaline ultrabasic annular massifs with carbonatites.
Nowadays have also been investigated fenites around alkaline massifs
(without carbonatites), around carbonatites (without alkaline rocks) and around
kimberlites. Facies of fenites on sandstones have been described [Evdokimov,
1982] but alkaline-silicate metasomatites, accompanied by miaskitic syenites

216
and carbonatites of deep linear zones appear as facies of fenites on amphibolites
and micaceous and clayed shales [Sobachenko & Gundobin, 1993].
Fenitization as well as processes of ijolitization, turyaitization and
syenitization is a process of distinctly magmatic (progressive) stage, in which is
formed on biotite amphibole and, further, pyroxene. In some places a zone of
magmatic replacement is formed.
Distribution. Fenites, as well as other metasomatites of magmatic stage
are more widely developed in hypabyssal massifs, in which dimensions of fenite
aureoles equal those of the massifs themselves .In the Kola Peninsula in the
massif of Ozernaia Varaka the thickness of fenites equals two thirds of the
thickness of intrusive rocks, and in the Kovdor massif, 13% [Sergeiev, 1967]. In
the Kovdor massif, the introduction of alkaline intrusions along an annular
fracture at the contact of olivinites with enclosing gneisses was accompanied by
a thick metasomatism of these and other rocks. As a result, along the outer
contact was formed an aureole of fenites and fenitized gneisses with a thickness
from 1.2 km (on the western slope of mount Votsu-Vaara) to 4.5-5km (on the
southern slope of mount Pilkoma-Selga). In the Fen massif (Norway) fenites
form western and southern aureole (fig.15.1), occupying 20% of the massif’s
thickness, in contact of melteigite ijolites, silico-carbonatites and carbonatites.
Fenites of the cape Tur massif (Kola Peninsula) are formed in contacts of ijolite-
melteigite and melilite rocks with granitoids and ijolite-melteigite with
sandstones (fig. 15.2). Fenites of the Oka massif (Canada) form an almost
continuous aureoles in the gneisses around the rocks of the melteigite-urtite
series and around calcite carbonatites [Samson et al., 1995]. Fenites, fenitized
gabbro-pyroxenites and fenitized gneisses, granites and migmatites of the
Poltava zone present themselves as a lengthened zone along carbonatites (fig.
15.3).
Metasomatic column. As rock-forming minerals of fenites appear
potassic feldspar (orthoclase, microcline, sanidine) albite, nepheline, alkaline
pyroxene (aegirine, aegirin-diopside, aegirine-albite, sometimes with addition of
jadeitic minal), alkaline amphibole (arfvedsonite, riebeckite, hastingsite,
richterite); secondary mica (biotite, phlogopite), iron oxydes; accessory: apatite,
sphene.
The parageneses of these minerals regularly replace one another in the
space from unalterated alumino-silicate rocks to magmatic alkaline ones,
presenting themselves as successive zones of metasomatic columns of
fenitization: 0. granites, granito-gneisses, gneisses, sandstones, micashists. 1.
fenitized rocks. 2. pyroxene potash feldspar fenites. 3. nepheline-pyroxenic and
anchimonomineral nephelinic fenites. 00 alkaline magmatic rock (melteigite,
ijolite, nephelinic syenite) or carbonatite.
The facies of fenites on sandstones and granodiorites in the massifs of
cape Tur have insignificant chemical developments [Evdokimov, 1982].

217
 The predominant part of fenite aureoles, formed on granito-gneisses,
represents fenitized rocks and feldspathic fenites; nepheline-pyroxenic and
nephelinic fenites of rear zone abut to contacts with melteigites and ijolites. In
contact of a rear (3) zone with alkaline magmatic rock, melting frequently takes
place, resulting in an alkaline rock formed in situ, differing from the primary
magmatic (of the same composition) by structure and geochemical peculiarities.
Chemism. The basic tendency to change in the chemism of the rocks
forming successive zones of a column of fenitization of granito-gneiss is the
removal of Si. At first, quartz disappears in the forward zones, in the feldspar
fenites, SiO2 concentrations diminish to 45%, and in the rear zones, desilication
may lead to the fact that together with nepheline are formed non-silicated
minerals, corundum, anatase, spinel, baddeleyte.
Fenitization, by definition, occurs as a result of a significant addition of
alkali. Sodium concentrations monotonously increase from forward zones to rear
ones, and potash concentrations may be maximal in the pyroxeno-feldspathic
fenites. In relation to potash and sodium, fenites are divided, respectively, into
sodico-potassic and potassic [Rubie & Gunter, 1983], of which the potassic, at
comparatively low temperature, known exclusively in contacts with
carbonatites, consist in orthoclase with magnetite or hematite, whereas the
sodico-potassic, occurring in the contact with both carbonatites and alkaline
rocks (melteigites, ijolites, nephelinic syenites) at higher temperature, consist in
all the above-mentioned minerals of the fenites. The proportion of sodium and
potassium in fenites depends upon the composition of magmatic rocks, source of
fenitizing solutions. Fenites around epileucitic and calcicilitic syenites of the
Murinskoie massif (Aldan) are characterized as Na2O/K2O = 0.15 to 0.40, while
this ratio in fenites in contact with ijolites or nephelinic syenites is higher than
the unity [Bardina & Popov, 1994]. In the classification they have proposed is
taken into account the quantity of silica, as well as the total quantity of alkali,
but, in particular, the mentioned potassic fenites are by them related to
orthoclasites, i.e. to much later postmagmatic metasomatites.
In fenites of rear zones occurs a significant accumulation of alumina (up
to 29%), which get fixed not only in nepheline but also in clinopyroxene
(jadeitic minal) [Tykhonenkova, 1967] and in arfvedsonite.
Physico-chemical conditions of fenitization. According to data of
[Link] [1967] melting of fenites in contact or proximity of big apophyses
of intruding rocks testifies to the fact that temperature may reach 700 to 800C.
Experimental research places the temperature of stability of paragenesis of
microcline-perthite + aegirine-augite, starting with 500C [Zaraisky et al.,
1984], appearance of nepheline at 580 to 600 (the same autors), but
disappereance in fenites of fluoric arfvedsonite, at 50030C [Kovalenko et al.,
1977].

218
 On experimental and calciculated data of [Link] and [Link]
[1994] the pH of the fluid, in equilibrium with mineral associations of fenites, is
not less than 8-10. With the method of measuring the pH of rocks in suspension
of aureoles in exocontact it has been shown that a long interaction of alkaline
solutions with gneisses leads to a decrease of pH of solutions to a value nearing
7 [Sergeev, 1967]. The gradient of chemical potentials of Ca and Na in a
metasomatic solution is expressed in the direction of change of concentration of
these components in the rocks of successive zones. The value of the Fe 3+/Fe2+
ratio in these rocks also grows in proportion to the proximity to the source of the
solutions, ijolite or nephelinic syenite, which is brought about by the high
oxidation potentials of alkaline solutions.
Source of fenitizing solutions. The sources of fenitizing solutions must
evidently be magmatic rocks with the necessary content of alkali; moreover,
seemingly, these rocks were formed as a result of a sufficiently high degree of
differentiation of initial magmas, because xenoliths of crustal rocks, entrapped
in nephelinitic lavas, i.e. less differentiated derivative, do not experience
fenitization [Le Bas, 1977].
As far as fenites are known around alkaline rocks, as well as in immediate
contact with carbonatites (see fig.15.1, 15.3) the problem in discussion is
whether ijolite or carbonatite is the source of solutions derived of fenitization
[Morogan, 1994].
Change of composition of pyroxenes from successive zones of a
metasomatic column of fenitization, from forward to rear zone, is characterized
by two tendencies: (1) aegyrine  hedenbergite  diopside and (2) aegyrine 
hedenbergite (fig. 15.4). In fenites of the cape Tur massif, the first of them (T 1
on fig. 15.4) is characteristic of apogranitic fenites, and the second (T 2) of
aposandstones. However, both trends take place in fenites of the Fen massif (F1
and F2), although the fenitized rocks are exclusively granitogneisses. [Link]
[1994] links the first one with ijolite-melteigite sources of fenitized solutions,
but the other with carbonatites (?), as these trends go towards meeting trends ij
and [Link] of change of composition of pyroxenes from successive differenciates
of the melteigite-urtite series (diopside  hedenbergite  aegirine) in the first
case and, in the second, trends dv of change of composition of pyroxene in rocks
of the damkjernite-vibetoite series1 (diopside  hedenbergite). In this way, two
types of fenitization are distinguished: ijolitic and carbonatitic [Morogan 1994].
The main factors [Morogan, 1994] determining the ijolitic type of
fenitization are: CO2 < H2O (determining, in particular, scarcity in the fenites of

1
Damkjernite is a nephelinite monchikite (alkaline lamprophyre, consisting in phenocysts of olivine,
pyroxene- augite, titanium-augite, biotite and/or amphibole-barkevicite, kaersutite and basic mass, consisting of
analcime, amphibole, pyroxene, biotite, sparely nepheline, sodalite, cancrinite, leucite, hauyne); vibetoite is a-
calcicitic jacupirangite [Petrographic dictionary, Moscow: Nedra, 1981].

219
calcite and abundance of aqueous mafic minerals); high activity of alumina and
comparatively low CaO activity; comparatively low FeO/MgO ratio,
determining, in particular, the aegirine  hedenbergite  diopside trend of
change of composition of pyroxene, and predominance of magnesian
arfvedsonite; Na2O > K2O; relatively high fugacity of oxygen; and highly
gradual fall of temperature (at great distance from the magmatic source).
The carbonatite type of fenitization is controlled on the contrary, by the
following factors: CO2 > H2O, determinig an abundance of calcite and scarcity
of aqueous mafic phases, a very low activity of silicic-acid and alumina, a very
high activity of CaO, a comparatively high FeO/MgO ratio (aegyrine 
hedenbergitic pyroxene trend); however, phlogopite may form; the most various
proportion of alkali and very progressive temperature gradient (at short distance
from the magmatic source).
Discovery of soda carbonatites of Oldonio-Lengai and research of fluid
inclusions in minerals of carbonatites [Samson et al., 1995] testify that
carbonatic magmas are enriched with alkaline, basically, sodium. [Link]
[1982] links the process of fenitization with the evolution of carbonatitic melt, in
the course of which process are liberated sufficient quantities of sodium. There
are in fenitizing fluids a certain quantity of dissolved carbonates of alkaline
metals fully really [Samson et al., 1995], and CO2 content in the fluid together
with contents and ratio of alkali, temperature and pressure, appears as an
important parameter, determining the composition of parageneses [Rubie &
Gunter, 1983]. Despite the significant role of the content of carbon dioxide in
the fluid, the significant addition of alumina in contact fenites contradicts the
hypothesis linking fenitization to the action of alkalino-carbon dioxide aqueous
solutions that form with leaching of (Na, K)2CO3 from carbonatites [Le Bas,
1990]. Also the development of magnetite (hematite) – orthoclase rocks in
contact only of carbonatites, without development of parageneses at higher
temperature of fenites containing nepheline, permits to conclude that the source
of fenitizing solutions is not carbonatites but alkaline or alkalino-ultrabasic
rocks.
It has been possible in recent years to show [Rass 1986; Rass & al.1996,
1998] that rocks containing melilite in alkalino-ultrabasic-carbonatite complexes
present themselves as differentiates of initial mantle magmas of specific
composition, with a Ca/Mg ratio higher than in the initial magma giving rise to
the jacupirangite-melteigite-ijolite-urtite-nephelinic syenite serie. Most
probably, melilite-containing rocks may also be the source of fenitizing
solutions. Confirmation of this hypothesis is found in trends to change of
composition of pyroxenes of melilite effusive rocks and fenites of cape Tur: in
the successive differentiates of more calcicium-rich initial magma, the trend is
from diopside to hedenbergite (see fig.15.4. Tm), on the whole, coinciding with
the trend of the pyroxene of the damkjernites-vibetoites of the Fen massif; from

220
forward zones to rear zones of a metasomatic column of fenitization, the trend
goes from aegyrine to hedenbergite (T2) both trends encountering each other.
Experimental melts jointly with carbonatite and fenite of the Kovdor
massif [Kapustine, 1990] led to occurrence of an alkaline melt, close in
composition to a melilite-turyaite melt, which order of crystallization was
wollastonite-melilite-nepheline, which also confirms the conjecture that the
source of fenitizing solutions together with melteigites, ijolites and nephelinic
syenites, may be the turyaites and okaites. This conjecture may clarify these
peculiarities of composition and temperature of the formation of fenites, which
contradict the notion of a carbonabite source of fenitizing solutions, in
particular, the accumulation of alumina in rear zones of a metasomatic column
of fenitization.

15.2 Metasomatites of alkalino-ultrabasic carbonatite massifs

Definition and geological position. The geological position of the

metasomatites described in the present chapter is determined by the geological
position of alkalino-ultrabasico-carbonatite complexes with which they are
genetically linked. Annular alkalino-ultrabasic complexes with carbonatites, the
silicate rocks of which are characterized by the Na/K >1 ratio, are confined to
cratons and their marginal parts; but complexes in which the ratio of alkali in the
silicate rocks in reversed (i.e. Na/K <1) are confined, together with old
platforms, in phanerozoic ones and their marginal parts. In the last decades have
also been recognized linear alkalino-ultrabasico-carbonatite complexes confined
to deep zones of folded domains. As to annular complexes, their link is obvious
with initial mantle magmas (isotopic relations; enrichment with rare elements, in
particular Nb, Zr, Ti and Y, and also phosphorus); for linear complexes, this link
is manifested only in Nb enrichment, but isotopic ratios testify to conditions
existing at the base of the crust.
For magmatism of alkalino-ultrabasic carbonatite annular complexes is
specially characteristic a sodic introduction of successive differentiates of at
least 5 sub-series: ultrabasic rocks, pyroxene-nepheline alkaline rocks; melilite-
bearing calcicalkaline rocks, nephelinic and alkaline syenites; carbonatites
(strictly speaking carbonatites and apatite-forsterite-magnetite rocks).

Considering their depth formation, alkaline-ultrabasic carbonatite

complexes are divided into 1) effusive and subaerial, 2) hypabyssal, 3)
mesoabyssal, 4) abyssal (already mentioned linear zones at the bottom of the
crust).
Introduction of each magmatic phase is accompanied by metasomatism at
magmatic stage of enclosing rocks and rocks of preceding magmatic phases.

221
 The widest and brightest manifestation of metasomatites is in hypabyssal
complexes, where their dimensions are comparable to those of the complexes
themselves.
In the Kovdor massif (Kola Peninsula), which may be taken as standard
for hypabyssal massif of a given formation, they occupy not less than half of the
outcroping rocks [Ternovoy et al., 1969] (fig. 15.5). The core of the Kovdor
massif is composed of olivinites, representing the first phase of intrusion. Relicts
of olivinites (measuring from a few to tens of meters) are found amid pyroxene,
mica-pyroxene, nepheline and melilite rocks, surrounding the olivine core. The
quantity and dimension of these relicts at the massif’s periphery gradually
decreases. Alkaline rocks of the second intrusive phase form an almost
continuous peripheric ring uneven in thickness. They represent homogeneous
median-grained massifs of ijolites and ijolite-melteigites (in the southern part of
the massif), heterogeneous middle and coarse grained ijolite-urtites partly
recrystallized, and turyaites (in the northern parts of the massif). In the ijolites,
ijolito-melteigites, ijolito-urtites are found xenolites of olivinites (and gneisses).
Turyaites form in the northern part of the massif a semi-circular zone 0.6-1.0 km
thick and 5 km long. In the east a big body of turyaites is linked with ijolites. In
the turyaites are now and then found xenolites of olivinites with the same zonal
phlogopite-pyroxenic fringes as around the xenolites of olivinites in the ijolites.
Introduction of alkaline intrusions in the annular fracture at the contact of
olivinites with enclosing gneisses was accompanied with a powerfull
metasomatism of both rocks. Metasomatites formed on enclosing rocks of the
complexe (rocks of the frame, in particular: acid-granitogneisses), under the
action of alkaline, calcico-alkaline or calcic solutions at the magmatic stage, are
related to the formation of fenites and are described in section 15.1. It is thus
convenient here to consider metasomatites: (1) formed on olivinites and
peridotites during the intrusion of rocks of the jacupirangite-urtite series in the
process of ijolitization; (2) formed on olivinites and peridotites during the
intrusion of melilite-containing rocks in the process of turyaitization; (3) formed
on magmatic and metasomatic rocks of pyroxenic and nepheline-pyroxenic
composition during the intrusion of nephelines and alkaline syenites in the
process of syenitization; (4) formed on magmatic and metasomatic rocks of
olivine-pyroxenic, pyroxene-nephelinic composition and melilite-containing
rocks during the intrusion of carbonatites in the process of carbonatization.
All four mentioned processes are metasomatic processes of magmatic
stage, i.e. occur at increased temperature. With the formation of metasomatic
columns of ijolitization and turyaitisation, parageneses of glimmerites (biotites)
are replaced by pyroxene-nephelines or melilite-nephelines. With formation of
metasomatic columns of syenitization a paragenesis containing phlogopite is
similarly replaced by an anhydrous anchimonomineral pyroxenic zone. With the
formation of a metasomatic column of carbonatization, parageneses with

222
tremolite and tetraferriphlogopites are replaced by parageneses with newly
formed forsterites. The rear zone in the forming metasomatic column may be
represented by melts of corresponding composition: ijolites (fig. 15.6),
turyiaites, nephelinic syenites or carbonatites.
With introduction of alkaline intrusions on an annular fracture between
olivinites and enclosing gneisses in the Kovdor massif, on internal contact has
formed a continuous annular zone of apoolivinite metasomatites, (but in external
contact, an aureole of fenites). The thickness of the zone of apoolivinite
metasomatites reaches 3-4 km. With alteration of olivinites, parageneses of
metasomatic rocks zonally replace one each other from the center of the massif
to the periphery in the following succession: olivinite – phlogitized and
pyroxenized olivinite – mica – nephelinized pyroxenite – pyroxene and
nepheline-ijolite rock; and olivinite (often with monticellite) – olivine-melilite
rock and/or melilitonite – melilite-phlogopite rock – melilite-nepheline rock –
turyaite. Appointed successions present themselves as metasomatic columns of
respective ijolitization and turyaitization of olivinites.
Successive zones of an infiltration metasomatic column of ijolitization of
olivinites are above all represented in the south-south-eastern part of the massif,
where their summary thickness approximates 2.5 km, but the ratio of thickness
of successive zones from the least alterations to the rear ones is 49:29:15:8.
Coincidence of the most prolonged section with the submeridional fracture
[Krasnova & Sokolova, 1978] appearing as magma-internal channel (together
with annular fractures), permits to relate this zoning to the vertical metasomatic
zoning in the interpretation of [Link] [1982]. On the pyroxene-phlogopite
thermometer of [Link] [1970] the temperatures of formation of rocks of the
ijolitization column is 700 to 760C for the forward and rear zones respectively
(gradient: 60C on 2.5 km).
Metasomatites of infiltration metasomatic zoning of turyaitization of
olivinites in the district of northwestern profile prolonged on 0.9 km and with
relative 50:30:20:13 thickness of successive zones coinciding with the annular
fracture, the magma-internal channel. Vertical metasomatic zoning is a normal
extended arrangement of various phases of metasomatites in vertical direction,
occurring as a result of filtration trough rocks of a flow of solutions and
perpendicular to the flow’s direction. A possible model of formation is
represented on fig. 15.5.
Change of mineral composition of metasomatites of the successive zones
of a ijolitization column is characterized by the following stages: at the limit of
phlogopitized olivinite and mica, olivine disappears; at the limit of glimmerite
and nephelinized pyroxenite appears nepheline, which does not replace all
phlogopite; at the limit of nephelinized pyroxenite and nepheline-pyroxene
rocks phlogopite disappears.

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 For the mineral composition of the metasomatites of successive zones the
columns of turyaitization are characterized by the following peculiarities: at the
limit of phlogopitized olivinite and olivine-melilite rocks appears melilite; at the
limit of olivine-melilite and melilite-phlogopite rocks disappears olivine and
arises nepheline; at the limit of melilite-phlogopite and melilite-nephelite rocks
disappears phlogopite.
From the paragenetic analysis of these associations it appears that their
regular replacement is due to the inert behaviour of Mg, Fe, Si, Al in
dependence upon change of chemical potentials of Ca and Na, leading to
modification of the minerals’ composition. The composition of minerals of
variable composition at the limits of metasomatic zones changes abruptly and
almost imperceptibly inside each zone (fig. 15.7) [Rass, 1986]. These
regularities testify to a primarily infiltration character of the ijolitization and
turyaitization processes.
Modification of the chemism of rocks formed in successive zones of
metasomatic columns of ijolitization and turyaitization of olivinites, is
determined by removal of Mg and Fe (fig. 15.8). The gradient of chemical
potentials of Ca and Na in metasomatized solutions is marked in directional
modification of the content of these components in the rocks of the successive
zones; moreover, the formation of all zones of the metasomatic column of
turyaitization occurs with greater chemical potential of Ca than the formation of
all zones of the column of ijolitization. The value of the Fe3+/Fe2+ ratio in these
rocks also grows in proportion to their proximity of the source of the solutions,
either ijolitites or turyaitites [Rass, 1982]. Iron oxidation cannot be dependent
upon the presence of a strong oxidizers (ions V3O5, Cr2O3, MnO, Co, etc.)
whose quantity in the studied rocks vanishes a little [Kukharenko et al., 1965]
and, very probably, is determined by the presence of aqueous solutions of
increasing alkalinity. Judging from the directional change of the Fe3+/Fe2+ ratio
and the (Na + Ca) concentration in the successive zones of apoolivinite
metasomatites, it is possible to consider an indisputable lowering of alkalinity
(an increase of acidity) of the metasomatic solutions in proportion to their
distance from the source. On the modification, in the coexisting minerals, of the
TR/Ca, Y-TR /Ce-TR , Fe/(Fe + Mg) ratio (appearing as acidity indicators) it
has been established [Rass, 1972] that on the background of common increase of
acidity of the minerals’ composition from the rear zones to the forward zones, a
maximum gets fixed of the most acid compositions of minerals in the middle
zones of the column.
With syenitization is linked apatitization, studied in detail in the Magan
massif (north-western Siberian platform), 42 km² wide, formed in four intrusive
phases: ultrabasites phase (olivinites, pyroxenites), melteigite-urtite phase
(including also feldspar rocks, malignites and juvites), syenitic phase (nepheline
and alkaline syenites) and carbonatites (rocks of the series of kamaphorites and

224
properly carbonatites). On 80% of the massif are situated rocks of the second
phase, but apatite-pyroxene metasomatites coincide with annular peripheric
zones from 60 to 70 m thick, in a length of about 219 km and an area of 5 km2.
Rocks are until 400m deep apatitized and metasomatized in different degrees.
They lie between enclosing quartzites and ijolites. In the south-western and
south-eastern parts of the massif, between apatite-pyroxene rocks and ijolites is
a layer of pyroxenic phlogopitized rocks, probably representing phlogopitized
pyroxenites and jacupirangites. Nepheline and alkaline syenites of the third
phase of intrusion represent intermediate annular discontinuous layer in the
northern part of the massif, parallel to which are noted apatitized ijolites.
Linking of apatite-pyroxene rocks in the south with phlogopitized pyroxene
rocks, in the north, with ijolites, and a detailed petrographic study of apatite-
pyroxene rocks, their contacts with ijolites and with nepheline syenites have
permitted [Kravchenko et al., 1987] to consider in a certain measure the
apatitized rocks of Magan as successive zones of a column of syenitization,
arising at magmatic stage with intrusion of nepheline and alkaline syenites in
early formed rocks of the jacupirangite-urtite series and apatitized pyroxenites,
In the study of mineral associations resulting from syenitization of
preceding magmatic and metasomatic nepheline-pyroxene rocks are observed
stable parageneses, regularly replacing one another in the following succession:
Pxi + Ne + Ap – Pxi + Kfsp + Phl + Ap – Wo + Kfsp + Phl + Ap – Pxs + Ap –
nepheline syenite (Pxs + Ne + Kfs). Ijolite and/or nepheline pyroxenite are
submitted to potassic feldspathization and phlogopitization with preservation of
part of diopside (Pxi); with passage to the following zone there occurs a
complete replacement of diopside and formation of wollastonite; the following
(rear) zone, anchimonomineral “aegirinite” consisting of aegirine-diopside (Pxs)
and in combination with apatites presents itself as ore zone. The described
change of mineral parageneses occurs with increasing chemical potentials of
Fe2O3 and Na2O, i.e. with increased alkalinity and oxidation potential, with
decrease of the CaO chemical potential. The change in the chemistry of rocks
forming in successive zones of a metasomatic column of syenitization, as well
as with formation of metasomatic columns of ijolitization and turyaitization, is
determined by decrease of Mg and Fe.
In the study of mineral associations of the phlogopite complex of the
Kovdor massif it has appeared [Rass, 1974] that they replace one another in the
following succession: (Ol) + Di + Phl + Ap (gigantogranularity) – Tr + (Ap) +
(Cc) – Ol + Tfphl + Ap + (Cc) – Ol + Ap + (Cc) – carbonatite (Cc + Ap) (fig.
15.9). Rocks of this metasomatic column develop into olivine, olivine-pyroxene
and phlogopite-pyroxene rocks, magmatic and metasomatic rocks at the
magmatic stages. Similar metasomatites are also well-known in the Odikhintcho
massif (north-western Siberia), where with them are also linked ore-occurences
of phlogopite (zone of gigantogranularity of phlogopite-pyroxene rocks). On

225
consideration of mineral associations forming the zones of this column, one
must note the presence, ordinary in them, of bimineral parageneses, which
testifies to the inertia of only two components; and instability of the Ol + Px
parageneses, which testifies to mobility of MgO. From diagrams of parageneses
of a phlogopitic complex (cf. fig.15.9) it appears that to zones of empirical
removal of the column correspond spots of the diagram 1  2  3  4,
successively replacing one another with an increase of chemical magnesium
potential.
With the method of phase correspondence [Perchuk, 1970] is established
the temperature of formation of gigantogranularity of diopside-phlogopite rocks,
equal to 700-720C.
Metasomatites at postmagmatic stage. Together with the above
described metasomatites at magmatic stage, forming in processes of ijolitization,
turyaitization, syenitization and carbonatization of earlier formed rocks, with
intrusion, respectively, of melteigites and ijolites, turyaites, syenites and
carbonatites, to the formation of metasomatites of alkaline-ultrabasic-
carbonatitic complexes we must also relate such metasomatites at postmagmatic
stage, each of these processes apparently forming at last at lowering of
temperature. Moreover, if the nephelinization process proves local, and the
postmagmatic metasomatic processes, accompanying turyaitization and
syenitization, prove indistinct, the postmagmatic processes of carbonatization
(taking place with temperature decrease of the solutions with corresponding
replacement of higher temperature parageneses by lower temperature ones) have
a sufficiently wide spreading and in a number of cases a great significance for
ore-formation, especially for the genesis of phlogopitic deposits and ore
occurences.
Research with the method of paragenetic analysis of the replacement of
mineral associations of postmagmatic metasomatites of alkaline-ultrabasic rocks
of the Gulinskoie massif (north-western Siberian platform) in dependence upon
change of chemical CaO potential and growth of H2O potential has shown that
heterogeneous processes characterizing these rocks, phlogopitization and
cancrinitization [Epstein et. al., 1961], formation of pyroxene-garnet and
phlogopite-garnet rocks (autoreaction skarns) [Zharikov, 1968], and also
hydromelilite rocks [Lapin, 1965] lead to the production of metasomatites, the
rear zone of which is substantially carbonatic, and the distinction between which
is determined by the composition of the replaced rocks. The repetition of
paragenetic associations and the regularity of their change, the direction of
change of ferruginosity of coexisting phlogopite and pyroxene permits to present
them under the aspect of the following metasomatic columns, different facies of
carbonatized rocks: 1) olivine-pyroxene rock (magmatic or metasomatic-
magmatic stage), i.e. phlogopitized olivine-pyroxene rock, pyroxene-phlogopite,

226
porphyroblastic mica2 phlogopite-calcite rocks. 2) Nepheline-pyroxene rock (at
magmatic or metasomatic-magmatic stage), nepheline-pyroxene with melanite,
phlogopitized and/or cancrinitized, phlogopite-melanite, phlogopite-calcite rock;
3) Melilite-containing rocks (at magmatic or metasomatic-magmatic stage),
phlogopitized melilite-containing rock, hydromelilite-olivine, hydromelilite
phlogopite, hydromelilite-calcite rock.
With chemical analysis of rocks [Epstein et al., 1961] establishing
different zones of above-adduced generalized columns is traced the
displacement of figurative spots on the diagram (fig. 15.10), reflecting a
tendency to convergence of composition of the metasomatites, facies on various
initial rocks.
Link with mineralization. Alkaline-ultrabasice-carbonatic formation
possesses on the whole a unique ore-potential; linked with it are important and
very important deposit of apatite, phlogopite, vermiculite, rare and rare-earth
elements. Metasomatic processes promote concentration and localization of
these useful components.
We examined above the mechanism of formation of the apatite deposit of
Magan, with syenitization of earlier formed pyroxene and pyroxene-nepheline
magmatic and metasomatic-magmatic rock stages. The source of phosphorous is
undoubtless in the mantle, which is shown in the spreading of accessory apatite
in practically all differentiates of alkaline magmas and carbonatites. It has been
experimentally established [Kogarko et al., 1981] that phosphorous solubility in
early alkaline differentiates is four times higher than in melteigites, and that in
the differentiation arises a massive crystallization of accessory apatite, not
forming, however, deposits or ore-manifestation. The latter only form with high
range syenitization on a front of syenite intrusion. It was recently possible to
count the fixed association of the gigantic Khibine massif of alkalino-ultrabasic
carbonatic formations, and the genesis of gigantic apatitic deposits coinciding
with them may be interpreted in the afore-mentioned manner.
All testimonies of alkaline-ultrabasic massif simply link the formation of
industrial (with little iron and coarse grains) phlogopite in them with
metasomatic processes. Indeed, any metasomatic process leads to the formation
of metasomatites, in which are present phlogopitized rocks and, often,
anchimonomineral glimmerites. In the massif of the Maimetcha-Kotuysk
province (NW of the Siberian platform) have been distinguished [Prokhorova et
al., 1966] 5 types of phlogopite deposits, depending upon composition of
phlogopite-containing rocks: 1) olivinite type; 2) apomelilite type; 3) diopside
pegmatoide veins in apojacupyrangites, apoolivinites; 4) nepheline-pyroxene
pegmatoid veins in apopyroxenites, apojacupirangites; 5) garnete-nepheline-
pyroxene pegmatoid symmetric-zonal veins in nepheline-melilite rocks. As

2
Porphyroblastic glimmeriteis formed in the replacement of porphyrous rocks, particularly with melanephelinite.

227
regards solubility of these types in these or other metasomatites, it is expedient
to consider jointly types 1 and 3, as well as 2 and 5.
To the 1-3 type it is possible to relate the phlogopitic Kovdor deposit
[Ternovoy et al., 1969, Krasnova, 1972] the Ebe-Iurakh section of the
Odikhintsh deposit [Goldburg & Landa, 1963], the Kugda phlogopite occurence
[Egorov, 1964]. By comparing Mg, Fe, Ti content in phlogopites from
successive zones of metasomatic columns of carbonatization it has been
established [Rass, 1980] that the average ferruginosity of phlogopites decreases
from forward to rear zones, although maximal ferruginosity is characteristic of
phlogopite from intermediate zones. Average titanity of phlogopites decreases in
the same direction. In such deposits may be distinguished two stages of
metasomatism. In the first one, on intrusion of alkaline magma have formed
pyroxene and pyroxene-phlogopite rocks, and occurred mobilization of Mg from
olivinites and Al from ijolites, with potassium either mobilized from the
phlogopite of magmatic rocks or, as fully mobile components are abundant, they
occurred in the metasomatic solutions and with alkaline metasomatism have
participated in the formation of phlogopite. In the second stage of phlogopite
formation of deposit of the examined type occurred carbonatization of earlier
formed metasomatites in recrystalization of phlogopite with decrease of
ferruginosity and increase of the crystals’ dimensions. Substantially phlogopite
deposits are formed in the phlogopite-containing rocks at the postmagmatic
stage. If one of the stages took place, ijolitization with mica formation,
carbonatization of melanophelinites and ijolites, no concentration of industrial
phlogopite would occur. Nepheline-pyroxene pegmatoid veins (4 types),
phlogopites in which is ferruginosity characteristic 31, seemingly appears a
nepheline-pyroxene zone of a metasomatic column of ijolitization, with unlikely
relation with industrial phlogopite. In the formation of phlogopite deposits
linked with melilite-containing rocks (type 2 and 5) it is also possible to
distinguish two stages: ijolitization of olivinomelilite rocks [Egorov, 1969] and,
following them, carbonatization with formation of interfacial hydromelilite-
containing zones. Thus, in conditions favorable to the formation of industrial
coarse-grained underferruginosity (f from 6 to 14) of phologopite in alkaline-
ultrabasic massifs there occur 1) sufficient degrees of differentiation of alkaline-
ultrabasic magmas; 2) sufficient development of metasomatic processes; 3)
superposition of carbonatization processes on earlier formed metasomatites at
the magmatic stage. Substantial (and industrial) concentration of niobium
(pyrochlore), zirconium (baddeleyite) and rare earth (carbonates of rare earths),
also linked with carbonatites of metasomatic genesis.

228
Fig. 15.1. Geological ouline of the Fen massif [Mitchell, 1980].
1 – damkerite; 2 – ferrocarbonatites; 3 – dolomitic carbonatites; 4 – sövites (calcicitic
carbonatites); 5 – silicocarbonatites; 6 – vibetoites; 7 – urtites, ijolites, melteigites; 8 –
archean gneisses; 9 – 10 – limits of fenites (F).

229
Fig. 15.2. Geological outline of cape Tur [Evdokimov, 1982].
1 – olivine melteigite porphyries; 2 – carbonatites and camaforites; 3 – ijolite-urtites of the
second alcaline phase; 4 – undivided melilite rocks; 5 – ijolite-melteigites of the first alcaline
phase; 6 – undivided fenites; 7 – pyroxenites; 8 – red sandstones series (terskoi??); 9 –
aleurolites and quartzite-sandstones of the Tur formation; 10 – basal conglomerates; 11 –
undivided granitoids of the Umbin complex; 12 – geological limits: a – observed, - proposed;
13 – bedding elements: a – banding of magmatites and metasomatites, b – layering and
contacts; 14 – massifs (I – Kuznavolosk, II – Central, III – Letnegorsk, IV – Gornozersk, V –
Southern).

230
Fig. 15.3. Geological outline of the area of Novopoltavsk in Priazov [Kapustine, 1982].
a – central part of the carbonatite zone; b – cross section I-I; 1 – carbonatites; 2 – albitites; 3
– leuco-mesocratic nepheline-bearing fenites; 4 – fenitized gabbro-pyroxenites, often with
nepheline; 5 – fenitized gneisses, granites and magmatites; 6 – archean granites and
migmatites; 7 – sample locations.
I – III – fenites zones: external, medial and internal.

231
Fig. 15.4. Variations in pyroxene compositions.
F1, F2 – successive zones of the column of fenitization of the Fen massif [Morogan, 1994];
T1, T2 – successive zones of the column of fenitization of cape Tur massifs [Evdokimov,
1982]: T1 – apogranite, T2 – aposandstone; ij – ijolites, [Link] – melanite –bearing ijolites , dv –
damkerites and vibetoites, sc – silico-carbonatites of the Fen massif [Mitchell, 1980]; Tm –
melilite-bearing rocks of cape Tur massifs.

232
Fig. 15.5. Geological outline of the Kovdor massif [Ternovoi & al., 1969] with elements
of a structural-tectonical map [Krasnova & Sokolova, 1978] and most plausible model of
formation of vertical metasomatic zonality.
1 – carbonatites; 2 – apatite-forsterite-magnetite rocks; 3 – coarse-grained and coarse-grained-
phlogopite-olivine rocks; 4 – garnet skarns; 5 – turiaites; 6 – melilitolites; 7 – ijolite-urtites; 8
– ijolite-melteigites; 9 – jacupirangites; 10 – monticellite-bearing rocks; 11 – glimmerites; 12
– pyroxenized and phlogopitized olivinites; 13 – olivinites; 14 – fenites; 15 – gneisses; 16 –
phase I faults; 17 - annular faults; 18 – AB and CD - bore hole profiles accordingly; AB on
figure below – present day erosional profile.

233
Fig. 15.6. Thin section trough ijolite veinlet of nepheline-pyroxene rock, Kovdor massif.
Thin section 1469a from the collection of [Link], magnification 30, natural light.

234
Fig. 15.7. Variation of FeO, TiO2, Na2O concentrations in coexisting olivine (1),
pyroxene (2), phlogopite (3), melilite (4) from successive zones of metasomatic columns:
a – ijolitization, b – turiaitization. On the abscissa – position of samples [Rass, 1986] in the
cross-sections: olivinite (O) – ijolite (I) and olivinite (O) – turiaite (T); b – diagram of
concentration variations Cf of [Link] [1982] in solution and f/a in rock minerals in
function of variation in corresponding distance x/v.

235
Fig. 15.8. Shift of figurative points of rock compositions – successive zones of
metasomatic columns.
1 – phlogopitized olivinite; 1a – pyroxenite olivinite; 1b – glimmerite; 2 – nepheline-
pyroxene rock; 3 – nepheline-melilite rock; 4 – phlogopite-melilite rock; 4a – olivine-melilite
rock; 5 – melilitolite. Also shown the compositions of olivinites (I) and melteigite-ijolites (II).

236
Fig. 15.9. Carbonatization of pyroxene-nepheline rocks.
a – zonality: diopside+phlogopite (tremolite) olivine+apatite+tetraferriphlogopite. Thin-
section 5, magnification 20, natural light; b – carbonatite veinlets with reaction zones in
coarse-grained diopside rock (sketch of a sample, reduced 2 times); in insert circles – details
of the sections; 1 – diopside; 2 – tremolite; 3 – mineral agregates of olivine,
tetraferriphlogopite, apatite; 4 – tetraferriphlogopite; 5 – olivine; 6 – apatite; - 7 – magnetite;
8 – calcite; c – diagram of metasomatites parageneses of the phlogopite complex of the
Kovdor massif: 1 – 4 – zones of metasomatic column.

237
 Fig. 15.10 Diagram of facies of postmagmatic metasomatites of the Gulin massif
on (I) melteigites and pyroxene- nepheline rocks; (II) olivinite and pyroxene olivinite
rocks; (III) melilite rocks.
Ol – olivine; Phl1 and Px1 – phlogopite and pyroxene from olivine-pyroxene rocks;
Phl2 and Px2 – from nepheline-pyroxene rocks; Phl3 and Px3 – from melanite-containing
pyroxene-nepheline rocks; Phl4 and Px4 - from pyroxene-calcite rocks.

238
 CHAPTER 16

Skarns
Definitions. Types of skarns. The term skarn appeared in the literature at
the end of the last century from the vocabulary of swedish miners. So they
designated ore-containing rocks, formed of calcicium and magnesium silicates
and aluminosilicates spreading on deposits of central Sweden. However, the
notions of “skarns” and “skarn deposits” were confirmed in the thirties and
fourties of our century after the works of [Link] [1939] , [Link]
[1948, 1953] and other known researchers [Abdulayev, 1947 ; Karpova &
Ivashentsev, 1954], supplanting terms that were in circulation such as “tectites”,
“contact metasomatites”, contact metamorphic, pyrometasomatic deposits. Now
[Zharikov, 1968, 1970 ; Economic Geology, 1982], the terms skarns and skarn
deposits are generally accepted . More than a century ago, to be sure, were
investigated, with the works of B. von Cotta [1864] and [Link] [1876]
skarn deposits, the most varied hypotheses were put forward about their genesis
: 1) the hydrochemical [[Link], [Link] & al] ; the metamorphic
[[Link], [Link] & al.] ; 3) the magmatic [[Link], [Link] & al.];
4) a few variants of the metasomatic and the hydrothermal [[Link],
[Link], [Link], [Link], [Link] & al]
At the present time, the most commonly admitted proved to be the «
contact-reaction » theory of skarn formation advanced by [Link]
[1945, 1948, 1953] and thoroughly elaborated by his successors [Zharikov,
1968, 1985, 1991 ; Zaraisky et al.1986, 1989 ; Zaraisky, 1989] According to
present developments, skarns occur as a result of the interaction of carbonatic
rocks with magmatic and other aluminosilicatic rocks by means of
magmatogene solutions. From which follow definition and typization of the
skarns.
Skarns are called metasomatic rocks formed of calcicium,
magnesium and iron silicates and aluminosilicates, arising in a zone of high-
temperature contact aureole of intrusion resulting from interreaction of
carbonate rocks with a magma and other aluminosilicate rocks by means of
magmatic solutions.

239
 In mineral composition and parageneses are distinguished
magnesian skarns and calcic skarns ; they also differ in conditions of formation
and geological setting..
In the mechanism of formation are distinguished diffusion skarns
(bimetasomatic) and infiltration skarns (contact-infiltration and autoreaction
skarns).
Finally, depending on the composition of the initial rocks, they
differ into endoskarn and periskarn1 rocks, which form on aluminosilicate rocks
,and exoskarns, formed on carbonate rocks. If carbonate rocks contain initial
silicates or aluminosilicate material, the exoskarns are called skarnoids. They
are distinguished by the presence of numerous minerals (derived from the initial
aluminosilicate material) and they do not display a zonal distrbution of pyroxene
and garnet. Apart from those rocks originated in contact reaction, is
distinguished yet another group, the autoreaction skarns, arising in calcic
metasomatism without a necessary intervention of carbonate rocks. On table
16.1 the optimal subdivision of skarns rocks is adduced in a systematizing
aspect
Together with the marked types of skans generally accepted, some
researshers distinguishe sometimes also « ferruginous skarns », and relate to
them totally different metasomatites. In some cases [Burt, 1974] there are
ordinary calcic skarns with strong ferruginous pyroxene and garnet, ilvaite and
magnetite. In other cases [Strygine, 1964, 1978], to the skarn are arbitrarely
linked totally different metasomatites encountered amid ferruginous

Table 16.1 Types of skarns

On mineral composition On mechanism of formation

Infiltration (inf)
Magnesian Contact-infiltration
(MgSk) Diffusion (dif)
Bimetasomatic (bim)
Infiltration (inf)
Calcic Contact-infiltration
(CaSk) Autoreaction (auto)
Diffusion (dif)
Bimetasomatic (bim)

1
Are called periskarn rocks (enclosing skarns) formations of endoskarns composed shiefly of feldspars, scapolite
and other aluminosilicates, bringing about by desilicification of the initial aluminosilicate rocks.

240
table (continuation)

On composition of replaced Typomorphic minerals

rocks
Exoskarns Fo, Cpx, Spl (Per, Mtc, Gel – facies of
feeble depth)
Endoskarns, periskarns Cpx, Spl, Pl, Scp, Kfs
Exoskarns Cpx, Fo, Dol
Endoskarns, periskarns Cpx, Phl, Pl, Scp, Kfs
Exoskarns, skarnoïds Cpx, Grt, Wo
Endoskarns, periskarns Cpx, Grt, Pl, Ep, Sc, Kfs
Endoskarns, periskarns Cpx, Grt, Ves, Ep, Pl etc.
Exoskarns, skarnoïds Cpx, Grt, Wo
Endoskarns, periskarns Cpx, Grt, Ep, Pl, Sc, Kfs

quartzites or in contact with granitoids and built with almandine, spinel,

hypersthene, fayalite. These metasomatites have another origine than ordinary
skarns and calling them skarns is pointless Likewise, one should not called «
manganese » skarns rocks occuring in the metamorphism of rich manganous
sedimentary volcanogenic masses and built of minerals such as rhodonite,
babingtonite, spessartite, etc. Athough we must remark that manganous
pyroxenes and pyroxenoids : johannsenite, bustamite , rhodonite are hihgly
characteristic of skarn polymetallic deposits. Sometimes they have distinguish
«alkaline skarns » [Zhao et al.,1990] thus underlining the peculiarity of usual
contact skarns , occurring in connection with intrusion of alkaline rocks in
dolomitic or calcicitic marbles. Their peculiarities, naturally, are expressed in
the formation of « sodic minerals »: aegyrine, aegyrine-augite, akermanite,
nepheline, sodalite, lazurite, albite, and other «alkaline» minerals. With
predominance of those minerals the corresponding rocks must not be called
skarns, although their contact-reactional, bimetasomatic genesis, as a rule,
makes no doubt.
Geological setting of skarns and skarn deposits. Skarns are widely
distributed on the earth crust. However for their origin it is necessary to count at
least three indispensable conditions. In the first one, there is presence of contact
of two chemical environments in disequilibrium, carbonate rocks and
aluminosilicate milieu, which can be represented either by a magmatic solution
or an intrusive rock or any other aluminosilicate rocks (gneisses, micaschists,
etc.). In the second condition, skarns are formed of high temperature minerals,
therefore they always occur in immediate contact with intrusions, or in a zone of
high temperature contact aureole of intrusive massifs. Finally, in the third
condition, for the flow of intensive processes of contact infiltration or

241
bimetasomatic skarn formation, participation of hydrothermal 2 solutions is
necessary, usually of magmatogene origin. These symptoms are necessary for all
« genuine » skarns. Reduction of whatever factor leads to devolution in skarn-
like rocks or in other reaction metasomatites of « non-skarn » genesis.
A clear link between skarns and magmatism renders interesting an
evaluation of confined (not only spatially but also of genetically) skarns in
different magmatic formations. Such an evaluation (on more than 100 skarn
deposits) was made by us [Zharikov, 1968] and is presented on fig. 16.1.
Magmatic formations are taken oversimplifiedly (even eclectically, for exemple
formation of small intrusions, in counterpoise of others, on substantial
associations of intrusive rocks); however, the geological setting of each
formation is completely defined and sufficient for our aims. The figure clearly
shows a primary link between skarns and gabbro-syenito-plagiogranite and ,
especially with granitoid formations, which develop in early and middle stages
of fhe geosynclinal cycle or, in the contemporary terminology, are linked with
insular arc and collision (orogene) geodynamic regime.
For a more detailed characteristic of the geological setting of skarns
and characteristic mineralization is offered on table 16.2. This table, of coarse,
does not include all the varieties of skarn formations, but reflects the main
peculiarities (an enumeration of skarn types reflects only the relation of
extension but not genetic succession).
In this table are shown, apart from skarns, the composition of ores
developed in the various skarns, which have as is well known, a substantial
economic signification. Depending on correspondance of skarn formation
processes and mineralization , it is usual to distinguish several types of
mineralization or families of skarn ores [Zharikov 1960, 1965, 1968] :
1) type of simultaneous mineralization
2) type of concomitant mineralization
3) type of superimposed mineralization
The type of simultaneous mineralization, where the deposition of the ore
minerals occurs during the process of skarn formation, has a very limited
extension (we have in mind namely mineralization, but not in significant
quantity of, for example, magnetite usual in the outer zones of magnesian
skarns).To this type is related the borate mineralization in magnesian skarns, the
phlogopite mineralization in magnesian skarns and autoreaction skarns.
However in these cases, industrial borates and phlogopites are formed later, at
the succeeding recristallization of the initial skarns, and quite often are
accompanied with other aposkarnic minerals.

2
By hydrothermal solutions, we understand essentially “boiling” aquous fluids having properties of “liquid”
character, independently of their consistency. The source of these fluids (judging by isotopic composition) is of
magmatic origine, principally juvenile, although in some cases vadose waters are evidently present.

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 Table 16.2 Geological position of various types of skarns and ores

Geological setting Magmatism Skarns Mineralization

Old shields Granitization, Mg-Sk (inf, dif) Phlogopite
granitoïds, Ca-Sk (inf) rarely Fe, B (concomitant)
pegmatites

Activisation of old shields Granitoïds Ca-Sk (inf, dif) Cu, Pb, Zn, Au [Link]
(mixed series) (superimposed)

Platforms Alkaalino-ultrabasic Mg-Ca-Sk (auto) Phlogopite

Mg-Sk (inf) Fe, rare grounds, rarely,
Trapps (concomitant)
Ca-Sk (inf) Fe, polymetals
Mg-Ca-Sk (auto) (concomitant)

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Earlier stages Gabbro plagiogranitic Fe, Cu, Co, (Au,,
of geosynclinal development (island-arc Ca-Sk (dif, inf, auto) polymetals
regime) Gabrosyenitic Mg-Sk (inf) (concomitant and
superimposed)

Intermediary stages Granitoïd Ca-Sk (dif, inf) Wo, Mo, Sn, Cu, Zn
of geosynclinal development (grano-diorite-granitic Mg-Sk (inf) Pb, Be, B (superimposed)
(synorogene regime) formation)

Late stages Formation of Cu-Sk (dif, inf) Pb, Zn, Cu, W, Sn, B, Au,
of geosynclinal development feeble instrusions (various Mg-Sk (inf) Ag and oth. (superimposed)
(postrogene and late postrogene regimes) formations of granitoids to
alkaline rocks)
 Nevertheless, are renewed for some time attempts of several researchers
[Ezhov, 1994]] to relate part of the magnetite, scheelite and sulfide
mineralization immediately to skarn formation. As arguments are utilized facts
of discovery of disseminated metallic minerals in association wth pyroxenes and
garnets. To tell the truth we must remark that on experimentally reproducing
bimetasomatic skarn formation, under the influence of solutions, strongly
enriched in chlorides of ore elements, principally in contact of marbles with
exoskarns, is observed a dissemination of ore minerals : magnetite, sulfides (in
the presence of sulfur in the system) ; sometimes magnetite forms a continuous
« zone » [Zaraisky & al., 1986 ; Ezhov & Zaraisky, 1994]. If we turn to natural
objects, a detailed scrutiny shows that the appearance of ore minerals is always
accompanied with change of the initial skarn and, if this mineralization occurs at
high temperature, a recrystallization of skarn minerals happens with formation
of more ferruginous pyroxene and « ore » garnet (more ferruginous and with
greater content of pyralspite molecules).We can be persuaded that the
dissemination of those minerals, scheelite-sulfides, tends to be accompanied by
silicified skarns. If we now study the opposite geochemical tendencies of skarn
and ore process, presentation of a « simultaneous » mineralization of skarns
proves implausible.
Ore of the second type,, the family of concomitant ores, is
characteristic of various types of skarns. Mineralization of the concomitant type
immediately modifies the process of skarn formation and is usually
accompanied by a change of the initial skarn minerals. To this family are related
magnetite and ludvigite ores of magnesian skarns, phlogopite ores of magnesian
and autoreaction skarns, magnetite ores of calcic and autoreaction skarns,
magnetite-chalcopyrite and pyrrotite ores of calcic skarns and a few other ores.
This type of ore deposit arises at the earliest postmagmatic stage, which is also
the stage of skarn formation, and this is linked with a change in the properties of
the solutions at lowering of their temperature and alkalinity.
Finally, the familly of superimposed ores brings together ores, arising
in interaction of acid solutions at a much later stages (stages of acid leaching)
with basic environment of skarns. Mineralization occurs on the front of
interaction and is accompanied by peri-ore alterations of skarns, which appear as
a favourable environment for ore deposition. To this type are related various ore
deposits: scheelite-sulfidic (with SnO2), scheelite-molybdenite and polysulfidic
(often with Au) ores of calcic skarns, polymetallic ores of calcic skarns and
many others. Characteristically, each type of mineralization is accompanied, as a
rule, by specific metasomatic changes, corresponding to well known formations
of periore metasomatites. Skarn mineralization and, accompanying it,
metasomatic aposkarnic change represents a facial variety of these processes,
issuing preferably for the ore deposition of the main skarn environment.

244
Therefore the specific skarn mineralization is predetermined by the general
character of the occurrence of an acid stage in the given metaliferrous field.
As can be seen from what preceeds, skarn deposits are formed as a
result of the combination in space of several processes of formation and
mineralization of skarns ; moreover this combination reflects a deep genetic
regularity of development of one hydrothermal process. We offer table 16.3 in
which are shown the main genetic correspondences of the processes of
formation and mineralizations of skarns . In the same table, to complete the
description, are characteristic markings of temperature, pressure (depth) and
main peculiarities of the solutions, based on experimental data, on the research
of inclusions, more detailed data to which we refer infra.
As can be seen on the table, at magmatic stage in all the facies of depth
there occur contact-infiltration magnesian exoskarns, arising as a result of
interaction of dolomites (and other magnesian carbonate rocks) with solutions
produced from crystallization of the magma on a front of magmatic replacement
of carbonatic rock mass. In conditions of abyssal facies at magmatic stage,
outside the front of magmatic replacement, but in the zone of a high temperature
aureole, is possible the formation of contact-infiltration and bimetasomatic
endo-and exoskarns in contacts of gneisses with dolomites (and other magnesial
skarn rocks).
Calcic skarns at magmatic stage do not occur under the influence
of instability of calcic silicates in conditions of high pressure of carbon dioxide.
At the early postmagmatic stage, the processes of skarn formation
substantially depend upon depth. In conditions of hypabyssal and mesoabyssal
facies in contact with alumino-silicate rocks and with limestones and dolomites
arise calcic skarns of bimetasomatic and contact-infiltration type. Magnesial
skarns in these facies of depth are absent, only sometimes in the outher zone
appear calciphyres, formed most probably as remainders of magnesial skarns at
magmatic stage, at which are always formed calcic skarns. On the contrary, in
conditions of abyssal facies, at early post magmatic stage arise magnesial skarns
of contact-infiltration and bimetasomatic type. Calcic skarn formation in abyssal
facies conditions are practically absent, to them it is only possible to relate much
later garnet,epidote veins in endo- and periskarn rocks.

245
 Table 16.3. Main genetic properties of formation of mineralizing skarns

Facies of depth (h, km ; pf)

Stages T°C
Hypabyssal Mesoabyssal Abyssal

1-3(4) km, pf=0,25-1 kbar 3(4)-15(16) km, pf=1-3(4) kbar 15(16)-30(40) km, pf=3(4)-8(10) kbar
Magmatic 650-
900 Mg Sk (inf) Mg Sk (inf) Mg Sk (inf, dif)

Are formed under action of magmatic alkaline fluids with high CO2 activity

450-750 Ca Sk (dif, inf, auto) Ca Sk (inf, dif, auto) Mg Sk (inf, dif)

(800) Ca-Mg Sk (auto)
Earlier
postmagmatic Are formed under action of postmagmatic substantially chloridic solution;
CO2 activity depends upon depth
(alkaline)
300-

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Accompanying mineralizing skarns, linked with growth of acidity of chloridic solutions
500 des solutions chlorurées
(600)
Fe ; Fe-Cu, Fe-Cu-Co, Fe ; Fe-Cu, Fe-Cu, phlogopites
borates, phlogopites Fe-Cu-Zn, borates borates
Fe ; Fe-Zn

Imposition of mineralizing skarns linked with action of Usually lacking and studied
solutions and formation of metasomatites insufficient
at stage acid leaching
Acid 250- 1. metasomatism Q+Fsp (W, Mo, Sn, Zn)
500 2. metasomatism Q+Mc (Sn, Be, B, Mo, W)
(550) 3. metasomatism Q+Ep+Chl (Zn, Pb, Cu)
4. metasomatism Q+Ser, Q+Ser+Ank
(W, Cu, Mo, Au, Ag, Pb)
5. metasomatisme Q+Tu (B, Zn, Pb)
6. Other types
 Marked peculiarities of extended magnesian and calcic skarns
depend, as we indicate infra, upon the geochemical regime of carbon dioxide,
magnesium and calcicium in different facies and depth conditions.
Mineralization of concomitant type develops in calcic and
magnesian skarns in conditions of regressive evolution of development of the
early stage. Usually it is linked with greater basic intrusive complexes and
appear as gradual increase of acidity in replacement of initial skarns by ores and
aposkarn minerals.
In these conditions, when skarn deposits are linked with acid
intrusive complexes, the skarn process of alkaline stage rapidly transform by
metasomatic processes of the stage of acid leaching, the formation of which
leads to multiform skarn mineralization.

16.1 Magnesian Skarns

Definition. Among skarns, i.e. of high temperature contact-metasomatic

rocks, [Link] proposed to distinguish a type of skarns, characterized by
his substantially magnesian composition, calling rocks of this type « magnesian
skarns », in contrast to « calcic skarns » characterized by calcicium or iron-
calcicium contents. This delimitation proved important not only for composition
but for the genetic peculiarities and the ore’s specific character. [Link]
[1953] estimated that in chemical composition, magnesian skarns are even
nearer ultrabasic magmatic rocks than to calcic skarns.
We call magnesian skarns high temperature contact-metasomatic
rocks arising as magnesian minerals (mainly silicates), and forming in the
contact zone of silicate and magnesian carbonate rocks. Typomorphous minerals
of magnesian skarns are fassaitic clinopyroxenes, diopside, enstatite, forsterite,
humite minerals group, monticellite, merwinite, akermanite, spinel, serendibite,
phlogopite, pargasite, clintonite and magnesian borates (ludvigite, warvikite,
suanite, kotoite, singalite, fluoborite). They essentially differ from calcic skans,
arising usually as salite-hedenbergite clinopyroxenes, granditic garnets,
vesuvianite, epidote and wollastonite. Are proved specific useful minerals of
magnesian skarns : phlogopites, magnesian and magnesio-ferruginous borates.
Ferruginous and non-ferruginous ores are widely developed in magnesian as
well as in calcic skarns.
The first researchers of magnesian skarns were Swedish geologists
[Geyer, 1939], who described the mineral deposits of iron ore with boron
mineralization of central Sweden, and Watanabe [1943] who studied boron
mineralizations and the genesis of contact-matasomatic rocks in North-Korea.

247
 To an elaborate theory of magnesian skarn formation are devoted
works of [Link] [1947, 1953, etc], completed by the study of deposits
of Cisbaykal and Aldan in Siberia.
Further, magnesian skarns were minutely described by many
researchers [Tilley, 1951 ; Zharikov, 1959, 1968 ; Litsarev, 1961 ; Shmakine,
1961 ; Alexandrov & al., 1968; Pertsev, 1971, 1977 ; Shabinine, 1973, 1974,
1978 ; Shabinine &.al, 1984]. A large serie of experimental works concerning
the arising of diffusion metasomatic columns of magnesian skarn type was given
by [Link] & al.[1986].
Geological Setting. Magnesian skarns are expanded in carbonatic
(dolomitic) terrains in districts of inversed granitoid magmatism and in regions
of tectono-magmatic activation. They occur in aureoles of magmatic bodies and
zones of migmatization. In that space are not only skarns on carbonatic rocks, or
« exoskarns », but also formations on silicate rocks (developed magmatic or
metamorphic), or « endoskarns ». Like other types of contact-metasomatic
rocks, magnesian skarns may form bodies immediately in contacts, but also
veined and tubular bodies, extending in enclosing rocks on tens or even hundred
of meters from the contact. In intercalating patches of silicate and magnesian
carbonatic rocks, bodies of magnesian skarns may repeat themselves
[Link] of bodies of magnesian skarns vary from millimeters to
tens or a few hundred of meters.
Magnesian skarns of the magmatic stage are formed the earliest.
Their geological setting is defined : [Link] the presence in the composition of
enclosing rocks of magnesian carbonatic rocks ; 2. by intense magmatic
influence, accompanied by magmatic replacement of country rocks. Intrusions
may vary in composition from granites to nephelinic syenites and gabbroids, but
most typical is their link with granitoid formations (see fig.16.1).
Magnesian skarns at magmatic stage arise at all depths, except the
subvolcanic and near surface ones. Formation of these skarns occurs with the
following symptons :
a) in contact with skarns, the magmatic rocks are not skarnified ;
b) magnesian skarns intersect apophyses and veins of magmatic rocks,
carrying no vestiges of magnesian skarn replacement. As to mechanism, the
skarn formation at the magmatic stage is related to the contact-infiltration type.
Structure of of magnesian skarns deposits As cause of the formation of
magnesian skarns in high temmperature aureoles of magmatic bodies is revealed
a sharp chemical unbalance between magnesian carbonate and silicate rocks or
magmas in large intervals of pressure up to a condition of granulitic facies of
metamorphism. This unbalance provokes appearance of intermediate chemical
compostions of metasomatic zones. We consider this on the typical example of
the development of skarns on dolomite at its replacement by a granitic magma.
The metasomatic column arising in contact, has the following aspect : granite 

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clinopyroxene-bytownite zone spinel-fassaite zone  spinel-forsterite zone 
spinel-forsterite-calcite zone (calciphyre) dolomitic marble. All zones appear
simultaneously and expand in the direction of the arrows, and the
clinopyroxene-plagioclase zone is immediately replaced by the granite melt.
Formation of any thick skarn zones between granite magma and
carbonatic rock is impossible without participation of transmagmatic fluids, i.e.
flow of fluids arising through magmatic melts, realizing indispensable matter
transport at the formation of skarns. Emergence of skarns as a result of
magmatic replacement is marked 1) by the presence of skarn xenoliths in
precontact regions of magmatic rocks and magmatic veins in the skarns ; 2) by
expansion of all skarn zones aside from the granite, which may be observed
either in geological relations or under the microscope owing to incomplete
reactions of replacement. Approach of clinopyroxene-plagioclase zones over
spinel-clinopyroxene arises as replacement of spinel by basic plagioclases,
formation of a plagioclase border around spinel grains. A spinel-pyroxene
(fassaite) zone ensues on a spinel-forsterite one, which is reflected, basically, in
replacement of forsterite by fassaite on contact of these zones. Reversed
correspondences : approach of skarn zones over magmatic rock in these cases is
not observed.
The range of magma composition, in which are formed magnesian
skarns extends from granitoids to gabbros and dolerites, but also comprises
alkaline branches, including nephelinic syenites. In practically all intrusive
contacts of these rocks with magnesian carbonatic rocks, one encounters a body
of some thickness of magnesian skarn of magmatic stage, proving a high
participation of flows of transmagmatic fluids in skarn formation and magmatic
replacement of enclosing rocks. Possibly tectonic contacts or rapidly cooling
dykes do not contain skarns. Thus, one of the main differences from calcic
skarns, are contacts with limestone marbles, in which, with few exceptions,
skarns are not formed at a magmatic (progressive) stage. This is shown in the
equilibrium of calcite with many magmas in a very wide range of depth at
magmatic temperatures. [Pertsev, 1977] Replacement of limestone marbles by
magmatic rocks occurs without formation of intermediate reactionzones. So, for
instance, the studied cases of " porphyritization" of limestones [Korzhinsky,
1948; Pospelov, 1955]
Magnesian skarns on a progressive stage may form not only
immediately in contact with marble, but also in any other contact of silicate
rocks with magnesian carbonates in high aureoles of magmatic bodies (or zones
of migmatization) under influence of transmagmatic fluids.
We consider cases of skarn development in a stratified patch of rocks,
where dolomites alternate with gneisses and a flow of fluids crosses this patch.
Forming skarns in dolomites in contact with granitic magmas, the fluids leave in
the skarns such components as silica, alumina and get enriched at the same time

249
with calcicium and magnesium. Coming in this way in equilibrium with
dolomites, the fluid does not any more produce in them reactions of mineral
formation and can only recrystallize the dolomites. However, encountering on
their path a further gneiss patch, these fluids prove to be in disequilibrium with
the rocks, which initiates replacement of gneisses by endoskarns. Further
coming into equilibrium with the gneisses, the fluid ends the formation of
skarns, until it meets a new patch of dolomites and so on.
On formation of skarns on silicate rocks the direction of development
of the zones will be different. For instance, a spinel-fassaite zone may invade a
plagioclase-clinopyroxene one, which is expressed in replacement of plagioclase
by spinel and formation of spinel around grains of plagioclase. The skarn
formation process with a small quantity of one the reacting surroundings may
lead to zoning reduction. Thus, a fine layer of dolomite with full dolomite
expansion and prolonged skarn formation process may subsequently lose the
zone of spinel-forsterite composition, then that of spinel-clinopyroxene. There
may remain only the zone of spinel-plagioclase composition: under intense
granitisation this zone also changes into magma, i.e. there occurs a full dolomite
granitization. In the opposite case, when a fine layer of gneiss or an inclusion of
aluminosilicate rock changes into a skarn, there may remain in the dolomite only
a spinel-forsterite skarn.
Together with the infiltrations considered above, is also realized a
diffusion mechanism, prevalent in weak fluid flows or in infiltration along the
[Link] the formation of magnesian skarns at magmatic stage are prevalent
infiltration metasomatic columns The various successive zones and their mineral
composition in the magnesian skarns at magmatic stage depend upon the
chemical composition of two reacting surroundings as well as upon external
conditions, mainly temperature and depth of formation. As various carbonatic
surroundings the most usual are marbles rich in dolomite, magnesite-dolomite
marbles , magnesites. The influence of the composition of silicate rocks on the
general type of columns are not particularly great. At the passage from quartz-
containing rocks to quartzless felspars ( for instance syenite, gabbro) from the
column vanishes a first endozone (feldspar-pyroxene), it is true, in case of
nephelinic syenites, instead of which appears a zone of nepheline-pyroxene
composition [Koniev & Samoilov, 1974] The most typical columnn of
magnesian skarns was considered above. It is also represented on fig.16.2a In
conditions of less deep formation, and consequently small CO2 fugacity (as far
as CO2 and depth are linked in straight dependence) and increasing temperature,
this usual column is complicated by the appearance of an additional zone of
periclase marble (fig.16.2b), which essentially proves not metasomatic, but
contact metamorphic. The passage to more common "dolomitic » facies is
expressed as dolomitic decarbonatatization: CaMg(CO3)2 = CaCO3 + MgO +
CO2. This facies is usually called "periclase-calcite". It extends rather widely in

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the most recent regions with deep skarn formation between 1 and 3 Km [Pertsev,
1977].
In case of skarns developing in contact with basic magmas, i.e. at
increasing temperatures in condition of such small depths, there occurs a
prolonging alteration of the parageneses. Parts of spinel-pyroxene and spinel-
forsterite zones give up their place to spinel-monticellite and melilite zones
(fig.16.2c).Prolonged increased temperatures and reduced CO2 fugacity may
lead to formation of rare types of magnesian skarns with merwinites,
monticellite-periclase associations , etc. (fig.16.2d).
The succession and composition of zones are also preserved in case
of development of magnesian skarns on gneisses, quartzites and similar rocks at
a progressive stage ; only the direction of the zones development will be
different : from dolomitic to silicatic rock. Differences are observed in the
chemical composition of the zones. In endoskarns is usually increased the
ferruginosity of the mafic minerals, higher content of Zr and Ti and a few other
minor inert components, followed by silicate rocks. If magnesian skarns arise on
peraluminous quartzites, the frontal zone is plagioclase-cordierite or (under
higher temperature) plagioclase-sapphirine. To the cordierite-plagioclase zone
follows a biotite-plagioclase or a hypersthene-plagioclase zone (fig.16.3a-c)
depending on temperature and chemical activity of K2O and CaO. More interior
endozones (near the cabonatic rocks) may contain clinopyroxene-plagioclase,
then spinel-fassaite, spinel-forsterite zones, but in case of magnesian
composition of carbonatic rocks, instead of clinopyroxene in the corresponding
zones, there is magnesian orthopyroxene. This, however, is characteristic of all
exoskarns in contact with magnesites or magnesite-dolomitic marbles. A
metasomatic column takes on the aspect represented in fig.16.4a. It is possible,
with the skarn formation at low depth in contact with magnesites or brucites
between the latter and spinel-forsterite zones of skarns, for a contact
metamorphic zone to occur.
Narrowly abut to magnesian skarns by way of formation, metasomatic
rocks developed in contact not with carbonate rocks but with magnesian silicate
rocks of ultrabasic composition. In contact of granitic magmas with dunites,
olivinites and serpentinites , there arise zones analogous to magnesian skarns
columns, undersaturated in calcicium (see fig.16.4b). Exemples of such columns
are described in the Aldan shield and in other regions [Pertsev & Kulakovsky,
1988 ; Sack, 1982]. In contact of quartz-containing silicate rocks with
ultrabasites there may form analogous columns not as a result of granitisation
but with a simple diffusion exchange of magnesium and silica (cf. fig.16.4c).
Alkalinization in the vicinity of contacts. Magnesian skarns at magmatic
stage, developed in contact with marble, exert an influence on the chemical and
mineral composition of adjacent parts of the magmatic body. Such contact facies
are noticeably alkaline enriched. [Link] [1955] has explained this

251
appearance of reverse alkaline diffusion toward the magma from the contact
with a sharp increase of the activity coefficients of the alkalis on entry of
transmagmatic fluids in the basic surrounding, which led to an increase of K 2O
and Na2O chemical activities. There occurs thereupon a difference of activity (or
of the chemical potentials) provoking a reverse diffusion reflux of alkalis in the
magma. This mechanism is most probable : attempts to explain the given
appearance of assimilation of carbonatic rocks have failed since contact facies
get enrichhed in alkalis, but not in CaO and MgO. The existence of magmatic
rocks linked with contacts to magnesian skarns is very characteristic. We
distinguish, for instance, such pairs : granite + granosyenite, granosyenite +
syenite, syenite + nephelinic syenite. The thickness of alkalinization in endo
contact marbles varies from centimeters to tens of meters. Interestingly, in
contact with limestone marbles there is no such contact alkalinization. In
magmatic massifs adjoining either dolomite of limestone marbles, contact
alkalinization is formed only in magnesian contacts [Pertsev, 1971]
Postmagmatic alterations of magnesian skarns at progressive
stage. In connection with composition changes of fluids at postmagmatic stage
and temperature drop, mineral association in zones arisen at magmatic stage are
unstable and exchange place with other associations. Thereupon metasomatism
is prolonged, i.e. there is an exchange of components between solutions and
solid phases with variation of the chemical composition of the zones. The main
parageneses of postmagmatic magnesian skarns are shown on fig.16.5.
Postmagmatic alterations of early magnesian skarns are totally usual. They are
characterized by the preservation of a few peculiarities of the initial zoning at
magmatic stage with deposition of different metasomatic transformations.
Postmagmatic metasomatism of early skarns is characterized by appearance of
hornblende, pargasite, phlogopite and minerals of the humite group. Alumina-
enriched fassaitic pyroxenes are replaced by pyroxene , near to diopside, but free
from alumina redistributed in amphiboles and phlogopite. In the zones most rich
in silica and alumina, in conditions of small depth, arise calcic skarn
associations : wollastonite, wollastonite + grossularitic garnet, vesuvianite,
salitic pyroxene.
In (orthopyroxenic) skarns undersaturated in calcicium, a
posmagmatic transformation also leads to occurrence of phlogopite, pargasite
and hornblende instead of spinel-hypersthene and spinel-plagioclase
parageneses. In conditions of high pressure, presumably higher than 6 Kbar,
postmagmatic transformation of spinel-hypersthene pargenesis, leads to arising
of sapphirine in contact minerals.
Magnesian skarns minerals. . Minerals composing magnesian skarns
have specific properties. Thus there are observed substantial distinctions in
homonymous mafic minerals either in various zones of a metasomatic column or
in metasomatic columns at magmatic and postmagmatic stage.

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 Plagioclases in a pyroxene-plagioclase zone at magmatic stage
are usually presented in fundamental diversities (from bytownite to anorthite). In
same zone of postmagmatic stage, plagioclases are already andesites.
Clinopyroxenes in skarns at progressive stage are rich in alumina;
they sometimes contain an increased quantity of titanium. Al2O3 concentration
in pyroxenes of a clinopyroxene-plagioclase zone is somewhat lower than in
pyroxenes of a spinel-pyroxene zone; ferruginosity, on the contrary is somewhat
lower in the last. Clinopyroxenes, associated with spinels, appear as fassaitic or
near to fassaitic in content of Tschermak molecule. Clinopyroxenes of
postmagmatic skarns are distinguished by small content of alumina and titanium
and near to the diopside-hedenbergite series. Differently from calcic skarns, they
are not highly ferruginous.
Orthopyroxenes are distinguished in ferruginosity, which is
higher in association with plagioclases and lower with forsterites (in contact
with forsterite zones).
Spinels of magnesian skarns have a comparatively low
ferruginoity (up to 30%). In postmagmatic skarns, spinels sometimes contain a
noticeable quantity of zinc, up to some weigth %.
Olivines of magnesian skarns at progressive stage usually are
represented as forsterites. Their ferruginosity does not exceed 12-15% fayalite.
In postmagmatic forsterites, it may be rather high, up to 25% fayalite (in
association with diopside)
Calcites are encountered in various zones of magnesian
skarns. Amongst them are distinguished secondary and early parageneses with
skarn minerals. In association with clinopyroxenes they are little magnesian and
do not contain exsolution intergrowths, whereas in calciciphyres, in association
with initial dolomites, they have a noticeable admixture of magnesium, either
isomorphous or in the form of exsolution intergrowths of dolomites.
Amphiboles are formed only at postmagmatic stage. Blue-
green skarn hornblendes contain Al2O3 = 8.6-15.2 %; (Na2O + K2O) = 2.3-4.3 ;
Fe2O3 = 1.2-4.5 % and Fe/(Fe +Mg) from 10 to 55 (mol.). They are often
erroneously described as alkaline hornblendes. However, they possess
characteristic optical properties with noticeable or strong pleochroism from
blue-green on Ng, green on Nm, bright gray-green on Np ; 2V = -70 + - 80o,
with Ng = 19-22o. Pargasite is characteristic of magnesian skarns. It possesses
relatively low ferruginosty (Fe / Fe + Mg) from 1 to 35 % (mol).
Phlogopite is wholly typical of postmagmatic magnesian
skarns. TiO2 content in skarn phlogopites is as a rule not high, less than 1 wt. %.
In developing on early magnesian skarns, phlogopites are formed in contact with
spinel and clinopyroxenes.
Clintonite (xanthophyllite) is found in postmagmatic
skarns at small depth and is marked as origin of the passage from magnesian

253
skarns to calcic skarns. It usually developed in fassaite and spinel zones (or in
postmagmatic zones, corresponding to a spinel-fassaite zone on position in the
column) and stable in association either with magnesian clinopyroxene or spinel,
or with calcic skarn minerals, grossular garnet and vesuvianite, which may
develop by replacement of clintonite.
Humites minerals group are formed in magnesian skarns in
postmagmatic conditions with increasing fluorinity of fluids. More often fhan
others is found the less fluoric member of the group, clinohumite, afterwhich, in
order of diminishing participation, chondrodite, humite and norbergite.
Simultaneously may appear two orthosilicates of magnesium : forsterite +
clinohumite ; forsterite + chondrodite ; clinohumite + chondrodite ; humite +
chondrodite. Ferruginosity in accompanying orthosilicates is various, at the
passage of one mineral to another, sharply decreases, in order, forsterite,
clinohumite, humite chondrodite, norbergite. Clinohumite may contain
increasing TiO2 quantity (up to 5.4 wt. %), distinguished by a bright yellow
coloration and pleochroism. Such Ti-clinohumite may be found in equilibrium
with Ti-poor non-colored clinohumites. At postmagmatic formation of new
magnesian skarns may sometimes occur two orthosilicate independent zones :
calcite-forsterite and calcic-clinohumite or calcic-chondrodite ([Link].16.5).At
postmagmatic transformation of early magnesian skarns, forsterite at magmatic
stage is quite often partially or completely replaced by minerals of the humite
group.
There is a specific position in a metasomatic column of minerals of calcic
skarns, replacing magnesian skarns, or in postmagmatic magnesian skarns at
small depth. So, wollastonite in magnesian skarns always occupies a deep
position, representing an extreme endoskarn zone developed on silicate rocks.
Wollastonite in strictly calcic skarns always exists in extreme exozone,
developing on limestone . Rich grossular garnet develops in magnesian skarns in
a pyroxene-plagioclase zone or spinel-pyroxene, i.e. zones rich in alumina. Are
particularly easily replaced by grossular garnet thin veins of felspar rocks in
magnesian skarns, forming an effect of dissection of magnesian skarns by garnet
veinlets. Andradite garnets are formed only in exozones at completion of a skarn
process, in oxidizing conditions,and noticeably more rarely than garnets rich in
grossular. Vesuvianite, formed in magnesian skarns, after or together with
grossular, is according to [Link] (1973) MgO rich (more than 2.5 wt.
%).Clinopyroxenes, developing together with other calcic skarn minerals,
contain no noticeable quantity of alumina and, apart from association with
andradite, are poor in oxidized iron ; usually it is diopside-salite. Unlike
pyroxene strictly of calcic skarns it is magnesium rich (in calcic skarns is usual
ferrosalite up to hedenbergite).
Parageneses of minerals and zoning of magnesian skarns at
magmatic stage. To the peculiarity of skarns minerals at magmatic stage are

254
related : forsterite (fm = 0-15)3, clinopyroxenes (fm = 5-40), spinel (fm = 0-30),
calcite, magnetite, plagioclase (in periskarn rocks). In skarns and periskarns
rocks of abyssal facies are met orthopyroxenes (fm = 10-45).Skarns of
hypabyssal facies are characterized by such exotic abyssophobe minerals as
periclase, merwinite, akermanite, monticellite (although some of them are linked
with imposition on magnesian skarns of a calcic skarn process).
A noticeable property of clinopyroxene magnesian skarns at magmatic
stage is the fact that they are related to fassaites, i.e. to diopsides and salites with
increased Al2O3 and particularly Fe2O3 (together with FeO) content. Al2O3
content with fassaites range from 1-2 to 15-16wt.%, with average 4-9wt.%.
Correspondingly, Al4 ranges from 3 to 20, with average 7-12. Naturally, the
greatest alumina content is in paragenesis pyroxene-spinel. At the postmagmatic
stage, fassaites « detrude » alumina, changing into usual diopsides and salites.
Coefficients of ferruginosity (fm) of minerals of magnesian skarns are
always inferior to 30 (except that for hypersthene endoskarns fm sometimes
reaches 40-50),and the ferruginosity ratio is fmSp > fmCpx > fmOpx.
Correspondingly, ferruginosity coefficients are less than 1.
For KFe/MgOpx = 0.2-0.3, for KFe/MgCpx = 0.3-0.5, for KFe/MgSp =0.3-0.4.
However, this distribution is fully right only for magnesian skarns..
For other formations with more ferruginous composition arising at another
temperature, the distribution of Fe-Mg in the pairs olivine-clinopyroxene and
olivine-hypersthene changes. KFe/Mg increases and takes a value geater than 1.
The natural passage is not sufficiently clear. The majority of researchers count
that KFe/Mg for Ol-Cpx and Ol-Opx passes through extremes, which is linked
with a non-ideal distribution [[Link], Kretz, [Link]]. Others
[Bartolome, [Link]] suppose that Ol-Cpx and Ol-Opx approach
complete mixture,and KFe/Mg is determined by temperature [Korzhinsky,1973 ;
Zharikov, 1976].
Magnesian skarns are all characterized by various postmagmatic
alterations, linked with posterior and other processes, juxtaposed to initial
skarns. Amongst them, one may distinguish three groups of minerals. The first
consists in minerals linked with regressive alterations and superimposition of a
magnesian postmagmatic skarn process. This group is characterized by
phlogopite, minerals of the humite group, pargasite , serpentine, minerals of the
chlorite group, hornblendes , scapolite. A second group of minerals is linked
with a juxtaposed calcic skarn [Link] is calcic garnets and pyroxenes,
vesuvianite, clinozoisite, scapolite. In conditions of hypabyssal facies with

3 Fe
fm – Fe content = x 100.
 Fe  Mg  Mn
4 Al
al – Al content- = x 100.
[Si  Al]  [Mg  Fe2   Fe3  Al]

255
alteration of magnesian skarns and superposition of calcic skarn process there
develops a complex of very varied calcicium-magnesium silicates :
xanthophyllite, monticellite, gehlenite, spurrite and other sparse minerals.
Finally, must be noted mineral associations, linked with postmagmatic
mineralization of magnesian skarns : magnetites, phlogopites and borates, with
moreover, the last, linked wth their original complexes of minerals, including
also minerals such as ludvigite, suanite, kotoite, fluoborite, szaibelyite and
others [Pertsev, 1971].
Parageneses of minerals and zoning of magnesian skarns at magmatic
stage are determined by two main factors. First of all fugacity or, more
precisely, activity of CO2, which in turn directly depends upon depth,
significantly extended at pressure increase. Moreover, on parageneses of
magnesian skarns appears a relative activity of calcicium and iron.
On fig 16.6 is represented a T-P diagram of equilibrated, limited facies
of depth of magnesian skarns. The diagram is based on experimental data
[Zharikov & al. 1977 ; Zharikov, 1968, 1985 ; Walter & Helgeson, 1980] but
constructed for an optimal fluid regime at magmatic stage (XCO2 = 0.6 and
XH2O = 0.4). For these conditions are plotted stroke-point lines of solidus of
granites and basalts. We distinguish four main facies of depth (more precisely T
and P, although P has a far more important significance). I merwinite, II
monticellite, III periclase, IV non- periclase. The facies are meant on « critical
»[Link] last facies ,of course, would be better called forsterite-diopside-
spinel, but this paragenesis is also stable in periclase facies. For each facies are
constructed diagrams of composition-paragenesis in CaO-MgO-SiO2
coordinates, reflecting in greater relief parageneses alteration depending on CO2
fugacity. The first three fields, I-III, reflect a condition of hypabyssal facies
which, as we have noted, are characterized by an ensemble of relatively sharp
Ca-Mg minerals : merwinite, akermanite, monticellite, periclase. Apart from
those attested in the limits of I and II fields, other substances are also possible
with paragenes, for exemple Fo + Cc together with Per + Mtc or Per + Ap
together with Mtc + Di, , but their field are very small in comparison with those
indicated on fig.16.6. We observe (as is well visible on the diagram) that the
greatest range of depth contains the non-periclase facies IV : Fo + Di +Cc,
which accordingly, is also the most extended amongst skarns at magmatic stage.
At this stage are observed the typical parageneses in MgO-Al2O3-SiO2
coordinates. Finally, on the diagram is indicated for comparison the field V, of
postmagmatic magnesian skarns, spreading in conditions of abyssal facies and
distinguished in parageneses with phlogopite.
Apart from the considered dependence upon depth, parageneses of
magnesian skarns and types of zoning in them are also distinguished in their
dependence upon chemical potentials of calcicium and iron in non-magnetite
associations. Here the main difference consists in the appearance of

256
orthopyroxenes in conditions of low CaO. On fig.16.7 is represented a diagram
of dependence of parageneses of magnesian skarns at magmatic stage upon
chemical potentials of calcicium and iron. On the diagram are indicated in
Roman digits (I-V) the signs of different facies and dependences upon Ca and
Fe, for which are given diagrams of composition-paragenesis in Mg-Al-Si
coordinates. Are also plotted lines of ferruginosity of coexisting Ol-Opx-Spl.
On the diagram are well visible two main groups of facies : non-
hypersthenic (fields I and V) and hypersthenic (fields II, III and IV). The main
reaction limiting them (Pl)(Spl) (Cpx + Ol = Opx + (Ca)) practically depends
upon the chemical potential of calcicium. As far as in the diagram‘s reckoning
the real compositions of the minerals are taken, in the reaction are present spinel
or plagioclase (owing to preservation of alumina and fassaite), and the lines of
equilibrium have a small slope owing to the sharp ferruginosity of the minerals.
From the paragenses marked on the diagram a Fo + Pl association is not found
in magnesian skarns, their parageneses answer to fields I, II and III. Moreover,
if the paragenesis of field I Ol + Cpx + Spl is characteristic of depth
levels, parageneses with Opx (fields II and III) are met only in conditions of
abyssal facies anf chiefly in contact with magnesitic masses. These properties
are undoubtedly linked with the geochemical regime of calcicium in skarn-
formed solutions.
The following main types of metasomatic columns are the most spread
in magnesian skarns at magmatic stage :
1. magma – Cpx + Spl – Ol(Fo) +Spl +Per – Dol ;
2. magma  Cpx + Spl – Cpx + OL = SPl – Ol + Spl + Cc – Ol + Spl
+ Dol (Per) + Cc – Dol ;
3. magma – Cpx + Pl(Scp) – Cpx + Spl – Fo + Spl – Fo + Spl + Dol -
Dol .
In the outer zones, fronts of magmatic replacements as a result of reaction
of interaction of dolomites with gneisses and cristalline schists in abyssal
conditions, arise bimetasomatic skarns with charactristic zoning : gneiss
(crystalline schists) – Cpx + Pl – Cpx – calciciphire – Dol.
For contact – infiltration endoskarns arising under the influence of
magmatogene solutions, on schists or gneisses , which arise in them through
dolomites, the following zoning is observed :
Gneiss – Cpx + Pl (Scp) – Cpx + Spl (Phl) – Dol.
Parageneses and zoning of skarns at postmagmatic stage.
Postmagmatic magnesian skarns are reliably studied only in gneiss complexes of
Precambrian. They are formed as a result of contact reaction of dolomites and
aluminosilicate rocks by means of a diffusion or infiltration mechanism. The
regime of magnesium and calcicium and the reactions of skarnification are
determined by depth conditions. This is manifested in decisive factors
exclusively determining coincidence of magnesian skarns at magmatic stage to

257
old shields and zones of Precambrian folding with active manifestation of
granitoid magmatism. Mineral composition of postmagmatic magnesian skarns
is varied. We may distinguish two main mineral associations : a) strictly post
magmatic skarns and b) postmagmatic replacements of earlier formations
(preferentially at magmatic stage) of magnesian skarns.
To the main minerals of strictly postmagmatic skarns are related
olivine (forsterite), clinopyroxenes, spinel, phlogopite, hornblende (usually
pargasite), plagioclase, scapolite, orthoclase, calcite, apatite. In determined
conditions arise lazurite, hauyne, nepheline. Unlike skarns at magmatic stage,
postmagmatic clinopyroxenes are usually diopsides and salites (Al2O3 content
does not exceed 1-2wt.%). Usual range of ferruginosity (fm) of minerals :
clinopyroxenes (0-54),olivine (0-20), spinel (4-40), phlogopite (0-30), pargasite
(10-35). There is a characteristically great ferruginosity in endoskarns and
periskarns. Scapolites have an average 40-60% content of meionite molecules,
plagioclases contain 20-30% of anorthite.
Mineral association of alterated magnesian skarns is very varied. The
most characteristic minerals are chondrodite, humite, clinohumite, phlogopite,
amphiboles, chlorites, serpentine, talc, calcite, borates, magnetite, apatite. In
conditions of hypabyssal facies in replaced magnesian skarns are also found
monticellite, clintonite, brucite and other abyssophobe magnesian and calcicio-
magnesian minerals.
Parageneses and zoning of postmagmatic magnesian skarns are also very
varied. Paragenetic analysis shows that a determined significance of their
formation, apart from the depth condition, has a regime of alkalinity and
ferruginosity. Here are the following facies of alkalinity and ferruginosity: a)
pyroxene-spinel facies arising in conditions of low alkalinity and ferruginosity ;
b) spinel-pargasite facies, arising in conditions of increasing ferruginosity and
non-high alkalinity ; c) phlogopite facies, distinguished by moderate alkalinity
and low ferrugonosity ; d) phlogopite-pargasite facies in conditions of inceased
ferruginosity and normal alkalinity.
Metasomatic zoning arises under the consequence of reaction interplay of
inert components (Si, Al, Mg) under the influence of high temperature
metasomatic solutions. Zonation peculiarity is then determined by activity of
interacting inert components, the mechanism of their mixing, the general regime
of postmagmatic solutions, their alkalinity and ferruginosity.
We distinguish, corresponding to the separate facies, the following
main types of metasomatic columns of postmagmatic bimetasomatic magnesian
skarns :
1. Gneiss, crystalline schists – Cpx + Pl(Klf) + Scp  Cpx + Scp
Cpx + Spl  Cpx  Fo + Cc + Dol.
2. Gneiss – Cpx + Pl(Klf) + Scp  Cpx + Scp  Cpx + Prg  Cpx +
Spl  Cpx + Fo + Cc  Dol.

258
 3. Gneiss  Cpx + Pl(Klf) + Scp Cpx + Scp  Cpx + Phl Phl 
Cpx Fo + Cc  Dol.
Contact-infiltration skarns are characterized by the same types of zonality
.
The main lines of chemistry are the following. Formation of exoskarns
zones is brought about by introduction of silica and removal of magnesium and
calcicium, but at the formation of endoskarns there occurs introduction of
magnesium and calcicium and removal of silica. Moreover alumina is limited to
local mixings only within endoskarns. No removal of alumina occurs in
exozones. Such postmagmatic magnesian skarns substantially differ from skarns
at magmatic stage. Activity of alkalis and iron is determined, chiefly by
influencing solutions and turn out, probably as peculiarities of magmatic
sources.
We now consider only parageneses of strictly magnesian skarns
formed at postmagmatic stage, not touching on the parageneses of replaced
skarns and other formations of contact-reaction. On fig.16.8 is represented a
diagram of the dependence of parageneses of postmagmatic magnesian skarns
upon the chemical potentials of potassium and iron, more substantially
influencing the paragenetic correlation in postmagmatic magnesian skarns. In
constructing the diagram the following compositions of minerals have been
taken : Scp60, Pl40, Prg25, Sp35, Di20, Fo10 (where have been marked by indexes
the contents of meionitic and anorthitic molecules and the ferruginosity of Fe-
Mg minerals). This diagram characterizes parageneses of all main contact-
reaction phlogopitic deposits. It is possible to distinguish the domains of
parageneses of low alkalinity and ferruginosity (II, III) without pargasite and
phogopite (phlogopite appears in these parageneses with following replacements
of the initial skarn minerals)5. Facies of increasing ferruginosity are
characterized by parageneses with pargasites (III, IV). Finally, the domains of
normal and increasing alkalinity occupy the phlogopite facies V-IX). The
mentionned phases are formed simultaneously,i.e. in conditions varying in
ferruginosity and alkalinity. At the same time we observe a definite tendency of
ferruginosity growth in the course of skarn process, when phlogopite facies are
replaced by phlogopite-pargasite.
The diagram may be widened to the domain of high alkalinity and the
different correlations of chemical potentials of calcicium and potassium. In these
conditions arise contact-reaction formations with nepheline, lazurite, hauyne.
The classic description of these deposits was made by [Link] [1948].
However, they do not relate to skarns, athough their contact-reation,
bimetasomatic nature in the mechanism of formation is completely similar to the
nature of bimatasomatic skarn deposits.
5
In all parageneses, exploitable phlogopite appears almost ever later during recrystallization and replacement of
the skarn minerals.

259
 Alteration of magnesian skarns. With the temperature decrease of
postmagmatic solutions, percolating through magnesian skarns, there occur
exchange reactions between the minerals of the rocks and the solutions, as a
result of which the skarns change their composition. Spinel-forsterite skarns are
then transformed into clinohumite or chondrodite rocks with a certain quantity
of phlogopite, but spinel-fassaite skarns are transformed into phlogopite more
rarely pargasite skarns. Pyroxene-plagioclase periskarn rocks are transformed
into hornblende, phlogopite, sometimes tourmaline rocks. Sometimes
plagioclase is replaced by scapolite. All these skarn transformations occur
without alteration, preservation of the inert components in the rocks, and the
processes prove . metasomatic column arises, although the mineral compostion
of the zones of the initial column is changing.
Fairly frequenfly are magnesian skarns subjected to replacement by
calcic skarns. These skarns are widely combined with bodies of magnesian
skarns and develop with replacement of the latter, absorbing simultaneously
parts of adjacent active intrusions and hornfelses intercalations.
Periskarn rocks are formed with pyroxene and one of the felspars,
basic plagioclase or orthoclase ; sometimes is formed instead of them scapolite,
i.e. the mineral composition of the rocks of this zone of endocontact is close to
the composition of periskarn rocks of normal calcic skarns. In them are spread
wollastonite, grossular garnets and pyroxenes of the dioppside-henbergite series.
Contrariwise, skarns of exocontact have a series of differences from
skarns formed on limestones . These zones of apomagnesian calcic skarns are
characterized by clinopyroxene of salite-augite type, essentially magnesian
vesuvianite, grossular garnet, xanthophyllite and rarely gehlenite. These hihgly
aluminous minerals develop with exchange of spinel and basic plagioclase of
magnesian skarns, i.e. they sharply distinguish apomagnesian calcic skarns from
the usually non-aluminiferrous skarns formed on limestone.
Thus, in rocks of magnesian skarn formation spatially coexist groups
of high temperature mineral associations : 1) magnesian skarns at magmatic
stage (fassaite, forsterite, spinel, basic plagioclase, periclase); 2) post magmatic
transformations of magnesian skarns (phlogopite, pargasite, anthophyllite,
tremolite) ; 3) apomagnesian calcic skarns (salite-augite or ferrosalite up to
hedenbergite, monticellite, xanthophyllite, vesuvianite , grossular, wollastonite).
Moreover, in the last group predominate minerals essentialially magnesian and
aluminous, unusual in skarns formed on pure limestone.
Mineralizations of magnesian skarns. The most usual
mineralization of magnesian skarns is magnetite or borates, also other other
types are found of skarn metals ores (W, Sr, Mo, Cu, Zn, Pb, Ag, Au).The most
important non-metallic raw material in magnesian skarns is phlogopite.
Magnetite and borate ores, as well as phlogopite, deposit in a postmagmatic
process, but also at the time of formation and transformation of skarns.

260
Magnetite, primary borates and phlogopites are in equilibrium with skarn zones
combined with them and, consequently, are formed at high temperature, even to
the stage of hydrothermal alteration of skarns. The remaining types of metallic
ores, on the contrary, as in calcic skarns, are linked with acid hydrothermal
alterations, precipitating after the passage of the « acid wave ».
Iron ores, magnetite rich, occupy in magnesian skarns a definite
position : they are formed most often in a forsterite zone, almost wholly
replacing its minerals. Somewhat more rarely do they appear in a clino- or an
orthopyroxene zone , where the olivine zone may be oreless. It has been noted
[Pertsev & Kulakovsky,1988]] that in the development of magnetite in a
pyroxene, olivine ferruginosity in an oreless olivine zone is high, reaching 15-17
% Fa. A more basic and more acid surrounding, conditioned by the presence of
weak forsterite ferruginosity, was favorable to magnetite precipitation.
Magnetite may be stable in any zone of skarns and in surrounding rocks, but it
forms rich ores only in replacement of a forsterite or more rarely of a diopside
zone. Interstitial development, similar to sideronitic, of magnetite inores with
replacement of such postmagmatic minerals as phlogopite, pargasite, minerals of
the humite group, gives evidence about postmagmatic and epigenetic magnetite
formation
Of another character is the magnetite mineralization in calcic skarns.
In ore composition are present, apart from magnetite, andradite garnet, ferrous
epidote, clinopyroxene rich in oxidized iron (ferriaugite), sometimes very rich in
marialite scapolite, is found a ferrous blue-green hornblende.
Borates ores are displayed as magnesian borates : kotoite, suanite
and Mg-Fe borates of the ludvigite group. In industrial quantities may exist
aqueous borate szaibeleyite (ascharite), proving a product of low temperature
decay of initial skarn borates mentionned above. In industrial quantities may
probably also be found carbonate-borate groups of sakhaite, charkerite and
kurtshatovite, characteristic of magnesian skarn at low depth [Pertsev,1971].
Borate mineralization occupies a characteristic position in skarns, that is an
extreme spinel-forsterite (clinohumite, chondrodite) zone and / or calciciphyre,
including formation of monomineral (or nearly so) borate ores. Thin kotoitic
mineralization only occurs by means of replacement of magnesian carbomates
(or magnesium oxides) in the form of kotoite marble (on dolomite) or kotoite
ore on magnesite or periclase. Suanite ore may be formed either by substitution
of calciciphyre or forsterite, sometimes also pyroxene zones.
Concentrations of accumulation of ludvigite usually confined to a
forsterite zone. Kotoite mineralization is specific to a condition of small depth,
not more than 2-3 Km.
Phlogopite raw materials. Although phlogopite mineralization
characterizes all magnesian skarns, coarse-leaved industrial phlogopite is
characterized only by deep deposits. Moreover it is established that industrial

261
phlogopite is formed at recrystallization of fine-grained phlogopite [Murzaiev,
1974].More than that, all minerals found in association with coarse-leaved
phlogopites, also present gigantic crystals. Apparently, the process of formation
of coarse critallized phlogopite is akin to the process of formation of alpine
veins. In phlogopite deposits it arises in conditions of protracted thermostatic
control in regions of stretching. In conditions of small depth such thermostatic
control is unlikely because of the high rate of cooling of the rocks.
Scheelite mineralization of small depth occur at silicification of
calcic skarns developed on magnesian skarns, where it is associated with
postskarn pyroxenes and garnets. Scheelite of deep deposits is formed together
with post skarn replacements of magnesian skarn minerals as well as at acid
stage but, as a rule without silicification. It associates with such minerals as
serpentine, talc and tremolite.

16.2 Calcic Skarns

Mineral association of calcic skarns is characterized by the compulsery

presence of calcic pyroxenes alongside diopside-hedenbergite ( or series of
diopside-hedenbergite-johannsenite) and calcic garnets alongside grossular-
andradite Moreover, to skarn minerals are related wollastonite, epidotes, more
rarely vesuvianite, pyroxenoid of rhodonite type, bustamite, monticellite,
gehlenite. To periskarn rocks are usually plagioclases and/or calcite, feldspars,
scapolites. Secondary minerals are tremolite-actinolites, chlorites, epidotes,
sometimes axinite, usually calcite.
A self-formed complex of minerals is formed in conditions of slight
depth with deposit of calcic skarns on magnesian ones. Apart from the usual
minerals of skarns, garnets, pyroxene and vesuvianite, are met in those
conditions monticellite, melilite (gehlenite),spurrite,cuspidine and other more
rare calcic and calcicio-magnesian minerals.
In deposit on calcic skarns of ore processes, a complex of ores and
periskarn minerals is highly multiform.
Hundred of analyses of skarn minerals have been published in the
literature [Zharikov, 1968 ; Sobolev, 1964 ; Karpova & Ivashentsev, 1954 ;
Indikaev, 1980. Einaudi et al., 1981] and it is not possible to enumerate here
their results. Most impottant is the revelation of regular correspondences in
composition of minerals of calcic skarns.
We have established [Zharikov, 1968]) that the composition of
corresponding pyroxenes and garnets are noticeably distributed in ferruginosity
to different skarn deposits. Fig.16.9 shows a comparative diagram, where on the
ordinate axis is put XFe Cpx / 1- XFeCpx, on the absciss axis XFeGrt / 1- XFeGrt.. In
conformity with earlier publications, the diagram is completed with some new
data, the number of which may be greatly increased insofar as a comparison of

262
ferruginosity of corresponding pyroxenes and garnets has firmly penetrated the
practice of skarn research. As can be seen on the diagam, molybdene skarns,
wolfram-molybdene skarns, tin-wolfram skarns, polymetallic and other skarns
are characterized by parageneses of ferrous (hedenbergitic) pyroxenes with
aluminous (essentially grossular) garnets. On the contrary, copper-iron skarns,
polymetallic skarns are distiguished by reverse correlations : parageneses of
more magnesian pyroxenes and more ferrous garnets. Are also widespread with
neighbouring correlations ferruginosities of pyroxene and garnet, for exemple in
copper-wolfram skarn deposits, sulfide skarn deposits with Au, Co, As and a
few others.
Iron distribution between calcic pyroxenes and garnets corresponds
with equilibrium [Zharikov, 1966, 1968] :
Ca Fe Si2O6 +. Ca1.5AlSi1.5 + Mg (OH)3 + H2O =
hedenbergite grossular solution
CaMgSi2O6 + Ca1.5FeSi1.5O6 + Al(OH)3 + H+ + e-
(16.1)
Diopside Andradite Solution
The constant of distribution is recorded as follow :
[CaFeSi2O6] / [[Ca Mg Si2O6] : [Ca1.5 Fe Si1.5] / [Ca1.5Al Si1.5] =
KDO.[Al(OH)3][H+][e-]/ [Mg(OH)2][H2O] = K
(16.2)
where in square brackets are the activities of corresponding components
in solid phases and in solution. Taking with approximate activity of alumina
hydroxide, magnesium and water as constant but the distributions of minerals
between ideal phases, we get :
XFeCpx/ 1- XFeCpx XFe Grt : XFeGrt / 1- XFeGrt = KD*[H+][e-] =KD**[H+] = KD
(16.3)
Equation (16.3) reflects also our supposition, that the most decisive
significance for iron distribution proves to be the acidity of the skarnification
solution. In condition of increasing actidity KD > 1, and are characterized
parageneses of ferrous pyroxenes with aluminous garnet. On the contrary, in
conditions of decreasing acidity KD < 1 and in parageneses with pyroxene are
found more ferrous garnets ([Link].16.9)
A confirmation of this is seen in the peculiar geological stucture of
the deposit. Molybdene-wolframite skarns and other rare metal skarn deposits
are linked with leuco-granitoides, processes of skarn formation on them are
replaced by mighty processes of silicification, greisenization, quartz
feldspathization quartz sericitic metasomatosis, accompanied by mineralisation
of the skarns All this bears witness to increasing acidity of the solutions, which
is also manifest at the skarn stage
However,it was necessary to give a direct confirmation of the
influence of the acidity on the remarquable distribution of iron between

263
pyroxene and garnet . This was obtained as a result of experimental research
[Zharikov&.al., 1979].On fig.16.10 is presented a general diagram of
dependence of the constant of iron distribution between pyroxene and garnet
upon acidity of the solution conforming the correlations (16.2) and (16.3) .
lgKD = lg (XFeCpx / 1-XFeCpx : XFeGrt / 1-XFeGrt) = lg KD + lg[H+] + lg(CAl
/CMg) (16.4)
for experiments with Pf = 1kbar, T = 600, 700oC in the presence of CaCl2
and HCl soutions of mineral and oxidizing-reduction [Link] can be seen
from correlations (16.3) and (16.4) we have adopted in the experiments the
influence on equilibrium of the activities of various soluble forms of Al and Mg,
whose concentration ( lg CAl :/ CMgs ) was determined by the presence in the ex
periments of a mineral buffer of olivine + wollastonite + anorthite. It should be
noted that the lg CAl / [Link] is insignificant and constant [Zharikov et al.,
16.3) and can be completely neglected establishing that K D depends on pH
which has besides been done in equation (16.3). In our experiments equilibrium
constantKD included K'D = KDO. [e-] / [H2O] (16.5).
KDO depends upon pressure and temperature. Dependence of KDO upon
temperature is visible in comparing lines 1 and 2 on the diagram 16.10, decrease
of temperature brings about diminuition of KDO, combining reaction in the
stucture of the diopside-andradite paragenesis at lesser temperature.(at lesser
entropy)
The influence of redox conditions is visible in comparing line 4 (Ni-
NiO buffer) with line 5 (QFM buffer).Increase of activity of the electron
(decrease of oxidation potential) leads to an increase of KD.
However, the most important result of the experiments is the
confirmation of the sharply reflected dependence of KD upon the acidity of the
solutions. In all experiments, increase of lg[H+] = - pH leads to the increase of
of KD and dependence of lgKD upon pH is practically linear.
Apart from the examined distribution Cpx  Grt , for the
characteristic acidity may be utilized also the coexisting compositions of garnet
and plagioclase which, incidently does not depend upon redox conditions. Not
stopping at this detail [Vlassova & Zharikov, 1975], we present a diagram of
accompanying compositions of garnet and plagioclase (fig.16.11) for some of
the skarns deposits adduced above. It is easily seen that molybdene-wolframite
skarns, wolfram-polymetallic skarns are characterized by parageneses of
aluminous garnets with more acid plagioclase (KDGrt /Pl > 1), while in ferruginous
skarns are usual parageneses of garnets, rich in andradite molecule, with more
basic plagioclases (KDGrt/Pl <1). The constant of exchange reaction may be
simply expressed as
1-XAdrGrt / XAdrGrt : XAnPl / 1 - XAnPl = KD**[Na][H+]2 / [Fe3+] = KDGrt/Pl
where is evident its dependence upon the acidity of the solutions. The
correctness of the decisive influence of acidity on this distribution is seen from

264
the correlations KDGrt /Pl and KDCpx/Grt. On fig 16.12 , this correlation is expressed
in the form of a graphic lgKDGrt/Pl and lgKD Cpx /Grt for some skarn deposits
represented on fig.16.9 and 16.11 A practically linear dependence between
constants confirms the possibility of utilizing them as indexes of acidity of
skarnforming solutions
Two main conclusions follow from the considered correlations. The
first one : the coexisting compositions of clinopyroxene and garnet , garnet and
plagioclases may serve as indicator of acidity of postmagmatic solutions, but,
insofar as acidity of solutions is a significant measure predetermines the
character of the mineralization, coexisting compositions may be utilized to
foretell possibly the mineralization of calcic skarns. Another second more
general conclusion: component distribution between coexisting mineral
metasomatic parageneses depends upon the activity of perfectly mobile
components, arising in these minerals and may serve as indicators of activity
(chemical potentials) of perfectly mobile components in natural processes.
Let us take one more exemple of dependence of the composition of
coexisting minerals upon the activity of perfectly mobile components having an
important significance for understanding the condition of a skarn occurrence.
On fig 16.16 is presented a diagram of coexisting compositions of
scapolite and plagioclase for various skarn deposits, contact reaction and
metamorphic formations. The exchange reaction of distribution of calcic and
sodic end-members between scapolite and plagioclase may be expressed as :
NaAlSi3O8.0.33NaCl + CaAl2Si2O8 + 0.33CaO + 0.33CO3 =
marialite anorthite solution
CaAl2Si2O8 .0.33CaCO3 + NaAlSi3O8 +0.33 NaCl
meionite albite solution
The constant of distribution, reflecting main factors, is expressed in the
form :
XMeScp:/ 1- XMeScp : XAnPl / 1- XAnPl = KDO.[CaO]0.33[CO2]0.33 / [Na Cl]0.33
=KD*[CO2]0.33 = KDScp /Pl

(16.7)
where in square brackets CaO and NaCl activities are taken as constant.
From equation 16.7 it follows that, apart from the influence of
temperature (KDO noticeably depends upon temperature) on the distribution of
calcic end-members between scapolites and plagioclases, an important influence
indicates activity or fugacity of carbon dioxide. Increase of fugacity (real partial
pressure) of carbon dioxide leads to redistribution of calcic end-member from
plagioclase and scapolite. As well known, carbon dioxide fugacity substantially
depends upon pressure and, consequently, upon depth [Korzhinsky 1949 ;
Shmulovich & al.1982] ; therefore the compositions of coexisting scapolite and
plagioclase or constant volume of reaction between their KDSpl is indicative of
depth of formation of corresponding mineral parageneses. As can be seen on the

265
diagram of fig.16.13, for deep complexes, particularly for Precambrian
formations, KD >1, and parageneses are characterized by more meionitic
scapolite with less basic plagioclases. On the contrary, in complexes of middle
or small depth, KD < 1, and in paragenesis with plagioclase (usually oligoclase-
andesite) are found more acid marialitic scapolites.
An experimental research has been made about the dependence of K DScp /
Pl
upon PCO2 [Kotelnikov,1977]. On fig. 16.14 are presented a few results of the
PCO2 = experiments. The main position of line KD at 500oC for PCO2 = 0.3 kbar
and 0.4 kbar may show precisely the dependence of KDScp/Pl upon pressure of
carbon dioxide. On the other side, must be deduced from the diagram a
noticeable (reverse) dependence of KDScp/Pl upon temperature : temperature
increase shifts the equilibrium toward plagioclase. However, for skarn
formations of neighbouring temperature (on data in which is also based, in main
form, the diagram of fig.16.14), the dependence of KD* upon pressure of carbon
dioxide and, consequenly, upon depth is obvious.
It was interesting to try to evaluate the depth range, answering the
change of KDScp / Pl from 0.40 to 4.5, if we suppose that it is linked only with
change of PCO2. It is of course only possible to do so approximately. To the
change of KD in 11.25 times (4.5 / 0.40) answers the change of PCO2 to 1,533
bar (lg PCO2 11.25 = 0.33 lg). If we take a molar proportion of carbon dioxide
XCO2 = 0.2, the change of fluid pressure amouts to 7,665 bar. Further, taking Ps
= Pf and density r = 2.70, we obtain depth range of 28 Km. If we suppose that
fluid pressure is less than lithostatic pressure, the range of depth, answering to
the change of KD from 0.40 to 4.5. For exemple with Pf = 0.7 Ps, the change of
lithostatic pressure amouts to 10,949 bar, which will answer to a depth change in
40 Km. Of course, all these digits are approximate, it is wonderful that they do
not contradict the geological position of the considered prageneses.
Parageneses of calcic skarns are distinguished, grosso modo,
according to the temperature of their formation and alkalinity, more precisely, to
the importance of the chemical potentials of calcicium and sodium in the skarn
forming solutions. Apart from that, the composition of the coexisting minerals is
indicated by the influence regime of acidity of skarn forming solutions (which
has been considered above in detail), redox conditions and exchange of chemical
potentials of iron and manganese. Change of depth does not prove noticeably
influencing parageneses of calcic skarn (except the examined properties of
composition of scapolite and plagioclase), apart from extreme conditions.
First, there is the absence of typical bimetasomatic calcic skarns in
abyssal facies of depth. Secondly, manifestation in conditions of particularly
small depth and high temperature of calcicium rich silicates of the larnite ,
tilleyite, spurrite types.
Let us first consider facies of calcic skarns in dependence upon
temperature and pressure. On fig.16.15 is represented a T-P diagram to which is

266
experimentally related the study of equilibrium in the CaO-MgO-Al2O3-SiO2-
H2O-CO2 system .Experiments in different parts of this complex system were
made by us and other researchers [Zharikov, 1969 ; Zharikov & al., 1977 ;
Bulatov, 1974 ;Shmulovitch, 1973, 1975 ; Harker, 1959 ; Harker & Tuttle, 1956
; Hoshek, 1974 ; Walter, 1963, 1965]]. Some curves have been calciculated by
us from experimental and thermodynamic data. The diagram presented is not a
complete T-P diagram of the system. On it are indidated the separate most
important equilibrium curves. Omitted, for exemple, is a series of
experimentally studied curves in the highest temperature parts of the CaO-
MgO-SiO2-CO2 system with participation of such rare minerals as spurrite,
tilleyite, rankinite. All the experimental curves are established for the condition
in which the the molar fractions of the fluid’s components equal XCO2 =0.2 and
XH2O = 0.8. For the characteristic T-P condition of stability of minerals with
ferric oxide have been adduced calciculated on thermodynamical and
experimental data of equilibrium with participation of andradite, garnet with
40% of andradite molecule and equilibrium Grt 40  Ep20 Are also adduced
curves of solidus of granitic and basaltic melts also for the condition XH2O = 0.8.
Although each curve delimits the corresponding T- P field, it is
expedient to distinguish the following T-P facies of calcic skarns ([Link].16.15) :
[Link]-merwinite
[Link]-melilite
[Link]
[Link]-garnet
[Link]-epidote
The larnite-merwinite facies (I)(which naturally may be subdivided into
larnite and merwinite subfacies)occurs in conditions of high temperature
(>900oC) and small depth, realized in contact with basic intrusions. Typical
skarns in these conditions do not occur (garnet unstable) and mineral
parageneses characterize the skarnic contact hornfelses with local diffusion
fringes.
The monticellite-melilite facies (II), which is also easily subdivided
into monticellite and melilite subfacies, represents a high temperature facies of
essentially calcic [Link] range of the facies = 700-900oC. It is
characteristic of small and hypabyssal depth. The skarn body combines in
contact with basic, intermediate and alkaline intrusions. Together with
typomorphic minerals (monticellite, akermanite gehlenite) are widely spread
usual skarn garnets, pyroxenes and wollastonite. On the whole however, skarns
of this facies have a limited extension.
On the contrary, the following three facies, wollastonite (III),
pyroxene-garnet (IV) and pyroxene-epidote (V) are usually spread skarn facies.
Temperature range : wollastonite 600-700oC, pyroxene-garnet 600-500 (450)oC,
pyroxene-epidote 450 (500)-400o C . Some garnets and epidote are minerals of

267
changing composition, passing from pyroxene garnet to pyroxene-epidote facies
gradually and stretch in temperature (from 50 to 80 oC) then spread intermediate
pyroxene-garnet-epidote skarns ( in which fmGrt>fmEp)), and the epidote develops
on aluminosilicate rocks. Temperature limits between facies in greater or lesser
degree depend upon depth, the digits adduced above correspond to pressure of
1.0 to 1.5 Kbar or depth of 4-6 Km. The determination of temperatures of skarn
minerals on gas-liquid inclusions nicely corresponds to these temperature
garnets [Zharikov, 1968 ; Indukaiev, 1980].
Let us note also that, unlike lesser deep facies I and II, wollastonite (III) ,
pyroxene-garnet (IV) and pyroxene-epidote facies occupy a greater range of
depth, all the field of existing calcic skarn parageneses, hypabyssal and
mesoabyssal facies.
The upper limit of skarn formation occurs in depth of 1.0-1.5 Km,
insofar as with lesser pressures high temperature solutions arise in gaseous
condition and intense high temperature metasomatic processes of the type of
skarn formation are not realized. The lower limit of typical calcic skarn
formation, it is expedient to conduct on the line of stability of wollastonite 3.5-
4.0kb (crossing the line of solidus of granite), which corresponds to depths of
15-16 Km. Middling in composition and ferruginosity between calcic garnets
and pyroxenes stable within all the earth crust, they are aso found in conditions
of abyssal depth facies.
A variety of parageneses of calcic skarns in significant degree is
determined by the regime of alkalino metalliferosity of skarn forming solutions,
[Link] upon the greatness of chemical potentials of calcicium and sodium
in skarn forming solutions.
On fig.16.16 is presented a diagram of dependence upon K and Na
of high temperature parageneses (with wollastonite) of calcic skarns. Insofar as
calcicium and sodium occur only in composition of feldspars and scapolite,
dependence upon alkalinity is reflected in parageneses of periskarn rocks. Initial
compositions : Pl50Sc40Kfs, Cpx, Grt (of intermediate composition), Wo. To
construct the diagram we have taken account of the composition of Scp and
feldspars in dependence upon K and Na. Owing to this diagram, the line
complicates the extreme ext. Scp Pl + Cpx with the extremal correspondences
of composittion Pl46Scp40, Pl41Scp35,etc.
In agreement with the diagram it is possible to distinguish the
following facies of alkalinity (more precisely metallic alcalinity) of calcic skarns
:
[Link]-plagioclase (or simply plagioclase) facies of normal
alkalinity (field I of the diagram). Scapolites are absent in this facies. Usual
paragenesis of pyroxene with plagioclase is in the periskarnic rocks.
[Link]-scapolite (or simply scapolite) facies of increasing
alkalinity (increased Na) occupying fields II and III of the diagram. Field II has

268
a sort of « intermediate » character : it proves to be scapolite, but again stable
paragenesis is Cpx + Pl. Field III reflects typical parageneses of scapolite facies.
[Link]-garnet or orthoclase increased alkalinity (field IV
increased mK, and field V increased mK and mNa). Characteristic of the facies
is paragenesis of orthoclase with garnet in periskarnic rocks, but in field
V,scapolite is found in paragenesis with them.
Parageneses of plagiocase, scapolite and orthoclase facies are usually
highly spread in calcic skarns.
Much more rarely are found parageneses of fields VI, VII and VIII,
distinguished by the presence of wollastonite with scapolite and/or orthoclase in
periskarnic rocks. These are parageneses of high alkalinity, they are well known
in some skarn bodies linked with alkaline intrusions.
Alkalinity facies may also be divided similarly for other facies or
temperature degrees of the skarn process : pyroxene – garnet and pyroxene –
epidote. For the pyroxene garnet, naturally will be absent parageneses of high
alkalinity (with wollastonite). Pyroxene – epidote (and intermediate pyroxene-
garnet-epidote) are characterized by parageneses of plagioclase-epidote and
orthoclase-epidote periore rocks. Facies of alkalinity are usually of the same
type for different deposits, skarn fields and even districts. The conditions of
alkalinity usally remain uniform at all stages of the skarn process.
A final review of parageneses of alkaline skarns allows us to
conclude that they noticeably depend upon the regime of wholly mobile
magnesium, manganese and iron. Of general regularity is an increased
ferruginosity of all skarn minerals according to the process of flow, from the
earlier stages to the last ones, up to the andraditization of exoskarns and deposit
of magnetite, which are not skarn minerals any more but are linked with later
accompanying processes.
Another peculiarity of some chiefly skarn polymetallic deposits
consists in wide expansion of manganese silicates : mixed pyroxenes of the
diopside-hedenbergite-johannsenite series (mangano-salites, mangano-
hedenbergites), bustamite, rhodonite. They are particularly characteristic of
«vein-like » contact-infiltration skarn polymetallic deposits (skarn « pipes » of
Karamazar, Dalnegorsk, Trepchi, state of New Mexico and other districts.
Correlations of magnesian and calcic skarns. We have remarked
above the peculiarity of extension of magnesian and calcic skarns in their
dependence upon stages of the process and the condition of depth. These
peculiarities, to repeat them once again,consist in the fact that at magmatic stage
on all levels of depth on dolomites and other magnesian carbonatic rocks
(magnetite masses and others) are formed magnesian skarns. Calcic skarns in
these conditions do not exist. Limestones recrystallize in calcic marbles. At
postmagmatic stage, the type of skarn formation depends upon depth. In abyssal
conditions in contact with magnesian carbonatic rocks (dolomites,magnesites)

269
appear magnesian skarns. Typical calcic skarns do not occur in these conditions.
Elsewhere, in endoskarn zones appear veines of ferrous clinopyroxenes and
garnets, depositing on magnesian skarns In hypabyssal conditions of depth at
postmagmatic stage and on limestones and dolomites are formed calcic skarns
Typical magnesian skarns do not occur in these conditions Elsewhere on
dolomites (with admixture of silica, clayed matter) in the lower zone of the
calcic skarns arise calciciphyres
The mentionned peculiarities of expansion of skarns are determinded
by the activity (fugacity) of carbon dioxide, by the activies of magnesium, of
calcicium and by the acidity of the solution. The diagrams on fig 10.3 and 10.12
show the influence of the activity of carbon dioxide..Here we give the results of
our [Zharikov & Khodorevskaya, 1987]) experimental study of the dependence
of skarn parageneses upon aMgCl2, aCaCl2, aHCl. An attempt was made to study
boundary reactions between calcic and magnesian skarns : grossular 
forsterite + spinel, and grossular  diopside + spinel in the range of P= 1-3 Kb
at 700oC in reasonable HCl concentations (10-1-10-3). However, it appeared
that in all those attempts, with variable CaCl2, MgCl2 and HCl concentrations,
between the field of grossular and magnesian parageneses (Fo + Sp, Di + Sp) a
field of stability is displayed, « intermediary » in composition, of the mineral
clintonite. Indeed, these correlations completely correspond to the natural
observations, which show that deposition of calcic skarns on magnesian ones
always precede a replacement of magnesian skarns with such minerals as
clintonite, vesuvianite and phlogopite.
Nevertheless, experimental data characterize the principal
correlations between calcic and magnesian skarns in dependence of CaCl2,
MgCl2 concentations (avtivities) and acidity of the solution. On fig.16.17 is
given an experimental diagram of dependence of equilibria : garnet diopside +
clintonite, garnet diopside + anorthite, clintonite forsterite +spinel, clintonite
diopside + spinel upon CaCl2 and MgCl2 concentration in the solutions with
various acidity (mHCl = 0.1M and mHCl = 0.02M). The calciculated dotted line
represents the diopside forsterite equilibrium. There chiefly follows from the
diagram, that increase in CaCl2 activity produces a replacement of the magnesian
parageneses by the calcic ones, and an equilibrated CaCl2 concentration on full
order, an order higher than MgCl2. Acidity decrease shifts the equilibrium in the
field of lesser significance of equilibrated CaCl2 and MgCl2 concentrations.
Thus, the mentionned geological properties of the formation of
magnesian and calcic skarns are determined by the following factors :
[Link] high pressure of carbon dioxide at magmatic stage (XCO2 > 0.6)
and abyssal facies of depth,impeding the occurrence in these conditions of calcic
silicates and aluminosilicates (grossular, wollastonite and specially, high calcic
minerals : larnite, spurrite, tilleyite).

270
 [Link] low pressure of carbon dioxide and high activity of calcicium at
the postmagmatic stage and in hypabyssal and mesoabyssal conditions,
favorable to the occurrence of calcic skarns and their replacement by magnesian
skarns, where they were formed at the magmatic stage.
[Link] skarn formation is favorable a low acidity of the skarn forming
solutions, on which depends the formation of skarns at magmatic and early
postmagmatic stage.

271
Fig. 16.1. Histogram characterizing confinement of skarns to various magmatic
formations (on 120 deposits).

272
 Fig. 16.2. Diagrams of composition-paragenesis for different facies of magnesian
skarns of progressive stage.
a – moderate – great depths (dolomite); b – small depths (periclase); c – small depths
and increasing temperatures (monticellite); d – small depths and high temperatures (melilite).
Hatched line with arrow indicates tendencies to change of composition in metasomatic
columns. Unbroken circles with digits indicate compositions of reacting rocks and
metasomatic zones formed between them.

273
Fig. 16.3. Diagrams of composition-paragenesis of facies of magnesian skarns of
dolomite – peraluminous quartzite contacts.
a – biotite ; b – cordierite; c – sapphirine.

274
Fig. 16.4. Diagrams of composition-paragenesis of magnesian skarns facies
a – hypersthene – cordierite on magnesite ; b – hypersthene on olivinite; c –
hypersthene on contact olivinite and gneiss.

275
 Fig. 16.5. Diagrams of composition-paragenesis for some most typical
postmagmatic (regressive) facies of magnesian skarns.
a - c - facies of great depths: a - phlogopite ; b – pargasite c – phlogopite-pargasite; d
- f – facies of small depths: d – clintonite-spinel; e – wollastonite -diopside; f –hornblende-
grossularite. Tendencies to change of compositions, to composition of zones of metasomatitic
columns and symbols of minerals, as on fig.16.2.

276
Fig. 16.6. Diagram of dependence of parageneses of magnesian skarns upon T-P at XCO2
= 0,6, XH2O = 0,4.
Calculated on experimental data. I-IV – facies of depth of magnesian skarns; V –
parageneses of magnesian skarns at postmagmatic stage. basalt solidus; granite solidus

277
 Fig. 16.7. Diagram of dependence of parageneses of magnesian skarns at
magmatic stage upon chemical potentials of calcium and iron.

278
Fig. 16.8. Diagram of dependence of parageneses of magnesian skarns at magmatic stage
upon chemical potentials of potassium and iron.

279
 Fig. 16.9. Diagram of coexisting compositions of pyroxene and garnet for
different deposits in calcic skarns.
1-tungsten deposit of Ingichka, Uzbekistan; 2-tungsten deposit of Fuyogatin, Japan [Yto,
1962]; 3- tungsten-polymetallic with SnO2 deposit of Maikhura, Tadjikistan; 4 - tungsten-
polymetallic with SnO2 deposit Lost River, Alaska [Dobson, 1982]; 5 – molybden-tungsten
deposit of Tyrniauz, Russia; 6 – tungsten deposit with polymetals and gold, British Columbia,
Canada [Ettilinger and Roy, 1983]; 7 – copper deposits with gold, British Columbia, Canada
[Ettilinger and Roy, 1983]; 8 – copper with tungsten deposit of Darinskoe, Russia [Indukaev,
1980]; 9 – polymetallic deposit, Empire, New Mexico [Burton and al, 1982]; 10 – Turin
copper deposit [Podlesski, 1979]; 11 - polymetallic deposit, Kansai, Tadjikistan; 12 -
polimetallic deposit Tamperico, Italy [Burton et al., 1982]; 13 – copper – iron – deposit of
Milko-Tirnov, Bulgaria [Vassiliev et al., 1964]; 14 - Gorno-Blagodatskoe and Vysokogorskoe
iron deposit , Russia [Podlessky, 1979]; 15 - polymetallic deposit Altyn-Topkan, Tadjikistan;
16 – iron – ore deposit of Gorna Shoria, Russia; 17 – iron –ore with ilvaite and sphalerite
deposit of Kern, New Mexico [Burton et al., 1982]; 18 – iron – ore deposit of distinct of
Fudjay, China [Zhao – Yiming et al., 1982]; 19 – other skarns manifestations.

280
 Fig. 16.10. Dependence of logarithm of distribution constants of iron between
Cpx Grt
xFe x Fe
pyroxene and garnet (KD =  ) upon acidity of solutions
1  xFe 1  x Fe
Cpx Grt

(pH+lgCAl/CMg) on experimental data [Zharikov & al., 1979].

281
 Fig. 16.11. Coexisting compositions of garnets and plagioclases in different skarn
deposits.
1 – tungsten deposit of Ingichka, Uzbekistan; , 2 – tungsten sulfides deposit of
Maïkhura, Tadjikistan ; 3 – molybden – tungsten deposit of Tyrnauz, Russia ; 4 – molybden –
tungsten deposit of Chojruh-Dajron, Tadjikistan ; 5 – Turin copper deposit, Russia
[Podlessky, 1979] ; 6 – Tyshelginskoe, Russia [Miroshnikov & al.,1969]

282
 Fig. 16.12. Comparison of distribution constants distribution of KFeCpx/Grt et
Grt/Pl
KAl as indicator of acidity for various skarn deposits.
Symbols as in fig. 16.9 and 16.11.

283
 Fig. 16.13. Coexisting composition of scapolite and plagioclase

1 – skarn deposit of Gavasay, Uzbekistan ; 2 – skarn deposit of Choirux-Dairon,

Tadjikistan ; 3 – skarn deposit of Ak- Djilga, Kirghistan; 4 – skarn deposit of Lebazhin,
Russia ; 5 – skarn deposit of Sokolovo – Sarbay , Kazakhstan ; 6 - skarn deposit of
Dashkesan, Azerbaidjan ; 7 – skarn deposit of Glafirine, Russia [Solodovnikova, 1964] ; 8 –
phlogopite deposit of Emeldjak [Lazarev, 1963] ; 9 – skarn deposit of Aldan [Marakushev,
1958] ; 10 – skarn deposits of Quebec, Canada [Show, 1960 ; Haughton, 1975] ; 11 – skarns
of Ontario province, Canada [Haughton, 1975] ; 12 – metamorphic shists and gneisses of
Quebec and Ontario provinces, Canada [Haughton, 1975] ; 13 – other skarns manifestations at
small depth [Show, 1960].

284
 Fig. 16.14. Experimental determination of distribution constant of calcium
minerals between scapolites and plagioclase [Kotelnikov, 1977].

285
 Fig. 16.15. Main border minerals in equilibrium of calcic skarns calculated for
condition of X H O  0,8, X CO  0,2 from experimental and calculated data.
2 2

Equations of reaction are described in univariant lines. For reaction with Mt et O2,
oxygen fugacity is taken as f O2  10 20 . Position of granite and basalt solidus melts calculated
for X H O  0,8, X CO  0,2 .
2 2

286
Fig. 16.16. Diagram of dependence of parageneses of calc skarns upon chemical
potentials of potassium and sodium.

287
 Fig. 16.17. Diagram of dependence of parageneses of calcic and magnesian skarns
upon CaCl2, MgCl2 and HCl.
Results of experimental researches at T = 700°C and P = 1 kbar [Zharikov &
Khodorevskaia, 1987]. Unbroken and dashed lines, experimental results at mHCl = 0,1 M and
mHCl = 0,02 M. Dotted line, calculated data.

288
 CHAPTER 17

Greisens

Definition. Greisens are high or middle temperature metasomatic rocks of

quartz-mica, quartz-topaze or quartz-tourmaline composition accompanied by
deposits of tin, wolfram, molybdenum, beryl and genetically akin to
leucogranites. The link of greisens with rare metals Sn-W-Mo-Be
mineralizations is obvious and in the Russian literature the term «greisen
deposits», introduced by [Link], has been generally admitted.. In western
literature a similar notion is absent, and the deposits are designated by an
important metal name (W, Mo, Sn, Be deposits). Originally the term greisen
designated essentially quartz-muscovite rocks, formed through metasomatism of
rocks of granitic composition, sandstones, schists and volcanogenic rocks. The
process of greisen formation is consequently called greisenization. Subsequently
to the term «greisen» was attached a formation significance and under this
designation was understood an aggregate of metasomatites, formed by
greisenization .So the narrow significance of this term is preserved, designating
a rock of a determined mineral composition. Slightly or moderately transformed
varieties are usually called greisenized rocks.
Amongst constant evidence of greisens are found 1) a tight spatial and
genetical link with ultra-acid granites ; 2) a specific collection of rare metals (W,
Mo, Sn, Be, Bi) ; 3) characteristic types of periore alterations, i.e. greisenization,
reflected by the development of quartz, white micas, topaz, fluorite, tourmaline ;
4) high participation in the processes of mineral formation of volatile acid
components : F, Cl, B, S, CO2 [Nakovnik, 1954 ; Shcherba, 1968, Rundqvist et
al., 1971]
Geological setting and correspondances with other metasomatites.
The main geological and-structural features accompanying greisenization are
[Rundqvist et al, 1971]: 1) fringe zones of intermediate massifs of folded
domains; 2) external fringe zones of folded domains; 3) zones of uplifted
internal anticlines of folded domains; 4) zones of internal activization of
domains of completion folding. Granites with which greisens are related, are of

289
postorogenic type. These enter regions of stability, developing diapirs having at
their basis a mantle plume and zones of lesser density in the upper mantle and
lower crust. The interval between completion of the geo-synclinal regime and
intrusion of postorogenic granites reaches 75-100 million years .
Greisenized rocks spread in near-contact zone and in the roof of granitoid
intrusions, mainly in those of higher silicic acid composition. Most greisen
deposits are confined to bodies of granites, small compared with the surface
showings, but the greisens of exocontacts are partially related to dike belts.
The morphology of parts of greisenization in endocontacts, is basically
determined by the shape of intrusive contact, but in enclosing rocks the greisens
are localized in zones of tectonic dislocation.
In most cases, a direct genetic link is not indicated with defined discrete
small granitic intrusions. It is most probable [Omelyanenko, 1978] that
greisenized solutions have a deeper source, and their link with concrete granitic
bodies is paragenetic. The basic lines of the geological position of greisens is
well illusrated, for instance, by the wolfram-molybdenum greisen deposit of
Akchatau in Kazakhstan [Zharikov & Zaraisky, 1995]. This deposit is localized
in cupola parts of a granitic pluton (fig 17.1 and 17.2). According to gravimetric
data the massif has the shape of a lopolith, extending in length on 28 km, in
breath to 12-16 km and in thickness to7-8 km in the central part. The greatest
part of the granite body is deeply hidden in terrigenous deposits of upper
Silurian and in acid and intermediated effusive Carboniferous rocks. The
diameter of the outcropping cupola is nearly 4 Km. It is supposed that the
Aktchatau pluton is mainly composed of coarse grained porphyroid granites at
first phase of penetration (cf.fig17.2). Flat bodies of medium-grained granites at
phase II are concentrated towards cupolas and apical crests of the massif. Fine-
grained granites of phase III form small rods , dikes and more complex bodies of
stepped type in granites of phases I and II [Shcherba, 1960]. In chemical and
mineral composition the granites of the three phases are similar, and are related
to subalcaline leucocratic granites with predominance of potassium and sodium.
Country rocks around the Aktchatau are hornfelsed in the distance of 800 to
1000 m.
About 300 small vein-greisen bodies in general quantities are spread on
all the outcrop of the granite cupola, but predominantly at their periphery. All
the small bodies are confined to the upper near-contact part of the massif and
extend with a thickness not exceeding depth to 40-60 m, but extending to tens
and hundred of meters with a 3m thickness. Their industrial value is of low
importance The basic supply of W-Mo ore at Akshatau are concentrated in a few
coarse veinous bodies at the S-E slope of the cupola. These bodies are controlled
by elongated fractures which have a submeridional direction and steep dip. Ore
veins are characterised by thickness increase in the direction of the contact
surfaces of granite massif with dissociation of one greisen body in a serie of

290
subparallel and fan-like smaller upwards flowing greisen bodies (“greisen
bundels”) [Bogopolov et al.,1971]. The extension of such bodies reaches in
length 2-3 Km, in breadth 500m with a thickness 2-3 to 20-50m. Wolframite and
molybdenite form thin dissemination and also nests and veins, in association
with quartz, phlogopite, beryl, muscovite, topaz, pyrite and dickite. Industrial
mineralization is concentrated in compact quartzic greisens and quartz veins, in
which are localized the richests ores ; riches global reserves are nevertheless
situated in the greisens [Shirkunov, 1981]. Quartz veins, as a rule, occupy an
axial postion in greisen bodies, but some appear later in age.
Thick greisen bodies in granites are modified in the roof zone in series of
thin veins, with formation of linear and net-like stockwork with a productivity
that rapidly falls with distance from contact [Gulyaeva ,1978]. On the whole, in
Akshatau, endocontact bodies within granites rarely predominate , and the rocks
of the roof are weakly greisenized.
Greisenization in Akshatau and other deposits is accompanied by other
metasomatic transformed rocks, for instance, albitization and potassic-feldspath
atization of granites, skarnization, propylitization-albitization and potassic-
fedspathization precede greisenization and occupies wider near-contact domains
in granitic massifs. On the other hand greisenization may extend far away from
the contact by violent fracturation of the roof. Greisens affix themselves on
skarns at the contact of granites with carbonatic rocks. Propylitization at
postmagmatic stage arises later after greisenization at lower temperature and
occupies a greater volume of rock either in exocontacts-or endocontacts of the
granites. A schematic sequence of processes including greisenization is
indicated on fig.17.3.
Facies of greisens and metasomatic zoning. In the mineral composition
of internal zones of metasomatic zoning in greisens, a few facies are
distinguished depending upon the greisenization solution and the replaced rocks.
According to these last criterion, greisens are distinguished into aluminosilicate
rocks (granites, quartzo-micaceous schists, sandstones) and rocks poor in silica
and alumina (carbonates and basic magmatics). In the first group are
distinguished the following facies : quartz-muscovite, quartz, muscovite,
muscovite-feldspar, quartz-tourmaline, quartz-topaze. In the second group are
distinguished only two non- quartzic facies : phlogopite-muscovite and feldspar-
fluorite.
A typical column of metasomatic zoning in apogranitic greisens has the
following aspects : 0) unalterated granite (quartz, calcic feldspar, oligoclase,
biotite, magnetite) ; 1) muscovitized granite (quartz, calcic feldspar, albite,
muscovite, biotite, magnetite) ; 2-3) greisenized granite 2) quartz, calcic
feldspar, albite, muscovite ; 3) quartz, calcic feldspar, muscovite) ; 4-6 ( greisen
(4-quartz, muscovite ; 5-quartz, topaze, 6- quartz). Topaze and monoquartzic
zones are frequently absent. For exotic products of greisenized limestones

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zoning is different : O) limestones ; 1) calcite, fluorite ; 2) fluorite, muscovite ;
3) fluorite. However, in the products of limestone greisenization are present
albite and phlogopite.
The greisen bodies of Akshatau cover a well expressed lateral and vertical
metasomatic zoning [Bogopelov et al.,1971]. In axial parts of all big ore bodies,
traditionally named at Akshatau « ore veins », is established a monotypic
replacement by compact quartz veins, passing vertically upwards to porous
quartz greisens, then to quartz-topaze and quartz-muscovite greisen (fig 17.4). In
the limits of greisen bodies basic industrial ores occupy a determined
hypsometric level, delimited by a zone of development of compact quartz
greisen and by the he lower part of quartz-topaze greisen, but above and
beneath mineralization is weaker. In a longitudinal projection of this so-called «
ore belt » [Tchukrov, 1960], it has the aspect of a near-horizontal ore lens.
Vertically it totals 150-200m, and moreover, in axial quartz veins, industrial
mineralization extends to 20-50m, higher than in the greisens surounding them
[Bogopelov, 1992].
Lateral metasomatic zoning in all basic ore-producing horizons within the
« ore belt » has an unique stucture (fig. 17.4b). The body’s central part
immediately contiguous to the axial quart vein is composed of a mineralized
compact quartz greisen, replaced in both directions by ore-free quartz-topaz
greisen and quartz-muscovite greisen, greisenized granite replacing leucocratic
granite. In the upper, supra-ore part of the greisen body ( cf. fig 17.4.A) an
internal zone of quartz greisen is lacking and the lateral zoning has the following
structure :
Quartz Qtz-Toz Qtz-Ms Greisenized Leucocratic
vein greisen greisen granite granite
0 0.55 1.0 14m

In the lower sub-ore horizons (cf. fig. 17.4, C), the quartz-topaz zone of
the greisen falls, but the thickness of the other zones, particularly the quartz
greisen zone, increases [Gotman & Malakhova, 1965].

Quartz vein porous quartz Quartz Greisenized Leucocratic

O greisen muscovite granite granite
9.5 greisen
10,5 > 14 m.

Total thickness of strictly greisen zones (without greisenized granites)

usually varies from 10-20cm to 1-2m. Relatively weak lateral zoning, apparently
due to diffusion. Vertical and longitudinal zoning of big greisen bodies, is
measured in tens and hundreds of meters, undoubtedly linked with infiltration.

292
 Chemistry of greisenizing process. In greisenization two extreme cases
are observed: 1) process with accumulation of silica ; 2) process with
accumulation of alumina.
In the first case, the quartz content increases in the rocks, for instance,
from 30-35 volume % in granite to 70-90 % in quartz-topaze or to 60-80 % in
muscovite-quartz greisens. To this are related removal of alkali, alumina, but
also calcicium, magnesium and iron. Alumina accumulation leads mainly to the
formation of muscovite or of topaz greisens. In these cases, quartz content in
rocks approximates 9-10%, but muscovite and topaz content reaches 70-90%.
Apparently, alumina accumulation may promote as decrease in acidity of
greisenized solutions.
Caculated addition or substraction of rock-forming components for the
Akshatau deposit, based on data of grid-sampling [Gotman &Malakhova, 1965 ;
Zaraisky et al.,1994] show that granitic greisenization induces steady
substraction, from all zones, of Na2O and K2O, addition of SiO2, Fe, F, H2O,
CO2 and rare metals. Alumina is substracted in great amounts from the lower
parts of the greisenized body and redeposits in the upper parts, at the level of
development of quartz-topaz and quartz-muscovite greisens in axial zones of big
greisen bodies (17.5)
Physico-chemical conditions of mineral formation. Physico-chemical
conditions of greisenization were studied in detail and are exposed below in the
example of the Akshatau deposit. They rather well characterize the typical
greisenization processes [Zaraisky et al., 1994].
Temperature evolution. On data of two-feldspar and oxygen-isotope
geothermometry, T of crystallization of I, II and III phases of leucogranite
intrusions amounts to 750, 700 & 650 oC (± 50 oC) Formation of chambered
pegmatite arises between 620 and 560 oC ( ±40 oC). Comparison of results on
oxygen isotope distribution in mineral greisens and ore veins of Akshatau
[Korotaev et al., 1988 ; Zharikov et al., 1982] with data on fluid inclusions
[Doroshenko & Pavlun, 1981 ; Korotaev & Matveeva, 1989 ; Reif, 1990]
permits rather definitely to say that the formation of greisens and the localization
of W-Mo mineralization, on the whole, occupies the high temperature interval
between 550 and 350 oC. Quartz veins are formed, on average, at 60oC lesser
than the greisens they contain. Temperature of 350oC, apparently, indicates the
lower limit of the Akshatau proper greisen-ore stage by deposition of the
principal mass of rare metals (W, Mo, Be, Bi, Sn) Lower temperatures (350-
150oC) are related to terminal sulfide stages of ore processes in the course of
which may arise also some recrystallization of earlier W-Mo ores [Bogopelov,
1979,1992]. On the basis of mineral paragenesis of contact hornfelses it is
possible to suppose that their formation in a thermal field of granite massif
arises at temperatures from 450 to 350 oC.

293
 Pressure evolution. On paleolithological reconstructions, structural and
morphological properties of granites, the thickness of rocks of the roof at the
time of formation of the Akshatau pluton is evaluated by various authors from 1
to 4 km, which correspond to a lithostatic pressure of 0.3 to 1.0 kbar
[Shcherba,1960 ; Rare metal mineralization, 1988 ; Nergei, 1983]. On
calciculated data of F.G. Reif, [1990] founded on P-V-T correlations in melt
inclusions in the quartz of the granites, the fluid pressure in deep residual focus
at the beginning of phase III intrusion attained 4.2 to4.8 Kbar. However, a
systematic study of fluid inclusions in veins of mineral ore bodies of Akshatau
[Doroshenko & Pavlun, 1981 ; Pavlun, 1984 ; Korotaev et al, 1994] indicates
that the fluid pressure in the course of the main ore stages periodically varied
from 1.6 to 0.5 Kbar, and at later stages decreased to 0.2 Kbar. At the same time
[Korotaev, 1994] is also displayed a group of high density inclusions with P
from 0.8 to 2.8 Kbar, homogenized in the liquid phase in the narrow temperature
interval of 350-400 oC.
All the determined data, possibly do not contradict one another but reflect
a complex evolution of the fluid-magmatic system. If we take that the Akshatau
intrusion was formed at depth of about 3 Km, fluid pressure in its upper part
could approximate the lithostatic pressure and reach about 1 kbar. In the deep
part of the intrusion pressure attained 2-3 Kbar end could rise even higher at
retrograde boiling of the magma, and thus oscillate as a result of the system
deconfinement.
Fluid regime of mineral system. On data of F.G. Reif [1990] the initial
water content in melt phase I of the Akshatau granite massif increased and
attained 4.5 ± 0.5 weight %. It increased even more due to the crystallization
differenciation of the magma and attained 5.2 ± 1.2 weight % in phase II and 6.7
± 1.5 in phase III. Salinity of this magmatogene fluid was insignificant. On data
of cryometry of peculiar fluid inclusions, it is limited to 13-23% eq. NaCl. It is
supposed that the chief saline components are Na and K chlorides and fluorides,
but admixture of Mg, Fe, Ca, Li chlorides all in all does not exceed 1 %. The
basic fluid consists of water containing CO2 and insignificant quantities of other
gases. Apparently in magmatic fluid, chlorine predominates on fluorine,
although the role of fluorides was also important, as evidenced by tentative
evaluations of HF concentration (0.2-0.8 m) in rock-forming biotites [Zaraisky
et al., 1994]. Due to granite crystallization, HF content in the residual melt has
increased. At the same time the activity of melt and of the aqueous fluid in
equilibrium with the melt increase and determine the evolution of the Si/Al and
(Mg + Fe)/Al ratios in biotites from phase I to phase III. On the basis of Fe and
Mg distribution between biotites and super critical chlorid fluids, it is possible to
conclude that the Akshatau magmatogene fluid was characterized by a high
Fe/(Fe + Mg) ratio extending from 0.85 at crystallization of phase I to 0.90 at
crystallization of phases II and III. We may also confidently speak of an

294
increasing Mn activity in the melt and in the fluid in equilibrium on the basis of
its noticeable content in biotite (up to 2.6 weight % MnO) and especially in
ilmenite (up to 24 %).
In magnetite, ilmenite and titanomagnetite of all phases of leucogranites,
W often occurs in quantities sufficient for microprobe determination (up to 0.1-
0.2 weigth % WO3 in phase I and 0.3-0.5 in phase III). Even higher WO3 is
measured in accessory ilmenorutile (1.3-1.4 weigth %) and rutile (0.4-0.8 weigth
%) from dykes of microgranites.
Entry of wolfram into primary minerals of Akshatau granites and their
enrichment in accessory minerals of later differentiates of magmatic chamber
unravels its concentration in granitic residual melts and permits to suppose an
orthomagmatic behaviour of the wolfram.
Postmagmatic solutions have a fluorid-chlorid-calcic-sodic composition
and high saline concentration (table 7.1). Similarity of composition and
concentration of magmatic and ore-forming hydrothermal fluids may serve as
indicator of their genetic kinship and evolutionary inheritance. Laser-ablation
analysis of fluid inclusions in quartz and fluorite from quartzic and quartz-
topazic Akshatau greisens reveals high concentration of W (up to several g/l), of
Mo (up to 0.7 g/l) and the presence of Cu, Zn, B and Ti [Basheev & al., 1986 ;
Reif, 1990]

Table17.1. Succession and physico-chemical parameters of mineral formation

in ore bodies of Akchatau deposit after data of study of fluid inclusion
[Doroshenko & Pavlun, 1981 ; Pavlun, 1984 ; Pavlun & Simkiv, 1982]

%mass
Mineral T°, C P, bars Fluid composition concentration,
association eq. NaCl+KCl
Molybdenite- 440–320 1200–1000 Chloridic- 41–27
quartz hydrosilicato-
sodic
Rare-metals, 480–300 1600–700 Fluoridic- 65–30
molybdenite- chloridic-potassic-
wolframite- sodic
quartz
Pyrite- 415–260 750–500 The same 48–28
wolframite -
quartz
Galenite- 310–150 550–350 Hydrated Not high
sphalerite- carbonic-acid-

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quartz hydrocarbonic-
sodic
Phlogopite- 180–80 ~200 Substantially Low
quartz hydrated, potassic
Zeolite-Quartz 60-20 ~200 Idem Low

Analysis of regular minerals formed at magmatic and postmagmatic

stages of evolution of the ore-magmatic Akshatau system leads to the conclusion
that the occurrence of acid greisenized fluids enriched in F, Cl, B and other
volatile acid components do not arise at the earliest, but at sufficiantly advanced
stages of crystallization of the granite melt. This was already observed by G.N.
Shcherba [1960], who stressed the special role of the coarse-grained granites of
phase II, after emplacement of which in Akshatau began an active hydrothermal
regime. F.G. Reif has established that there is lacking of independent fluid
inclusions in quartz of phases I and II, and first appears together with melt
inclusions in veins of derivates of phase II and especially in products of phase
III [Reif, 1990]. Replacement of the main products of the rare-metal stage of ore
deposition (W, Mo, Be, Bi) by much later sulfide-quartz (Cu, Zn, Pb Bi) is
acccompanied by replacement of highly concentrated fluorido-chloridic
solutions by more diluted chlorido-hydrocarbonatic ones, carbon dioxide
enriched (cf. table 17.1) [Doroshenko & Pavlun, 1981]. Fluid pressure then falls
to 550-380 bar, temperature decreases to 310-150 oC.

Greisens and metallization. Greisens are related to industrial

concentrations of tin, wolfram, molybdene, beryllium, lithium and bismuth.
Mineralizations of tantalum, niobium, zirconium and rare earth elements,
formed in greisenized rocks, are linked with earlier processes of albitization.
Formation of minerals occurs at various stages of the process of formation of
greisen-ore bodies and with a decrease of acidity and temperature of the process.
The evolution of the greisen-ore process is examplified by Akshatau for which
have been ptoposed models of evolution of a thermal field around and inside a
cooling granite pluton. The results of modelling have permitted to evaluate the
duration of the greisenization process and related ore-deposits (table 17.2)

296
Table 17.2. Life-span of evolution of the ore-magmatic Akchatau system (model
of innermeasured differentiation of thickness of roof over granite cupola 1 km,
introduction of II phase after 150000 years and initial temperature of granite
melt 700° C)

Geological events and processes Time,

in 1000 years
0
Intruduction of phase I
Introduction of phase II 150
Introduction of phase III 180
Completion of crystallization of phase III 200
Formation of greisens: beginning 200
end 300
Formation of quartz veins and: beginning 220
tungsten-molybdene mineralization end 320
Completion of crystallization of phase II 320
Completion of crystallization of phase I 570
Sulphido-quartzic stage: beginning 300
end 1000
Fluorite-quartzic and zeolite-quartzic stages >1000

Thus, greisens are formed as a result of a hydrothermal high-temperature

process of acid metasomatism with high activity of fluorine in the solution, and
a strong link with post orogenic granitic magmatism. Greisenization follows
albitization of granites, skarn formation, and precedes deposition of ore
mineralization.

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 Fig. 17.1. Geological outline of Akchatau ore field.
1 – low Permian leucocratic granites of the Aktchatau complex (outlet cupola on
surface); 2 – contour of the Akchatau intrusion at depth, on collective data of gravimetric
survey ; 3 – adamellites C2-3 ; 4 – sandstones, schists, conglomerates S2 ; 5 – lavas and tufas
of andesites, dacites, liparites C1 ; 6 – acid effusive C2-3 ; 7 – limit of contact aureole of
hornfelses on surface ; 8 – tectonic break ; 9 – zone of deep fracture on geophysical data ; 10
– greisen deposits ;
I – Aktchatau, II – Aksay ; A – B line of geological cross-section.

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 Fig. 17.2. Schematic longitudinal geological A-B cross-section (cf. fig. 17.1) of the
Akchatau granite pluton, on collective geological, exploratory and geophysical data.
1 – coarse- grained granites of phase I ; 2 – middle- and fine-grained granites of phase
II and III ; 3 – terrigenous and volcanogenous enclosing rocks ; 4 – crystalline rocks of
precambrian basement ; 5 – ore bodies ; 6 – contact hornfelses.

299
Fig. 17.3. Outline of evolution of acidity and temperature of postmagmatic solutions in
time.

300
 Fig. 17.4. Schematic lateral and vertical metasomatic zoning of main industrial
greise bodies of Akchatau.
1 – medium- grained granites ; 2 – greisenized granites ; 3 – quartz-muscovite greisens ; 4 –
quartz-topaz greisens ; 5 – dense quartz greisens ; 6 – porous quartz greisens ; 7 – quartz-ore
veins ; 8 – limits of metasomatic zones (a – sharp, b - gradual) ; A, B, C – levels of greisen
bodies with different types of lateral zoning.

301
Fig. 17.5. Addition – removal of components at greisenization.

302
 CHAPTER 18

Propylites and propylitized rocks

Definition. We call propylitized rocks greenstones who have suffered

hydrothermal transformation. Unlike this wide notion, “propylites” have a quite
definite petrographic significance: this is hydrothermal transformation of green
andesites. Often, however, are called propylites generally any propylitization of
rocks. Some authors choose a shorter term, and sometimes they mix up these
notions and use the term propylite in different senses. To avoid confusion it is
better to indicate which of them is meant.
Rock propylitization may form as a result of various processes 1)
greenstone metasomatism of vulcanogene masses in regions of deposition of
non-ferrous and noble metals (“propylites” in the terminology of [Link]);
2) hydrothermal metasomatism of the argilization type in domains of active (and
paleo-) volcanism, in which in deep zones of argilization together with clay-
minerals are formed adular, albite, chlorite, in places also epidotes
[Naboko,1963]; 3) a weak transformation of the rocks in the outer zones of
periveinous acid metasomatism of the beretization and argillization type
[Nakownik,1954]. Moreover, [Link][1970] identifies rock
propylitization with products of regional metamorphism of greenschiste facies
based on affinity of mineral composition.
In all the enumerated types of processes, greenstone rocks are
formed under the influence , principally, on magmatic rocks (but also on certain
sedimentary) of feebly aggressive hydrothermal solutions from feebly acid to
neutral at temperature in the range of 200-350°C. The narrow interval of
variation of the external condition determines the generality of mineral
composition and similarity of outer appearance of those greenstones formed in
these processes. However, the peculiarities of geological position allows us to
distinguish marked types of metasomatism from one another. In the first
instance these distinctions are correlated with magmatism and ore deposition,
which is clearly visible on the example of the various propylitzed rocks and the

303
products of regional metamorphism. Propylitization is linked with intrusive
hypabyssal and subvolcanic granitoids and their postmagmatic hydrotherms
[Korzhinsky, 1948; Zharikov, 1959]. Within propylitized rocks are included
zones of acid metasomatites and ore veins, but on the outer contour they border
with unchanging (feebly changing) enclosing rocks. Unlike these, products of
regional metamorphism, facies of green schist are included in regional
metamorphic belts, no direct links are displayed with granitoid intrusions;
regularly in them, ore depositions are formed in geological processes, not
directly linked with immersion metamorphism. Rocks of greenschists facies
border, on one side, with a prenite-pumpellyite or zeolitic, but on the other side,
with an amphibolitic facies. Regional metamorphism arises with much lower
CO2 fugacity than the popylitization, under whose influence in metamorphism
are stable prehnite and pumpellyite, uncharacteristic of propylitized rocks
[Logininov & Rusinov, 1974;Rusinov, 1989].
During argilization of domains of active volcanism and outer zones of
periveinous acid metasomatism are also formed rocks similar in mineral
composition with the propylitized. However, they, forming an outer aureole
around strictly argilizites or berezites, do not prove characterized products of
corresponding processes. They are only the result of the influence on the rocks
of “exhausted” solutions losing their character. The main characteristic products
of volcanic hydrotherm influence are facies of argilized rocks essentially
consisting of clayed minerals, zeolites, opale, quartz and relict minerals. Such
facies characteristic of the products of periveinous acid metasomatism may be
quartz-sericite, quartz-kaolinite-alunite, quartz-sericite-carbonate etc. forming
the inner zones of periveinous metasomatites.
Thus, the products of the enumerated processes, except the first one
(Richthofen’s “propylites”) prove to be facies in the composition of an ensemble
(formation) of argillized, berezitized and other rocks. Geologically independent
formations are propylitized rocks in ore fields. They form the greatest volume of
the rocks, usually comparable with the dimensions of the ore field, coinciding
with small intrusions of porphyre granitoids formed in the process of their
introduction, and after hardening they include ores of non-ferrous and noble
metals and precede metal deposition. The ensemble, or formation of such
propylitized rocks include a series of facies, distinguished in dependence upon
composition of the initial rocks, temperature, oxygen fugacity and activity of
calcicium, sodium and magnesium. This complex of propylitized rocks, formed
as an independent formation, presents the greatest interest for the study of a
specific metasomatic process, propylitization and its products as hearths of
enclosing mineralization. They receive therefore the main attention in the
following exposition.
Propilitized rocks of various genetic types are composed of albites,
chlorites, calcites and quartz. Usually they contain either pyrite or magnetite. In

304
medium temperature facies, moreover, there is typical epidote, actinolite and
biotite. In near-surface high-gradient conditions at along with epidote, there may
deposit prehnite and calcic zeolite (usually laumontite). They are quite often
found in small quantities of sericite or hydromica replacing feldspars and
chlorites. In feebly propylitized rocks olivine and orthorhombic pyroxenes are
replaced by serpentine. In epithermal gold-silver deposits amid intensively
propylitized rocks are present zones of adularization in which albite is mixed
with calcic feldspar. [Link] [1965] has related adular-containing propylites to
the “advanced phase” of propylitization. Apart from new mineral formations, in
the composition of propylites occur also relict minerals of magmatic initial
rocks, preserved owing to slowness of chemical reaction.
Geological setting. To the analysis of the geological position of
propylitized rocks has been devoted an abundant literature [Korzhinsky, 1948,
1963; Nakovnik, 1954; Zharikov , 1959; Vassilievsky, 1970; Russinov,
1972,1989]. The complication of the characteristic geological setting of
propylitized rocks consists in the fact that, as remarked above, rocks with
analogous mineral compositions are formed in various hydrothermal processes.
Their varieties, occurring in the ore fields, starting with a progressive stage of
hydrothermal magmatic process, i.e. at a time of advancement of a magmatic
front, and isotherm surfaces, in the enclosing rocks were emitted in a genetically
sole ensemble, or formation, of propylitized rocks [Rusinov, 1989] distinguished
from other rocks of similar composition by the geological conditions of
formations.
Formation of propylitized rocks begins parallel with magmatic
replacement of enclosing series, but a zone of corneification of enclosing rocks
separates this formation from the magmatic contact. . At a magmatic
(progressive) stage resulting from the process of propylitization a vertical zoning
is formed, in which a deep zone, close by a hornfels, is composed with biotite-
actinolite, or biotite-epidotite, more rarely epidote- aktinolite or albite-calcite-
chlorite facies. Moreover, a deep, high temperature zone is formed at the
expense of the upper one. Biotitization spreads upwards along cracks in the form
of steeply diping linear zones in epidote-chlorite facies, moreover chlorite and
albite of the upper zone are replaced by biotite and actinolite. An example of
such interrelated facies of propylites in the gold ore deposits of Mnogovershinoe
in the lower Amur Basin is shown on fig.18.1.
Propylites at the progressive stage characterize copper and molybdeno-
porphyric, tin ore and epithermal gold and gold-silver deposits, linked with
granitoid magmatism. Propylitization proves a pre-ore process and occupies a
great volume of the rocks owing to encounter of meteoritic groundwaters
reheated by fluids of magmatic origine. After crystallisation of the magmatic
chamber and replacement of the progressive by a regressive regime in the ore
fields a circulation continues of hydrothermal solutions whose temperature

305
decreases in time. Therefore isotherms change downwards and low temperature
associations of hydrothermal minerals superimpose themselves on earlier, higher
temperature ones. Then the associations, characteristic of propylites, may
develop into skarns and hornfelses. Such propylitization at regressive stage,
corresponding to that of increasing acidity in [Link]’s terminology,
continues the propylitization of the progressive stage, but may also appear
without it. As examples of products of “exclusively regressive” propylitization
serve propylitized rocks in ore fields of pyrite deposits, facies of “feeble”change
in the outer zones of periveinous zoning or deep zone of hydrothermal
argilization in geothermal domains of active volcanism.
The geotectonic position of propylitized rocks is highly multiform. In
risings of ocean bottom have been studied transformations of basalts, in which
plagioclase is replaced by feldspar, pyroxenes by chlorite, smectite and calcite,
but glass by smectites, chlorite and calcite. We also find high temperature
association with epidotes and actinolite and albite. Investigations of their
appearance in deep water drilling did not reveal, however, any characteristic of
propylites of the zoning, such as propylitization of rocks of oceanic bottom
occurring in very feeble vertical gradient of temperature. Formation on
plagioclase of potash feldspar instead of albite may supposedly be linked with
the influence of the composition of sea water on the temperature of plagioclase
replacement by those or other feldspars [Rusinov, 1983]. In the form of
appearance and geological setting, this aspect of metasomatism presents itself as
specific process of transformation of basalts of oceanic bottom in rift zones and
is not related to the formation of propylitized rocks in conformity to the data
defined above.
In volcanic masses of initial geosynclinal depression spilitization
processes appear widely similar in chemism to propylitization, but in geological
setting and facies peculiarities relate to products of regional metamorphism. An
approaching situation is observed in volcanic depressions of insular arcs, where
are whole horizons of volcanogene sediments, chiefly pyroclastic rocks
transformed into “green tufa”. To the latter has been devoted an abundant
literature concerned with Pacific insular arcs, in the first place Japanese and
Kuril islands. These rocks compose stratified horizons of acid pyroclasts
stretching on tens and hundreds of km. Magmatic minerals in them are replaced
by albite, zeolites, chlorite, clayed minerals (smectites, mixed-layered minerals,
hydromicas), calcite. In a lesser measure green tufas are characterized by
prehnite and epidote. Horizons of extrusive subvolcanic bodies of dacites and
rhyolites accompanied with aureoles of chlorite-calcite or epidote-chlorite
propylites and ore mineralization of epithermal or pyrito-polymetallic type.
Prehnite and epidote, other minerals of green tuffa, may appear in a lesser
measure. These horizons are cutted by subvolcanic bodies of dacites and
rhyolites, associated with an aureole of chlorite-calcite or epidote-chlorite

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propylites and an epithermal or pyrite-polymetallic mineralization Supposedly
these green tufas arise in island – arc volcanism of contrast – differenciated type
in young continental crust owing to activization of seawater, impregnating
horizons of pyroclasts at regional warming up of the territory. Warming up is
linked with lifting and evolution of mantle diapir, whose final derivatives are
acid subvolcanic intrusions. Thus, geologically, these formations are not related
to that of propylized rocks. Most likely, they may be considered as interstitial
between products of synvolcanic argilization and regional metamorphism of
zeolite and prehnite-pumpelyite facies.
As a matter of fact the familly of propylitized rocks, defined above,
is characteristic of the orogene stage of crust development in the region of
continental margins, island arcs, zones of intercontinental tectono-magmatic
activization. Propylitization accompanies conclusive stages of formation of
volcano-plutonic associations, comprising granitoid intrusions which have
entered the volcanic mass. Usually all varieties of magmatic rocks in a region
undergo propylitization independently of the difference in age, but sometimes
young dykes are found most of them of basic composition which have entered
after propylitization of the mass and are not affected by alterations.
Propylitization is not genetically linked with concrete intrusive massifs, but with
time it approaches introduction of granitoid porphyric intrusions. This is attested
by temperature zoning with increasing temperature towards the contacts and
within intrusions up to epidote-actinolite facies.
Mineralization is applied on propylitized rocks usually in the form
of intersecting veins or veinous zones, accompanied by periveinous
metasomatism of berisitization, adularization and argilization types. The most
characteristic aspects of mineralization in propylitized rocks are the lead-zinc,
copper-zinc, silver-polymetallic, gold-silver, porphyric copper-molybdenum,
etc. In most cases mineralization is a noticeably younger process than
propylitization and differs from it by the occurrence of acid metasomatism,
which proves properly a peri-ore, periveinous process, only a little forestalling
ore deposition. In other cases mineralization appears in propylites in the form of
zones of metasomatic sprinkling and veins, such as, for instance, in the Round
Mountain mine (Nevada). Zoning of propylites and position of mineralization in
them in this deposit is indicated on fig.18.2.
To propylitization are subject tufas of rhyolites of the Round
Mountain series (26,7 million years old). Propylitization are replaced by more
local processes of adularization, but at the moment of replacement there has
deposed a great mass of gold mineralization. Age of this mineralization is less
than 2 million years of enclosing tufas [Sander and Einaudi, 1990]. In the given
case mineralization was closely linked with propylitization and close to it in
time.

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 Minerals of propylitized rocks. Chlorites in propylitized rocks have an
intermediate Mg-Fe composition within the daphnite-clinochlore serie and
differs from ore chlorites, which are characterized by high ferruginosity
(fig.18.3). Diversity reigns not only in composition but also in structure:
propylitic chlorites are formed in structure packets of IIb97 type and possess a
monoclinic system, but the ore chlorites are built from orthogonal packets of the
1a90, 1b90 types and sometimes instead of them is present berterite (7A-
chlorite-like phase). The enumerated varieties of chlorites are diagnosed by X-
ray and electron diffractometry analyses. On diffractogram monoclinic chlorites
have a noticeable peak of first basal reflection around 14A, with orthochlorites
this peak is reduced, but with berthierites it is generally lacking.
Correspondences of intensity of peak of the first three basal reflections of the
various groups of chlorites is indicated on the diagram (fig.18.4). Electron
diffractograms show that the reflexions relative to oblique textures are also
different.
Magnesium content of chlorites in association with iron minerals is
regulated by sulphur and oxygen fugacity. As a result of thermodynamic
calciculations [Brindzia and Scott, 1978] in paragenesis with hematite may exist
chlorite with a content of not more than 20%, iron, with pyrite not more than
60%, but with pyrrhotite variations of magnesium content of chlorites are
unlimited. Additional limitation on the composition of chlorites imposes
participation in paragenesis with them of ilmenite or magnetite: with magnetite
(with rutile) stable chlorite content is from 20 to 40% ferrous end-member, but
with ilmenite, greater ferruginosity up to daphnite. It is possible approximately
to estimate the condition of chlorite formation on the diagram of fig.18.5, on
which are tentatively indicated the limits of propylitization parameters. It must
be taken into account that calciculation of equilibrium composition of chlorites
was produced in accordance with reactions with participating andalusite. In
natural propylitic associations that mineral is absent, but alumina may get mixed
up with albite. This circumstance insignificantly displaces the isolines of
magnesianity of chlorite on the diagram at the expense of alteration of free
energy of reaction, but the correlation of fugacity is, in principle, not altered.
More substantial displacement of composition in the direction of increase of
chlorite ferruginosity may anticipate their equilibrium with biotites, but in
propylites this is of rather rare occurrence: more often these minerals are found
in reaction relations.
Upper T-limits of chlorite stability are estimated on data of [Eugster
and Wones, 1958] at 525°C for water pressure of 2 kb with magnetite-hematite
buffer, 600°C with QFM buffer and 650°C with MW buffer. Products of chlorite
decomposition are quartz- hercynite and magnetite (or fayalite). These
parameters have been confirmed by the works of [Turnock,1960] in which as
intermediate products to chlorite synthesis there arise metastable 7A phases.

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Their passage to the stable 14A structure of monoclinic chlorite occurred at
more than 450°C for the Mg-chlorite and 525°C for Fe-chlorite compositions.
At high water pressure (Pt being equal) of 3,5-10kb chlorite decomposited to
enstatite, forstetire and spinel at 768-830°C [Fawcett and Yoder, 1966]. On the
side of low significance of T the field of chlorite in these experiments was
limited by the occurrence of smectite whose quantity increased in the interval
between 425° and 350°C. Below these temperatures chlorite was absent. In
natural conditions the limits of stability of chlorites varied in the domain of low
temperature because of multicomponent natural systems and possibilities of
formation of products (e.g. actinolite, biotite and muscovite) at lower
temperature than in the experiments.
The limits of chlorite stability depending on the environment’s
acidity have not been experimentally studied. Geological observations have
established that in acid metasomatism Mg-Fe chlorites mix with sericites with
substraction of magnesium more easier than in Fe chlorites, which can be
preserved in sericitized rocks. The least pH height may be tentatively to
estimated starting from the assumption that chlorite is sericitized with
approximately the same acidity as albite. Then at a temperature of 300°C and
[KCl]=0.1M [Ivanov, 1973; Khemli, 1965; Zarikov et al., 1976] the acidity
index of chlorite decomposition is equal to pH=4.
Epidotes. In the composition of propylitic epidotes are observed
high variations of correlation of iron and aluminium from clinozoisite to
pistacite. The average height of epidote ferruginosity from low temperature
hydrothermal formations amounts to 0.2 [Kepezhinskas & Khlestov, 1971],
decreasing in propylites to 0.15, but increasing to 0.35. Manganese epidotes, as
a rule, are not formed in propylites: manganese content does not exceed 0.02
formular units. Other admixtures are immaterial. Analyses of epidotes published
in literature often contain a small quantity of manganese and alkali which in
most cases are made conditional upon pollution of trial by other minerals
(usually chlorite, sericite) or poor-quality analysis. [Link] and
[Link] [1971] mention the possibility of limited heterovalent
isomorphism of the 2Ca=Na +TR or Ca +Al=Fe +Ti type which however with
propylitization are practically unrealizable.
The limits of Al=Fe isomorphism in epidotes on geological observation
extend to a higher temperature [Miyashiro & Seki, 1958; Kepezhinskas &
Khlestov, 1971]. Available information on fields of epidote stability, apparently,
are related to the influence on fields of synthesis, to the extent that it strongly
depends upon condition and kinetic reaction. So, upper limits of temperature of
epidote stability depend upon composition of initial matters in the experiments
[Merrin, 1960]: epidote is synthesized from stoichiometric glass mixture
(Si02)+Ca(OH)2+Al(OH)3+Fe2O3. In experiments with anorthite +wollastonite+
gehlenite+ quartz+water mixture [Myer, 1960] at 2 kb the equilibrium shifts to a

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higher temperature, which only decreases with abundance of quartz.
[Link] and [Link] [1971] adduce a crooked expansion of
epidote on Ca+garnet+ anorthite + hematite having a steeper slant compared
with the preceding data.
About propylitization the lower limits of epidote stability are informative.
To which correspond, according to data [Liou & al., 1983], epidote + garnet =
prehnite + hematite equilibrium. Between the fields of these parageneses the
authors’ works mention a “transition zone” in association with epidote + garnet
+ prehnite which in reality constitutes a domain of metastable transition. Thus,
the results of all experiments with epidote participation depend upon kinetically
corresponding reactions, which permits to suppose a greater energy of activation
of the latter.
Evaluations of stability parameters of natural epidote confirm
experimental data on the upper limit of its stability, but indicate a lower
temperature of the lower limit. In holes on contemporary geothermal fields
formation of epidote is fixed to the minimal temperature of 146°C in depth of
2,2 km (Reikyavik) and 232°C in depth of 450 m (Khveraherdi) [Sidvaldason,
1963], 200°C in depth of 600 m (Vairakei) [Steiner, 1965] and in other regions
for temperatures between 180 and 200°C and higher in depths more than 500m.
There develop two morphological varieties of epidote, forming in various
conditions: 1) prismatic epidote, grain aggregates to which are mixed
plagioclase and other calcic minerals and make up veins; 2) needle-shaped
epidote in the form of small crystals sparsely disseminated in the rock,
principally growing in cavities. The first variety is the usual metasomatic
epidote, characteristic of propylites, in equilibrium in the solution. The second
variety are metastable skeleton crystals, growing outside the field of epidote
stability in case of missing competition with stable phases in free expansion.
Epidote, encountered at depth of 0.5 km and less, is related to the second
variety.
In the literature are described epidotes occurring in unchanging or little
changing magmatic rocks, principally dykes, where epidote forms phenocrysts
together with calcic plagioclase, which does not display signs of replacement by
epidote [Evans, 1987; Dawes & Evans, 1991; Zen E-an & Hammarstrom, 1982].
This epidote contains a significant admixture of rare earths, and its grains reveal
oscillator zoning of R.E. distribution. It forms at 700-800°C, P=7-12 kb and
relatively high oxygen fugacity in the region of buffer of
biotite+almandine+muscovite+magnesite [Dawes and Evans, 1991]. Formation
of such dispersed epidotes is supposedly magmatic. On experimental data,
however, the field of epidote stability is separated from fusion by the field of
anorthite+garnet+hematite (magnetite) and epidote crystallization directly from
melt is possible as unbalanced process, if the activation energy of its
crystallization is lesser than for crystallization of a small paragenesis. This

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manner of epidote formation displays signs of resorbtion and is preserved only
in conditions of rapid rise of magma and hardening.
Epidote in propylites associates with albite and chlorite; actinolite, biolite
and albite; prehnite and albite. In all these parageneses are present, as a rule,
magnetite (or hematite, or pyrite) and quartz. Often enough, especially in veins,
epidote associates with calcite. Rare enough are associations of epidote with
calcic zeolites (mainly with laumontite), which prove metastable to the extent in
which between fields of stability of zeolite and epidote there extends a field of
prehnite.
Albite, together with chlorite, are the more extended and characteristic
minerals in propylitized rocks. Pseudomorph replacement by albite of magmatic
disseminated calcic plagioclase serves as petrographic signs of relation of
metasomatic rocks to propylitized ones. Sometimes are called propylitized
generally peri-ore bleached rocks, composed of quartz, sericite, pyrite, in which
may also be present carbonate and chlorite. Essentially, such rocks form as a
result of activity of carbon dioxide solutions substantially more acid than the
propylitizing, and such rocks are more closely related to the beresitized. In
conditions of very small depths (first hundreds of meters) at low temperature the
reaction of plagioclase albitization runs sluggishly and plagioclases spread on
sericite and carbonate already in a feebly acid surrounding. However, in these
condition there form not sericite, but hydromica and other clayed minerals,
symbolizing passage to argilized rocks.
Propylitic albite contains not more than 2-5% of anorthite molecules (near
intrusive contacts is found oligoclase) and contains practically no potassium (not
more than tenths per cent). Albite in average temperature propylites with epidote
and actinolite shows a regular Al-Si distribution in structure, which
characterizes “lower” albite, and has a positive angle of 2V= 60-70. Its crystals
are polysynthetically twinned according to albite law. In low temperature near-
surface propylites albite is characterized by an irregular Al-Si distribution, a
great negative angle (of) 2V=70-80, which is characteristic of “ high” albite, and
is feebly twinned, or not at all [Rusinov, 1972]. The degree of twinning is on the
whole correlated with that of the mineral’s structure regularity. Irregular albite
appears as intermediate metastable product of plagioclase albitization, and with
time or under thermal influence it passes to a stable regular form at low
temperature.
Albite associates with chlorite, epidote, actinolite and calcite. Around
quartz-ore veins it gets reinforced by sericitization, but in the stage of “advanced
propylitization” is replaced by adular.
Actinolite is present in propylitized rocks in facies of increased
temperature in endo- and exocontacts of prophyric granitoid intrusions. It is
represented as an intermediate member of the tremolite-actinolite series with 20-
50% ferruginosity. Ferruginosity variations are determined by the composition

311
of initial rocks and the temperature (with temperature increase there is a
tendency to formation of less ferrous varieties). As a rule, the mineral does not
contain aluminium or sodium except its appearance at relatively high
temperatures at the level of the temperature at the boundary with epidote-
amphibolite facies. Magmatic pyroxenes and amphiboles are replaced by
actinolite. Sometimes is observed replacement of chlorite by actinolites, which
corresponds to the progressive type of propylitization development. More often,
on the contrary, actinolite is replaced by chlorite at the regressive stage of the
process. In equilibrium with chlorites actinolite is not observed in propylitized
rocks.
Actinolite associates with epidote and albite, or with biotite and albite-
oligoclase. In both cases there exist, moreover, quartz and magnetite (or pyrite).
At peri-ore metasomatism actinolite is replaced by sericite, but usually chlorite
is formed as intermediary product.
Biotite. In propylitized rocks greenish biotite is frequent with pleochroism
from dark greenish on pg to light-greenish on pp. It extends in deep zones of
propylitization , near contact with magmatic bodies. Colouring of biotite appears
with low content of titanium (0.1-1.5%ToO2) and increasing content of ferrous
oxide (up to 19% FeO). In the vicinity of magmatic contact there increases in
the biotite composition the titanium content (up to 4%) and decreases magnetite
with 0.5-0.7 to 0.3-0.4 (relation of magnesium to the sum of magnesium and
total iron). Colouring biotite also changes from greenish to red-brown with
pleochroism from bright red-brown to light red-brown. Brown biotites with
relatively high titanium content are formed also with propylitization of terrigene
rocks (quartz-muscavite-chloritic-schist) also far from intrusion.
Biotite in propylites associates with quartz, orthoclase, magnetite,
actinolite, epidote. However, epidote is often subject to replacement by biotite or
by biotite and amphibile. By biotite are also replaced chlorites, muscovite, at
places pyrite. In biotitized rocks there is commonly enough development of
small scale biotite on albitized phenocrysts of plagioclases. In most cases biotite
scales are disseminated in the rock, but there occurs condensation and
metasomatic veins. In a zone of magmatic contact there may arise bimineral
orthoclase-biotitic rocks. Are also found biotite veins with turmaline. Around
quartz ore veins biotite is replaced by sericite.
Biotitization is accompanied with entry in the rocks of magnesium, iron
and potassium and removal of calcicium. Apparently, the process is brought
about by solutions of increased alkalinity compared to the condition of epidote-
chlorite propylitization. Paragenesis with turmaline and presence in the biotite’s
composition of fluorine in 0.15-0.20% quantity testifies to increased activity of
volatiles (F,B) in the propylitized solutions.

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 Associations of minerals, facies and physico-chemical conditions of
propylitization. Propylites contain minerals precipitated from solutions, and
relicts of solution minerals of the initial rocks. So, usually propylites are formed
of an unbalanced mineral association; therefore their mineral composition may
be represented in the form of pellets newly formed minerals (n%)/relicts (r%)
where n and r(%) indicate content of newly formed minerals and relicts in the
rock. In feebly intense propylitization there do not always occur “definitive”
propylite minerals. For instance, in outer zones of propylitization olivine and
pyroxenes are replaced by serpentine with quartz, while plagioclase is preserved
in these zones. As far as the process is reinforced, plagioclase is replaced by
albite and calcite, but liberated alumina reacts with serpentine, producing
chlorite. Like pyroxenes, plagioclases are unstable in propylitization; therefore
relative preservation depends only upon the kinetic reaction of the replacement.
This example shows that precisely the chemical kinetics determines in a given
case the pace of the process, and propylitization may occur in a kinetic domain.
With intense metasomatism in conditions of increasing temperature (250-
300°C) propylitization leads to complete replacement of magmatic minerals by
newly formed, in equilibrium with hydrothermal solutions, i.e. to formation of
parageneses of minerals of propylites. Parageneses of minerals in propylitized
rocks depend, grosso modo, upon composition of initial rocks, temperature and
activity of magnesium and potassium. With metasomatic replacement of acid
rocks is formed a quartz-orthoclase-epidote facies with a small quantity of
chlorite with increased ferruginosity. At the same temperature there forms on
andesites a chlorite-albite-epidote facies. A distinction is defined by low content
of magnesium in acid rocks with inertia of its component in the propylitization
process. Another distinction is linked with formation of potassium feldspar
instead of albite. Usually potassium and sodium are mobile in metasomatism of
the mentioned type, but, apparently, potassium shows inertia in case of rocks
initially enriched in it. Somewhat different conditions accompany adularization
in propylitized rocks, when adular develops on propylitic albite forming earlier
at the stage of “advanced” propylitization. Later adularization is possibly linked
with alkalinization of a hydrothermal solution as a result of boiling up in small
depth with withdrawal of acid components in gaseous phase.
The main facies of propylitized rocks depending upon temperature and
magnesium activity are indicated on fig 18.6. The diagram is qualitative, the
boundaries of the facies field correspond to monovariant equilibria, for all of
which there do not exist thermodynamic data. With increasing T the albite-
calcite facies is replaced by an epidote chlorite, but then by an epidote-actinolite
one. In the epidote actinolitic facies in albite calcicium content increases to 5-
10% of anorthite molecules, which corresponds to a temperature about 300°C.
To a further temperature growth corresponds an albite-actinolite facies. Growth
of magnesium activity brings about reactions of biotitization and formation of

313
biotite-actinolite facies, which usually borders on contact hornfelses of diopside-
orthoclase-phlogopite or diopside-orthoclase facies. Appearance of a biotite-
actinolite facies in a deep rear zone of propylitization is linked with mobility of
magnesium and its addition to magmatogene solutions. In portions of intense
biotitization by these minerals are replaced not only chlorites, but also albites,
are formed nests and veins of monomineral biotite, or biotite in paragenesis with
actinolite and epidote. As a rule the main mass of mineralization extends above
the limits of the actinolite facies, in lower temperature epidote chlorite
propylites.
As agents of propylitization serve solutions formed from two sources or
more. A portion of magmatic fluids is remarkable by the high activity in them of
magnesium and potassium, which makes conditional magnesian or potassic
trends to propylitization (biotitization or adularization, respectively). Together
with magmatic in hydrothermal solution indubitably exist also water
components buried in the thickness of the rocks undergoing propylitization. This
follows from an enormous volume of propylitized rocks in hundreds of cubic
kilometers, but also from data on oxygene isotopy. Instructive instances of
mapping of distribution of oxygen isotopes are found in rocks of some ore
districts. A gold –silver deposit of Bohemia (Oregon, E.-U.) included in
propylites is formed at the expense of andesites and dacites. In unchanging
volcanites distant from the ores the value of 18O=6‰, but in propylitized rocks
near the ore zones this value decreases (fig.18.7) more than 10, attaining in ore
zones negative significance up to -4 18‰. Apparently, in hydrothermal solution
a significant share consists of waters of meteoric origin. Analogous data are
obtained for the sulphidic gold-copper deposit of Kizilbulak in Azerbaijan
[Gavriluk et al., 1991].
In propylitized submarine masses mixed with pyrite deposit, a significant
part of hydrothermal solution consists of sea water the presence of which is
proved by correlative values of D and O, near to those in sea water. There exist
quantitative estimations of the share of magmatic components in a hydrothermal
ore-forming solution, but concerning propylitized solutions there are not
sufficient data.
A comparison of adduced data on the conditions of synthesis and stability
characteristic of propylitic minerals with the data on the study of contemporary
volcanic hydrotherms and thermodynamic calciculations permits to evaluate the
extent of the conditions at which propylitization occurs. The general temperature
interval of propylitization is situated near 200-350°C; for albite-calcite-chlorite
facies, 200-250°C; for epidote-chlorite, 250-300°C; for actinolite-epidote,
actinolite-albite and biotite-actinolite facies, higher than 300°C. Estimations of
composition of propylitized solutions are few in the literature. Research on
fluids of an inclusion in adular from propylites, mixed with the gold deposit of
Round Mountain (Nevada), and thermodynamic calciculations [Sander and

314
Einaudi, 1990] have shown a low salinity of propylitized solutions (0-0.2%
equivalent NaCl), proximate to the neutral alkaline value pH=7-7.5 at 250°C,
potassium concentration in the order of 10-3M. Ore deposition in these
propylititized solutions is linked by the authors with the concluding stage of
propylitization, in which a typical propylitization gives way to adularization.
Later adularization is caused usually not only by growth of potassium activity as
far as through temperature decrease and in its influence by growth of relative
potassium activity and sodium activity in the solution. Propylitized rocks in
formation of synvolcanic argilitites are formed in a more acid environment
(pH=5,5-6,5).
Propilytization and mineralization. Propylitized rocks forming in
border facies in ensembles of synvolcanic argilized rocks and in acid
periveinous metasomatites, as a rule do not contain ore concentrations. Ores in
these objects are concentrated in outer metasomatic zones of maximally
transformed rocks. Propylitized rocks forming independent ensembles (of
propylitized formation), mix with mineralizations of various types: stannous,
lead-zone, silver-polymetallic, gold-copper, gold-silver etc. Ore bodies may
have the form of intersecting veins, zones of veins, vein- interspersed zones.
Usually easily come to light signs of later ore formations in relation to propylites
[Vassilevsky, 1970]. As such signs serve, for instance, depositions of peri-ore
acid metasomatism on mineral associations of propylites and intersection with
ore bodies of boundaries of propylitic facies. Intersections depositions we
generally characteristic of lead-zone and most gold-silver ores. Deposition
determines extended correlation for disseminated (vein-interspersed)
mineralization, but also in this case it is usually accompanied with local peri-ore
metasomatism, deposited on propylitized rocks.
A special case is dissemination of gold or gold-silver mineralization in
adularized propylites. Judging from described Transylvanian gold-silver
deposits [Giusca, 1945] and gold deposit of Gold Mountain in Nevada [Sanders
& Einaudi, 1990], adularization immediately continues the propylitization
process, manifesting its conclusion. Gold deposition with accompanying ore
minerals occurs simultaneously with formation of late adular, with which the
contour of industrial gold content occupies a predominant part of the volume of
propylitized rocks and does not trespass their limits (fig.18.8). The conditions of
ore formation in that case, according to the cited authors, practically coincide
with the conditions of propylitization. This means that propylitizing solutions
contain soluble gold and other metals, but their condensation results from
temperature fall and variations of acidity-alkalinity of the rock.
For the deposition of tin [Razmakhnin & Razmakhnina, 1964] and
gold [Russinov, 1989] is noticeable a limited deposition of ore bodies in zonings
of propylitized rocks. Tin mineralization coincides fundamentally with the
biotite facies in the roof of a granitoid massif, but gold mineralization

315
concentrates above the limits of the biotite facies with the epidote-chlorite
surrounding it.
From the adduced analysis of geological setting and the conditions
of formation of propylitized rocks it follows that a characteristic feature of
propylite formation is its occurring in volcanic masses as a result of a
hydrothermal process linked with entry of a porphyric granitoid intrusion of
increased content of alkalimetal. In the formation of propylites occurs a
metasomatic zoning: the rear zone, contiguous with contact hornfelses, is
deposited in a biotite-albite-actinolite facies and is characterized by addition of
magnesium; above is placed an epidote-chlorite facies with linear zones of
epidotes and portions of epidote-actinolite facies. Similar deposition and zoning
are precisely characteristic of ore- bearing propylitic fields.

316
Fig.18.1. Outline of expansion of metasomatic facies in ore-field of the Mnogovershine
deposit (Lower Amur) [Rusinov, 1989].
a- plane; b- cross-section through line A-B-C; 1-alluvium, 2-granodiorite-porphyries,
granite porphyries and syenite porphyries of phase V intrusion; 3 - granodiorites and syenito-
diorites of phase IV intrusion; 4 - alcaline granodiorite porphyries of phase IV intrusion ; 5-6
- andesito-dacitic volcanic formation (5-subvolcanic and crater facies; 6-mantle facies), 7 -
aleurolites and sandstones, 8 - contact hornfelses; 9-10 - facies of propylite (9-biotitic, 10
epidote-chloritic), 11- peri-veinous beresites with quartz-ore veins; 12 - zones of supra-ore
metasomatic veinlets of altering rocks.

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Fig. 18.2. Extension of metasomatic facies in ore-field of Round-Mountain after [Sander
and Einaudi, 1990].
1 unalterated tufa-rhyolites; 2-4 propylitized rocks with various degree of replacement
of magmatic plagioclase by adular or albite (2-initial replacement; 3-medium degree; 4-
complete replacement; 5-6- adularized rocks with adular content < 100% (5) and = 100% (6);
7-intensively silicified rocks; 8-limits of argillization; 9-limits of quaternary deposit; 10 -
lower limit of expansion of tufas of the Round-Mountain formation; 11-triangulation points;
12-lines of cross-sections and boring holes on the plane; 13-position of boring holes on
cross-sections.

318
Fig. 18.3. Composition fields of chlorites from propylites (1) and synore metasomatites

Fig. 18.4. Rates of intensity of the first three basalt reflections of chlorites from
propylites (1) and synore metasomatites (2).

319
Fig.18.5. Dependence of ferruginosity of chlorites upon fugacity of sulphur and oxygen
[Brindzia and Scott, 1987].
Denotation by rectangles of the field of chlorites from propylites (1) and from ore-
accompanied metasomatites and ore veins (2).

320
Fig. 18.6. Parageneses (a) and facies (b,c) of propylites formed at mobile behavior of
magnesium and iron.

321
Fig. 18.7. Schematic map of ore field of Bohemia (Oregon, USA) with isolines of isotopic
composition of oxygen of enclosing volcanic rocks [Taylor, 1977].
1-intrusive diorites; 2-volcanic rocks; 3-sample locations; 4- δ18O values; 5-limit of
contact-metasomatic aureole; 6-isolines of δ18O; 7- propylized rocks.

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Fig. 18.8. Distribution of gold in propylitized rocks of the Round-Mountain deposit
[Sander and Einaudi, 1990].
1-3 aureoles of various gold content (1:  0,72 g/t; 2: 0,38-1,42 g/t; 3:  1,41 g/t); 4-
steep sloping mineralisation fractures; 5-old outputs; 6-gently sloping veins previously
exploited; 7-limits of non-oxidized sulfides and carbonates; 8-main fissures; 9-contacts of
rocks; 10-lower limit of extention of tufas of Round-Mountain; 11-limits of alluvium; 12-
triangulation points; 13-position of drill holes on map; 14-position of drill holes on fractures.

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 Chapter 19

Secondary quartzites

Definition. Secondary quartzites (SQ) are substantially quartzic rocks

(quartz content 50-100 vol.%) formed through metasomatic silicification of
initial rocks of various composition. The term was first proposed by
[Link]. A further elaboration of this notion can be found in the works of
[Link], [Link], [Link]. The term is not used in English
language literature, where it is not admitted to isolate the corresponding specific
types of metasomatic alterations, but to utilize concrete designations of altering
rocks (corundic quartzites, andalusite-quartz rocks, alunite-quartz rocks). The
framework of the term “secondary quartzite” is defined conventionally enough,
since a process of silicification may be linked with the influence of acid
solutions, compositions, temperature and geological setting which strongly vary.
Rock silicification is typical of greisenization argilization and quartz-
sericitization processes of rock alteration, in which quartzic cores sometimes
present rear zones of metasomatic columns.
The term SQ has also aroused objections amongst Russian geologists.
They proposed to replace it by “metasomatic quartzites” or “hydrothermal
quartzites”, but these changes were not accepted in the literature. Unlike the
designation of rocks and metasomatic facies, the term SQ, apart from a specific
mineral composition and physico-chemical parameters, implies a particular
geological environment for the appearance of the metasomatic process. Amongst
the geological situations in which SQ is found, most typical are the fields of
development of medium-acid volcano-plutonic components in active continental
margins and on insular arcs at orogene stage of development. Silicification
process have a distinctly deposit character and are related to the postmagmatic
stage. Most SQ appearances are linked with porphyric magmatism of
hypabyssal-subvolcanic facies. [Link], after [Link] and
[Link], have related to SQ postintrusive metasomatic rock
slilicifications in apical parts and roofs of porphyric granitoid massifs.
[Link] has widened the notion, introducing into it products of solfatar
processes in near-surface conditions on volcans. Some researchers of epithermal

324
deposits have scrutinized zones of quartz, quartz-alunite, quartz-kaolinite
composition in periveinous metasomatites as well as SQ. Similar widening of
the form are explained by the similitude of mineral composition of the
scrutinized zones, but they lead to the unification of the genetically various
formations, which contradicts the formation approach. Solfatar alterations,
quartz “hats” and zones of silicification on epithermal deposits form zones or
facies in composition of a complex of solfatar-argilized or periore-argilized
rocks, i.e. no geological independent formations appear, and only as facies of
argilizitic formation.
As the main mineral SQ appear quartz, sericite, pyrophyllite, alunite,
kaolinite, dickite, andalusite, corundum, fluorite, rutile, diaspore, pyrite,
hematite. Often are found dumortierite, zunyite, topaz, lazulite, turmaline,
geikielite, svanbergite.
Basic mineral equilibria for SQ may be described in the framework of the
Al2O3 - SiO2 -H2O systems, which was studied by [Link] et al. [1972],
[[Link] et al. 1980]. Moreover, interest was later directed to studying the
solubility of oxid alumina and alumino-silicates Al2O3 -H2O , Al2SiO3 -H2O
systems [Korzhinsky 1987, Ostapenko et al. 1987].
Specific paragenes of SQ are diaspore-pyrophyllite-corundum+andalusite,
zunyite-diaspore, alunite-pyrophyllite. In most of them quartz may be present,
although usually the enumerated minerals are found in later silicified rocks and
may be in unbalance with the quartz. In particular, this proves to be corundum
[Korzhinsky, 1963, Popov 1977].
So, analysis of geological deposits, of mineral composition and ore
mineralization in intensively silicified rocks permits to distinguish among them
a few genetic types (table 19.1), including strictly SQ, in the interpretation of
[Link] and [Link], and facies of silicification of rocks in
argilizite formations.

Table 19.1. Genetic types of products of silicification.

Metasomatic Deposits Paragenesis of Type of mineral
formations main facies of
replacement
Secondary High-aluminous Qtz – Crn Al
quartzes Porphyric Qtz – Ser – Py Cu, Mo, (Au)
Advanced Epithermal Qtz – Alun – Kln Au, Ag, (Cu)
argillisites Pyritic Hydromicas Cu - Zn

Secondary quartzites linked with corundum mineralization. An

outstanding specimen of development of high alumina mineralization in
silicified rocks is the deposit of Great Semis-Bug (Central Kazakhstan). SQ on

325
the deposit forms in connection with hercynian acid magmatism. Magmatic
rocks are present in a complex of rhyolites, their tuffs, subvolcanic dykes and
stocks of granite-porphyries.
The greatest development amongst metasomatic rocks is that of silicified
varieties. [Link] [1964] has defined a few fundamental mineralogic types
of SQ: sericitic, monoquartzitic, sericito-andalusitic, alunitic, andalusitic (SQ
types are numbered in the order of diminution of their relative expansion).
Corundum SQ are not divided in independent types, since corundum is
exclusively localized in central parts of the deposit, where it forms a sprinkling
and small veins in other SQ types. On the plan (fig.19.1) the most extended
sericitic SQ constitute a general background of metasomatic alterations.
Monoquartzites form a thick vein-like, steeply dipping body composing the
massif of the Great-Semis-Bug mountain. The quartzic body divides the SQ
massif into two parts, controlling SQ distribution in extension: an inner
corundum-andalusitic and an outer one with alunitic mineralization.
A characteristic feature of monoquartzites is the presence in them of a relict
structure of quartzitic porphyry and sprinklings of unalterable initial quartz. This
testifies to the fact that monoquartzites do not appear in vein fulfillment but are
formed metasomatically. This is indicated by the gradualness of transition from
monoquartzites to other SQ types: sericitic, andalusitic and alunitic.
Amongst secondary quartzites are found high aluminiferous mono- and bi-
mineral rocks. Their morphology is varied: veins, nodules, mineralized nests and
steeply dipping lenticular deposits. The largest of them, an andalusite-corundum
deposit, a body 160-180m long, with thickness of 40m at the utmost, has an
asymmetrical, funnel shape. Judging from data of geological works, the deposit
is steeply subparallel to the incidence of the monoquartzite body. The core of the
deposit is in a corundum rock bordered by a thin andalusite corundum shell. The
outer zone consists of andalusite-sericite SQ varying in composition.
[Link] has established a vertical zoning in the structure of the core. The
corundum body of the upper part contains hematite, rutile and barite, in depth
they are represented by pyrite-muscovite-corundum rocks, which further down
are replaced by small grain pyrite-corundum rocks.
Corundic bodies have a taxitic breccia texture and possess a significant
porosity, up to 10-12% [Nakovnik, 1964]. In the mineral composition
predominates corundum (72-95 vol.%), andalusite (2-5 vol.%), sericite (7
vol.%), are present rutile, pyrite, diaspore, topaz, barite. Corundum develops
later than basic SQ minerals, and therefore testify to corrosion correlation of
corundum by muscovite and andalusite, but there are also present nodules of
andalusitic and sericitic SQ, cemented by corundum. At places gross crystal
corundum associated with rutile and barite form thin branching veins,
intersecting grayish thin-grained corundum rocks.

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 Many features of geological structure of the SQ massif of Semis-Bug, in
the opinion of [Link], testify to the fact that SQ is localized in central
parts of volcanic apparatus. This is indicated by signs characteristic of volcanic
centers: abundance of volcanic tuffs, bombs and breccias, steep sinking
structures of elements in lavas, arc-shaped deposits of quartz, developed,
probably on a system of contraction cracks and collapses at caldera formation.
Secondary quartzites linked with deposits of porphyry type. Processes
of silicification on deposits of porphyry type are widely spread and represent the
result of acid metasomatism of quartz-feldspar, quartz-sericitic (phyllitic) and
argillisitic types. To porphyry metallization are habitual the many stages of
hydro-thermal process and, respectively, some stages of SQ formation. A
detailed description of the development of silicification processes can be found
for the deposits of Island-Copper, San Manuel, Butte, Kunrad, Kalmakkir,
Assarel [Popov, 1977]. [Link] [1977] remarks that SQ represent inner or
upper parts of porphyry bodies, linked with the products of “advanced
argilization” and with phyllites. The complexity of interactions with complexes
of SQ was also pointed out by [Link] [1989], who defined appearance of
SQ in conditions of porphyry deposits or as intermediary metasomatic zone
between quartz-feldspar and quartz-sericite metasomatites, or as inner parts of
argillite aureoles. In this way, processes of silicification and development of
high alumina mineralization (andalusite, corundum) in time get detached from
the appearance of potassium metasomatism (Qtz-Or, Qtz-Bi). An example of SQ
development linked with porphyry types of mineralization is to be found in the
copper deposit of Kunrad in Kazakhstan [Gasisov, 1957; Nakovnik, 1968; Udin,
1969] and molybdeno-porphyric Climax in USA [White et al. 1984].
The Corundum deposit is confined in a stock of granite-porphyry, an
intruding patch of effusives. Metasomatic alterations and metallizations are
precisely controlled by a body of granite-porphyries. A vertical zoning has been
determined in the distribution of metasomatic rocks. The inner one (deepest
zone, about 100m thick) is represented by propylites (or potassic propylites
[Popov 1977] ), in which initial intrusive rocks are replaced by
Bi+Chl+Ep+Ab+Py(+-Or) association. Above the quarry a transition is
established to strongly silicified rocks. Transition from propylites to SQ occurs
in an interval of about 10m. Here associations with kaolinite and sericite are
close in composition to argilisites.
Strongly silicified rocks constitute the main part of the metasomatites in the
deposit. According to [Link] [1968] estimate the vertical scale of their
development amounts to no more than 400-500m. Amongst them the most
spread are sericite-quartz rocks. Andalusite-sericite types develop exclusively on
acid lavas in close contact with stocks of intrusive rocks, formed in an extended
structure, recalling contact aureoles. In the zones of andalusite-sericite quartzites
is recorded the development of high-potassic mineralization: pyrophylite,

327
corundum, alunite. Sericite-quartz rocks consist of quartz (30-60 vol.%), sericite
(40-50 vol.%), pyrite and rutile. SQ, developed on intrunsive rocks, are
characterized by abundance of thin quartz veins, intersecting the altered rock.
Unlike apointrusive varieties, in apovolcanic SQ, as a rule, such veins are
not observed, and silicified rocks even preserve signs of flow structure of initial
lavas. Transition from sericite-quartz rocks to andalusite-sericite is gradual, with
varying quantitative correlations of the minerals. Andalusite content varies from
5 to 80 vol.%. The interrelations of sericite and andalusite are contradictory:
they are observed as signs of combined growth as well as corrosion correlation.
In tight association with andalusite develop alunite, dickite, pyrophyllite,
diaspore and corundum. Judging from the interrelations, these minerals, except
corundum, have formed on concluding stages of SQ formation at declining
temperature. Corundum also forms after andalusite crystallization and is
observed in the aspect of idiomorphic crystals developed on porphyroblastic
andalusite. Judging from the absence of corundum-alunite, corundum-
pyrophyllite association, etc., corundum is formed at an independent stage. This
is also indicated by the distinctly extended control of distribution of andalusite-
corundum SQ facies, exclusively concentrated in the inner parts of andalusite
rocks. A similar picture of development of the process of silicification and high
potassic mineralization is observed on the copper-porphyritic deposits of El
Salvador [Gustavson & Hunt, 1975]. Here development of quartz-sericite
metasomatites (phyllites) have preceded formation of potassic (orthoclase-
biotitic) metasomatites. In the inner parts of the phyllite aureole develop
andalusite-quartz metasomatites, where in the form of single finds is recorded
corundum, replacing andalusite. Later, with declining temperature, in argillized
rocks are formed pyrophyllite and alunite. On the El Salvador deposit phyllitic
type of metasomatism is linked with formation of pyrite-bornite mineralization.
Ore mineralization on the Kunrad deposit is tightly linked with processes of
silicification. Veinous and sprinkled mineralization (chalcopyrite, pyrite,
galenite) develops in quartz-sericitic rocks. At the same time most copper-
porphyric deposits show extinction of he extent of mineralization in the zones of
highest acidity of leaching [Popov, 1977].
SQ linked with pyrite ores. SQ were first distinguished as independent
types of alteration by [Link] and [Link] on the Ural pyrite deposits.
Later on SQ in the Kaban pyrite deposits (Northern Ural) were described in
detail by [Link] [1951]. Similar types of zoning were described in the
deposit of Chizeuil (France) [Lemiere et al., 1986], where SQ replace sulphide
deposits, built with pyrites and sulphides of copper with accessory gold.
Sulphide bodies in SQ of the Chizeuil deposit has the form of lenses, and
they show tendencies to forming massive deposits, stockwerk bodies. They are
surrounded by bright quartz-andalusite rocks, with numerous intersecting pyrite
veins. The initial rocks present subvolcanic dacites. The structure of

328
metasomatic quartzites is variable: massive in sprinkled pyrite and muscovite;
banded (the zones alternate, enriched either in quartz or in andalusite); jointing,
with separation, parallel extension of sulphide bodies; breccia-like containing
fragments of massive ores, in their turn cemented by sulphide cements. Mineral
composition and zoning of metasomatic alterations are presented on table 19.2.
Metasomatic alterations around sulphide bodies in the Kaban deposits are, on
the whole, similar to those of Chizeuil, but differ in developing corundum in
quartz-andalusite rocks and presenting fluor minerals (topaz and fluorite) in the
frontal parts of the aureoles, surrounding sulphide pipes [Loginov, 1951].
Silicified rocks are described in metasomatic aureoles of sulphide bodies on
pyrite deposits of Chypriot type [ Richards et al., 1989] in the region of pyrite
deposits of Bulgarian and Yugoslav Central mountains (Chelopech, Elshitza,
Kracen, Bor, Maydanpek)[Radonova & Velinov, 1974].
Silicified rocks in epithermal deposits. The wide development of
silicification processes is characteristic of acid sulfatic (or, in another
terminology, high sulphidized) type of epithermal deposits [Herald et al., 1987],
linked with the development of argillization in them. Silicification, as a rule,
represents formation of ore bodies. Such correlations are established, for
example, on epithermal deposits in the province of San Juan Mountain
(Colorado, USA), where are well known some big deposits of noble metals such
as RedMountain Pass and Summitville. Silicified rocks of this type are related
by American

Table 19.2. Mineral composition and zoning of metasomatic alterations in

bodies of secondary quartzites of Chizeuil (Morvan, France) [Lemiere et al.,
1986]
Massive Secondary quartzites Adularized Initial
sulfide bodies Zone 1 Zone 2 dacites dacites
Quartz Quartz Quartz Quartz Quartz
Andalusite Andalusite Feldspar Albite Oligoclas
Kaolinite Kaolinite Muscovite Adular Albite
Pyrite Muscovite Rutile Muscovite Chlorite
Chalcopyrite Pyrophyllite Pyrite Chlorite Sphene
Enargite Diaspore Biotite
Corundun Rutile
Rutile Sphene
Pyrite Pyrite

geologists to products of “advanced argillization”.

The Summerville deposit has been studied in full detail by [Stoffregen,
1987]. Intrusive rocks in the deposit are represented by quartz dacites (fig. 19.2).

329
They burst patches of andesites and rhyodacites formed in aggregates of
cauldron complexes of lava.
The youngest eruptive rocks of the region are represented by subvolcanic bodies
of rhyolites of Grospy Mountain. The deposit is confined to a zone of fracture
intersecting a complex of cauldron formation, and gravitates to a contact of lava
with massive quartz latites. The structure of the deposit is represented by
numerous extended mineral zones of north-western and northern course. Their
deposition is controlled by the position of contacts between intrusive phases of
quartz latites and between quartz latites and rhyolites.
Hydrothermal peri-ore alteration of rocks occupies a well defined zoning.
Inner parts represent nearly pure quartz (“cavernous quartz”) and are surrounded
by zones of quartz-alunite, illite and montmorillonite composition (fig. 19.3a).
In the zone of “cavernous” quartz arises a leaching of all rock forming
minerals, and it is composed of quartz, sulphides, second generation anatase and
zircon. Silicified rocks form irregular tubular bodies from a few centimeters to
70m thick, deposited at a depth of 100-200m (fig. 19.3.6). The morphology of
the quartz distribution is varied: the basis consists of very fine-grained
aggregates (grains from 10 to 100 microns). They contain great relicts of
sprinkled magmatic quartz, preserved through metasomatism, and other quartz
formed in cavernous cavities. In interstices of fine-grain quartz are formed pyrite
and anatase. In cavern quartz stand out portions of massive structure, lacking in
voids. The distribution of such portions in the limits of the zone is accidental.
A quartz-alunite zone either shows itself as very internal, or borders with a
quartz kern. Mineral composition of the zone: quartz, alunite, individual grains
of svanbergite. Quartz and alunite form a very fine-grained mass (grains of 100-
250 microns). Alunite contains 10-25% of Na molecules. From ore minerals
pyrites are usually knitted with alunites. Are present in small quantities covellite
and native sulphur. In the outer parts of a quartz-alunite zone develops an
association of quartz+alunite+kaolinite, with a thickness from a few centimeters
to one meter. This paragenes is transient to a zone of illite alteration.
The inner zones have a sharp contact with more outer illite and
montmorillonite-chlorite zones of hydrothermal alteration. Mineral composition
of the illite zone: quartz, illite, with a subordinate quantity of montmorillonite
and kaolinite. Of ore minerals predominate pyrite on biotite, and are registered
as of second generation chalcopyrite, galenite, sphalerite and covellite. The illite
zone of alteration in the direction of lateral mineral gradually turns into
montmorillonite-chlorite, built of smectite (mostly, montmorillonite), pyrite,
Mn-chlorite, carbonate. This zone is replaced by feebly altered quartz latites.
Fresh latites are represented by porphyric rocks with phenocristals of potassic
feldspar, plagioclase, biotite and quartz, a basic mass represented by the same
minerals in association with magnetites. Accessory minerals are apatite,
magnetite, zircon.

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 Zones of cavernous quartz and quartz-alunite alteration are traced in depth
up to 400m from the day light surface (see 19.3b). It is established that in depth
the thickness of alteration substantially diminishes and in depth of more than
150-200m the thickness of cavernous bodies rarely exceeds 2m. On outer parts
of these tapering out bodies are formed thin margins of quartz-kaolinite
composition, but alunite is recoded as sporadic. The structural interrelations of
kaolinite and alunite permits to suppose that part of the kaolinite is product of
replaced alunite.
Sulphid and gold mineralization in deposits are concentrated mainly in
bodies of cavernous quartz. Two fundamental types of sulphid mineralization
are distinguished. In depths of more than 200m develops an association of
chalcopyrite+tennantite in association with pyrites and rarely encountered
sphalerites. Above predominate covellite and luzonite, but pyrite, chalcopyrite,
sphalerite and tennantite are rare. Gold is mineralized in the form of enclosed
native gold in sulphides (mainly in pyrite). Silver mineralization on the deposit
is present as electrum and admixture of covellite and stromeyerite.
[Link] [1987] has shown that silicification processes precede
deposition of sulphide and gold. Sulphide mineralization forms in cavities of
quartz bodies, or cements brecciated quartz. In depths of more than 200m in
coalescence with sulphides there usually appears kaolinite, which is formed in
exchange of alunite. Physico-chemical analysis of the parageneses performed by
[Link], has shown that deposition of ore minerals occurs in more reduced
and basic surroundings, in comparison with environments of acid leaching.
Solfataric rock silicification. Solfatara appears as manifestation of
hydrothermal influence of volcanoes with significant share of joint sulphur (H 2S
and SO2) in fluid phase. Condensation of steam gas mixture in solfatara
channels leads to formation of acid and ultra-acid solutions. Interaction of these
aggressive solutions with lateral rocks leads to formation of metasomatites in
which an important place is occupied by silica minerals (opal, crystobalite,
quartz), alunite, native sulphur, kaolinite. [Link] [1990] has brought
different types of metasomatic zoning on solfatara fields of Kurile volcanoes,
under influence of fumaroles and paleofumaroles. A detailed description of the
geological structure of influencing fumaroles in the domains of contemporary
volcanism has been given by [Link] [1972]. As an example is given a
description of the solfataras of volcano Ebeko (Kurile islands).
On the slopes of this volcano (fig. 19.4) are observed outlets of thermal
waters characterized by ultra-acid compositions and temperatures from 40º to
90º. The thermae come to the surface from numerous cracks in bleached rocks,
opalites. At the place of exit, underlining the cracks, gets deposited colloidal
sulphur. The waters in the compositionare ultra-acid with a pH from 1,12 to 1,8.
Amongst anions predominate sulphate-ions and chlore (SO2/Cl = 12), cations
are composed of basic rock-forming components: alumine, iron, alkalis.

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[Link] [1972] has shown that the correlation of cation composition of
thermal waters and that of the corresponding components in unchanging
andesites are identical, which testifies to the departure of cations from enclosing
rocks – in sum turning into monosilicic formation. On the sketch, altering rocks
form mantle-shaped covers with a common area of more than 15km², with
visible thickness of 200-250m (cf. fig. 19.4). Mineral composition of altering
rocks is uniform: opal, much more rarely is recorded cryptograined quartz; in
the form of constant admixture is present in the rocks rutile forming minute
crystals. In 80% of the studied specimens is established alunite (0-10 vol.%,
sometimes up to 50 vol.%). In the opalites alunite fills cavities and cracks, forms
monomineral accumulation in the form of veins; in the lower part of silificized
rocks are recorded barytes, zeolites, pyrites in the periphery. Chemical analyses
of opalites have shown that with hydrothermal altered initial rocks Fe, Ca and
Mg leach completely. Al comes out either completely or partly gets linked with
sulfate-ions in alunite. Unfortunately vertical and horizontal metasomatic zoning
with this occurring process of silicification has not been studied. This gap may
be filled, utilizing the genetically similar examples of development of acid
geotherms of Steamboat Springs.
The geothermal waters of Steamboat Springs (Nevada, USA) [White et al.,
1964, Shoen et al., 1973] interact with andesites and granodiorites in the course
of the period from 1 million to 100 000 years ago. In depths of 50 to 120m, at
temperatures up to 170ºC, on initial rocks with interaction with near-neutral (pH
= 6.1) waters are formed associations of illite, quartz, chlorite, adular, albite. In
near-surface conditions the outgoing geothermal waters acquire an ultra-acid
character, and the initial rocks are transformed in monosilicic formations.
Silicificized rocks crop out on the surface in the form of mantle-shaped bodies.
Owing to drilling, it was possible to study the mineral zoning of sulfatara
alterations in depth (fig. 19.5). The upper part of the section is presented as
opalized rocks with admixture of tridymite, alunite, kaolinite, montmorillonite,
anatase. Alteration of the rocks coincides with sets of communicating cracks,
filled with a mixture of opale and alunite, in those trimmings arises “bleaching”
of the rocks. The earliest process is the development of montmorillonite mixing
minerals of the basic mass and volcanic glass. In more altered rocks are
kaolinite, mixing kaolinite and plagioclase of initial rocks. At the same stage of
alteration occurs replacement of ilmenite (mineral of the matrix) by anatase. In
the most transformed rocks, opalites, kaolinites and anatase are displaced by
opals. The zone of opalites in depth is about 30m thick. Shoen with co-authors
[1974] have established that the lower limit of opal development coincides with
the level of ground waters. Lower down predominating mineral of metasomatic
alteration is alunite. Alteration gives way under down to zones of development
of kaolinite and montmorillonite. Pyrite usually concentrates in vacuities and
cracks of altered rocks in the lower part of the opalite body and

332
montmorillonitized, kaolinitized and alunitized rocks. In the upper part of the
opalites instead of pyrite are formed hematite and hydroxide of iron, which is
linked with the passage of hypogene to hypergene regime with more oxidized
conditions.
On the whole, as observes [Link] [1990], in the alteration of
mineral composition horizontally or vertically in solfatara bodies is observed a
strikingly marked tendency to passage from strongly acid to feebly neutral
associations. The character of mineral zoning is very much determined by the
structure of the network of fissures: the presence of tubular wholly permeable
zones is strikingly marked a horizontal shift of association (solfataras of the
volcanoes of Baran and Chirip. Kurile islands) [Znamensky, 1989]. Analysis of
the paleohydrological environment on the Maletoivvaiamskoe neogene sulphur
deposit (Kamchatka)
has permitted [Link] [1969] to establish that this deposit of sulphur-
containing SQ is controlled by great crack structures drained by well aerated
superficial waters at the time of ore-deposition. This occurs, for instance,
specially in the zoning of SQ, which presents itself in symmetrical aureoles
around monoquartzites, having replaced permeable layers of pyroclastic rocks.
Remarkable is a regular displacement of sulphur-bearing facies of
hydrothermally altered rocks from the centre of the deposit to the roof and the
base. In the centre of the ore body are observed dense siliceous rocks, which in
the base of the deposit give way to sulphur-bearing quartzites, but the last rocks
through kaolinite-quartzitic rocks pass to montmorillonized and pyritized tuff
breccias. In the roof of the deposit the zoning takes another aspect: dense
monoquartzites pass into sulphuric alunite-containing quartzites, which above
give way to kaolinite-quartzitic rocks, but the last varieties gradually through
montmorillonite-kaolinite pass to montmorillonitized effusives displayed on the
surface. In the presence of a network of small jointing in the rocks, the solfatara
development is characterized by a clearly marked vertical zoning, and passage
from acid associations (superficial and near-superficial parts of solfatara) to
neutral ones (in depth) is observed on the vertical (Steamboat Springs).
Specific products of superficial silicifying of rocks are siliceous sinters in
domains of contemporary geothermal systems. Siliceous sinters are widely
spread in geothermal domains (Steamboat Springs, Yellowstone, Wairakei,
Beovava, Pauzhetka, etc.). The study of epithermal deposits shows that their
formation, as a rule, was accompanied by deposition of silica on paleo-surface in
the aspect of terraces, which appear as fully analogous to the now formed
sinters[Sunneen & Silitoe, 1989]. Unlike solfatara environments, formation of
siliceous minerals in sinters is not accompanied with rock-leaching, but SiO2
arises from oversaturated solutions, discharged on the surface. Therefore the
sinter bodies have a hydrothermal sedimentary genesis.

333
 P-T parameters of S.Q formation. Experiments with the Al2O3 - SiO2 -
H2O system permit to confidently enough evaluate the temperature of SQ
formation. Temperature facies of SQ according to [Link] [1993] are shown
on fig. 19.6, where monovariant lines of dehydratation reaction define the
temperature intervals of stability typical of SQ minerals: gibbsite, kaolinite,
pyrophyllite, diaspore, andalusite. The highest temperature SQ mineral is
corundum. Thermodynamic calciculations and experiments have shown
[Zharikov, 1969, 1972; Hemley, 1980] that the corundum-quartz association is
unstable (fig. 19.7). As follows from the position of monovariant lines (cf. fig.
19.6), pressure feebly influences the equilibrium determining the stability of SQ
minerals. The large development of andalusite and the absence of quartzite in
SQ undoubtedly testifies to the small depth of the formation of metasomatites
(hypabyssal and subvolcanic facies of depth). This also corroborates the clearly
marked contact character of the development of aureoles of SQ, with sharply
outlined boundaries of the field of high temperature acid metasomatism
deposited in lateral rocks. For a finer evaluation of pressure in SQ formation
may be utilized indirect data. [Link] [[Link] et al.,1987] with co-authors
have given a report of valuation of deep formed metasomatic rocks on
epithermal deposits, linked with appearance of acid leaching. Most valuations
correspond to an interval of 100-500m, which, in the opinion of the authors, is
determined by a pressure interval where there is boiling of a H2O-NaCl flow.
[Link] [1987] has evaluated pressure in hydrotherms on the Summitville
deposit at 30 bar, at the temperature about 250ºC, as a result of homogenization
of an inclusion in quartz.
Mobility of alumina in SQ formation. Most experimental works on
hydrothermal synthesis of minerals indicate a small solubility of alumina in
aqueous near-neutral solutions.
Corundum dissolves in pure water in reaction:
0.5 Al2O3 + (1.5+n)H2O = Al(OH)3 - nH2O [Anderson et al., 1970]
With increasing pressure, corundum solubility in supercritical aqueous
solution grows [Becker et al., 1983]. This growth forms about 7.24ppm Al2O3 on
1 Kb in the interval from 2.5 to 20 Kb and temperature from 670º to 700ºC.
[Link] & [Link] [1983] have revealed the maximum of corundum
solubility at 500ºC and the minimum at 600ºC in the pressure interval from 1 to
3 Kb. Increase of acidity of the solution brings about a significant increase in
alumina solubility. [Link] [1987] has shown increase of Al solubility
in salt-acid solutions in equilibrium with corundum, with the existence of the
additional reaction of dissolving corundum:
0.5 Al2O3 + HCl + 0.5H2O = Al(OH)2Cl
and/or
0.5 Al2O3 + 2 HCl = Al(OH)Cl2 + 0.5H2O.

334
 Growth of alumina solubility is also experimentally established in aqueous
HF solutions [Haselton et al., 1988]. On fig. 19.8 is shown a combined diagram:
solubility of alumina in solutions, in equilibrium with different associations and
pH, constructed on data of various authors. These values have been either
obtained in experiments or calciculated especially for temperatures of 250-
450ºC. Noted are two fields of composition: 1) for solutions where acidity turns
out HCl and SO4 , and 2) for solutions with HF. Chlorido-sulfatic environments
are characterized by a sharp increase of Al solubility on 6 orders of magnitude
with the growth of acidity. The highest values of those present on the diagram
are obtained for solutions in equilibrium with Al2SiO3 (andalusite – cyanite)
[Ostapenko et al., 1987]. In contrast with alumina, silica solubility slightly
grows with increasing acidity of the solutions. This fact is marked in
experimental works [Haselton et al., 1988, Hollands & Malinine, 1982] as well
as in calciculations of silica solubility in salt-acid solutions [Ivanov, 1993].
These regularities can be seen on fig. 19.9: with the growth of alumina solubility
in solutions from near-neutral to ultra-acid on 6 orders of magnitude, silica
solubility increases only on 0.2 orders of magnitude.
Evolution of metasomatic systems leading to SQ formation. SQ
formation presents itself as an extreme degree of bleaching of metals from rocks
with acid and ultra-acid solutions. As the main source of acid components in
metasomatizing solutions serves a cooling magmatic melt, from which separates
a fluid consisting mainly of H2O+ CO2+HCl+ H2S+HF. From the preceding
section it follows that bleaching processes are linked with a high activity in
gradual dissociation of strong acids (HCl, H2SO4, HF) in aqueous solutions.
Small acidities (H2S, H2CO3) are lightly buffered by mineral enclosing rocks
and cannot create a sufficiently acid environment indispensable for SQ
formation. Correspondingly, amongst solutions producing silicification (forming
SQ and products of “advanced argillization”) two groups are distinguished: a
chloridic, with which is linked a substantial SQ, and a sulfate, producing
argilization.
In the process of cooling of magma and of a flow separating from it, HCl
is redistributed in the flow. The contemporary state of the question of HCl
behaviour in magmacrystallization is minutely examined in the work of
[Malinine & Kravchuk, 1995]. It may be cited as established that with pressure
of less than 1Kbar concentration of chlorides in fluid phase grows with time
until complete cristallization of magma. A reverse picture is observed at a
pressure of more than 1 Kbar. The higher the initial water content in the melt,
the higher the speed of decrease of chlore content in the separating flow. If we
admit that chlore concentration in acid melts reaches 3000g/t and the coefficient
of distribution Kcl= Xfl/ Xmelt=30, chlorine concentration in cooling magmatic
fluid solution may reach the value 0.09 g/l (or 2.5m).

335
 Oxygenous combinations of sulphur also play an important role in SQ
formation. [Link] [1971], on the example of Central Kazakhstan, was
one of the first to draw attention to the fact that variations of the temperature and
H2O/ H2SO4 ratio in solution determine SQ paragenes and the character of ore
loading. Formation of sulphuric acidity may occur by several means [Rye et al.,
1992]: 1) by oxidation of sulphides in hypergene conditions; 2) by oxidation of
atmospheric oxygen in horizontal ground waters H2S, acting from deep boiling
hydrothermal systems; 3) by means of disproportional magmatic SO 2 on H2S
and H2SO4, with concentration of the magmatic flow on intermediate depths of
hydrothermal systems. The first of the proposed mechanisms is determined by
formation of zones of hydrogene oxidation (for example, at solfatara
argilization); a second type is realized in epithermal deposits of adular-sericitic
type (“low sulfidation”) [Hedenquist, 1992]. A third mechanism, in which one
of the basic factors is an increase of oxygen activity in motherly magmas,
leading to a type of acid sulfidation (“high sulfidation”) of epithermal and
porphyric deposits. The SO2/H2S ratio in the magmatic flows is a function fO2,
determined by the reaction:
H2 + ½ S2 = H2S and O2 + ½ S2 = SO2.
This dependence is shown on fig. 19.10, illustrating the alteration of
volatile SO2 and H2S in the flow as function fO2 for a magmatic flow existing in
equilibrium with a magnetite-pyrrotite association (solid solution) (P=0.5Kb,
T=727ºC).
Concentration of magmatic flow at decreasing temperature leads to
disappearance of SO2. [Link] [1965] and later [Link] [1988] have
considered alternative reactions, determined by transformation of magmatic
sulphur (mainly SO2):
4SO2 + 4 H2O = 3 H2SO4 + H2S, (1)
and
SO2 + 6 H2 = H2S + 2 H2O. (2)
Thus, the H2O/ H2 ratio in magmatic fluid will determine a corresponding
deposition of reactions 1and 2 in transformed SO2 at cooling. Starting from
this, [Link] [1988] has shown that the sulfate type of metasomatism is
very much determined by an oxidizing – reduction condition in the
motherly magmas. Namely, the evolution of the flow of oxidized magmas by
disproportioned SO2 leads to metasomatism with high activity of sulfate
sulphur.
An additional mechanism, special to the appearance of hydrothermal
solutions in high H2SO4, HSO4-, SO4²- concentration is boiling in hydrothermal
reservoirs. The mv/m ratio (mv, m is the molarity of volatile in steam and liquid
phase respectively) at a temperature of 350-200ºC for H2S is 2-5 times greater
than for SO2 [Drummond & Ohmoto, 1985]. Therefore boiling of solutions must

336
lead to enrichment of the liquid phase of SO2 and unification of slightly volatile
components, H2, H2S (fig. 19.11).
Isotope research. Isotope researches, immediately touching metasomatites
forming bodies of SQ are relatively few. As most interested in fine grain of
actual material and method of investigation may be cited the work of [Link]
[Rye et al., 1992] in which for establishing the genesis of solutions is utilized
the isotope composition of alunite. The informative value of such an approach is
conditioned by the fact that this mineral can take four positions in which may be
distinguished variations of stable isotopes: H/D, 18O (in position OH), 18O(in
position SO4), 34S/32S. As a result of such research it was shown that
silicification processes in the epithermal deposits of Summitville are linked with
a disproportional magmatic SO2 and the formation of ultra-acid solutions. In
contrast to that, alteration of the outer shell of metasomatic bodies of quartz-
kaolinitic composition is linked with combined solutions of magmatic-meteoric
origin. Research on isotope composition of alunite on the contemporary
hydrothermal systems of Steamboat Springs, Waiotapu, have shown that
processes of ultra-acid leaching are linked with H2S oxidation of meteoric
waters at the level of ground waters.
Isotopes of oxygen has been studied on solfatara appearances of the
province San Juan [Larson & Taylor, 1987]; one appearance in this province is
the epithermal Summitville deposit, characterized above in detail. It is
established that variation of isotope composition of oxygen of metasomatite
(chiefly quartz) is closely correlated with depth, which in the opinion of the
authors, testifies to predominating control of isotope composition of oxygen by
processes of boiling of hydrothermal flows (fig. 19.20). Interesting are the
results of comparative analysis of isotope oxygen on solfatara appearances in
this province. Amongst the studied occurences highest 18O values in
metasomatic quartz are observed on the occurences accompanied with
mineralization. Moreover, a maximal height of 18O is observed on the
Summitville deposit, the richest ore object of the province, which may be linked
with an increased share of magmatic flow in the source of hydrothermal
solutions on ore-bearing manifestations [Larsson & Taylor, 1987]. Thus,
independent results of isotope research on alunite and quartz, with use of
different methods, lead to an unambiguous conclusion about the participation of
magmatic fluids in the formation of metasomatic SQ zones.
Detailed isotope studies have been carried out [Klein & Criss, 1988] on
paleohydrothermal systems of Precambrian early Paleozoic age of the Carolina
State belt (USA) [Schmidt, 1985]. The example is interesting in that an erosion
section of metasomatites represented on outcrops overturns on the side after the
formation of this hydrothermal system has been completed. A schematic
geological map of one of the zones of Pilot Mountain is offered on fig. 19.13.
The region is mainly situated in middle-acid volcanates intersecting stocks of

337
dacitic porphyries, and quartzic monzonites. Zones of metasomatic alteration
spacially gravitate to the stocks of dacitic porphyries. Metasomatic changes are
distinctly zonal. Background alterations are weak sericitization and pyritization.
An interesting metasomatosis has been produced on an area of 4x2 km and
presents intense rock silicification, development of lenticular bodies of quartz-
pyrophyllite, quartz-andalusite-pyrophyllite composition and massive bodies of
pyrophyllite composition. The general expansion has intersecting veins of
quartz-pyrophyllite composition (±sericite, ±kaolinite). The central part of the
metasomatic body is characterized by intense crushing of silicified rocks,
development of a quartz-topaz association. With development of metasomatites
are spatially connected geochemical Cu, Mo, Sn, Au, B anomalies. The authors
of the cited works have closely studied the variations of  18O/16O in mineral
metasomatites. Calciculated temperatures of isotopic quartz-H2O equilibrium
characterize the interval of 300±50ºC, and at the same time isotopic equilibrium
between pyrophyllite and quartz is broken (some authors compare this with the
subsequent metamorphic history of the region). Calciculated isotopic oxygen-
hydrogen of flow mark come across the line of isotope composition of meteoric
waters. An interesting detail in the development of SQ is the distribution of the
18O value in space. A relatively back stage value is that the field of
development of silicification is comparatively clearly distributed at increasing
values of 18O (5-6‰), whereas the stock of dacite porphyries is characterized
by minimal values of 18O (< 2‰). So, in a small part of the development of
metasomatites the zones are linked with highest and lowest 18O values.
Most data on isotope sulphur characterize copper-molybdene-porphyric
hydrothermal systems, which are discussed at length in a series of research
works. The chief peculiarity of isotopic composition of sulphur, sulfides and
sulfates is a narrow range of 34S, from –3 to +1 and from +8 to 15‰
respectively. As an example of such values is characteristic an isotope
composition of sulphur on epithermal deposits [Heald et al., 1987], which may
indicate a predominantly magmatic origin of the sulphur.
So, formation of SQ is linked with metasomatic influences of ultra-acid
solutions of polygene genesis. In rear zones of transformation, where acidity of
the solutions is maximal, arises a full dissolving of minerals, except quartz. As a
result of interaction with the rocks, acidity of the solution decreases, to which
testifies the exchange of monoquartzic with quartz-clayed or quartz-sericitic
composition of zones. Therefore must occur a sharp diminution of equilibrated
concentration of alumina in the solutions and an intense deposition of high
aluminous minerals such as andalusite, corundum etc. Such alterations of
alumina solubility contrasts with the behaviour of silica solubility, for which
such a jump of solubility is not observed. Consequently, filtration and
interreaction of ultra-acid solutions with rocks must lead to formation of

338
monoquartz bodies in kernel parts (where arises dissolving of all rock forming
minerals) and a high alumina halo around these bodies.
Similar zoning and succession of mineral formation with change of
solubility of the metals and their deposition reflects the passage of a wave front
of acid components, detected and studied by [Link] [1955]. In
conformity to this model, components depositing in various acidophily behave
differently in acid metasomatism. Amphoterites (alumina) dissolve, but do not
experience a significant displacement in space. After the passage of the acid
front they deposit here, in rocks and cracks in the quartz. Alkalis and alkaline
earths are not related with the solution and may either precipitate on limits of
silicified rocks or scatter in subterranean waters. The most effective processes of
formation of ultra-acid solutions occur at boiling and disproportional magmatic
fluid. Namely in this process are attained the highest concentrations of sulphuric
acid, which provides for the high solubility of such solutions. Peripheric parts
(in horizontal as well as vertical direction) present alkaline metasomatites
(advanced argilization) formed by mixing of ultra-acid magmatic fluids with
meteoric waters.
Ore mineralization in S.Q. High aluminous corundic SQ develop as raw
materials for obtaining aluminium, but basically for obtaining technical
corundum (abrasive). Rocks of the SQ type are studied in molybdene –
porphyric deposits, situated in contact zones of huge massifs of granite-
porphyries. In the Climax deposit molybdenite forms networks of veins and
accumulation in quartzites, associating with sericite, but, in deep horizons, with
orthoclase. In connection with more basic magmas of granodiorite-porphyry
silicification occurs more seldom, and the chief type of exchange of rocks
occurs with sericitization. In seriticized rocks stockwerk appears made up of
veinlets of chalcopyrite and molybdenite, associated with quartz and sericite.
Other spatial correlations are observed between silicified rocks and pyrite ores.
Zones of silicification and quartz-sericite rocks dispose themselves under a
deposit of massive sulfides in the domain of the channel on which have entered
ore solutions. Habitually the composition of these zones are of quartz+pyrite or
quartz+serecite+pyrite, but in comparatively rare cases have been described
quartzites with corundum, andalusite and diaspore, accommodated in the same
position.
The situation is more complex with silicified rocks in intervals of gold-
silver deposits. There usually appear facies of hydrothermal argilitized rocks,
which also appear as ore- containing. Silicified solutions (monoquartzites,
quartz-kaolinite, quartz-alunite rocks) often compose a field of deposited lenses
or layer-formed bodies, which serve as screen for ore-bearing solutions in a
sericite-adular type of deposit. In the acid-sulfatic type of
deposit silicified rocks with diaspore, andalusite, sometimes with alunite are
encountered immediately in ore veins of steeply diping metasomatic zones.

339
 In volcanic domains are spread opalites and near-surface quartzites,
contained as deposit fossil native sulphur, which forms veins, lenses and
disseminated accumulation in quartz or in opal. Vertical zoning is observed,
consisting of sulphur opalites in succession from below upwards with massive
sulphides of iron (Matsuo deposit in Japan, on volcan Mendeleev on Kunashi
island). Sulphur quartzites contain gold pigment and set down tubular bodies,
traced on Paramushir island on a depth up to 300m.

340
Figure 19.1. Geological outline of alunite-andalusite-corundum deposit of Semiz-Bugu
[Nakovnik, 1964].
1 granites; 2granite-porphyries; 3-acid affusives; 4sericitic secondary quartzites
(SQ); 5quartz-sericitic rocks; 6quartz-sericite-andalusitic rocks; 7  monoquartzites; 8, 9 
andalusitic SQ; 10alunitic SQ; 11alunite-andalusitic SQ; 12area of development of
veinlets and dissemination of corundum; 13main corundum body; 14small corundum
bodies; 15detritic corundum; 16dykes of diabases; 17alluvium; 18axial lines of ridges.

341
Fig. 19.2. Geological map of district of Summitville deposit [Stoffregen, 1987].
1- quaternary; 2-rhyolites (18-20 million years); 3-quartzic latites (21-23 million
years); 4-andesites (26,6 million years); 5-rhyodacites (27,7 million years); quadrangle
surrounds limits of area on fig. 19.3a.

342
Fig. 19.3. Distribution of basic types of altered rocks on Summitville deposit [Stoffregen,
1987].
a- areal distribution: 1- bodies of cavernous quartz; 2-undifferentiated quartz-
alunite-kaolinite alterations; 3-acid alterations; 4-fresh rocks; b-cross-section in A-A profile.
Distribution of bodies of cavernous quartz (1) and quartz-alunite alterations (2) on vertical
with depth transition into slightly thick (1-2 m) bodies of cavernous quartz (3) with quartz-
kaolinite margin.

343
Fig. 19.4. Geological map of Ebeko volcano [Zelenov. 1972].
1-fresh basic lavas and tufas; 2-old volcanic cavernity; 3-zones of opalite
development; 4-young andesites; 5-pyroclastic rocks; 6-acid source and lake; 7-solfatara;
8-craters of volcano. White spring Hotter lake South crater

344
Fig. 19.5. Distribution of newly formed minerals in a vertical cross-section of the
Steamboat-Springs deposit [Schoen et al;, 1974].

345
Fig. 19.6. T-P diagram of the Al2O3-SiO2-H2O [Ivanov, 1993]
Univariant reactions: 1. Gib = Dsp+H2O, 2. 2Qtz+Kln=Prl+H2O, 3.
2Kl=Prl+2Dsp+2H2O, 4. Prl + 6 Dsp = 4 And + 4H2O, 5. Prl+6Dsp = 4 Ky + 4 H2O, 6. Prl =
3 Qtz + And + H2O, 7. Prl = 3 Qtz + Ky + H2O, 8. 2Dsp = Cor + H2O, 9. And = Sil, 11. Sil =
Ky, 12. αQtz = βQtz. A-F parageneses of facies on triangular composition-paragenesis.

346
Fig. 19.7. Stability fields of minerals on diagram T-log mSiO2 in Al2O3-SiO2-H2O system
along curve of boiling of water [Hemley et al., 1980].
Notation for reactions: 1. Prl+5H2O= Kln+2H2SiO4, 2. Kln+3H2O=2Dsp+2H4SiO4, 3.
Prl+8H2O=2Dsp+4H4SiO4, 4. Prl+5H2O= And+3H4SiO4, 5. And+3H2O=2Dsp+H4SiO4, 6.
And+2H2O=Crn+H4SiO4, 7. Qtz + 2H2O = H4SiO4, 8. Crn+3H2O=2Dsp.

347
Fig. 19.8. Dependence of solubility of aluminium (mol/kg) upon acidity of saline and
sulfate solutions (quadrants and curve 1) and fluorid solutions (triangles and curve 2) in
temperature interval 250-4500C.
Constructed on data of experiences and thermodynamic modeling [Becker et al., 1983;
Stoffregen, 1987; Korzhinsky. 1987; Ostapenko et al., 1987; Haselton et al., 1988; Ivanov,
1993].

348
Fig. 19.9. Correlations of solubility of silica, solubility of aluminium (mol/kg) in muriatic
and fluorid solutions at 4000C after data of [Haselton et al., 1988; Ivanov, 1993].

349
Fig. 19.10 Volatility of basic components of a magmatic fluid in equilibrium with
magnetite and pyrrhotite at fO2 equal QFM, QFM+1, QFM+2, QFM+3 and 7270C, 500
bar, Xc=0,1.
Values fS2 and fO2 are given for equilibrium of pyrrhotite (solid solution)-magnetite
after data of [Whitney, 1984]. The parameter Xc equals the sum of mole parts of CO 2, CO,
CH4 in the fluid.

350
Fig. 19.11. Temperature dependence of parameter lg(mν/m) for basic components of an
aqueous hydrothermal fluid [Drummond and Ohmoto, 1985].
mν and m, molar concentrations of gases in steam and liquid phase respectively.

351
Fig. 19.12. Calculated model of isotopic composition variations (δ18O) of hydrothermal
quartz in equilibrium with an acid fluid with initial boiling temperature of 275, 300,
3250C for solfatara manifestation in the San Juan province [Larson & Taylor, 1987].
Points indicate dimensions of δ18O value in hydrothermal quartz in vertical cross-
section of a hydrothermal system.

352
Fig. 19.13. Geological map of ore area of Pilot Mountain [ Klein & Criss, 1988].
1-acid volcanic rocks; 2-arenites, clays; 3-andesites; 4-quartz monzonites; 5-dacite
porphyries, altering rocks; 6-Qtz-Prl-And; 7-Qtz; 8- Chl-Ser; 9 -Qtz-Ser; 10 -points of gold
ore mineralization; 11- abandonment of gold ore reefs. Dotted lines indicate isolines of δ18O
in the rocks.

353
 CHAPTER 20

Beresites and beresitized rocks

Definitions. The term “beresites” in its original sense designates

metasomatically altered granites near quartz-gold ore veins, composed of
sericite, quartz, pyrite and ankerite. Beresites are formed as a result of acid
metasomatism with high carbon dioxide fugacity. Subsequently similar ones
have been investigated in the composition of rocks transformed not only at the
expense of granites but also on other intrusives, volcanic and volcanogene-
sedimentary rocks in an analogous process of acid metasomatism. The term
“beresite” is applied to metasomatic rocks of quartz+sericite + ankerite + pyrite
composition, i.e. to rocks of inner zones of metasomatic columns. To
moderately or feebly altered rocks of outer zones of transformation is applied
the term “beresitized rocks”. Such an interpretation of so-called ore-enclosing
rocks was already put forward by [Link] and M.B. Borodaevskaia
[1947], and the process of their formations was called beresitation. The mineral
composition of beresitized rocks varies: apart from ankerite, may be present
other carbonates, and principally are encountered quartz-sericitic (non-
carbonatic) varieties, etc.
Beresitation presents itself as one of the most widely spread types of near-
vein transformation and was seen in connection with deposits of gold, silver,
polymetals, uranium, fluorite, molybdenum. Beresites have long since attracted
the attention of researchers, which can be seen in the abundance of works
devoted to this type of transformation. The term “ beresite” was proposed by
[Link] in the middle of the nineteenth century for sericitized granite-porphyries
and aplites of the gold ore Berezov deposit in the Ural. Later these metasomatic
formations were studied in detail by [Link], [Link],
[Link], [Link], [Link], [Link] and
many others. Thanks to [Link]’s ideas in the succeeding time progress
was made in the study of the genesis of this type of transformation which was

354
specially accompanied by the works of [Link], U.B. Shapovalov,
[Link], V.A. Zharikov, devoted to theoretical and experimental
modeling of beresitation processes. These processes, forming on rocks of
ultrabasic composition, have received the name of listwaenitization owing to the
green colouring of arising metasomatites. They have a quartz-carbonate, talc-
carbonate and fuchsite-quartz-carbonate composition. “Beresitation” is a notion
used only in Russia. In foreign literature, a synonym is “sericitization”, but if the
term beresite is utilized, it is only concerning the gold-ore deposits of Russia and
with reference to Russian researchers.
Parageneses of quartz with sericite and carbonates are of themselves yet
no indicator of metasomatic family of beresites, insofar as it can also be
observed in rocks of another genesis, for instance in sediments having
undergone initial metamorphism. In complex cases it is necessary to employ a
combination of signs, the principal of which are geological setting, structure
control, mineral composition, character of metasomatic zoning and presence of
ore mineralization. Non-carbonatic facies of beresites arise in acid magmatic
rocks (aplites, leucogranites), impoverished in calcicium and magnesium.
Quartz -sericitic metasomatites sometimes preceed in a special formation,
characteristic, grosso modo, of pyrite and pyrito-polymetallic deposits [Zharikov
and Omelianenko, 1965]. Quartz-sericitic near-ore rocks are characteristic also
of deposits of copper and molybdene of porphyric type, in which they closely
associate with SQ.
Geological position of beresite formation. Beresite extension is limited
to domains of development of an orogene granitoid magmatism in a crust of
continental type. The time interval of their development is from late
Precambrian to Mezozoic-Cenozoic, but the maximal extension of beresites
occurs in the hercynian and mesozoic epochs. The process of beresitization
occurs after full completion of intrusive and effusive magmatism, and they are
preceded by the appearance of metasomatism at the magmatic stage.
Intersections of beresites with magmatic bodies are possible if the latter belong
to a later magmatic cycle. In the evolution of the hydrothermal process, after
beresitization occurs ore mineralization and may develop low temperature
argilization.
Beresitized rocks present themselves as typical peri-ore metasomatites on
many middle-deep (2-3 km) deposits in paleozoic domains (Ural, Kazakhstan,
Central Asia, Central Europe, Appalachians, Eastern Australia), and also
Mesozoic deposits (Transbaikal region, Mongolia) of orogenesis and
tectonomagmatic activization. In domains of quaternary and contemporary
volcanism typical appearances of beresitization are unknown.
Areas of extension of these metasomatites wholly coincide with the
domains of development of granitoid intrusive massive subvolcanic bodies or
regional dyke belts, characteristic of ore-districts of the Transbaikal, Central

355
Asia, etc. A genetic link of beresites with magmatism was established on the
example of the Kurama volcano-plutonic belt in Central Asia [Abramov et al.,
1995].
Beresites belong to metasomatites of local extension. They are distinctly
controlled by fracture zones or thick zones of lamination and cataclasm. In the
latter case the total thickness of beresitiization aureoles attains many hundreds
of metres. Thus, the predominating form of metasomatic bodies is near to
veinous or stratiform but the thickness of this strata reaches 100 and more
metres in effusive and sedimentary rocks. The problem of the familly-belonging
of such so-called back-ground regional zones of sericitization in volcanic masses
remains until now under discussion, and the criteria of development zones of
regional quartz-sericitic transformation and near fracture beresites are
undefined. A direct link between them may also not exist and the geologico-
structural conditions of their appearance may be strongly different. So, strictly
beresites or “full-appearing metasomatites”, according to [Link]
[1981]superficially distinct gravitate around fractures and are linked with
hydrothermal flows, whereas slightly changed beresitized rocks may attain
thickness of tens of km2, not displaying however a distinct confinement to
cracks and fissures and an obvious link with magmatism.
Beresites preceed ore-deposition occupying a volume of rocks,
significantly exceeding the volume of the ore bodies. Veinous metasomatites
associates to ores or periveinous metasomatites (chloritic, carbonatic, albitic,
etc) are spread only in inner zones of beresitization columns.
Mineral composition. To the number of chief minerals occurring in the
composition of beresite familly are quartz, sericite, carbonates, chlorite, pyrite,
fuchsite.
Sericite is the chief typomorphic mineral of beresites. Crystallo-chemical
and structural peculiarities of sericites are uniform, independent from the facies.
The problems of nomenclature of dispersed potassium mica have been partially
treated in a work devoted to this group of minerals [Omelianenko et al., 1982].
To sericites it is proposed to relate fine scale micas, varying in composition
between muscovite, phengite and illite; moreover isoorphism of the muscovite-
phengitic type is predominant in the strictly beresites, but isomorphism of the
illitic type predominates in their lower temperature facies. Content of swelling
interstices of the smectitic type in sericites may not exceed 5%, that of
hydromicas 15%, but in mixed-layered minerals of micasmectitic type it varies
from 15 to 45%. These definitions of sericites and hydromicas are not universal,
and in foreign literature to sericites are related all fine-scaled potassic bright
micas of hydrothermal genesis, containing up to 40-50% interstices of the
smectitic type. Fine-scaled micas of beresites answer to polytypical modification
2M1, or a mixture of 2M1+1M with predominance of the first, the polytype 3T
much rarer.

356
 Chemical composition of sericites differs from theoretical muscovite by
increased content of silicon and decreased content of aluminium (fig. 20.1).
Near the muscovites are micas from gold-bearing hypabyssal beresites. Degree
of mica phengiticity may change in the limits of one deposit, changing in the
direction of the ore vein. Micas from low temperature facies of beresitized rocks
have illitic composition (formula of illite K0,75(Al1,75R+0,25)Si3,5Al0,5O10(OH)2). It
can be seen on the diagram that mica compositions from typical beresites are
approximately embedded on the line of muscovite-phengite. Distinctly
distinguished from them are the dispersed micas from lower temperature
hydromicaceous metasomatites. These differences are also well surveyed in
other diagrams (fig.20.2). Sodium micas (paragonites) are relatively rare in
beresitized rocks, they are more often encountered in listvenitized basic rocks.
Examples are known of development in periore metasomatites of a mixture of
paragonite and muscovite or combined minerals of the muscovite-paragonitic
type, which are counted as result of imposition on metasomatic processes of
regional metamorphism. However, research by [Link] [Grabezhev et al.,
1945] of gold ore deposits of the Ural have revealed the regular presence there
of paragonites and beresites. It is possible that this mineral was not replaced
earlier because of its similarity with potassic micas.
Anion composition of sericites has on the whole no clearly marked
specific character. In some gold-silver-polymetallic epithermal deposits, but also
in uranium deposits in volcanic masses, sericite contains a noticeable quantity of
fluor, up to 1 mas.%. This is comparable with the fluorine content in micas from
higher temperature metasomatic formations (apogranites, greisens, zwitters) and
indicates a significant fluorine activity in hydrothermal solutions at pre-ore stage
of acid bleaching [Perry et al.,1984; Rusinov, 1989].
In listvenites mica is often represented by fuchsites containing chrome in
which it fluctuates in wide limits, from 0.2 to 3.5 mas.% [Sazonov, 1975].
Fuchsites of many gold-ore deposits on corresponding Al and R+2 in octahedric
coordination approach phengites. Micas from listvenites are characterized by a
bright iron coloration and usually a great dimension of the flakes (up to 3 mm).
Fuchsites are found also in beresitized rocks on volcanites of medium and even
acid composition in some gold and pyrite deposits. If in basic or ultrabasic
chrome with listwaenitization mica is borrowed from lateral rock, with
beresitization of dacites there is an obvious influx of chrome from an outer
(deep) source.
Carbonates together with sericites appear as minerals typomorphic for
beresites, and are wholly varied in composition. They are represented in groups:
1) dolomite –ankerite, 2) calcite, 3) magnesite –siderite and their manganese
varieties. Appearance of this or of another carbonate is determined by the
composition of enclosing rocks. In listvenites carbonates are usually represented
by magnesites, rarely by brennerites. More ferruginous varieties are mezitite,

357
siderite, magniosiderite, pistomesite, rare in listvenites. Carbonates of the calcite
group are usually developed in outer zones of beresitization columns, which
sometimes may contain a noticeable quantity of iron and manganese. Ankerite
and other minerals of this group are the most universal and spread in beresites
on various types of rock. Content in them of ferro-ankerite minal does not
exceed 25%, often is present a significant manganese mixture (up to 4,5 mas.
%MnO).
General content of carbonates in rear zones on rocks of medium and basic
composition may reach 60% of their volume. The total picture of carbonate
extension, synchronous with acid leaching is complicated by the repeated
appearance of later acid stages. The latest low temperature stages are present
only in veins of pure calcite.
Chlorites are characteristic of outer zones of beresitization aureoles,
where they develop pseudomorphically on dark-coloured minerals. Further, with
the increase of metasomatic transformations, chlorites mix with ankerites or
siderites and bright mica. Much more widely chlorites are spread in close
association with ore minerals in the composition of ore-accompanied or post-ore
veins. The composition of chlorites from beresitized rocks varies widely
(fig.20.3). The diagram shows that these chlorites noticeably differ from the
metamorphic in AlIV content, which is lower than 1,3 but higher than 0,8 (the
latter value characterizes the swollen chlorites). Ferruginosity varies within wide
limits, but already in chlorites from listvenites the value of the Fe/Fe+Mg ratio
does not go below 0,2 [Sazonov, 1975]. As the most ferrouginous are observed
ore-accompanied berthierites and chlorites from ore association. Iron content in
chlorites is also conditioned upon sulphur activity which controls chlorite
ferrosity on the following reactions:
ChlFe + H2S  ChlMg + Pyr + H2O.
Existing analytic data, the shown Fe+3/Fe+2 ratio in chlorites testify to a
rare predominance of ferrous oxide.
The development of this or of other types of chlorite in beresites may be
for ore regions typomorphic signs of a definite aspect of mineralization. For
instance, in the Eastern Transbaikal ore province the uranium deposit in
hydromicaceous metasomatites is characterized by a wide extension of
berthierites, but the polymetallic and gold-polymetallic deposits have normal
14A chlorites of varying ferruginosity.
Peculiarities of chemical composition of beresites. The chemism of the
beresitization process is defined by the acid character of the solution as well as
by the composition of the initial rocks. For rocks of acid composition is recorded
an intense removal of bases and addition of silica, water, sulphur and carbon
dioxide. In the outer zones of metasomatic columns functions a removal of Ca
and Mg to the extent of approaching the central zones: Fe, and then : Na. In the
inner zones of quartz-sericitic composition, where disappear relicts of potassic

358
feldspars, may decrease the K content, and in the monoquarzitic zone occurs a
full removal of K and Al. In intermediary and inner zones, at the expense of
disseminated pyrite may grow the Fe content. In the course of transformation of
rocks of medium and basic composition is characteristic an influx of carbon
dioxide linked with massive development of carbonates. In dependence upon
their composition occurs a redistribution of Ca, Mg and Fe. In intermediary and
inner zones of the columns is observed a partial removal of silica and
accumulation of K and Al at the expense of sericite development. Characteristic
are opposite tendencies in the behaviour of SiO2 and CO2: from outer to
intermediate zones decreases the content of silica and increases carbon dioxide.
In the inner zone silica content increases and correspondingly carbon dioxide
provokes an increase of silicification.
Upon serpentinite listvenitization Si is removed, and in most columns also
Al, Fe, Ni, Mg and Ca, K, C, S are added. Titanium is in most cases inert. Al,
Fe, Cr, Mn in a few cases are added, linked with fuchsite and pyrite. On the
whole, the direction of chemical transformation at berisitization is accompanied
by removal of alkaline-earth elements and hydrolysis of feldspars according to
the scheme:
albite + K+ + H+  muscovite + quartz + Na+;
potassic feldspar + H+  muscovite + quartz + K+;
Often in beresites on rocks of basic composition there is no inner
monoquartzic zone. In a quartz-sericite zone may be observed sharp increase of
Al and K content and abundance of sericite. Moreover sericite forms a full
pseudomorphosis on feldpars:
potassic feldspar + H2O + Al2O3  muscovite + 2SiO2 (solution);
which is linked with a shift of aluminium in conditions of low pH of the fluid.
Facies varieties of beresites. Facies of beresitized rocks are determined
in dependence upon the influence of the composition of initial rocks and
intensive factors, chief of which are T, fCO2, fS, pH. Facies conditioned by the
influence of the initial composition of the substratum, are represented by
beresites and listvenites. The former are characteristic of altering rocks of a wide
spectrum of compositions, from rhyolites and granitoids to gabbro, the second
are only for rocks of ultrabasic composition or serpentinites developed on them.
To this same group are related non-carbonatic facies of beresites on united
alkaline-earth elements of ultra-acid granitoids.
Apart from the most widely spread quartz-ankerite-sericitic facies, to the
number of facies determined by intensive parameters, are related calcite-sericite,
sericitic-chlorite-calcite facies (low pH and fCO2) and hydromica-quartzic facies
(low temperature).
Facies of quartz-ankerite-sericite metasomatism (substantially beresites)
represent the most spread type of hydrothermal medium-temperature periore

359
transformation. The chief typomorphic sign is the development of inner zones of
parageneses of quartz with sericite, ankerite and pyrite.
According to [Link] [1978] to each metasomatic facies
corresponds a determined type of metasomatic columns. The zoning present
below reflects the basic tendency to metasomatic transformation in granites: 1)
granite-quartz, potash feldspar (pfs),oligoclase, biotite, amphibole,
titanomagnetite; 2) feebly altering granite, quartzite, potash feldspar, albite,
calcite, chlorite, dolomite, sericite, pyrite; 3) beresitized granite, quartz-sericite,
potash feldspar, ankerite, pyrite; 4) beresite, quartz, sericite, ankerite, pyrite; 5)
quartz, sericite, pyrite (inner zone of full silicification is observed rarely
enough).
The general direction of the metasomatism process does not depend upon
the composition of the rocks. As an example of alteration of rocks more basic
than granites may serve berezitized diorites of the uranium deposit Ishimskoe in
Central Kazakhstan (fig.20.4), where beresitization ends in the formation of an
inner quadrimineral zone of quartz+sericiteankerite+pyrite.
In the development of hydrothermal transformation on bifeldspar rocks
plagioclase most often dissolves first, the potassic feldspar (kfs) is much more
stable, and its relicts are often preserved in inner zones, even in contact with ore
veins. This manifestation in general conforms well with data on equilibrium
albite + K+ = Kfs + Na+
At 300ºC the constant of equilibrium nears 1, but sharply grows with the
sinking of temperature, which increases the stability of kfs relatively to albite. A
reverse correlation corresponds to beresites of higher temperature, in which are
noticed sodic micas (paragonites) [Sazonov, 1979; Grabezhev, 1995].
The facies of listvenites is less spread than the quartz-ankerite serititic, and
coincides with serpentinized ultrabasic rocks. Listvenites are characteristic of
gold-sulphid deposits of the Ural, Altaï, Sayan and other regions. In foreign
literature these rocks are described as quartz-carbonate magnesite
metasomatites, but also under the name of “duelo”, “virginite”. Listvenites are
met in homogenous rocks, forming zonal aureoles, as well as in contact of
various surroundings, for instance of granites and serpentines. Typomorphic
minerals of listvenites are ferro-magnesian carbonates (breunnerite, magnesite,
dolomite, parankerite), fuchsite,pyrite. Quartz is less significant. A source of
chrome for fuchsite are chrome-spinelites, incoming in the composition of
ultrabasic rocks. Initially, according to [Link], [Link], [Link]
hydrothermal transformations of ultrabasic rocks, replaced by breunnerite,
quartz, potassic mica (fuchsite) were called listvenites. Talc is not observed in
compositions of synchronic zoning. A typical metasomatic column of
listvenitization, with a general thickness of altered rocks not greater than 25m,
has the following aspect [ Borodaevsky and Borodaevskaja, 1947, Borodaevsky,
1958,Sazonov, 1975]:

360
 1. “Grey” listvenite on serpentinite or talc-carbonatic metasomatite:
breunnerite or dolomite, quartz, chromite, pyrite. 2. “Ferrous” listvenite:
breunnerite, ankerite (the zone does not exist everywhere).
[Link] [1979] has obtained data of definition of K-Ar growth for
granite-porphyrite and fuchsite-containing listvenites developed in them, which
indicated a genetic link of the latter with granite porphyries.
In hydromicaceous facies exist mixed-layered mica-smectites and
hydromicas instead of sericites. Other differences from beresites are reduced to
the decrease of pyrite extension and increase of hematite, and also to a large
development of berthierites, mixed-layered chlorite-smectites. From their
argillisites differs the absence of metasomatic kaolinites and smectites.
In the limits of some deeply laid open deposits of acid type with
increasing depth is traced a mixture of hydromicaceous metasomatites with
typical beresites in the limits of single aureoles of hydrothermal transformation
and coinciding with one the same solution-producing structure [Andreeva et al.,
1996]. Isotopic K-Ar datation, adduced on dispersed micas of the Streltsov
uranium deposit, the biggest uranium deposit of Russia, reveals a superficially
identical growth value for all the interval of deeply laidopen ore-bearing zones
(table 20.1). Thus, the

Table 20.1. Results of isotope K-Ar datation of dioctahedric dispersed micas

from metasomatic various hydrometric levels of the Antei-Streltsov deposit
40
Depth of Content of K, % Arrad, Growth, Enclosing rock
chosen swelling ng/g in 1000
samples, mixed layer, years
m %
190 8-10 5,24 51,0 136±6 Trachydacite
250 6-8 6,22 84,8 130±5 Trachydacite
broken down
320 8-10 6,70 67,2 139±6 Basalte
430 10-12 6,87 66, 134±5 Granite
598 6-8 6,40 157,8 129±5 Granite
broken down
1031 6-8 6,12 59,1 134±5 Granite
1070 <5 6,98 69,5 138±5 Granite
1422 6-8 7,28 68,8 134±5 Granite
1596 5-7 5,84 57,9 138±6 Granite
2145 0 6,80 65,0 133±5 Granite
2161 0 7,63 74,0 135±5 Granite

361
beresitic and hydromicaceous type of alteration does not have precise
boundaries; sometimes they coexist with the limits of one deposit and a single
metasomatic aureole; they can therefore be maintained in the composition of one
familly.
Ore-accompanied metasomatic and veinous formation in beresites. To
ore-accompanied are related mineral associations formed simultaneously or
nearly at the same time with the deposition of ore minerals. They are spatially
very closely linked with ore. Of ore-accompanied metasomatites, as was already
established by [Link], is typical the gathering of minerals, the
composition of which is in a significant measure conditional by chemical
components leached from enclosing rocks in the process of their hydrothermal
transformation.
Meatsomatites of acid bleaching type of beresites in the composition of
ore-accompanied associations are characterized by chlorites, berthierites,
carbonates (mainly ferriferous and magnesian-ferriferous), pyrite, hematite,
albite, adular, fluorite. These minerals are spread in veins as well as in
metasomatic form, laying borders, edgings on the periphery of accumulation and
veins of ore minerals. The thickness of the manifestation of these metasomatites
is usually interrelated with the power of ore bodies, but much smaller than the
thickness of aureoles of beresitization. A very important peculiarity of these
transformations consists in the full absence of zoning, which undoubtedly
testifies to the distinct disquilibrium of the whole process of acid mineral
transformation (including periveinous metasomatosis), following a stage of acid
leaching.
Chloritization is known practically on all deposits, sulphidic, gold-ore
uranium, molybdene-uranium, fluoritic. Chlorite accumulations, sometimes
nearly monomineral, form uneven zones of thickness of up to tens of
centimetres, bordering ore bodies. Chlorite deposition may come significantly
later then relatively important ore stages. The predominant type of chlorites
usually depends upon facies of metasomatites: in beresites develop ferrous and
magnesian-ferrous chlorites and in hydromicaceous metasomatites, ferrous
berthierites or swelling chlorites.
Albitic ore-accompanied transformations were for a long time studied in
uranium deposits [Andreeva & Golovine, 1979; Naumov, 1985], but later albite
was discovered in some metasomatic gold-ore deposits [Moissenko et al., 1978;
Rusinov et al., 1996]. An example of development of albite metasomatites is the
Streltsov uranium deposit, where these transformations are developed in various
rocks of effusive thick cauldrous and granitoid substratum (fig.20.5). The
thickness of the zone of veinous metasomatic albitization isn’t great and only in
granitoids can they reach the first metres, tracked down to a depth of 1800m.
Albite corrodes and mixes with hydromicas, rock-forming potassic feldspar and
plagioclases. Quartz mixes with albite only in areas of maximal interaction.

362
 Na2O content in albitized dacites may reach 7%, in granitoids up to 10
mas.%, but content of trivalent iron in albitites is of 1-2% relatively to the initial
rocks. Hematite-albitic metasomatites always contain increased concentration of
uranium, basically in the form of urano-titanates.
In the limits of sulphid gold-ore deposits, metasomatic-veinous albite is
displayed only on deep and medium horizons and also near in time to chief ore
stages.
Paragenetic analysis and basic physico-chemical parameters of
beresitization. Mineral parageneses of beresites are determined above all by
temperature conditions, rock composition and CO2 activity. According to
definitions given by [Link], the conditions of beresite formation are at
rather low temperatures, at which there are stable parageneses of carbonates
with potassic mica in the absence of calcic silicates.
Available data of study of fluid inclusions display a significant Thom
dispersion, but quartzes, which maximally approach in time the formation of
zonal aureoles of metasomatites, are characterized by temperatures of 280-
320ºC and pressure up to 1 kb. For the determination of T-P conditions of
beresitization are also utilized various mineral thermobarometers: dolomite-
calcicitic, muscovite-chlorite, plagioclase-muscovite, breunerite-ankerite.
According to these data, beresitization temperature oscillates between 490-
350ºC at pressure of lithostatic burden [Sazonov, 1984] or corresponds to a
wider temperature interval of 450-250ºC with pressure from 0,5 to 2 kb
[Martynov, 1992].
Surface temperature limit of beresitization according to these data is
somewhat increased. So, with an experimental modeling of beresitization
[Shapovalov & Zaraisky, 1978] it was established that its surface temperature
limit, although it depends in a significant degree upon carbon dioxide, all with a
high enough share of XCO2 = 0.2, does not exceed 380ºC. Above this
temperature there develop quartz-sericitic metasomatites, or, in alkaline milieu,
gumbeites. And higher temperatures do not promote stability of ferrous
carbonates, particularly of carbonates in the order of siderite-magnesite.
According to experimental data of several authors, temperature stability of
magnesian-calcic carbonates grows correspondingly in the magnesite 
dolomite  calcite order. With this association of quartz with magnesite with a
share of carbon dioxide, equal 0,2, stable at a temperature not above 300ºC, but
the dolomite association not above 380ºC.
The lower temperature limit of beresitiization is conditioned by
displacement of sericite by mixed-lagered minerals of micasmectite type and
other clayey minerals. Temperature regulation of the stability of hydromicas and
adaptation of micasmectites to high content of mica layers is difficult to evaluate
inasmuch as they present themselves as metastable formations. Available data of
direct observation of contemporary mineral formation in thermal fields indicate

363
manifestation of non-swelling illites already at a temperature of 210-220ºC
[Muffler & White, 1969]; Cathelineau, 1988]. According to experimental
researches on beresitization, at temperature of 250ºC and higher, mixed-layered
phases are not fixed, but calciculated data [Redky & Omelianenko, 1983] on the
model K-Na-Si-Al-H2O-NCl system show the possibility of formation of mixed-
layered illite-smectite already at 250ºC. Apparently, to this temperature may be
counted the lowest temperature limit of beresites. Hydromicaceous
metasomatites correspond to the interval of roundly 230-250ºC.
At lower temperatures, metasomatic columns are formed with
participation of smectites and mixed-layered illite-smectites with a great content
of swelling interlayers (rectorites and rectorite-like phases) and kaolimites.
Hydrothermal solutions, called beresitiization have a complex cationic
and anionic composition. Data of study of flow inclusion in vein carbonates and
quartzes [Sazonov, 1984] show the constant presence of Na +, K+, Ca+2, Mg+2,
HCO3-, Cl-, rarely of SO42-, F-; in gaseous phase of inclusion are present H2O,
CO2, N2; Na+ always predominates on K+. CO2 content in inclusions of vein
minerals oscillate within wide limits, and sometimes carbon dioxide occupies
almost the whole volume of the vacuum. From model experiments it is known
that with XCO2 values about 0,01 in altering rocks is calcite noticeable, and
ankerite is observed only if this value exceeds 0,05. Metasomatic zoning of
usual beresites develops with the value of carbon dioxide about 0,1.
Carbon dioxide fugacity at constant temperature has a decisive influence
on the growth of ferruginosity of carbonates towards inner zones of metasomatic
columns, which is a nearly general manifestation. This impartially for the
dolomic-ankerite and magnesitic-siderite. Extension of carbonate ferruginosity
in this direction is promoted by the growth of acidity of the milieu, and a
diminished activity of magnesium compared to iron [Korenbaum, 1967;
Sazonov, 1984; Martynov, 1992].
The dependence of parageneses of inner metasomatic zones upon
intensive parameters is illustrated on a diagram (fig.20.6). They give the
possibility of evaluating the possible variation of solution in relative
concentration of potassium and carbon dioxide and the possible T-P conditions.
Potassium content ought to correspond to the value of the ratio lg(aK+/aH+) =
1,5-2,5. Otherwise, at less than 300ºC, sericite ought to mix in the rear zones of
the kaolinite columns. Above 320ºC beresites give way to non-carbonatic
quartz-sericitic metasomatites, analogous to low temperature greisens. In higher
concentration of potassium and increasing temperature beresites turn into
gumbeites.
Growth of pressure (with constant carbon dioxide concentration) favours
reactions of carbonatization, with which the formation of carbonates ought to go
on in a succession of calcite  ankerite  breunerite. However, as far as
beresites are related to metasomatites principally of one hypabyssal facies of

364
depth, pressure variations at beresitization are immaterial. Moreover, the
enumerated order of carbonates often does not correspond to the vertical zoning
of beresites observed in real conditions. Mineral associations with calcites does
not characterize near-surface horizons but the deepest ones, and ankeritic and
breuneritic associations characterize the superficial and middle ones. This
peculiarity is mostly observed in metasomatites with significant vertical
amplitude of mineralization (fig.20.7), linked with the existence of a vertical
temperature gradient, which is strengthened by a distinct replacement depth of
hydromicas and illite-smectites by non-hydrated sericites. The values of surface
pressure, which are sometimes based on data of research on fluid inclusions in
veinous minerals, are related to later veinous stages of mineral formation and
may be linked with tectonic constraints already in postmetasomatic periods of
development of a hydrothermal system.
Significance of beresites as periore rocks. With beresites are linked
many ore deposits of uranium, polymetals and gold. Beresites may even be
mentioned as metasomatic familly, typomorphic of polymetallic and gold ores.
In these cases, when polymetallic ores are spatially associated with higher
temperature metasomatic formations, for instance with skarns, a detailed
research always indicates a later development of beresite parageneses (or
listvenites). Low temperature facies of beresites (hydromicaceous
metasomatites) are typomorphic of deposits of uranium and fluorite.
Mineralization in beresites is related to a connected type, on the
localization of any ores regularly linked with a horizontal and a vertical
metasomatic zoning. Rich ore, as a rule, coincide with the inner zone of a
metasomatic column in its section of their greatest thickness. Ore bodies may
also be localized outside the limits of the inner zone, but sometimes they do not
leave the zonal aureoles of beresitization. Practically in all cases of appearance
of ore mineralization are traced accumulations of ore-accompanying minerals,
chlorite, carbonates, berthierite, albite, adulare, sericite of 2M2 modification, etc,
the formation of which occurs after a stage of leaching. Their secretion has a
combined metasomatico-veinous character, but the intensity of their
development is nearly always proportional to the scale of mineralization. In
practical relation the level of manganosity of the carbonates, is very marked as
far as they are wholly characteristic precisely of a Pb-Zn and Au-Ag-Pb-Zn
deposit, in which the manganese activity habitually increases in the last stage of
development of the hydrothermal process, at the moment of ore deposition
[Rusinov, 1989].
Localisation of ore bodies relatively to vertical metasomatic zoning is
regular. Industrial accumulation of ore minerals is never fixed on upper or lower
tapering out of the general aureole of beresitization, but gravitates to places of
maximal thickness in the superficial part of the aureole. As one of the signs of
the presence of ore mineralization may serve such a degree of development of

365
metasomatic carbonatization, which depends upon fullness of manifestation of
transformation and a corresponding deep erosion section. The carbonate/(quartz
+ sericite) ratio with similar composition of initial rocks proves to be a direct
indicator of depth [Sazonov, 1984].
The extension of carbonates in vertical zoning proceeds along two
schemes. The first one corresponds to a decrease, from deep to superficial
horizons, of the content of ferrous carbonates in the outer and intermediate
zones of beresite column and an increase of the quantity of calcite. This
condition corresponds to an insignificant temperature gradient, and the
replacement of calcite-containing parageneses by ankeritic ones may occur with
an increase with depth of the carbon dioxide fugacity from –0,5 to 1 [Rusinov,
1989]. There often occurs another variant, when associations with calcites are
observed on deeper horizons compared with ferrous carbonates. Such
correlations are linked with a significant vertical gradient of temperature, which
is usual to beresites of hypabyssal and subvolcanic facies of depth. This is also
true of the hydromica facies ([Link].20.7). Maximal concentration of useful
components gravitate to intervals of development of ankerite-containing
parageneses.
In the mentioned Streltsov uranium deposit at deep hypsometric levels,
where occur calcite-sericitic and dolomite-sericitic parageneses, ore bodies are
absent and only narrow zones are seen of increased radioactivity.
So, the scale of development, facial composition and vertical zoning of
beresitized rocks prove to be indicators of the type and scale of mineralization
and assist in evaluating perspectives of extension of mineralization in depth.

366
Fig. 20.1. Composition of hydrothermal sericites and hydromicas in coordinates A(Al)-
S(Si)-F(Mg+Fe+Mn).
1- calcic micas and mixed-layered illite-smectite from argillisites and hydromicas; 2 -
micas from beresites; 3-micas from Ural beresites; 4 - from corundum-containing secondary
quartzites; 5-from sedimentary rocks at various stages of epigenesis; 6-points of end-
member minerals: Ms – muscovite, Ill – illite, Fg – phengite, Lf – leucophyllite. Contours of
field of composition of micas of various genesis: I-mica from argillisites and hydromicatites,
II- and III- mica from beresites, IV- sedimentary epigenetic mica, V- metamorphic mica of
facies of low and moderate pressures.

367
Fig. 20.2. Composition of sericites and hydromicas in dependence upon Al distribution
on positions (a), composition of sericites and hydromicas of various genesis in AlIV-K+Na
coordinates (b).
Notation is the same as on fig. 20.1.

368
Fig. 20.3. Diagram of compositions of hydrothermal chlorites in AlIV-Fe/Fe+Mg [Curtis
et al., 1985; Jahren & Aagaard, 1989; data of [Link]].
IIb-field of composition of metamorphic chlorites with predominant polytype; Ib-
chlorite from sedimentary rocks; 7A- bertierites, [Link] – swelling chlorites. 1- chlorites from
periore beresites, 2-bertierites from gold deposits; 3-bertierites from uranium deposits; 4-
ore-bearing 14A chlorites.

369
Fig. 20.4. Outline of structure of aureoles of beretisation near an ore-bearing zone.
Uranium deposit of Ishim, Kazakhstan, documentation of walls of ort???? by
[Link] [Zharikov & Omelyanenko, 1965].
1-porphyry diorite, unalterated; 2-feebly beresitized porphyry diorite (albite,
carbonate, chlorite, quartz, sericite, pyrite); 3-beresitized diorite (carbonate, albite, quartz,
pyrite); 5-intensively pyritized rocks; 6-areas of development of veinlet-disseminated
uranium deposit; 7-areas of brecciation; 8- break dislocations; 9- zones of fracturation.

370
Fig. 20.5. Character of development of hydromicaceous metasomatites and albitic ore-
bearing formations in granites of Streltsov uranium deposits (East Zabaikal) (after
[Link]).
1-coarse-medium grained biotite granite; 2-small dimension granites of composition
Qtz+Kfs+Ab+H-mic+Ank+Hem (Ls) and Qtz+Kfs+H-mic+Ank+Hem; 3-intensively altered
granites Qtz+H-mic+Ank or Qtz-H-mic; 4-veinlet-metasomatic albite; 5-uranium
mineralization; 6-areas of development of ore-bearing hematitization; 7-veinlets of
chalcedonomorphic quartz; 8-break dislocations, zones of fracturation.

371
Fig. 20.6. Boundary conditions of formation of beresites (B) relatively to gumbeites (Gu),
argillites (A), quartz-sericites (QS), and quartz-feldspars (QF) of metasomatites in
dependence upon: a -T - lg(mKCl/mH+(ref)), b - XCO2 - lg(mKCl/mH+(ref)), c - T -
lg(mKCl/mH+(ref)), d - P - lg(mKCl/mH+(ref), law, composition of solution of late chilling
[Shapovalov & Zaraisky, 1978; Zaraisky, 1989].

372
Fig. 20.7. Aureoles of extension of periore transformation in the Streltsov uranium
deposit (in material of [Link], [Link] and own data).
1-granitoids; 2-basalts, andesito-basalts; 3-trachydacites; 4-tufas; 5-conglomerates,
gravels, sandstones; 6-zones of weak hydromicatization and beresitization; 7-zones of
intense hydromicatization and beretization; 8-portions of development of ore-bearing
chlorites and bertierites; 9-ore-bearing albitization; 10-areas of development of disseminated
uranium mineralization; 11-ore bodies; 12-dislocation breaks. Sericite and 14A chlorite
begin predominating at depths of 1600 to 1800m.

373
 CHAPTER 21

Alkaline metasomatites

The chief properties of alkaline metasomatites are: increase of alkaline

content in the rock; formation of minerals in conditions of high activity of the
alkali; predominance of addition of components over removal, decrease of
porosity and permeability of the rocks. In the process of alkaline metasomatism
there occurs a linkage of alumina with containing rocks in feldspars, rarely in
nepheline, zeolites, leucite. Here are considered only the most spread
metasomatites, in which alumina-containing minerals are represented by
feldspars. Mineralogical criteria of alkaline metasomatism are the replacement
of quartz by albite and (or) potassic feldspars, but also by alkaline amphiboles
and (or) aegyrine. It must be noted that the formation of the indicated minerals
with stability of the quartz testifies only of the high alkaline content of the
solutions, but does not prove their alkaline character. One distinguishes two
groups of formation of alkaline metasomatites: the sodic and the potassic. In the
extension in the rock sodic alkaline metasomatites substantially predominate
over potassic. As type of transition is distinguished the formation of sodico-
potassic (bifeldspathic) metasomatites.
The chief property of sodic alkaline metasomatites is the wide
development of albite in them. In connection with them, sodic metasomatites of
various formations are quite often described under the name of “albitites”. This
term undoubtedly is wider than a familly, and without supplementary
typomorphic signs does not permit determining the metasomatites.
As to temperature of formation sodic metasomatites are divided into those
of medium temperature and those of low temperature. The first ones, together
with albite, are characterized by the development of aegyrine, alkaline
amphiboles, micas, epidote; the other ones, by carbonate and chlorite.
Medium-temperature sodic metasomatites are represented by three familly
types: albitized granites, sodic metasomatites of contact zones of nepheline-

374
syenitic massifs, and sodic metasomatites of zones of fracture of precambrian
basement.
Low temperature sodic metasomatites are represented by the formation of
aceites.

21.1. Familly of albitized granites.

Definition. Albitization is one of the most widely spread processes of
postmagmatic alteration in the granitoids. In an overwhelming majority of cases
it is relatively feebly developed and manifests itself in perthitization of potassic
feldspar with formation of chessboardic and fringe albite. Intensive occurrence
of albitization with formation of ore-bearing albitites is recorded only in
connection with intrusions related to much later phases of granitoid complexes.
According to [Link] [1975], collecting materials on a great number of
massifs of albitized granites, their share forms not more than 1% compared with
the whole area, occupied by granitoids of the corresponding assemblage.
Consequently the great accumulation of sodium in residual solution may be
considered as property of postmagmatic processes, conditioned by specific
compositions of highly differenciated magmas.
The term albitized granites in a sub-familly sense was propounded by
[Link] [1975] and we think it is the most successful. In many publications
albitized granites are described by the name of “apogranites”. This term was
suggested by [Link] in connection with granites substantially transformed in
postmagmatic processes in which, apart from sodic metasomatism, quite often
also occur potassic feldspathization and greisenization. Thus, the term
“apogranitic” unites metasomatites relative to three metasomatic formations,
which are often spatially combined. No information whatever on the relative
role of the different processes and intensities of metasomatic transformation is
carried by the term “apogranite”. Albitized granites also are divided under the
names of albitites, rare-metal granites, lithic-fluoritic granites and others. The
most characteristic sign of granite albitization is the development of a great
quantity of tabular and lath-like albite mixed with microcline and quartz. Below
are given the chief formation peculiarities of albitized granites.
Geological setting. According to [Link] [1968], albitized granites are
formed on all stages of development of the earth crust. Analysis of concrete
manifestations of metasomatites of this familly show, however, that for them, as
for greisens, is typical the phanerozoic age. Albitized granites are met either in
regions of superficial folding or in the limits of platforms and intermediate
massifs. Many of the massifs are linked with processes of activation of ancient
structures. The regions of development of albitized granites are characterized by
intense occurrence of granitoid magmatism with predominance of granites of
standard geochemical type. Bodies of albitized granites are represented by
typical fracture intrusions, formed in conditions of moderate and small depth.

375
Albitization is superimposed on dykes of granite-porphyries, intersecting parent
granites. Consequently, the latter have fully crystallized at the beginning of
albitization.
Regular building of zones of sodic metasomatism in vertical direction is
determined by the presence of a general tendency to accumulation of intense
albitization from below upwards. Intense albitization is characteristic only of
apical parts of intrusives, but in depth they extend on the first hundreds of
metres. In depth, control of albitites by fracture zones appears most distinctly
and on any scales, from control of tectonic zones of thick and extensive parts of
albitization to formation of albite along separate fractures and microfractures.
The thickness of albititic bodies is usually insignificant and rarely reaches
hundreds of metres. A feeble albitization has a coarse extension, occupying a
great volume of the granites. Albitization is undoubtedly related to an earlier
alkaline stage of a postmagmatic process. With time it gets replaced by a coarse
greisenization and later by the development of perifissural greisenization
[Grabezhev, 1981].
Peculiarities of mineral and chemical composition. Spatial combining
of processes of potassic feldspathization, albitization and greisenization
sometimes does not permit precisely to delimitate the mineral and chemical
transformations, linked with the different stages of the postmagmatic process.
The given circumstance substantially hampers formation of metasomatic
columns. The basic mass of albitized granites is submitted to associations to the
outer zones of the column consisting in albite, quartz, microcline and mica, to
which are added fluorite, but also various accessory minerals. In the rocks is
observed a partial replacement of microcline and magmatic plagioclase by lath-
like and tabular albites. An overwhelming mass of published chemical analyses
deal with this variety. The difference of chemical composition of metasomatites
and initial granites is insignificant. Na2O content grows to 1-2,5%, K2O
diminishes to 0,5-1,5%. Variations in the content of other components are not
great and may be linked not only to sodic metasomatism. Non-completion of the
reaction of albitization of potassic feldspar is accounted for by its relatively high
content also of granites. As a result, corresponding activities of sodium and
potassium in solutions are kept on level, by the corresponding stability of
bifeldspar association. Full replacement of potassic feldspar by albite has been
carried out only in relatively narrow zones of most intense circulation of
postmagmatic solutions. In the final products of intense metasomatism of
leading minerals appears albite. The second place, after albite, is most often
occupied by mica. In dependence upon mica content, [Link] [1975] has
distinguished muscovite-lepidolitic, lepidolite-biotitic, ambligonite-lepidolitic,
zinvalditic, muscovite-protolitionitic type of albitized granites. [Link]
[1981] has described microcline-albitic metasomatites with a sharply
subordinate quantity of muscovite. Quartz in them is replaced not only by albites

376
but also by microcline. [Link] and [Link] have described quartzic
albites formed of fine-plate albites and quartz. The correspondence between
these minerals oscillates between granite proximity and significant
predominance of albite over quartz.
Full replacement of quartz by albite is very rarely observed. With it are
formed sacharoidal monomineral albitites. In albitized granites fluorite is usually
present, the content of which varies in very wide limits. In many cases is topaz
recorded. Formation of this mineral in conditions of high alkalinity presents
itself as unlikely and, apparently, it occurs at stages of increased acidity.
Data of chemical analyses testify to the fact that albitization of granites is
accompanied by addition of sodium and alumina and removal of silica and
potassium (table 21.1).

Table 21.1. Chemical composition of initial and albitized granites in % en

weigh [Koval, 1975]

Components Granite Albitite

Bi- Musco- Albitized
micaceous vite moderate strong
SiO2 74,24 78,83 75,87 71,90 69,27
TiO2 0,20 0,16 0,08 0,03 0,00
Al2O3 13,27 13,16 12,74 15,74 17,33
Fe2O3 0,55 0,93 0,38 0,57 1,36
FeO 1,04 0,88 0,72 0,38 0,54
MnO 0,03 0,05 0,13 0,05 0,11
MgO 0,10 0,28 0,22 0,13 0,12
CaO 0,87 0,99, 0,55 0,49 0,55
Na2O 4,01 3,31 4,73 6,50 9,69
K2O 5,07 4,69 4,07 3,29 0,30
Rb2O - - 0,08 0,11 0,01
Li2O - - 0,01 0,01 -
P2O5 0,09 0,05 0,04 0,03 0,03
Loss. Ign. 0,50 0,71 0,50 0,56 0,41
F 0,13 0,15 0,11 0,05 0,04

Horizontal metasomatic zoning occurs very indistinctly. Several authors

have adduced metasomatic columns which in great measure are characterized by
the direction of the process, rather than by really documented metasomatic
zoning. The most real are the following types of colomns:
I 0) Quartz + microcline + oligoclase + biotite; 1) quartz + microcline +
albite + muscovite; 2) quartz + albite + muscovite; 3) albite + muscovite;

377
 I. 0) Quartz + microcline + oligoclase + biotite; 1) quartz +
microcline + albite + muscovite; 2) quartz + albite + muscovite;
3) albite + quartz; 4) albite;
II. 0) Quartz + microcline + oligoclase + biotite; 1) quartz +
microcline + albite + muscovite; 2) microcline + albite; 3) albite.
Recorded facies of albitized granites are forming in conditions of very
high sodium activity. They are characterized by development of aegirine and
alkaline amphiboles, and sometimes astrophyllite.

Metallogenic and geochemical specialization. To albitized granites are

related industrial concentrations of berylium, tantalum, niobium, lithium,
zirconium, rare earths, tungsten and tin. The characteristic ore minerals are
beryl, euxenite, bertrandite, phenakite, columbite, microlite, pyrochlore,
fergusonite, zircon, wolframite, cassiterite and a few others. The brightest
geochemical property of albitized granites is the accumulation in them of fluor,
ratio-active elements, increased relation of sodium to potassium. Zones of
increased concentration of niobium, tantalum and zirconium get sufficiently
clearly revealed with the help of radio-active appliances, so that the content in
them of uranium and thorium reaches hundredths of mass %. Despite the
available numerous radio-active anomalies, industrial accumulations of uranium
and thorium in albitized granites are not established. In the process of
albitization also are dug up hafnium, rubidium, caesium, bore and phosphory.
Concentration of these elements in metasomatites was roundly of a higher order
than in unaltering granites. It was established that the greatest concentration of
the foregoing elements was characteristic of metasomatites corresponding in
composition to the intermediate zones of a metasomatic column. They are
replaced by albite, quartz, microcline and mica. In albites the content of rare
elements diminishes. Coincidence of the maximum of ore mineralization with a
definite zone of a metasomatic column testifies to the synchronism of the
process of albitization and ore-formation. The cause of ore deposition,
apparently, is the neutralization of alkaline solutions in their mutual reaction
with granites.
Conditions of formation. A thorough analysis of thermometric data
shows the most probable value of albitization temperature in the 520-460oC
interval. Pressure corresponds to conditions of depth in the order of 1,5-2,5 km
[Koval, 1975]. The results of the study of gas-liquid inclusion with calciculation
of petrographic and experimental data show that albitization occurs under the
influence of hydrocarbonate-sodic solutions with general mineralization of 10-
15 mas.%. Content of carbon dioxide is of tens of grams to the litre. Amidst
cations is sharply predominant sodium, amidst anions, carbonic, hydrochloric,
fluorite-hydrogen and silicic acidity. Undoubtedly increasing alkalinity of the

378
solutions is determined by their soda composition. Instead, albitized solutions
are characterized by a high concentration of fluor, whose complex combination
plays an important role in the transfer of elements.

[Link] of sodic metasomatites of the contact zones of nephelinic-

syenite massifs.
In connection with intrusives of nephelinic syenites there widely occur
postmagmatic processes. Their temporal succession is reflected in the following
order: potassic feldspathization; albitization; low temperature metasomatism
(liebeneritization, sodalitization, zeolitization, carbonatization). Concerning the
scale and intensity of manifestation the leading place belongs to albitization,
which is linked with an accumulation of valuable elements. The final products
of albitization are dealt with in the literature under the name of albitites.
Transformation of nephelinic syenite into albitite is accompanied with addition
of silica, in connection with which albitization relatively to nephelinic syenites
may be considered as at acid stage. In relation to parent rocks albitization
occupies the same situation as does greisenization relatively to granites. Instead,
the mutual reaction of albitized solutions with intermediate quartz-containing
rocks is accompanied by sodium addition, removal of alkali, full replacement of
quartz by albite and other minerals formed in conditions of increasing alkalinity.
Therefore in relation to quartz-containing intermediate rocks albitization proves
to be a typical manifestation of alkaline metasomatism.
The geological setting of sodic metasomatites is determined by their
narrow spatialo-genetic link with massive nephelinic syenites. The latters’
formation occurs under various geodynamic regimes [Andreeva & al., 1984]. A
necessary conditions of the manifestation of alkaline magmatism is the
destructuration of earth crust consolidated in platform as well as in folded
domains. Such conditions arise at all stages of geological development of the
earth crust on the latters’ extension to about 2,7 billion years. Most favourable to
the development of alkaline rocks are structures of deep tectono-magmatic
activation.
Processes of albitization occur mainly in a contact zone of nephelinic
syenite massifs wide a few hundred metres, occupying a zone of exocontact,
apophyse and dykes and also of rocks enclosing them. The most intense
albitization occurs in portions of contact characterized by the presence of
various dislocation fractures and other structural elements, controlling the
movements of albitizing solutions. With the various dislocation fractures are
linked linear bodies of metasomatites characterized by a clearly expressed
metasomatic zoning.
Mineral properties and chemical composition. A general property of
albitized nephelinic syenites is the development of the fine lamellar albite
(cleavelandite). Content of anorthitic molecules in metasomatic albite does not

379
exceed 5%. The dimension of its crystals (0,2-0,3 mm) does not depend upon
that of the initial minerals, in connection with which sacharoid albites are
formed at the expense of fine-crystal syenites and of pegmatoid varieties of
nephelinic syenites. Of relict minerals in albitites the greatest part is nepheline.
Their replacement by albite proceeds through gradual increase of the quantity of
inordinately orientated inclusions of cleavelandite. Rocks distinguished in the
Octiabrskoe alkaline massif under the name of mariupolites, present themselves
as substantially albitic rocks with aegyrine and relict nepheline. In
correspondence with the quantities of sacharoid albite and nepheline may be
estimated the intensity of the metasomatic process. In final products of
albitization the content of albite reaches 95-97% of the volume of the
metasomatites.
The most characterized of the dark-coloured minerals of albitized
nephelinic syenites is aegyrine. Its quantity is directly proportional to the content
of lepidomelane and other iron-containing minerals in the initial rocks. In most
cases aegyrine is isolated in the aspect of inordinately oriented elongation of
crystals measuring from a fraction to 5 mm, distributed in albitites highly
invariantly. There are radiant aggregates of coarse crystals (“aegyrinic suns”).
Content of acmitic molecules (NaFe + Si2O6) in metasomatic aegyrine always
exceeds 70%. With these it is distinguished from magmatic pyroxenes, which
usually present aegyrine-augites.
Sometimes instead of aegyrine in albites dark mica is present. Particularly
spread are micaceous albitites in the alkaline massifs of the east-Ural elevation.
According to [Link] [1976], mica from albitites differs from magmatic
mica by lesser ferruginosity (which testifies to decrease of the alkaline process)
and in most cases there are ferriphlogopites. Its content in albitites does not
usually exceed 5%. A characteristic property of micaceous albitites is the wide
participation of microcline in their composition. Although in the final products
of albitization albite always predominates over microclines, the latter’s full
replacement by albites is very rare.
In a series of cases there is superimposed on albite mineralization of later
stages of a postmagmatic process. The latter minerals are liebenerites, calcites,
zeolites, fluorites. With calcicitization is sometimes linked collective
crystallization of accessory minerals, partially zircon.
Final products of sodic metasomatosis in zones of exocontact nepheline-
syenite massifs are also albitites. The predominating dark-coloured mineral is
aegyrine, more rarely ferriphlogopite. In exocontact of the Djilisuiskoe massif
(Altaï range) are seen astrophyllite-bearing albitites, formed at the expense of
fenitized aleurolites. The latter reflects stellate aggregates of aureate crystals of
2 cm diameter, whose albitite content reaches 15%. The compositions of
astrophyllite corresponds to the following formula: (K0,82Na0,64Ca0,15Mn0,39)
(Mn0,29Mg0,16Fe++2,12Fe+++0,07Al0,37)3,01[Ti0,78Nb0,07Fe+++0,15][Si3,73Al0,27]

380
[OH1,78F0,22]2 [OH1,37O12,63]14. Dissimilar compositions and structures of initial
rocks are clearly fixed in metasomatites on particular extensions of dark-
coloured minerals. Together with albites in subordinate quantities are often
encountered microclines. In zones of transit from intervening rocks to albitites
are highly usual alkaline amphiboles (arfvedsonites) and also relict minerals.
Quite often sodic metasomatism is superimposed on enclosing rocks
undergoing keratinization and fenitization, which exert a substantial influence
on composition and structure of metasomatites.
Albitization of nephelinic syenites is accompanied by addition of alkali
and removal of alumina, potassium, calcicium, iron (table 21.2). Sodium content
does not substantially change. With albitization of quartz-containing rocks take
place removal silica and addition of alumina and sodium.

Table 21.2. Change of chemical composition of nepheline syenites of

Djilisuiskoe massf and aleurite slates at their albitization in weight % .

Compo-
1 2 3 4 5 6
nents
SiO2 55,44 58,00 66,00 78,09 67,43 65,56
TiO2 0,38 0,20 0,07 0,62 0,69 0,65
Al2O3 22,47 21,74 21,06 8,13 11,63 17,07
Fe2O3 1,39 3,31 0,47 0,47 2,61 2,21
FeO 1,35 0,62 0,08 3,09 1,33 1,07
MnO 0,11 0,05 0,01 0,05 0,38 0,65
MgO 0,22 0,25 0,02 1,70 1,63 0,70
CaO 1,37 0,70 0,46 3,36 3,85 0,70
Na2O 9,57 10,84 10,31 1,08 6,88 8,18
K2O 5,37 3,05 0,33 1,46 1,12 1,95
H2O- 0,05 - 0,25 - - -
H2O+ 0,49 0,08 - 0,04 0,04 0,16
Loss. fire 2,00 1,17 0,55 1,19 2,71 0,55
P2O5 0,10 0,02 0,03 0,25 0,10 0,08
Nb2O5 n.d n.d 0,16 n.d n.d n.d.
Ta2O5 n.d n.d 0,02 n.d n.d. n.d.
Total 100,31 100,03 99,82 99,53 100,40 100,63

1 – nepheline syenite; 2 - albitized nepheline syenite; 3 - albitite on nepheline

syenite; 4 – aleuritic slates; 5 - albitized hornfels on aleuritic slate; 6 - albitite on
aleuritic slate. n.d. - element non determined; dash – content of element under
the limit of detection

381
 Horizontal metasomatic zoning in nephelinic syenites appears
indistinctly. The basic volume of albitized rocks is composed of transient
varieties, in which are present relicts of nepheline, more or less mixed with
albite. Albitites in which nepheline is not preserved, do not constitute more than
10% of the total volume of the metasomatic bodies. The study of sections
selected on cuts across the strike of metasomatic bodies permits to outline the
following scheme of the structure of metasomatic columns: Unchanging
nephelinic syenite  nepheline + microcline + albite + biolite  nepheline +
microcline + albite + aegyrine  albite + nepheline + aegyrine  albite +
aegyrine  albite. The ore minerals pyrochlore and zircon strictly coincide with
zones of albitite-aegyrine and albite composition.
In much greater contrast appears the zoning in the zone of exocontact. The
boundaries between zones are precisely and easily fixed in the process of
documentation. The composition of outer and intermediate zones is strongly
linked with the composition of initial rocks. The albitization process is often
preceded by contact keratinization and fenitization; moreover, the deposit of
each of these processes in the final composition and structure of the
metasomatite cannot always be evaluated. Below is given as example a
metasomatic column, arisen at the expense of keratinization of aleuritic schist:
quartz + chlorite + biotite + sericite + calcite  quartz + actinolite +biotite+
albite + calcite  quartz + albite + arfvedsonite + microcline + calcite  quartz
+ albite + arfvedsonite + microcline  albite + arfvedsonite + microcline 
albite + aegirine + microcline  quartz + albite + aegirine  albite.
Coincidence of ore minerals with determined zones in metasomatic zones of
exocontact appears very clearly. So, thorite together with fluorite in the form of
fine bi-pyramidal grains (tenth or hundredth fractions of mm) is formed in zones
of stability of quartz with arfvedsonites and albites. In a quartz-albite-
arfvedsonite-microclinic zone thorite content reaches a maximum, and in the
following albite- arfvedsonite-microclinic zone is recorded its collective
crystallization on a background of replacement by other minerals. Here thorite
forms prismatic crystals with pyramidal ends measuring up to 5 mm. In thorite is
present a great quantity of inclusion of albite, microcline, arfvedsonite and
fluorite. In the albite-aegirine-microclinic zone, together with prismatic grains of
thorite, is formed coarse xenomorph thorite (grain dimension up to 1 cm).
Quantitatively the inclusion in thorite increases so significantly (up to 95%) that
in essence we have to do with pseudomorphoses of rock-forming minerals on
thorite. The thorite itself deposits like a skeleton, depending on the general
peculiarity of the thorite’s form of secretion. In the albite-aegirine-microcline
zone thorite is completely replaced by rock-forming minerals. Instead of thorite
grains remains a reddish-brown patch, giving the possibility of judging
preceding contours of the mineral. Thus, in a metasomatic column is established
a new formation of thorite on outer zones, its crystallization with formation of

382
skeleton forms in the intermediate zones and completely replaced in the inner
ones. It is obvious that thorite is indissolubly linked with the processes of
formation of metasomatic columns, occupying in them a clear position.
Pyrochlore forms tiny granules (of tenths of mm) characterized by a regular
octahedric form, it is found in irregular accumulation and close grouping. It is
recorded exclusively in inner zones of metasomatic bodies essentially of albitic
and albite-aegyrine composition, independently of the initial composition of the
rocks. We must emphasize that the described metasomatites are clear examples
of contemporary processes of metasomatic rock transformation and ore
deposition.
Metalogenetic and geochemical specialization. Under its predominant
aspect of mineralization , is pyrochlore-zircon, concentrated in albitites. Thorite
(ThSiO4) is formed only in the albitization of rocks, enriched with silicic acid,
which characterizes only metasomatites of zones of exocontact of nephelinic
syenitic massifs. Uranium under the aspect of isomorphic admixture exists in
thorite, pyrochlore and other minerals. Of rare minerals characteristic of albites
there are monazite, orthite, aeschynite, chevkynite. [Link] [1976] has
presented an extensive list of other minerals with high concentration of rare-
metal and rare-earth elements.
Geochemical specialization of metasomatites is determined by increased
temperature, alkaline character of the solutions and high sodium activity. So, as
with the formation of sodic metasomatites of other genetic types, such
conditions favour migration of titanium, silicon, phosphory, zircon, thorium,
niobium, tantalum, rare earths.
Conditions of formation. Temperature conditions of albitization, judging
from available data, oscillate between 500 and 400oC. Oxidized form of iron in
albitites (aegyrine present) testify not only to the high oxidizing-reducing
potential but also to the high alkalinity of the solutions. The wide extension of
albitized nephelinic syenites with relicts of nepheline (mariupolites) proves that
the process of rock formation of the zone of endocontact, basically, is hampered
by the reaction of replacement of nepheline by albite. This is linked with the fact
that a full replacement of nepheline by albite may occur on condition of removal
of alumina, or of inert behaviour of alumina, on condition of increase of the
metasomatite volume compared to the initial rocks. Realization of these
conditions in nature is difficult. The change of nephelinic syenites into albites,
basically, occurs at the expense of relatively thin dykes and apophyses.
Transformation of quartz-containing enclosing rocks into albites is produced on
great scales. With this is recorded a clear metasomatic zoning, and on the whole
volume of metasomatic bodies the albitites have a leading role. Albitite zones of
exocontact in relative ore-content proves very productive.

21.3. Aceites, a familly of low-temperature sodic metasomatites.

383
 Definition. The first large development of periore albitization was
recorded in an uranium deposit of Ace in the region of Beaverlodge Lake in
Canada, where albitization is accompanied by formation of chlorite, carbonate
and hematite [Dawson, 1951]. Later, this process was studied in detail in the
uranium deposits of Kazakhstan [Omelyanenko, 1970; Omelyanenko &
Lisitzyna, 1974], where it was proved that albitized rocks of that sort present
themselves as specific formation types of periore metasomatites. One calls
aceites metasomatic rocks mixed with uranium deposits, and deposits of albite,
carbonate, hematite and chlorite.
Geological setting. To aceitization are subjected rocks of various form:
granites, sandstones, limestones, basalts, gabbro etc. in hinge zones of basins,
completed by sedimentary rocks, with upheavals. In northern Kazakhstan, where
periore aceitization in uranium deposits is wide-spread, that process coincides
with zones of fractures and takes place either in intrusive rocks or in sediments
mixed with them. On the Manybaïskoe deposit aceitization is situated along the
zone of the main north-eastern fault and the system of finer dislocations
connected to them on a few kilometres and reaching to a depth of 1 km. The
thickness of the metasomatic aureole reaches a few hundred metres. The N-E
fault divides its aureoles in two parts: in the eastern one metasomatism is
situated on the sedimentary rocks of the East-Kokchetavsk basin, and in the
western on the quartz diorite Aksuisk massif.
The degree of transformation of the rocks varies and depends upon the
intensity of their fracturation.
Mineral composition, facies and zoning of aceites. The main mineral of
aceites is albite; carbonates and hematite are present as accessory minerals;
chlorite and quartz are often present as intermediate products. In calcicium-
enriched rocks, the chief role is played by uranium-containing fluorine-apatite,
up to formation of uranium-bearing apatitic metasomatites on limestones
[Omelyanenko [Link]., 1974]. There is characteristic

Table 21.3. Change of chemical composition of red- colored quartzitic

sandstones in process of aceitization, % weight

Compo- Unaltered
Aceitized quartzitic sandstones
nents sandstone
SiO2 77,08 73,62 76,02 74,22 57,00 42,30
TiO2 0,18 0,20 0,14 0,20 0,20 0,20
Al2O3 12,10 11,35 11,65 11,59 17,89 13,43
Fe2O3 1,95 0,74 - 0,52 1,50 8,84
FeO 0,29 0,24 0,58 0,13 0,21 0,30
MnO 0,01 0,01 0,01 0,01 0,04 -
MgO 0,04 0,08 0,21 0,05 0,31 -

384
CaO 0,43 3,42 2,46 2,40 5,01 12,30
Na2O 4,60 4,50 5,09 6,31 8,37 6,05
K2O 2,40 2,09 1,59 1,51 1,39 0,57
-
H2O - - - 0,51 1,92 0,53
+
H2O 1,20 0,99 1,43 0,56 0,61 1,38
CO2 - 0,25 - - - 0,33
S - - 0,02 - - 0,11
P2O5 0,08 1,95 0,94 1,36 3,31 6,67
ZrO2 n.d. n.d. n.d. n.d. 2,50 6,030
Total 100,36 99,44 100,14 99,37 100,26 99,31
Analyses performed in the Central laboratory of chemistry of [Link]. of USSR
by E.F. Kalachnikova

instability of quartz during aceitization, which is replaced by albite. In

correspondence with the variation of mineral composition, determined, grosso
modo, by the composition of enclosing rocks, are divided the facies of aceites:
quartz-albite, calcite-albite, chlorite-albite, ankerite-albite, albite-apatite, apatite-
albite and apatite.
Periveinous zoning in beresitized rock has usually the following structure.
On granites: 0) granite (quartz, oligoclase, microcline, biotite, magnetite); 1)
quartz, albite, sericite (on microcline), microcline, chlorite, calcite, hematite; 2)
quartz, albite, chlorite, calcite, hematite; 3) albite, ankerite (or chlorite),
hematite; 4) albite, hematite. On diorites: 0) diorite (ankerite, hornblende,
magnetite); 1) albite, chlorite, calcite, sericite, hematite; 2) albite, chlorite,
calcite, hematite; 3) albite, ankerite (or chlorite), hematite; 4) albite, hematite. In
external and middle zones occur minerals which disappear to the extent of the
growth of intensity of the process into the inner zone (sericite , chlorite).
Chemism of the aceitization process. Upon aceitization are added
sodium and carbon dioxide, in certain cases phosphory, partly calcicium. There
is removal of potassium, silica and magnesium. The tendency to change of
chemical composition of rocks with aceitization is shown on table 21.3. The
behaviour of alumina is multiform, though, on the whole, it is little mobile and,
as a rule, it is not added (albite is formed only on alumina-bearing rocks). With
exchange of interstratified argilites, aleurolites and sandstones there occurs local
mixing of alumina with its removal form argillites and addition in sandstones.
Judging from the forming parageneses of minerals, aceitization is a typical
alkaline process, parageneses produced by hydrocarbonate-sodic solutions with
low activity of sulfide sulphur and high activity of oxygen. One notices a high
mobility of titanium, phosphory, zirconium and silica.
Aceitization and ore deposition. Aceites are distinctly specialized on
uranium. This is a clear type of metasomatites, which is almost never found
without uranium mineralization and does not carry industrial concentration of

385
practically any other metals. In a few uranium deposits are found portions with
molybdenum and zircon ore, but these ores have the character of accompanying
the uranium.
The evolution of metasomatic-uranium-ore processes is reflected in the
succession of aceitization, apatitization, carbonatization, ore deposition with
chloritization, post-ore veins and veinlets. The basic mass of hematite is
accompanied at the beginning of an ore stage and is deposited together with an
apatite-arshinovite association on the inner zones of columns of peri-ore
aceitization. In some cases, intensive hematitization is accompanied with
addition of iron. Following this association ankerite is deposited in the form of
veinlets and metasomatic accumulation. An ore stage is completed by formation
of micro-veinlets and accumulation of pyrite, pitchblende, molybdenite and
coffinite, which are accompanied with “ore” chlorites. The post-ore stage
presents sparse veins and veinlets of quartz, chlorite, baryte, calcite, fluorite and
pyrite.

386
 CHAPTER 22

Gumbeites

Definition. Gumbeitizited rocks were distinguished by D.S. Korzhinsky

[1948] as products of an independent metasomatic process in the Gumbeyka
basin in southern Ural. This is a periveinous alteration of granodiorites with
distinct manifestation of lateral zoning. Strictly, the rocks called gumbeites
occupy an inner zone in a column of gumbeitization and consist in the typical
case of quartz, orthoclase and carbonate. Usually there exist in them ore
minerals of sulfides and scheelite. In the outer zone of gumbeitized rocks are
characteristically present phlogopite or slightly ferrous biotite. Intrusive massifs
containing quartz veins with fringes of gumbeitization are composed of alkaline
granodiorites and varieties transient to syenites. In contact with a volcanic mass
of diabasic porphyrites they are replaced by syenite-diorites. Quartz veins
outside the intrusive massif are accompanied by beresitization, but there is no
potash .feldspathization
Gumbeites of the Gumbeika deposit of scheelite. Gumbeites of the
Gumbeika deposit of scheelite [Spiridonov et al.,1997] have replaced
monzonites quartz syenodiorites, syenite-porphyry and serpentinites, but also
hornfelses, biotite-amphibole metasomatites and propylites. The gumbeite
margins are 3-10 cm thick, rarely up to 50 cm. The thickest margins develop on
biotite-amphibole rocks and serpentinites.
Two types of quartz veins and the gumbeites accompanying them are
distinguished: earlier ones, formed of dark-grey quartz with admixture of biotite,
potassic feldspar and molybdoscheelite, with biotite-potassic feldspar vuggy
fringes in selvages, and the later ones, formed of bright quartz with admixture of
carbonates, potassic feldspars, scheelite, more rarely molybdenic scheelite,
sulfides, with carbonate-potassic feldspars vuggy fringes in selvages. A
succession of vein formations is established on their intersection. In gumbeites
with a biotite-potassic feldspar rear zone develops molybdoscheelite; in
gumbeites with a dolomite-feldspar zone develops scheelite. Possibly scheelite
has developed simultaneously with the usual gumbeites, or has been replaced by

387
molybdoscheelite. Starting from these mutual reactions one may surmise that the
usual gumbeites form later than these with a biotite-feldspars-quartzic rear zone.
The typical zoning of early gumbeites with biotite-orthoclase (or
microcline) rear zone:
Zone 0. Unalterated quartz-syeno-diorite: hornblende (10-15%), biotite
(5-10%), micro perthite (40-50%), plagioclase An 20-25(15-20%), quartz (5-
10%); accessory: titanomagnetite, sphene, apatite.
Zone 1. biotite (20-30%), calcite (10-15%), albite(15-20%), quartz (up to
10%), orthoclase (microcline) (40-45%), pyrite, sphene, apatite, sometimes
monazite. Biotite ferruginosity amounts to 35-40%, Al content = 1-1,2 formula
unit.,TiO2 up to 2,5 weight.%.
Zone 2. biotite (20-30%), calcite (10-15%), quartz (up to 10%), orthoclase
(microcline) (50-60%), pyrite, sphene, apatite. Quite often in orthoclase grains is
preserved relict albite. The thickness of this zone does not exceed 2-3 mm.
Zone 3, borders upon quartz vein: biotite (20-40%), orthoclase
(microcline) (up to 70%), quartz (up to 10%), pyrite, apatite, rutile. The zone is
3-5 mm thick.
Zone 4, a rear-zone: quartz-vein with mobybdoscheelite, biolite, rutile,
sometimes potassic feldspar. Molybdoscheelite has formed simultaneously with
other minerals of metasomatites, as far as it forms the boundary of joint growth
with biotite.
At the transition from granitoids to a quartz vein on the boundary zone
there occurs the following reaction of replacement :
0 zone  1 zone: Hb1 = Cc+Bi+Py; Olg = Ab+Cc; Ti-Mt = Py+Spn.
1 zone  2 zone: Ab = Mc.
2 zone  3 zone: Spn = Rt, Cc dissolves.
The zoning of late gumbeites with carbonate-feldspar rear zone is
distinguished by the development of dolomite instead of calcite.
Zone [Link] quartzic syeno-diorites: hornblende (10-15%), biotite
(5-10%), microperthite (40-50%), plagioclase an 20-25 (15-20%), quartz (5-
10%), accessory metals: titanomagnetite, sphene, apatite.
Zone 1: sericite (15-20%), biotite (up to 2-5%), dolomite (20-25%),
potassic feldspar (30-40%), albite(15-20%), quartz (up to 10%), pyrite, sphene.
Biotite ferruginosity 35-40%. Sericite is usually represented by phengite or is
close to it. Dolomite ferruginosity amounts to 10%. The zone thickness is from
3,5 cm to 10 cm.
Zone 2: dolomite (20-25%), potassic feldspar (up to 40-50%), biotite (2-
5%), albite (15-20%), quartz (up to 5%), pyrite, sphene, apatite. The thickness is
0,5-1 mm.
Zone 3: dolomite (20-25%), potassic feldspar (up to 70%), biotite (up to
5%), quartz (up to 5%), pyrite, sphene, apatite. In orthoclase grains is found
relict albite. The thickness is 0,5-1 mm.

388
 Zone 4: enjoining a quartz-vein: drusic crust of orthoclase (70-80%) with
dolomite (20-25%), quartz (up to 5%), pyrite (up to 5%), rutite and [Link]
thickness is 2-3 mm, up to 1cm.
Zone 5, a rear zone: quartz vein with scheelite, dolomite, orthoclase,
rutile. Scheelite forms simultaneously with other minerals of metasomatites.
On transformation from unalterated rocks to quartz veins on the boundary
zones occur the following reactions of replacement:
0 zone  1 zone: Hb1 = Dol+Ser+Bi+Py; Birelict=Ser+Dol+Py;
Olg = Ab; Ti-Mt = Py+Spn.
1 zone  2 zone: Ser+Qtz = Mc.
2 zone 3 zone: Ab = Mc.
3 zone  4 zone: Spn = Rt; Bi = Dol.
Chemical composition as gumbeites in initial rocks is given in table 22.1.

Table 22.1 Chemical composition of protolithes (1) and gumbeites (2) (%

weight)

Compo-
A1 A2 B1 B2 C1 C2
nents
SiO2 51,70 45,30 44,68 28,64 38,47 36,03
TiO2 0,83 0,84 0,71 0,64 2,98 2,79
P2O5 0,70 0,51 - - 0,56 4,14
Al2O3 14,72 13,47 11,49 8,87 14,02 13,48
Fe2O3 2,32 1,19 7,90 5,28 10,98 4,32
FeO 5,20 5,14 7,15 3,57 2,86 7,88
FeS2 0,19 0,36 0,86 11,82 0,67 0,84
MnO 0,09 0,09 0,17 0,15 0,25 0,28
MgO 7,24 6,14 9,60 6,84 3,45 3,68
CaO 6,74 6,60 10,64 11,68 20,63 16,99
Na2O 3,45 2,23 2,29 1,60 1,15 1,65
K2O 3,24 3,72 2,47 4,62 1,51 3,87
H2O+ 1,70 1,64 1,26 1,26 2,17 1,69
CO2 1,64 12,30 1,16 15,70 0,58 2,80
Total 99,76 99,53 100,38 100,67 100,28 100,44
density
gram/cm 2,86 2,84 - - 3,35 3,35
3

Note: A-C - Gumbeika ore field, D-F - Shartash ore manifestation.

Protolites: A1 - monzonites, B1 - oligoclase-biotite-amphibolic rocks, C1 – amphibolized
rodingites, D1, E1 - adamellites, F1 - microadamellites.
Gumbeites: A2 - dolomite-biotitic, B2 - calcite-dolomite-biotitic, C2, D2 - dolomitic, E2, F2 -
phengitic.

389
A, B - data of D.S. Korzhinsky; D, E – data of A.I. Grabezhev; C, F – data of E.M.
Spiridonov et al. [1997]. Quantitatively calciculated pyrite on quantitative sulfur, respectively
Fe2O3 content corrected in analyses.

Table 22.1 continuation

Compo-
D1 D2 E1 E2 F1 F2
nents
SiO2 72,48 70,82 70,12 65,00 67,45 62,99
TiO2 0,24 0,18 0,28 0,30 0,46 0,47
P2O5 - - 0,10 1,51 0,25 0,18
Al2O3 15,00 14,52 15,08 15,66 15,78 15,67
Fe2O3 0,26 0,21 0,92 1,01 2,17 0,11
FeO 2,47 1,41 2,10 0,64 1,19 0,87
FeS2 traces 0,66 - 1,93 traces 3,80
MnO 0,04 0,03 0,04 0,05 0,12 0,11
MgO 0,10 0,20 0,93 0,60 1,44 1,57
CaO 1,65 1,71 2,14 2,72 2,79 2,78
Na2O 4,26 2,40 5,22 1,60 4,87 0,34
K2O 2,76 4,82 3,18 6,18 2,96 7,89
H2O+ - 2,05 0,18 4,10 1,22 1,55
CO2 traces 0,65 - - 0,18 2,03
Total 99,26 99,66 100,29 101,30 100,88 100,45

For metasomatites on serpentinites is established addition of silica in rear

zones (outer zones are unsaturated with silica, in rear zones occur quartz-
containing parageneses. The ore mineral in these metasomatites is represented
by pyrrhotite, not by pyrite.
Zone 0: immobile serpentinite.
Zone 1: magnetite, talc, dolomite, phlogopite, pyrrhotite.
Zone 2 (rear) : phlogopite, talc, dolomite, quartz, pyrrhotite.
In the Gumbeika deposits it is possible to distinguish at least three degrees
of temperature of metasomatites and of the quartz veins linked with them.
1. Gumbeites with rear biotite-feldspar-quartz zone and associations
biotite+calcite+quartz+feldspar in intermediate zones. With these gumbeites are
linked veins with molybdoscheelite, forming at 400-400oC (according to data of
study of individual gas-liquid inclusions in quartz and molybdoscheelite
[Spiridonov et al., 1997].
2. Gumbeites with rear dolomite-feldspar-quartz zone and association
of dolomite +biolite+feldspar+ quartz or dolomite+calcite+feldspar+quartz in

390
intermediate zones. With these are linked quartz veins with molybdoscheelites,
formed at 395-360oC [Spiridonov et al., 1997].
3. Gumbeites with rear dolomite-feldspar-quartzic zone and
association of dolomite+biolite+feldspar+quartz or dolomite+calcite+feldspar
+quartz in intermediate zones of the column. To them are contiguous quartz
veins with scheelite and sulfides, formed at 350-290oC [Spiridonov et al., 1997].
Analysis of parageneses of gumbeitized rocks has established the
following series of mobility:
H2O, CO2, S, O  K2O, Na2O, CaO  MgO  Fe, SiO2, P2O5, Al2O3,
TiO2.
The first line distinguishes elements which on gumbeitization always
behave in complete mobility; the second line distinguishes elements moving in
the rear zone, correspondingly, the more to the left is an element in the series of
mobilities, the earlier it passes to a complete mobility; the third one
distinguishes elements with a thermodynamic mobility only observed for
metasomatites with a quartz-biotite-feldspar rear zone, i.e. at the highest
temperatures; to the right of the third line are elements always inert. For
elements rich in calcicium and poor in magnesium, the series of mobilities
somewhat changes:
H2O, CO2, S, O  K2O, Na2O, MgO  CaO , Fe, SiO2, P2O5, Al2O3, TiO2.
With gumbeitization is added first of all carbon dioxide, i.e. basically this
is carbonatization. Furthermore, addition is observed of sulphur, potassium, and
removal of sodium.
In rear zones of metasomatites is usually observed an increase of
phosphory content (accumulation of apatite), tungsten (scheelite and W-
containing rutile), often increase of silica content (particularly with
gumbeitization of serpentines). The quantity of apatite usually decreases
compared to that of scheelite: their richest accumulation is in nests amidst
marbles. Active migration of complex-forming elements (phosphory, tungsten
and silica) may be linked with infiltration of solutions along central fractures, so
that mineral composition of ore veins gets subordinated to the rules of
infiltration metasomatism. Zoning of periore gumbeites is formed with diffusion
metasomatism and is characterized by the small thickness of metasomatic zones.
In the Gumbeika deposit is established an exchange, habitual to
postmagmatic hydrothermal deposits, of high temperature mineral associations
with low temperature ones: molybdoscheelite is replaced by molybdenum-
bearing scheelite and scheelite, tennantite is replaced by tetrahedrite (tennantite
is a faded ore hotter than tetrahedrite). Presence of molybdoscheelite, hematite,
Cu2+ and Te in the composition of faded ores testify to increased oxidizing
potential, condition of mineral-forming gumbeitic formation. At low
temperature occurs a lowering of oxidizing potential: molybdenite (Mo 6+) is
replaced by scheelite with molybdenite (Mo4+), tellurium containing faded ores

391
(Te4+) by tellurides (Te2+), and the quantity of Cu2+ in the composition of faded
ores also diminishes.
Gumbeites of the Shartash scheelite ore deposit (Berezovskoe
auriferous field). The Shartash tonalite-granodiorite intrusive is situated in the
southern part of the Berezovo auriferous field. Its formation was assured by that
of post-magmatic hydrothermal metasomatites in succession from early to late:
1) quartz muscovite with quartz-turmaline veins, 2) quartz sericite
metasomatites with Cu-Mo-mineralization, 3) propylites with orthites, 4)
gumbeites (stockworks and periveinous) with scheelite mineralization, 5)
beresite-listwaenites with gold mineralization, 6) argillisites.
Metasomatites of gumbeite familly is the Shartash massif is composed of
symmetrical fringes around abruptly dipping quartz and carbonate-quartz veins.
Fringe thickness is usually 10-20 cm, rarely up to 1 m.
Two types of quartz veins and gumbeites accompanying them are
distinguished: an earlier one, composed of cream-white quartz with admixture of
dolomite (or calcite), feldspar, scheelite, molybdenite and other sulfides, with
dolomite-microcline (more rarely calcite-microcline) vuggy fringes, and a later
one, composed of carbonates and quartz with admixture of scheelite and sulfide,
with carbonate (dolomite or calcite)-sericite-microcline vuggy fringes The first
type of veins is linked with gumbeites of dolomite-feldspar facies. The second
type of veins is linked with a low temperature microcline-phengite facies of
gumbeites.
General lines of gumbeite formation in Ural. On the considered
material of gumbeites and the quartz veins linked with them it is possible to
distinguish three facies according to the temperature of the formation:
1. Biotite-potash feldspar facies. It is accompanied with biotite quartz
veins with pyrites and molybdoscheelite. Temperature of its formation is 440-
400oC.
2. Dolomite-potash feldspar facies. It is accompanied with carbonate-
quartzic veins with Mo-scheelite, scheelite, molybdenite, bismuthite, galenite,
aikinite, tetradymite, faded ores. In the quartz veins of the Shartash ore display,
are established, linked with this facies of gumbeites, solid solutions of aïkinite-
bismuthite and Cu-benjaminite-cupropavonite series Temperature of gumbeite
formation, 400-300oC; the ore minerals formed at 400-200oC.
3. Phengite-potash feldspar facies. It is accompanied by carbonate-.
quartz veins with sphalerite, galenite, tetrahedrite, bournonite, tetradymite,
hessite, gold. Temperature : 300oC.
The most extended facies of gumbeites is the dolomite-potash feldspar
(found in all the considered uranium deposits). A higher temperature biotite-
potash feldspar facies is established at present only on the Gumbeika deposit.
Low temperature phengite-potash feldspar facies is widely spread only in the
Shartash ore display.

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 The principal significance for the formation of gumbeites belongs to high
potassium activity, leading to the appearance of a steady paragenesis of quartz +
potash feldspar + carbonate under fully mobile behaviour of potassium.
Established is also a high oxidizing potential, with formation of
molybdoscheelite, hematite, cupreous and telluric faded ores. At the end of the
process potassium activity apparently decreases (display of potash feldspar-
phengite facies of gumbeites); at the same time the oxidizing potential also
decreases (with the potash feldspar-phengite facies are connected faded ores,
containing no Cu2+).
Gumbeites of gold-ore deposits. Gumbeites in gold-ore deposits ore
formed at lower temperature than in displays of mineralization of tungsten and
molybdenum, and are distinguished by mineral associations. Examples of gold
ore gumbeites were described by I.P. Shcherban [1996] for the Zarmitan deposit
in west Uzbekistan. The zoning of such periveinous gumbeites, substituting
granosyenites, according to his data, has several aspects: 1) unaltered
granosyenite (potash feldspar + plagioclase + quartz + hornblende + biotite); 2)
altering granosyenite (potash feldspar + plagioclase + quartz + chlorite + sericite
+ carbonate); 3) potash feldspar + plagioclase + albite + carbonate + quartz +
sulfides; 4) potash feldspar + albite + quartz + sulfides + carbonate. The
difference from tungsten gumbeites of the Ural consists in the absence of
phlogopite on the outer zones of the gumbeite column. [Link] links the
absence of phlogopite with the lower temperature of metasomatism, at which
instead of phlogopite appears chlorite. In the Zarmitan deposits are distinguished
5 stages of mineralization: quartz (350-500oC), gold-pyrite-arsenopyrite (230-
350oC), galenite-sphalerite (130-330oC), sulfosalts (100-150oC) and low
temperature carbonate. Gumbeitization was accompanied by a second stage
(gold-pyrite-arsenopyrite) and was produced between 250 and 350oC, with
corresponding middle temperature process. Other differences consist in the
correspondence of two feldspars in the inner zone of the gumbeite column. In
the presence of quartz this testifies to the inert behaviour either of potassium or
of sodium, which may be linked with increased alkalinity of the milieu and be a
consequence of increased alkaline activity. The presence of sericite in the
zoning, is most probably the result of extended combining of parageneses at
different times, since paragenesis of quartz with both feldspars and sericite does
not occur in nature.
In described gold-bearing gumbeites the potash feldspar contains a
noticeable quantity of sodium, judging by the extension of perthitic ingrowths in
them. From the description it is not clear whether they are relicts (from feldspar
in granosyenite) or linked with increased sodium activity at gumbeitization.
Thus, gumbeites present themselves as the result of metasomatism of
granitoids (more rarely of volcanic rocks), of high alkalinity under the influence
of solutions presenting high activity of alkalis,principally

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[Link] of the process, according to the available estimations,
strongly varies from zero to 400oC. The composition of the solutions forming
gumbeites has not been determined, but according to indirect data these
solutions, apparently, were fluor enriched. This is testified by data of
experimenting on forms of transfer of tungsten and molybdenum in
hydrothermal solutions, and also data of research on fluid inclusions in the
minerals of tungsten-bearing veins. Gumbeites are typical periveinous
formations and develop around quartz-carbonate-orthoclase veins in ore
mineralization of tungsten, molybdenum and gold.

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 CHAPTER 23

Argillisites and argillised rocks

Definition of the familly. The term , designating the replacement of initial

rocks by argillaceous minerals and invented in the second half of the 19 th
century, began to be widely employed in the geological literature in the forties
of the 20th, especially after the revelation in connection with these metasomatites
of deposits of various useful minerals. A substantial contribution to the
description of the argillization process was made by [Link], the first to
utilize this term to designate argillaceous alteration of enclosing rocks near ore
veins. To the further question of petrology and the geological aspects of
argillization was devoted a vast literature [[Link], [Link], [Link],
[Link], [Link], & al.]. The history of the origin and modification of
the notions of “argillization” and “argillisites” has been minutely investigated by
[Link] [1972]. According to him, argillization must be counted amidst
metasomatic hydrothermal processes occurring at more than 50°C, and is
expressed in the replacement of rocks by argillaceous minerals.
Argillisites are reliably known, starting with late Paleozoic, and
their maximum development occurred in Mesozoic and Cenozoic times. Unlike
the other metasomatic formations, argillisites extend practically to all
geotectonic structure both of the oceanic and continental crust.
Geological setting. Argillised rocks occupy local zones in crystalline rocks;
linear and complex stockwerk bodies in effusive and extrusive facies of
volcanites occupy an enormous area in the stratified permeable effusive-
sedimentary stratas. Mineral transformation is traced to the depth of the order of
1,5 km under the contemporary surface; moreover, feeble displays of
argillization may be observed at greater depth.
Argillization may be associated with magmatites of various composition or
they have no link at all with magmatic events (for instance, bentonites and a few
other various argillisites in sedimentary-effusive stratas and platform area).

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 Table 23.1. Geotectonic frame and mineralizations of main facies of argillisites

Geotectonic position

Fractures Island arcs and Areas of

of oceanic crust continental margins Intracontinental activation Platforms Mineralization
crust activity
Smectite- Kaolinite-smecite, A kaolinite-
Zeolitic (Severnoie) smectite-zeolitic, smectite U
controlling volcanic activity.

- carbonate-kaolinitic (Adamovka)
(Marysvale, Mogotcha, Olov)

Quartz-alunite- Quartz-illite-smectitic
kaolinitic (Baleï) Ag, Au
- (Karamken) -

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Quartz- A quartz-
hydromica- tossoudite- Hg, As, Sb
- kaolinitic - kaolinite
(Nikitovka)
Opal- Quartz-smectite- Zn, Cu
smectitic hydromicaceous
(Kuriles) (pyritic deposits of
uranium type
and type of kuroko)
Smectite- Opal-kaolinitic, Smectite-zeolitic ? Non-metallic
celadonitic solfatara- (deposits of bentonites Smectitic or ore-free
smectite-zeolitic and zeolites ) (bentonites) facies
of thermal fields
limits of volcanic fields. Portions of unloadings of thermal waters, accompanied
with large alteration of subneutral type (Pauzhetka, Wairakei, etc.) usually do
Direct links between argillisites and magmatic events take place only in the

not coincide with concrete volcanic activity, but are localized in fracture zones
 Argillization is usually compared with superficial stages of development of
geological processes, one nearly always younger than the latest magmatic
transformations, and displays of higher-temperature metasomatism. The
argillization process includes two branches: the hydrothermal argillization,
accompanied by ore mineralization, and the solfatara one, as a rule oreless,
coinciding with volcanic edifices [Korzhinsky, 1953; Zharikov & Omelianenko,
1965]. Their distinctions are linked with peculiarities of geological-structural
conditions of localization and acidity of the influencing solutions. So, the first
ones most often coincide with steeply falling fracture zones and are influenced
by slightly acid solutions, and the second may have a regional extension and be
conditioned either by sulfatic or by sulfato-chloridic solutions. Table 23.1
illustrates the dependence of the various phases of development upon their
geotectonic situation and the coincidence of mineralization with determined
metasomatic facies. It is evident that most potentially ore-bearing are argillisites
of continental margins and areas of superimposed intracontinental activization.
Mineral composition.
Smectites represent the most wide-spread group of minerals in all the various
argillisites, except the most acid facies. The composition of hydrothermal
smectites corresponds, grosso modo, to strictly montmorillonites and beidellites,
but nontronites and saponites are sometimes found only in basic alterites. This
property noticeably distinguishes smectites of hydrothermal genesis from
hypergenesis. On the whole, in hydrothermal smectites either of
montmorillonitic or beidellitic composition, the content of Mg and Fe in the
octahedrons does not exceed 0,5-0,6 f.u. already at their substitution to rocks of
basic composition, which is seen on fig.23.1, where the field of hydrothermal
smectites is distinctly outlined. The iron’s high acidity is characterized in this
way: usually the Fe+3/Fe+2+Fe+3 ratio is not less than 0,9. High-magnesian
smectites such as the so-called “even-type”(cheto) and the trioctahedric saponite
have a sedimentary genesis [Drits & Kossovskaja, 1990]. In connection with the
limited iron and magnesium content of the octahedric coordination the
hydrothermal smectites are similar to metasomatic micas of beresites and
hydromicaceous metasomatites, in which the total Mg+Fe content also does not
exceed 0.5 fu. Trioctahedric saponites are rare enough in the periore aureoles of
argillization in basic rocks and in much greater extension in meteoric alteration
crusts and sedimentary series. The value of the total layered charge of smectites
may vary from 0.23 to 0.65, and in the composition of interlayer cations Na and
Ca usually predominate over subordinate values of K and Mg. Si and Al
isomorphism in tetrahedres is limited: moreover, tetrahedric Al content
oscillates from a few percent in montmorillonites to 0.3-0.5 in beidellites;
consequently, the layered charge may be concentrated not only in octahedres but
also in tetrahedres. Highly charged smectites whose the charge of the layer is
displaced to the tetrahedres, display a much more greater tendency to an

397
irreversible compression; therefore mixed-layered mica smectite minerals form
readily [Howard & Roy, 1983; Dritz & Kossovskaja, 1990; Sato et al..,1996].
Highly charged smectites are particularly characteristic of periore rocks of
epithermal deposits in volcanic stratas. From experimental works, but also from
observed hydrothermal systems of contemporary volcanos [Eroshchev-Shak et.
al..,1985, 1996; Howard-Roy, 1985; Malla & Douglas, 1987; Sato et al., 1996]
it follws that high-charge smectites may be indicators of higher-temperature
condition than of low-temperature ones. Therefore a complementary charge is
established through replacement of part of silicon by aluminium in the
tetrahedres, which must be accompanied by partial structural reconstruction.
With further growth of temperature (150° and more) high-charge smectites turn
into mixed-micaceous minerals of the mica-smectite type.
Kaolinite mineral group of such wide extension. They represent, grosso
modo, kaolinites and dickites, sometimes as halloysites and, rarely, nacrites.
Kaolinite exists under two morphological aspects, as metasomatic thin-scaled
aggregates replacing feldspars and dark-colored minerals and, more rarely, as
filling of intersecting veinlets and zones of crushing. In the latter case may be
observed relatively coarse-flaked aggregates and wormlike growths. The degree
of crystallization of both varieties in periore argillisites is usually high (Hinckley
index about 0.6-0.8). In acid conditions (solfatara argillisites) is often observed
kaolinite with low degree of ordenning (Hinckley index about 0.3) and
halloysite.
Structural investigations [Eroshchev-Shak et al., 1996] reveal a
heterogeneous structure of hydrothermal minerals of the kaolinite group. It is
conditioned by the appearance of irregular dickite-kaolinite mixed-layered
phases (they usually contain not more than 5-10% of dickite-like layers).
Apparently this 120ºC temperature approximately corresponds to the limit of the
domain of kaolinite-dickite synthesis. Dickites in ore deposits either form
metasomatic secretions or fill cavities and fractures. Nacrite is observed only in
intergrowths with ore minerals in epithermal gold-silver deposits.
Amidst mixed-layered minerals predominate illite-smectites, but one may
also find chlorite-smectites, celadonite-smectites, kaolinite-smectites (the latter
studied only in ultra-acid facies of argillization). Illite-smectites are found in all
facies of argillization, usually in their outer and intermediate zones. Practically
all mixed-layered mica-smectitic minerals are related to a particular potassium
type, but sodium-containing paragonite-smectites (brammalites) are rare. This
totally corresponds with the narrow range of variation of the K/Na ratio, with
which may, in conditions of low temperature, co-exist sodium-containing micas
and mixed-layered paragonite-smectites. Starting from data concerning the
miscibility in the order of K/Na of dioctahedric mica [Popov, 1975; Iiyama,
1964], such minerals are established only in sodic milieu.

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 Hydrothermal mixed-layered illite-smectites contain 30% and more mica
layers and are nearly exclusively characterized by factors of neighbouring order
S>1 :S=0 in case of fully inordinate alternation of layers of micaceous and
smectitic type; S=1 when the position of arbitrary layers in the crystal depends
on one layer preceding it; S=2 upon two preceding layers and so on; in foreign
literature the factor of neighbouring order is designated by the symbol R or g
[Dritz & Sakharov, 1976].
The structure of these minerals strives to reach the maximum of possible
degree of order, which is reflected in the predominance of layers of the type
BAnB (A is a layer of illitic type) [Dritz & Kossovskaia, 1990]. In argillisites are
most often found mixed-layered facies with 50-70% micaceous layers. Absence
in hydrothermal metasomatites of mixed-layered illite-smectites with more than
50% content of swelling inter-layers and factor S=0 represents one of the
characteristic properties of hydrothermal mineral formations. This phenomenon
is noted not only for periore metasomatites [Diakonov & Volostnykh, 1979], but
also for many contemporary thermal manifestation [Steiner, 1977]. Kinetics of
illitization of smectites has been studied in enough detail and this has shown that
the mechanism of transfer of smectite to illite in hydrothermal conditions
substantially depends upon what takes place at the epigenesis of sediments.
Experimentally determined energy [Eberl & Hower, 1976] of activation of this
transfer at 260-390°C temperature, proving to be equal: E=19,6 Kcal/mol
(83Kj/mol). Actually it coincides with the theoretically calciculated one, coming
from the energy of breaking of crystal bond and structural reformation the value
of which must not be less than 80-100 kJ/ml [Velde & Vasseur, 1992]. For
diagenesis conditions this value is estimated by the authors at 37-70 Kj/mol. The
latter is rather characteristic of many exchange without destruction and
reformation of tetrahedric layers, which is apparently less characteristic of
hydrothermal conditions.
PH growth, preventing dissolution of initial smectite and decreased Al +3
activity increases the activation energy of transfer to 30 kcal/mol (~ 120 Kj/mol)
[Robertson & Lahann, 1981]. This circumstance may partly explain the wide
extension of hydromica and mixed-layered mica-smectites, specially in aureoles
of acid leaching, but of smectites in subneutral conditions.
Increase of content of illitic interfoliated in mixed-layered mica-smectites
from periore hydrothermal metasomatites is accompanied with a structural
restructuration in the hexagonal grids of the layers 2:1, increased content of
illite-layers and increase of concentration of layers with vacant transitions [Dritz
et. Al., 1966]. This structural peculiarity of hydrothermal illite-smectites
distinguishes them from diagenetic ones, which form without noticeable
structure reformation, basically through solid phase reactions.
In low temperature hydrothermal argillization of some gold,
uranium/mercury deposits in association with kaolinites is often found tossudite,

399
a di-trioctahedric mixed-layered mineral of the smectic-donbassite type with
factors of neighbouring order S=1. Lithium comes in compositions of octahedric
layers [Phineko et al., 1977] but its content may exceed 1 mas.%. chlorite-
smectites (corrensites) are relatively scarce and are found in altering basaltoids,
some of which are basalts of the ocean bottom.
Celadonite belongs to a number of low-temperature minerals. It is recorded
in argillized basalts or volcanoclastites of basic rocks on many uranium, gold,
fluorite deposits; moreover it appears one of the main mineral apobasaltic
argillisites of the ocean bottom. Undoubtedly the formation of this mineral
promotes iron enrichment of the strata as well as the oxidity character of
hydrothermal mineral formation in near-surface conditions at low temperatures
(not more than 120-140°C). The degree of iron oxidation in celadonites from
hydrothermal deposits from hydrothermal deposits and oceanic basalts is very
high, the Fe+3/Fetot. ratio is 0.7-1. Potassium content oscillates from 4 to 8.5
mas.%, mingled-layeredness is more expressed in oceanic basalts, and the
content of smectite mid-layers approaches 50%; moreover the factor of
neighbouring order is S>1, which proves to be one of the differences of
hydrothermal celadonites from sedimentary glauconites [Pritz & Kossovskaya,
1990]. Electronograms of celadonites, as a rule, contain clear enough reflexes on
first and second ellipse, corresponding to the polytype 1M.
Zeolites represent the very characteristic group of minerals for some
various argillisites. Amidst these are known low-silicic: laumontite, chabazite,
as well as high-silicic: mordenite, clinoptilolite. The latter develop nearly
exclusively on volcanoclastic rocks of acid composition and follow in
significant degree the initial composition of the substratum. So, in zeolitic
deposits of the Transbaïkal region predominate potassic and sodic-potassic
clinoptilolites and mordenites [Korobov, 1988], which apparently reflects the
potassic character of the volcanites of this region. On the other hand, these high-
silicic zeolites prove to be indicators of low-temperature conditions of
mineralisation (~130°C and lower). Low-temperature zeolites in volcanites are
much more rare and coincide with flows of basic lavas or with the horizons of
their volcanoclastites. Amidst them are observed chabazite, desmine, faujasite
harmotome, but this gathering of minerals, of course, is not conditioned by their
temperature conditions but by the properties of the substratum composition.
They are significantly absent in periore metasomatites as well as in veinous
secretions of wairakite, which is widely spread in altering rocks of contemporary
thermodisplays of the domain of active volcanism. It is known as the highest
temperature zeolites and may be stable up to the ~290°C isotherm, which
already exceeds the temperature condition of argillization. With periore
hydrothermal metasomatism in the same temperature conditions develop instead
carbonates in paragenesis with sericite (or other micaceous silicates).

400
 Carbonates develop in these argillisites, which form in subneutral or feebly
acid milieu. Metasomatic carbonates are represented, grosso modo, by ferrous
dolomites, paraankerites, ankerites, siderites, magnesiosiderites. Calcites and
dolomites are usually observed in intersecting veinlets and do not belong to
substantially argillitic parageneses. On the whole, argillisites with participation
in them of multiform ferrous carbonates are very characteristic of uranium
deposits, reflecting to some extent specific ore-forming processes, in a given
case of high activity of carbon dioxide and of the subordinate role of sulphur.
Alunite is typical of ultraacid facies of hydrothermal and synvolcanic
argillisites. It has chiefly a potassic and potasso-sodic composition; sodic
varieties are found very rarely. A high iron content, up to formation of jarosite,
is noticed in alunites, forming on the surface or in zones of intense aeration of
subterranean waters. Contents of potassium and corresponding K and Na in the
composition of alunites from argillized rocks are indicated on the diagram,
fig.23.2. Crystals of alunite of surface of near-surface genesis are strongly
stretched along the crystallographic axe and have the aspect of spindles and
needles. The temperature of their formation usually does not exceed 100-150°C.
Higher temperature alunite from hydrothermal veins forms short-columnar
crystals. Different morphologies are conditioned by disequilibrated growths in
the first case and near-equilibrated ones in the second.
Chemical composition. Changes of chemical composition of rocks at
argillization have their own properties in dependence upon conditions of the
flow of the hydrothermal process. The basic tendencies of removal and
redistribution of components in kaolinite-carbonate, kaolinite-smectite quartz-
kaolinite argillisites, on the whole, are close and express lines characteristic of
processes of acid leaching in general. Thus, in kaolinite-smectite facies is
observed a distinct removal of alkaline earths and sodium, and in lesser degree
of potassium. Noted are tendencies in various directions in the behaviour of
alumina and silica, and an increased content of alumina linked with the massive
development of clayed minerals replacing plagioclases, coloured minerals and
potassic feldspars. In quartz-kaolonite facies decreased silica content in
intermediate zones usually gives way to its increase in the inner one, linked with
the development in many cases of quartz core. All divergences in the
composition of alkaline-earth elements are linked with a more or less expressed
carbonatization, but some increase of potassium in inner zones is accompanied
with the possible later development of superimposed sericite, alunite, adular.
Other regularities are displayed by argillisites of zeolite-smectite facies. In
so far as it does not belong to the acid type, here a definite H2O content is
observed, and in the basic rocks also CO2, without change in the contained
principal rock-forming components (some Na removal is possible). A slight
increase of porosity is observed, up to 10-12%. In deposits with intense
appearance of zeolitization (Chikoi-Ingodinskoie part of Transbaïkal region)

401
may be recorded a noticeable Ca addition, for example in the metasomatic
Gornoie deposit, nearly double compared to the initial granites. This reflects a
specific process, i.e. the absence of a clearly expressed acid leaching.
Parageneses and facies of argillisites. Hydrothermal argillisites. Quartz-
kaolinite facies is extending in diverse epithermal deposits. It forms under the
influence of acid solutions in conditions of small depth and low temperature and
is accompanied by antimony-mercury, gold, gold-silver, more rarely fluorite and
uranium mineralization. Quartz-kaolinite argillisites characterize insular arcs
and continental mrgin areas and much less often are found in boundary zones of
inner tectono-magmatic activization. Typical instances of development of these
argillisites are metasomatites of gold-silver deposits of volcanic belts in N-E
Russia (Okhotsk-Chukotski belt), in the Transcarpathïa (Alpine belt), in
northern and southern Cordillera, on the island arcs of the Pacific Ocean, etc. A
great part of quartz-kaolinitic argillisites corresponds to the so-called sulfato-
acid (high sulfidation, advanced argillization) type of periore metasomatites
formed under the influence of high-acid sulfates and chlorid-sulfatic
hydrotherms, principally of magmatic provenance [Heald et al., 1987].
Important minerals of these facies are kaolinite, quartz, chalcedony, alunite,
dickite; in different varieties opal, jarosite, mixed-layered minerals (kaolonite-
smectite, illite-smectite), sulfur, hematite, iron sulfides, gypsum, baryte. To
accessory minerals belong anatase, apatite (and other phosphates), sulfides of
arsenic, antinomy, mercury etc.
Argillised rock of quartz-kaolinite facies form metasomatic perivenous
aureoles, the inner zones of which are replaced by quartz-kaolinite associations.
In its most general aspect the column of metasomatic periveinous zoning of this
facies has the following aspects (from axial solution-producing fracture to
enclosing rock): quartz  quartz + alunite  quartz + alunite + kaolinite 
quartz + hydromica  quartz + hydromica (or sericite)  chlorite (or
corrensite)  propylitized rocks (albite + chlorite + calcite + sericite). Alunite-
containing rocks in some deposits extend to depth of 1.2km, where they are
replaced by parageneses with diaspore, pyrophyllite, andalusite, zunyite
[Goldfield, Red Mountain, Cerro de Pasco etc.), in other cases zones with
reduced alunites. In a quartz-hydromicaceous zone there may develop carbonate
of the dolomite-ankerite type in case of increased oxygen fugacity. The latter
case may represent transfer from argillized rocks to beresite-like, i.e. essentially
represent an example of vertical metasomatic zoning. This phenomenon
corresponds to some epithermal gold-silver, antimony-mercury and other
deposits. Most often quartz-alunitic metasomatites form gently pitching
stratiformform or lenticular bodies, coinciding with the most superficial
hypsometric levels of deposits (fig 23.3).
An example of less sulfidized type of metasomatites is given by the
Baleiskoie gold-ore deposit in the Transbaïkal region [Rusinov & Rusinova,

402
1977]. A substantial difference of these metasomatites is the absence of alunite
in the composition of silicified rocks, which may be linked also with unstable
acidity, and in more reduced conditions with the formation of alterites. The
general picture of metasomatic zoning is distinguished by the presence of
steeply falling fractures, along which develops a superimposed
hydromicatization.
Less acid types of kaolinitic argillisites may be represented also by self-
formed carbonate-kaolinitic argillisites, known for the present only in relation
with uranium mineralization. This type of argillisites develop on some veinous
and stratiform deposits of the Transbaïkal region (Olovskoie deposit and part of
the deposit of the Streltsovskoie ore field) and in the Ronneburg ore field in
Thüringen (Germany). Metasomatites are localised in rocks of different
composition. Clayed minerals are represented nearly exclusively by kaolinite,
besides which exist in alterites, in various quantities, ferrous carbonates and
quartz. Smectites are not displayed in outer zones of argillization aureoles, as far
as transformations of feldspars start with their immediate replacement by
kaolinites and carbonates without reaction of the smectite zone. As standard
instance serves the Olovskoie deposit, where it is possible to follow the
consecutive development of these argillisites from superficial unchanging
granodiorites (fig 23.4). Metasomatic zoning is nearly not expressed. What
draws attention is the significant stability of biotite and potassic feldspar,
characteristic is also the replacement of parankerite or ankerite of outer zones by
siderite or pistomesite in sectors of more intense study. A monoquartzic inner
zone, should it occur, does not exceed in thickness a few centimetres, the
quartzic “hat” in the supra-ore zone does not develop. Some complicated
zonings are developments of mixed-layered minerals, rectorites and tosudites,in
intermediate and inner parts of aureoles. A vertical zoning of metasomatites is
not chacacteristic of the described type of argillisites of kaolonite facies (unlike
the sulfide-acid), which may serve as a complementary proof of a possible low
activity of sulfur in the process of their formation.
Facies of kaolinite-smectite argillisites are in polymetallic, uranic, fluoritic
etc. deposit domains of intracontinental tectono-magmatic activization and
continental margins.. Characteristic is the localisation of metasomatites in
crystalline volcanic or metamorphic rocks of distinct age in the form of
relatively narrow zones (a few metres and up to 10-20 metres), controlled by
coarse fracturation and zones of fissuration. Argillisites of the given type extend
to domain of development of meso-cenozoic volcanisation, for example
Mongolia, Transbaïkal region, a series of occidental states USA (Utah, Montana,
Colorado), Bolivia, domains of alpine folding of central and Eastern Europe etc.
In argillilisites on polymetallic and uranic deposits of western USA [Bonorino,
1959, Tooker, 1964] metasomatic zoning may be represented by the following
scheme: 0) unchanging rocks; in most cases this is quartzic monzonite of the

403
tertiary age; 1) chlorite zone, chlorite + pyrite + carbonate + hematite; 2)
montmorillonite zone, montmorillonite with admixture of kaolinite and mixed-
layered mineral; 3) kaolinite zone with sericite; 4) sericite with local
silicification and ore veinlets.
Sections 2 and 3 conditionally, as far as also kaolinite, and smectite develop
usually at the same time and only is noted a constant tendency to the growth of
kaolinite content in the centre of the aureole. Potassic micas, judging from their
intersecting position, represent a later formation of relatively general zoning.
On Russian territory similar appearance of argillization are known in a row
of uranium deposits of the Transbaïkal region (deposit of the Mogotchinskoie
group, Sigirli deposit). Possibly, close to them are also the periore rocks of some
mercury deposits (Nikitovka in the Donetz basin) etc. [Volostnykh, 1972;
Kazitzin, 1979]. A typical example of argillilisites with somewhat increased
carbonate content is the Mogotchinskoe ore field. Here the ore veins and the
aureoles of alterites surrounding them are controlled by steeply dipping fracture
zones. The thickness of the argillization zones never exceeds 25-30m. The
presence of various xenolites significantly complicates the aureoles’
morphology. The outline of the metasomatic zoning is as follows: 0) initial
biotite granite; 1) outer zone: quartz, microcline, biotite, smectite, kaolinite,
dolomite; 2) intermediate zone: quartz, microcline, kaolinite, smectite, ankerite;
3) inner zone: quartz, kaolinite, now and then microcline.
Hydrothermal genesis of this type of argillisites is undoubted, and their
extension (apparently also their genetic link) with mineralization is expressed
very clearly, unlike the other facies of the argillisites.
The zeolite-smectite facies includes various metasomatites, which are not
wholly locked up in the group of products of acid leaching. In their composition
predominate smectites or smectites in parageneses with zeolites. In other
minerals may exist kaolinites, celadonites, carbonates, mixed-layered mica-
smectites, chlorite-smectites with significant (about 50%) content of swelling
inter-foliated layers, berthierites, quartz, fluorite. Apart from contemporary
volcanic domains, this facies is also found in some ore deposits of the Mesozoic-
Cenozoic age, in uranic deposits and ore-displays of the Transbaïkal region,
Bulgaria, Chukotski, Tchechskoie massif, polymetallic and sulfidic with native
copper of displays in Bulgaria and a few others [Kostrov et al., 1971; Rogova,
1976; Petrossian & Buntikova, 1981; Tchernikov et al., 1983].
The relation of age and genesis of this facies of metasomatites with
mineralization is not wholly clear, as far as in many cases hydrothermal
transformations have a small extension. Metasomatites sometimes in themselves
represent an increased deposit of zeolite and bentonite raw material. In many
cases metasomatites coincide with fields of extension of basaltic volcanism or
develop in immediate vicinity with them (eastern and southern Mongolia,

404
Transbaïkal region), less typical of their vicinity with dacite-andesite volcanism
(Bulgary, Caucasus).
In the composition of facies are distinguishable three subfacies: smectite
with calcic zeolites, smectite with celadonite, cristobalite and high silicic Na-K
zeolites; and essentially smectites. In connection with the first one is known an
uranium deposit of the so-called monometallic -uranotil type (Transbaïkal
region,Russia). Subvertical zones of metasomatic transformation have here an
extension of a few km and a thickness up to a few tens of meters. Metasomatic
minerals are represented nearly exclusively by dolomite and calcic smectites,
veinous minerals: desmine, very rarely calcite, quartz; ore minerals: uranotil, in
a lesser degree uranophane and autunite, which basically develop in a zone of
near-superficial oxidation. The thickness of the ore bodies reaches 10m, but in
dipping they reach a depth of 800 m and more (fig.23.5). Ore bodies represent a
system of veins of breccia-like deposition, in which fractures of laumontitized
granites are cemented by desmine and -uranotil; moreover the last generation
of zeolites developed after the uranium minerals, and calcite ends the process of
deposition of vein minerals. Metasomatic zoning in periore rocks is nearly not
expressed at all and may be displayed only in increased zeolite (laumontite)
content in perifracture zones of maximal alteration.
Another subfacies of metasomatites with la portion of nearly exclusively
high-siliceous zeolites of the heulandite group is widely developed in many
domains of paleovolcanism, where it occupies an important area, but sometimes
contain economic ore mineralization. So, for instance, in the northern part of the
Tulukuievskoie caldera (Transbaïkal region) in connection with these
metasomatites develop pitchblende-coffinite ores with native arsenic (fig. 23.6).
Alterations occupy an area of 15-20 km2, the entire section of volcanic rocks,
500-600m thick and, partly, early paleozoic granitoids of the basement. The
form of ore bodies is stratiform fissurated. Zeolites are represented grosso modo
by Na-K clinoptilolites and mordenites; moreover the latter fill, basically,
sections of veinlets, and smectites are related to high-rank Na or Ca diversities.
Ore bodies are surrounded by aureoles of ore-accompanying metasomatic
berthieritization, but in the roof are observed Fe-Mg carbonates. Vertical
metasomatic zoning is hardly developed, and only at great depths are recorded
mixed layered mica-smectite minerals.
Ore-accompanied veinlet-metasomatic transformations in argillisites are
tightly linked in extension with ore depositions, they often have a metasomatic
nature, but can also result from depositing in open cavities and fractures. They
develop somewhat later zonal aureoles of argillisites, but precede productive ore
stages; in other cases they may appear simultaneously with ore minerals or after
them. Mineral composition of ore-accompanied metasomatites are relatively
simple, they are presented as berthierite, carbonate (principally of iron), adular,
mixed-layered minerals, rarely zeolite and fluorite, tossudite etc. Amidst them,

405
perhaps, the most spread are berthierites, which are particularly characteristic of
uranium and gold-silver deposits. The level of this development is always much
lower than with argillisites, but the dimensions of the aureoles always exceed
those of ore bodies. Metasomatic behaviour is what most characterizes
berthierites; moreover it most often forms pseudomorphoses on beforehand
kaolinized plagioclase and on biotite. Apart from the variety with 7A structure,
sometimes are also found mixed-layered ones. Carbonates form systems of thin
veinlets as well as zones of metasomatic carbonatization. Amidst them
predominate ferrous or manganous varieties such as siderite-magnesite, siderite-
rhodochrosite, and also ankerites. More rarely in contact with ore veins are
observed developments of thin edgings and narrow zones of hydromica and
mixed-layered mica-smectites. Adular as ore-accompanied mineral is nearly
always observed on many gold-silver epithermal deposits in argillisites of the
acid type, where they usually also extend to portions of development of gold-
sulfidic mineralization.
Deposition of the enumerated minerals submits, on the whole, to a well-
known plan of development of processes of acid bleaching and accompanying
deposition, when in the composition of ore-accompanying minerals entered
components secreted from enclosing rocks. However, there are frequent cases of
development of minerals requiring addition of complementary elements.
Amongst these, lenticular tossudite may be mentioned. This has been studied in
many near-surface, low-temperature deposits of gold, uranium, silver, mercury.
Tossudite usually spreads to masses of ore-minerals or fills intersecting post-ore
zones of jointing.
Synvolcanic argillisites of the domain of contemporary volcanism.
Metasomatites, confined to domains of active contemporary or young
Pleistocene-Holocene volcanism, contain a significant quantity of clay minerals,
but also a series of other minerals characteristic of low temperature conditions
(zeolites, sulphur, opal, etc.).
The character of hydrothermal formation is divided according to the type of
thermal waters and in a lesser degree to the composition of the initial enclosing
rocks. Amongst studies in present times of thermal waters are clearly enough
distinguished three fundamental types [Naboko, 1974; Lebedev, 1975]: 1)low
mineralised subneutral, principally chlorid-sodic waters, not linked with
concrete volcanic constructions; 2) ultra-acid and acid sulfato-chloridic waters
of volcanic apparatuses; 3) highly concentrated carbon dioxide brines of rift
domains. Correspondingly, three basic varieties of hydrothermal alteration are
distinguished, each of which is characterized by its own specific gathering of
mineral parageneses and zoning.
Argilliisation, linked to the influence of chlorid-sodic hydrotherms.
Alterites in the realm of unloading of thermal waters of a given type occupy a
very great area, up to 10.000 km2 and more, although the degree of alteration is

406
most often insignificant or moderate. Display of this type has been studied in
many regions of the world and coincide, grosso modo, with the Pacific ocean
volcanic ring (New Zealand, Kamchatka, Kurile islands, Indonesia, Japan,
Philippines) but also in other regions (Iceland, Italy). Thermal waters are usually
characterized by high temperatures, up to 300°C and more (Wairakei, Waiotapu,
Mutnovskoie deposit, Los-Azufres, Pauzhetka) and relatively low
mineralization, though it may in some cases reach 15-18 gr/l. In salted
composition NaCl rarely predominates (2-12 gr/l), Si, K, B concentrations
attains hundreds of mg/l, rarely up to 1-2 gr/l, but Ca not more than 200-300
mgr/l, very low usually Mg, Al, Fe contents. The content of silicic acid roughly
corresponds to the solubility of quartz at a given temperature. In gas
composition CO2 usually predominates, H2, N2 etc. contents are insignificant.
Some ion ratio, for instance Na/K, are characteristic, amounting as a rule to 10-
12, and only in diluted low-temperature waters, but also in systems with parts of
sea water it grows up to 20 and more. Value of pH of waters on the outflow after
degazation amounts to 7.2-8.2; however, in the existing conditions of vapour
separation acidity of the solutions is significantly higher. So, according to direct
pH measurement in borings these values at 140-150°C amount to 5.3-6.5
[Zhdanov et al., 1994]. Consequently, in the influence waters of this type are
near-neutral and feebly acid.
Approximately, vertical zoning of hydrothermal alteration may be defined
under four zones from above down-wards. The first one forms at the expense of
hydroyen sulphide, it is 0 to 50-60 m thick, its characteristic minerals are
kaolinite, opal, alunite; iron hydroxide. The second zone consists substantially
of argillilisites of zeolite-smectite composition. The third zone is characterized
by the development of mixed-layered mica-smectites, chlorite-smectite
(transferred, as temperature increases up to 200-300°C, to illites and chlorites),
wairakite, calcite, prehnite, quartz, epidote, adular, albite. In lower zones
temperature may reach 260°C. The fourth zone is represented by propylitized
rocks with chlorite, epidote, albite, adular, calcite, sometimes in the highest-
temperature systems with actinolite, andradite, apatite (Mutnovskoie deposit in
Kamchatka, Los Azufres, Philippines) [Steiner, 1977; Cathelineau et al., 1989].
Illite here is replaced by mica of phengite or muscovite composition in
temperatures between 270 and 310°C.
A few other types of zoning are observed in geothermal systems with sharp
predominance in sections of vulcanites of basic composition in Iceland in the
hydrothermal systems Hveragerbi, Reikyanes, Hengill [Kristmannsdottir, 1975;
Fridleifsson, 1991]. The composition of the hydrotherms, although near that of
sea water, differs in its very lower pH value, about 4.5 and much higher content
of ore components. Deep boreholes reach nearly 3 km and the vertical
metasomatic zoning has the following aspects (from above downwards):

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 1. Zeolite-smectite zone: mordenite, laumontite, calcite, analcime,
nontronite, saponite. The zone is limited in heat to 200°C and in depth to 400-
700m.
2. Zone of mixed-layered chlorite-smectites with variants, sometimes with
prehnite, calcite; limits: 230-240°C and 800-1200m.
3. Chlorite-epidote zone. Chlorite replaces mixed-layered minerals at about
230-240°C, epidote forms at 260°C ; depth limit : 1700m.
4. Epidote-actinolite zone (actinolite stable at 300°C).
On the whole, for this group of hydrothermal alteration the temperature
factor is commanding and shows the greatest influence on the character of
mineral transformation. So, for instance, in all geothermal systems are traced the
following series of alteration clay minerals (in rising temperature): acid volcanic
glass or plagioclase  smectite  mixed-layered mica-smectite  illite 
sericite (muscovite); or on basic volcanic glass: nontronite (saponite) 
corrensite  chlorite; for zeolites: clinoptilolite  mordenite  laumontite 
wairakite.
Hydrothermal alterations, linked with the influence of acid and ultra-acid
hydrotherms, belong to the solfatara types, i.e. to such replacements the
formation of which is in a high degree distinguished by the presence of sulfate
ion. This type may be divided into two groups: the near-surface, substantially
sulfatic type and in depth the sulfato-chloridic.
Near-surface argillization appears, grosso modo, as a result of oxidation
of hydrogen sulfide in hydrotherms, and may also be observed on slopes of
volcanic apparatuses. Water temperature usually does not exceed 100°C, pH is
between 1.5 and 4, general mineralization of a few gr. per litre. Thickness of
altering rocks oscillates between a few metres and 50-60m. Vertical
metasomatic zoning usually has the following aspects (from above downwards):
opalites, opalites and alunites, kaolinite with alunite, kaolinite, mixed-layered
kaolinite-smectites, illite-smectites, initial rocks. A peculiarity of near-surface
hydrothermalites is the wide development of disequilibrated associations and
metastable phases, for instance pyrite with marcassite, pyrrhotite and greigite,
kaolinite together with metahalloysite, mixed –layered kaolinite-smectite. An
important factor of mineral formation is oxidation of hydrogen sulfide and
diluted hydrotherms of rain waters.
Deep acid bleaching is characterized by a very great level of appearance.
It is conditioned by the influence of ultra-acid sulfato-chlorid waters genetically
and spatially linked with volcanic formations, as a rule of the andesite type,
situated in a condition of long rest. Temperature of the hydrotherms reach 320°C
(in deep parts probably even higher), pH from 0 to 3.5, amongst anions
predominate chlore and sulfate-ion, general mineralization reaches 10gr/litre,
but in acidest systems with pH near zero, up to 100 gr/litre [Delmelle &
Bernard, 1994]. As a rule these displays are characteristic of island arcs. They

408
are studied in Japan (hydrothermal systems of Otake, Hatchobaru, Matsukawa),
and Indonesia (Sumatra, Java), in Taiwan, Philippines, Kurile islands (Kunashir,
Paramushir).
A very clear example of development of acid argillisites is given by the
geothermal systems of the Philippines, in particular the thermal field of
Tongonan [Reyes, 1991]. Temperature of acid waters attains 320°C at depths of
2400 m, pH (at outflow) about 4-4.7, chlorine content is 3 to 20 times over that
of sulphate-ion, general mineralization amounts to 11 gr/l. Metasomatites are
concentrated exclusively along steeply falling zones of explosive fracture, their
thickness usually does not exceed a few tens of metres, but lateral zoning has
not been sufficiently studied. The basic motif of vertical zoning is represented
by the following zones, from above downwards:
1. kaolinite + alunite + sulfur +pyrite (up to 120°C)
2. dickite +kaolinite +alunite +anhydrite (120-200°C)
3. dickite + pyrophyllite (200-250°C)
4. pyrophyllite + illite (230-320°C)
In surface parts of the section, moreover, may exist opal, trydimite,
cristobalite, but in great depth in acid metasomatites exist zones of germinal
greisenization, characterized by the presence of topaz, lazurite, turmaline,
zunyite, fluorite, muscovite. Everywhere zones of acid metasomatites prove
much later than argillisites of the subneutral type (fig 23.7).
The question of the source of acid and ultra-acid hydrotherms is not fully
resolved, and some authors prefer a meteoric genesis of those waters as a result
of sulfur oxidation. But, considering the geological conditions of the thermal
manifestation of such a type, their coincidence with determined geodynamic
realms, high content of sulfur, chlorine and fluorine in the thermal waters, the
deep character of development of metasomatic transformations, all prove their
magmatic genesis. Like one of their possible variants, a likely process is the
formation of juvenile magmatic gases in meteoric waters of a mud of stratiform
fissural type. The observed vertical and lateral zoning of metasomatic alteration
coincides in a high degree to the metasomatic zoning in epithermal deposits of
the acid-sulfatic type (advanced argillization).
Hydrothermal transformations linked with influence of heated brines. This
type of alteration is linked with contemporary rift systems and coincides (but not
always) with volcanic or intrusive formations. It is linked to high-temperature
carbon dioxide brines of the geothermal fields of Salton-Sea (California), Cerro-
Prieto (Mexico) and other great copper displays in the limits of the rift zone of
the Californian gulf, apparently also in their vicinity the brines of the Cheleken
peninsula (Turkmenia), the graben of the red sea, etc. In the latter no
hydrothermal transformations have been noted, and there is no link with
magmatic display. Specific thermal waters exist in high general mineralization
(up to 260-280gr/l) and often in high contents of carbon dioxide (up to a few

409
gr/l). Temperatures of boiling brine in deposits of the Californian rift attain 350-
390°C. Enclosing rocks are here represented by delta-shaped facies of
sedimentary rocks. On the territory of thermodisplay of Salton-Sea are formed
five young rhyolitic and slag cupolas, the age of which amounts to 10-16
thousand years. These extrusions are often covered by sediments, but in three of
them occurs a gas secretion (mainly CO2) and vapour-water blends from cracks,
tracing coarser lineaments of the north-western course [Muffler & White, 1969].
It is not excluded, however, that the main source of heat in these systems be
linked with concrete magmatic displays, but with deeper processes, conditioning
the formation of “young oceans”, in which also occur rifts of the Californian
gulf, the Red sea and other regions.
Although the depth of drilled boreholes attains 4.5 km, maximal
temperatures are recorded in various records. Thermal waters are basically
potassic-calcic-sodic chloridic with high content of ore-components; the carbon
dioxide content attains 96% in gaseous phase and 5 g/l in brine; the value of pH
at 25oC is 4.6-5.5.
Hydrothermal alterations occupy an area up to tens of km2 and are
controlled by permeable zones and warming up fractures. Vertical metasomatic
zoning is very similar to one type of subneutral transformation in volcanic
realms. The main difference is the full absence of new formations of zeolite and
the very insignificant development of feldspars, adular and albite (fig.23.8).
Conditions of argillisite formation. Evaluation of the condition of
argillisite formation is complicated by the absence of reliable thermodynamic
constants for smectites, zeolites, berthierites, and also insufficient experimental
research in low temperature realms. Nevertheless, some conclusions may be
drawn.
Kaolinitic argillisites undoubtedly present a facies of maximal acidity and
have an obvious analogue amongst solfatara argillisites of superficial as well as
deep type. Judging from the high extension of quartz-kaolinite association with
alunites, the influence of hydrotherms may have a sulfatic or chlorido-sulfatic
character with pH at 4 and less. There may be some difference only in the
carbonate-kaolinitic variety of these argillisites, which corresponds to conditions
of greater CO2 fugacity. The relatively feeble similarity in the composition of
altering rocks of calcic hydromicas and mixed layered illite-smectites indicates a
(basically) non-high temperature of the process: about 250°C. A reaction zone of
smectites in contact with enclosing rocks will not develop in all cases, which
may be conditioned by the proximity of kinetic factors causing” vanishing
zones” in an infiltration metasomatic column. This phenomenon was predicted
by [Link] but later theoretically and experimentally studied by
[Link] and [Link] [1994].
A smectite-kaolinite facies of argillisites corresponds to conditions of
moderate acidity, but the temperature conditions, probably, were close to the

410
preceding facies. This permits to indicate the frequent presence of carbonates
with very feeble development of a quartz core, and relatively rare occurrence, in
the composition of intermediate zones of metasomatic columns, of illite-smectite
mixed-layered minerals. The latter was only possible at temperatures not above
180-200°C, as far as at its further growth smectites were on the whole replaced
by hydromicas and sericite.
As regards smectite and zeolite-smectite metasomatites, they are not
characteristic of acid conditions. These metasomatites have a few analogues in
the realms of unloading of thermal waters, which permits to determine the
conditions of their formation at low temperature (~130-150°C and lower) and
near-neutrality. According to data of [Link], direct pH measurement in
high-temperature boreholes [Zhdanov et al., 1994] points to the fact that these
parageneses are stable in near neutral or even feebly acid milieu with water pH
about 6 at 140-160° C. Extrapolation of these data in high temperature realms
reveals some replacement of a realm of smectite stability by a one of more acid
value, as, at 180-200°C water pH must correspond roundly to 5. Laumontite, so
widely spread in the metasomatites of the central Transbaïkal region, also
characterizes a completely determined temperature range, from 120 to 200°C
[Fridleifsson, 1991] with near neutrality of the solutions. At the highest
temperature calcic zeolite, wairakite are perfectly uncharacteristic of ore
deposits, though usual enough in high-temperature boreholes of contemporary
thermodisplays.
Ore-accompanying metasomatites, chlorite, berthierites, carbonates,
hydromicas, adulars, etc. may arise as a result of the boiling of solutions
[Naboko,1974] as factor of pH increase. The possibility of sharp pH growth of
thermal waters, under the influence of a part of CO2 was theoretically
mentioned on the example of the Broadlands deposit in New Zealand, relatively
rich in carbon dioxide [Browne & Ellis,1970]. It was shown that at the decrease
of carbon dioxide content to 0.15 m its loss to 0.03 at decontamination causes a
pH increase to 0.6-1.2 units, but this value does not prove certainly significant
for a sharp change of acid-alkaline condition; therefore in the given cases may
be applied a model of biphasic gas-liquid system [White et al.,1971], providing
for inflow of saturated metals of the brines after stage of acid bleaching.
Fig.23.9 presents an outline of spreading of different facies of argillisites
in dependence upon temperature and acidity. It has a qualitative character,
inasmuch as deposition of minerals in equilibrium, of course, depends also in a
significant degree upon the concentration of the corresponding components. For
some of them the influence of the temperature factor and acidity has a much
greater importance, which also permits to utilize such a kind of formation for a
rough estimate of the physico-chemical condition of argillization. The remaining
equilibriums are plotted, starting from available experimental and calciculated
data, and so also are observed in realms of contemporary mineral formation.

411
 In acid conditions the boundary conditions of argillization are determined
by kaolonite = pyrophyllite equilibrium, which according to numerous
experimental data, corresponds to a temperature of about 290°C. Alunite in low-
temperature conditions corresponds with a very acid condition of the milieu, as
at 90°C pH should not exceed 2.5 and at 200-300°C it is situated between 2 and
3, since with growth of alkalinity may occur the reaction of alunite + quartz +
H2O = dickite (kaolinite) + K+ +4SO42-+6H+ [Zotov, 1967;Hemley et al., 1969;
Inoue & Utada, 1991].
In subalkaline conditions the temperature limit of argillisites roughly
corresponds to 190°C, determined by the stability of analcime [Mattews, 1980].
This reaction is usually utilized to mark the boundaries of the zeolite facies of
metamorphism. In the field of hydromicas and mixed-layered mica-smectites the
limit between formation of beresites and argillisites, apparently, may lead
somewhere to a level of development with content of swelling stratas not above
20%, i.e. at a temperature roundly of 230-250°C.
Argillization and processes of ore-formation. Argillisites are characterized
by multiform low-temperature mineralization of gold, uranium, fluorite,
antimony, mercury, arsenic, silver, zeolite, bentonite. However, a multiform
deposit unique as to reserves does not characterize them. Practically every
display of ore mineralization in argillites is related to the deposit type, when
formation of metasomatites and ore bodies is divided in some time intervals.
Excluded are only deposits of zeolites and bentonite raw material, which in
themselves represent metasomatic rocks. As with other metasomatic low-
temperature types, ore veins and zones of disseminated mineralization only
sometimes coincide with a portion of maximal bleaching, in general they extend
arbitrarily in relation to the zoning, although in unalterated rocks they
sometimes do not grow.
Ore content of argillisites depends upon their facies belonging as well as
the geotectonic conditions of their display. Interrelation between degrees of ore-
content of argillisites with their geotectonic (geodynamic) position and the
facies varieties of hydrothermal alterations are shown on table 23.1. The degree
of ore-content of argillisites is very strongly diverse. So, in wide fields of
argillized rocks of island arc domains of active volcanization it occurs at
considerable depth intervals, basically from a few centimetres to a few
decametres, i.e. in portions with maximal display of gradient of outer condition.
The thickness of ore veinlets is insignificant, the concentration of metals is very
low and with rare exceptions they are not comparable with hydrothermal ore
deposits. Basically, totally oreless and oceanic apobasaltic argillisites, to the
exclusion of those that belong to the sulfide formation of the “black- smokers”.
Argillisites of the acid type (quartz-kaolinite facies) are widely spread in
connection with antimony-arsenic-mercury, gold, gold-silvery deposits and
displays, especially in realms of continental outskirts (western USA, north –

412
eastern Russia, low Amur area, Andes, etc.). The amount of mineralization may
be totally insignificant. To kaolinite-smectite argillisites found in slightly acid
milieu, correspond a wide spectrum of useful material either of ores (of uranium,
arsenic, polymetals) or oreless (fluorite). However, coarse deposits connected
with metasomatites of this type are unknown, except some deposits of fluorite.
Zeolite-smectite argillisites, as remarked above, either by themselves represent
deposits of sorbtive materials, or contain small deposits of uranium ore.

413
Fig. 23.1. Contents of silica and iron in dioctahedric smectites.
Field of hydrothermal smectites limited by dotted line: 1-figurative points of
hydrothermal montmorillonites and beydellites; 2-dioctahedric smectites of the crust
weathering; 3-sedimentary smectites; 4-smectites of alterated oceanic basalts [Dritz &
Kossovskaya, 1980, 1990; collective data].

414
Fig. 23.2. Dependence of content of potassium in alunites on temperatures.
a- isotherms of ideal distribution of potassium between alunite and solution, caculated
at 10, 25 and 1000C [Zotov, 1971]; b- histograms of distribution of content of potassium and
sodium in alunites of various genesis [Stoffregen, 1990]; in left upper corner, number of
locations of alunite and general number of analyzed samples; A-alunites from pyrophyllite-
containing metamorphic samples; B-alunites from hydrothermal ore deposits; C- hypergene
alunites (diagenesis and weathering crusts).

415
Fig. 23.3. Schematic geological cross-section of alterated tufas of polymetallic deposits of
Beganskoie [Volostnykh, 1972].
1-slope waste; 2-9 zones of alterated rocks; 2- monoquartzites; 3-silicified rocks
with alunites; 4-kaolinites and silicified rocks; 5-silicified, kaolinized and alunitized rocks;
6-montmorillonitized; 7-kaolinite-chloritic; 8-kaolinite-hydromicaceous; 9-
hydromicaceous-chloritic; 10-12-veins: 10-polymetallic, 11-baryte-polymetallic, 12-
barytic, 13-sedimentary argillites, 14 - dislocation breaks.

416
Fig. 23.4. Development of carbonate-containing kaolinitic argillisites on uranium deposit
of Olov (East Zabaikal), schematic geological cross-section (after [Link]).
1-granodiorites of the Orlov complex (J2,3); 2-3-rubbly and coarse-pebbled
conglomerates and gritstone; 4-sandstone; 5-tufas and tufo-sandstones; 6-aleurolites; 7-
zones of development of recent smectite; 8-greisenized granites; 9-10-weak and intense
manifestations of argillized carbonato-kaolinitic composition; 11-fractures; 12-ore bodies.

417
Fig. 23.5. Schematic geological cross-section through Gor deposit (on materials of
[Link], [Link], [Link] and collective data).
1-granites (J3); 2-zones of smectitization; 3-area of development of veinlet desmine;
4-zones of laumontitetization; 5-ore bodies; 6-holes.

418
Fig. 23.6. Schematic geological cross-section through the Dal uranium deposit (East
Transbaikal).
1-early Paleozoic granitoids; 2-conglomerates; 3-trachydacites and their ignimbrites;
4-lava breccias; 5-basalts; 6-andesites and andesito-basalts; 7-tufas; 8-rhyolites and
rhyolitic ignimbrites; 9-portions of development of weak or moderate smectitization; 10-
intense development of smectites and zeolites along dislocation breaks; 11-fractures; 12-
gentle fractures; 13-ore bodies.

419
Fig. 23.7. Character of development of argillisites of ultra-acid type in the hydrothermal
system of Tongonan (Philippines) [Reyes, 1991].
1-unalterated rocks; 2-smectite zone; 3-transitory zone; 4-illite zone; 5-
transformations of acid type; 6-limites of appearance of epidote; 7-limit of appearance of
biotite; 8-limit of appearance of amphibole; 9-flows of deep acid fluids; 10-flows of
subneutral chloridic waters; 11-sulfatic reversed flows (influx).
(1), (2), (3), (4)-successive phases of introduction of intrusive bodies from late
miocene to pleistocene; I-late pleistocene and contemporary lava flows and volcanoclasts; II-
late pliocene and early pleistocene hyaloclastites; III-late miocene limestones, aleurolites,
sand sedimentary breaches.

420
Fig. 23.8. Dependence of extension of hydrothermal minerals upon temperature in the
geothermal system of Salton-Sea [Muffler and White, 1969].

421
Fig. 23.9. Dependence of extension of argillisites of various facies upon temperature and
acidity.
1-limits of field of argillisites of various facies of acidity; 2-field of argillisites: I-
acid facies (kaolinite, alunite-kaolinite argillisites), II-field of argillisites of kaolinite-smectite
facies, III-field of smectites and zeolite-smectite argillisites; 3-area of newly distributed
transition of smectite-zeolites; 4-quantitatively swelling interlayers in mixed-layered mica-
smectites; 5-neutral pH value of water; exr – mixed-layered mineral of mica-smectitic type
with content of swelling layers not higher than 50%.

422
 CHAPTER 24

Metasomatic rocks of shear zones and

deep fracture zones

Carbonated metasomatites. The products of carbon metasomatism are

recorded in many groups of ore fields [Tomson et al., 1989] although the
question of the origin of carbon matter in them is still in discussion. The term “
carbonated metasomatosis” was introduced by [Link] [Ivankine &
Nazarova, 1984], who meant by it a process of deposition of carbon matter
(CM) in the aspect of graphite or various carbon combinations in terrigene
dedrital rocks. At the beginning, CM in such rocks was counted as organogene,
transformed and redeposited in a process of diagenesis and regional
metamorphism. It became apparent, however, that a definite part of terrigene
masses was carbon enriched coinciding to zones of important faults or regional
shear zones. Beside the fault CM decreases, as was observed in a black-schist
mass in Primoriei [Tomson et al.,1989]. In the region of the gold ore deposit of
Muruntau in Uzbekistan, CM enriches the mineralized serie of the “mottled
bessapane” in the limits of the ore field. In these this mass contains practically
no CM and presents muscovite-chlorite schists. Examples were observed of not
very distinct structures of replacement of silicate grains by CM, but in most
cases CM is distributed in intergranular extensions or fills small cracks in the
rocks. These signs permit to surmise a penetration of at least part of the carbon
in the rocks by solutions (or gases) and abiotic CM deposition. Complementary
arguments for the use of the endogene origin of the CM are the mass of different
black-schist-enriched metals, amongst which are elements of the platinum
group, noble metals, rare-earth elements and also the diffusion of CM spread in
pyrite fields in volcanic masses. Discussing the problem of “black schists”
formation is linked with the absence of reliable signs of metasomatism such as
metasomatic zoning and decreasing number of minerals in an increasingly
intense process, and also in the difficulty of observing distinct structural signs of
replacement and studying undetermined paragenetic relations of CM with
mineral rocks.

423
 Carbon matter is associated in black-schists masses with pyrrhotite, pyrite,
arsenopyrite, carbonates, sericite, ilmenite, albite and quartz. As constantly
associated accessories are present native metals (aluminium, tin, copper, lead,
zinc). It remains unclear whether these associations are paragenetic or in them
are mingled products of various processes.
As examples of display of carbon metasomatism serve the black-schist
masses in uranium or gold ore fields of Soukhoi Log in Siberia, Muruntau in
Uzbekistan, Stillwater in Canada, Schungite in Karelia. As mechanism of CM
deposition from endogene flows are proposed 1) oxidation of CM of reduced
deep fluid to carbon (graphite); 2) reaction of disproportion activated as far as
the decrease of the fluid temperature, for instance,
2CO  CO2 + Csolid; CH4 + CO2  2Csolid + H20.
3) deposition of paragenesis graphite + sericite as a result of compression
of the flow and increase of its acidity [Koltsov, 1995]. In any case the process is
linked with the occurrence of reduced deep fluids in a relatively high level of the
earth crust. Deep display of CM metasomatism is estimated at a few kilometres.
Black-schist masses include not only disseminated sprinkling of metals,
but also coarse deposition of uranium and gold. In the last years came to light a
perspective of black schist masses on revelation of industrial accumulation of
platinum and metals of the platinum group [Laverov et al., 1997]. Deposition of
noble metals and other ore mineralization on products of carbon metasomatism
represent an intense pre-ore biotitization (“corneification”) and feeble display of
acid metasomatism. It is supposed that an increased background of metals in
black schists forms at stages of sedimentogenesis or diagenesis, and as a result
of much later hydrothermal processes occurs a redeposition of metals in
concentrated form, but a reliable time of introduction of carbon and metals in the
sediments has not been established. The majority of researchers think that with
any of the enumerated variants this introduction is linked with that of an
endogene fluid along important faults of deep origin.
Albitites in zones of fractures of Precambrian shields. High temperature
metasomatic rocks, chiefly albite, are spread in Precambrian shields. They have
been studied in greatest detail in shields of Ukraine, Aldan and Canada. They
are characterized by a pronounced alkaline paragenesis of the inner zone of a
column of metasomatic zoning (albite + aegyrine + riebeckite), localized in
zones of deep long active faults and great extension either in breadth (from 100
m to a few km) or in length (up to 3 km), with a thickness of a few decametres.
As a result of studying albitites of the Ukrainian shield [Link]
[1996] distinguished four chief groups of these rock according to the
metallogeny: apogranitic, apogneisic, apojaspilitic and linked with carbonatite
assemblages.
Apogranitic albitites form lenses in places of conjugate regional
submeridional fault with the system of feathering structures. To metasomatism

424
are subject rocks of an ultrametamorphic assemblage: biotite-quartz-plagioclasic
gneisses and biotite-quartz-microcline-plagioclasic granites.
Metasomatic zoning on them has the following aspects (fig.24.1): 0)
unaltered granite (microcline + plagioclase + quartz + biotite); 1) microcline +
albite + quartz + chlorite + epidote; 2) microcline + albite + quartz + riebeckite
+ chlorite; 3) albite + riebeckite + aegyrine.
Columns are observed in which riebeckite is lacking in inner zone, and
bimineral paragenesis of albite + aegyrine is stable.
Such a zoning permits to predict a high oxygen fugacity and sodium
activity and extreme inertia of aluminium and ferric oxide amidst rock-forming
components. High alkalinity of the albitizing solution is emphasized by
dissolution of quartz in inner zones of the columns.
Apogreisen albitites are principally not distinguished from apogranitic,
except that in the inner zone there exists, at places, phlogopite.
Apojaspilitic alkaline metasomatites have been studied in the Belozersk
iron-ore region of the Ukranian shield [Shcherban, 1996]. I.P. Shcherban
describes them under the name of “apojaspilitic albitites”, but the rocks do not
contain albite and it is therefore expedient to call them aegyrine-biotitic or
simply alkaline metasomatites. Below is distinguished the zoning of
metasomatites of this type: 0) unaltered rock (quartz + magnetite + carbonate +
chlorite); 1) quartz + magnetite + carbonate + riebeckite+ chlorite; 2) carbonate
+ riebeckite+ quartz + magnetite; 3) riebeckite+ aegyrine + quartz + magnetite.
Excess of quartz in initial ferrous quartzites brings about in this case inert silica
up to the inner zones, unlike in the apogranitic column. For the rest the
tendencies are similar: the process occurring with growth of sodium activity and
of bi- and monomineral zones may be explained either by a less intense process
[Shcherban, 1996] or, more plausibly, by local occurrence of parageneses of the
inner zone under the aspect of isolated nests and lenses amongst isolated innerer
zones.
Albitites linked with linear bodies of carbonatites occupy thin (a few
meter) margins around carbonatites. In these cases a succession of processes
from early to late includes fenitization at magmatic stage, followed by
postmagmatic transformation of carbonatites and albitization. The latter is super-
imposed either on fenites or on rock containing a carbonatite assemblage.
Albitites linked with microcline metasomatites are observed in the north-
western part of the Ukrainian shield in a strip of deep faults. Along these faults
occurs a wide granitization. Albitization is here related to much earlier (after
microclinization) postmagmatic processes, it immediately follows granitization
and is accompanied by beryllium mineralization.
Mineralization in albitites of diverse type is represented in basic uranium
mineralization, apart from beryllium-bearing microcline-albite assemblages. In
the total of signs amongst albitites in zones of faults in the limits of crystal

425
shields are distinguished three metallogenic types [Shcherban, 1996]: 1)
periveinous albites of uranium deposits (apogranitic, apogneisic and
apojaspilitic); 2) albitites, accompanied with carbonates with rare-metal
mineralization; 3) albitites of beryllium deposits, associated with microcline
metasomatites.
Albitites in gold ore fields. Gold mineralization is often accompanied with
local occurrence of periveinous albitization. As a result albitic veinlets are
produced, to which coincides a realm of increased gold content (for instance in
the Muruntau deposit), albite fringing around ore veinlets and veins and veins
and bodies of lenticular form in ore fields. [Link] studied ore bearing
of albite metasomatites in the Transbaikal region and in Kuznetsk Alatau.
Metasomatites represented in zones composed of albite + quartz +actinolite
(albite up to 50-80% vl.) are developed on plagiodiorites [Korobeinikov &
Shubin, 1969]. In the outer zone are added to these minerals epidote, sphene and
apatite. The determined temperature of albitization varies from 630°C at the
beginning of the process to 300°C at the end. The temperature of formation of
gold ore veinlets (quartz + sulphides + gold) from a chlorid sodic solution
amounts to 360-250°C. In the gold-silver deposit of Tayoltita (Mexico) are
described feldspar dykes crossing volcanites and coinciding with ore bodies
[Randall, 1968]. Dykes are built of albite, sometimes with admixing of epidote
and chlorite. Thickness up to 10 m, extension in breadth and length, 50 m, age is
considered as preore . Immediately along the boundary of ore bodies are
developed metasomatic albite edgings relieved with removal from ore bodies of
epidotization which is transferred into propylitized enclosing rocks.
Phlogopite and biotite veins. In Bulgaria was described an uncommon
type of phlogopite rocks [Kotov et al., 1986]. They contain ore bodies up to 1-2
m thick, traced in dip to a few decametres and in length to 100-200 m. This
consists practically of monomineral phlogopite rocks with addition of apatite,
orthoclase and carbonates. In exocontacts were not noticed substantial
alterations of enclosing rocks. Veins coincided with a zone of deep fault; the
authors surmise their hydrothermal origin, but a plausible genesis of these
phlogopitic rocks has not been established.
In some degree analogous to them are tabashki (dykes of biotite-feldspar
composition) in the Berezovsk and Kotchkar ore fields of central Ural. Around
such dykes, however, is observed biotitization of enclosing granites and border
biotite around crystals of microcline. One surmises the metasomatic character of
the biotization in these dykes. Tabashki were formed after deposition of poor
gold ore [Borodaevsky & Cheremisov, 1981] and with the process of
biotitization is linked a redeposition of gold and formation of parts of rich ores.

426
Fig. 24.1. Change of chemical mineral compositions of granites of albitization
[Shcherban, 1996].

427
 Succinct glossary
of metasomatic terms
and synonyms

Zodites [Spiridonov, 1991] are synonyms of listvenites. Their specific

property is the presence of chrome-beydellite and chrome-
dickite in listvenite parageneses. They are displayed in the
Zod gold ore deposit of Armenia.
Quartz-feldspar metasomatites are metasomatic endocontact
transformations at early postmagmatic stage in hypabyssal and
subvolcanic granitoid massifs. They are found in diverse
geological environents : in rare-metal and polymetallic skarns,
in copper-molybdenum porphyries, in rare-metal greisens and
in some gold deposits. Their composition is quartz + K-
feldspar + albite. They preceed skarns, greisens and quartz-
sericite metasomatites. It is also employed for some
metasomatites of fracture zones which may lead to confusion
in questions of genesis.

Silica-alkaline metasomatism (K-Si metasomatism) is a collective term

designating processes of transformation, basically of quartz-
feldspar metasomatites of various genesis. In american
litterature it is mentioned in relation to quartz-sericite rocks
and products of « advanced argillization », which is inexact
since such rocks are the result of acid metasomatism (though

428
 potassium content in the rocks may grow, but its activity in the
solution is below the stability of feldspars).

Mantle metasomatism is a process of local change of chemical and

mineral composition of mantle matter under the influence of
rising flow of deep fluids. Strictly speaking, the process is not
metasomatic, but rather metamagmatic, since it presents itself
as interaction of fluid and magma. Products of mantle
metasomatism have been studied in xenolithes corresponding
to the assumed composition of mantle matter.
Oksetalites [Kazitsyn, 1970] is a term designating a combination of
facies : orthoclase, carbonate, sericite, turmaline and albite.
The term did not prevail and is hardly used in the literature.

Avanced argillization (advanced argillic alteration) is a low temperature

metasomatism with replacement of initial rocks by quartz with
kaolinite and hydromica, sometimes with alunite (of the acid
sulfatic type).

Rare-metal alkaline quartz-albite-microcline metasomatites

(qualmites) [Kudrine, 1978] is synonym to alkaline
metasomatites (potash felspars and albitites) in fracture zones
of crystalline shields.

Phyllisites (phyllic alteration) are quartz-sericite metasomatites in copper-

molybdenum porphyries. Hardly used in russian.

Fragmentary metasomatism [Tsarev, 1984] designates a process of

selective metasomatism, in which replacement occurs on a net
of fractures. Remaining blocks of unchanching rocks resulting
from replacement acquire a rounded form, similar to a pebble
in conglomerates. Such rocks often are described as tectonic
breccias from the morphological similarity.
Zwitters [Kovalenko & al.,1974] are greisens in which mica is present as
zinnwaldite. They contain mineralizations of tin, tungsten,
more rarely of tantalium and niobium.

Sharoitization [Biriukov & Berdnikov, 1992] is a process of alkaline

metasomatism, in which surrounding metamorhic rocks are
replaced by a fine-fibrous alkaline amphibole (sharoite),
discovered by [Link] and appearing as prized stones. Until
now only one region of occurrence is known, the basin of the

429
river Shara in the Baikal region from which come the names of
the mineral and the process.

430
 REFERENCES

Note from translators:

АН СССР = Академия Наук Союза Советских Социалистических Республик

AS URSS = Academy of Sciences of the Union of the Sovietic Socialist Republics

АН КазССР = Академия Наук Қазахской Советской Социалистической Республики

AS RSSKaz = Academy of Sciences of the Sovietic Socialist Republic of Kazakhstan

АН УзССР = Академия Наук Узбекской Советской Социалистической Республики

AS RSSOuz = Academy of Sciences of the Sovietic Socialist Republic of Ouzbekistan

АН АрмССР = Академия Наук Армянской Советской Социалистической Республики

AS RSSArm = Academy of Sciences of the Sovietic Socialist Republic of Armenia

РАН = Российская Академия Наук

ASR = Academy of Sciences of Russia

431
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