SHREYA MUKHERJEE & PRACHI KAR

FUNDAMENTALS OF FLUID INCLUSION IN MINERALS

AND THEIR PETROGRAPHIC STUDIES
Class 1 (21.01.2021)

Fluid inclusions are tiny fluid filled cavities in minerals whose sizes are generally in
micrometer scale. They commonly have a size range < 20micron. 100-150-micron fluid
inclusions are extremely rare.

Many geological processes have fluids –

- Magmatic: Felsic magma has more water than mafic magma. We consider it fluid only
when it separates from the magma because before that it does not have any characteristic
feature of its own as it stays dissolved in the melt.
- Metamorphic: Breakdown of hydrous phases during prograde metamorphism releases
water. Metamorphic fluid can contain either H2O, or CO2 or both.
- Hydrothermal: Maybe magmatic or heated seawater or other sources.
- Sedimentary: Diagenesis and burial leading to expulsion of pore fluids.
We consider the fluid as a separate phase only when it has reached a saturated quantity.

Role of Fluid

- Chemical: Mineral precipitation and transport (carrier of mineral components)

- Physical: Hydro-fracturing of rocks
Hydro-fracturing occurs due to volume expansion of fluid. When fluids come out from magma,
they initially come out as small bubbles which later coalesce and form a large volume of fluid.
As the density of fluid is less than magma, it expands and exerts pressure on the surrounding
brittle rocks and when they fail, fractures are generated. If the fluid pressure is greater than the
confining pressure, the rocks will break.

Inclusions are a direct clue of the paleo-fluid responsible for the mineralization of the sample or
for hydrofracturing provided that the fluid has not been modified to an extent that it has not lost
its original composition.

Orthomagmatic process (only crystals and no fluids involved): Common in ultramafic rocks and
other dry systems which have less water content. In that case almost no fluid inclusions are
present unless the rock was later modified by hydrothermal fluids.

PGE element mineralization genetically connected to ultramafic system yet also depends on
fluid phases as sulfide fluids scavenge PGE minerals and lead to their deposition.
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Granulite phase metamorphism is considered a dry system, but the system may have a lot of
CO2 which may be trapped as fluid inclusions. So, fluid inclusions may not necessarily be just
liquid, it can also be volatile gas phases.

Structural geologists are also interested sometimes in study of fluid inclusions as fluid
migration occurs along fracture zones and leads to mineralization along these conduits. Thus,
fluid inclusions hold important indications regarding the stages of fluid activities in the crust.
They might be interested in knowing the composition of the fluid and its evolution with time
that led to mineralization along cross-cutting veins.

Entrapment of Fluids inside Minerals

- During the growth/ formation of the host mineral – During the process of crystallization
of the mineral.
- After the growth/ formation of the host mineral – After the process of crystallization,
fluid migration through some fractures in the mineral which was followed by late stage
sealing and the fluid got entrapped.

Mechanism of Fluid Entrapment

During Mineral Growth:

A – The crystal was initially growing at a very smooth and slow rate as the surfaces we can see
are straight and very smooth. This was followed by a sudden change in the growth rate which
led some portions of the growing crystal to develop faster (variable growth of the crystal) than
the rest and dendritic growth pattern is result. Now the crystal is surrounded by fluid and melt
phases and some amount of fluid may get entrapped in the crystal along this dendritic end of the
crystal as fluids will try to remain attached owing to their surface tension. Then, solid growth of
the mineral continued and fluid inclusions were formed as the mineral growth continued over
the fluids which got accidentally trapped.

B – During sub parallel growth, if some kind of defect is present in the crystal surface, then
fluid phases will get entrapped along those boundaries and with time as the growth of crystal
will continue, those fluid phases will get surrounded by crystal and will form inclusions
ultimately.

C – It is not always that a growing crystal is staying in equilibrium with the surrounding fluids
and melts. At some stage it may be in disequilibrium which will cause partial dissolution of the
mineral surfaces and will thereby have a corrugated boundary. Hollow cavities will be created
on the surface of the crystal where fluids will get arrested due to surface tension. Smooth
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surfaces aren’t ideal for fluid arrest but

irregular boundaries have more chances
to arrest fluid. When the mineral growth
resumed in equillibrium, the fluids along
these hollow spaces get entrapped
forming inclusions.

D – If during growth of the mineral, it

enters a stress field, fractures may
develop within its crystal, and these
fractures are good conduits for fluid
migration allowing fluids to get arrested
and form inclusions in later stages when
mineral growth resumes. Fluid
inclusions will be present along the fracture zone (along a line). If the fractures don’t get sealed,
the fluids will escape the crystal.

E – Due to differential growth on crystal surface some portions develop at faster rate and
cavities will be formed at regions on the crystal surface which have relatively lower growth
rate. Fluid will get entrapped and form fluid inclusions when crystal growth continues.

F – If a foreign particle attaches itself on the surface of a growing mineral crystal, with time, it
will get incorporated into the crystal – fluids may get arrested at the contact zone between the
foreign particles and the crystal due to surface tension and later get entrapped when mineral
growth continues.

These mechanisms can trap the fluid inside the crystals and these fluids hold important clues
regarding the composition of the fluids from which the mineral crystallized provided they
haven’t evolved over time.

After Mineral Growth:

Crack-filling: Fluids can also get entrapped to form inclusions

after formation of the crystal. Fluids can percolate the crystals
through some micro-cracks which later get sealed and cause the
fluids to get entrapped.

Homogeneous Trapping Vs Heterogeneous Trapping

In carbonated water, at high pressure, only one fluid phase is present. The CO2 stays dissolved
in the soft drink and does not exist as a separate phase. This is a perfect example of
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Homogeneous Fluid. But when the pressure decreases, the CO2 tries to escape as gas bubbles
(boiling of fluid) and there are more than one phases having different compositions. Now, they
are being called Heterogeneous Fluid.

Homogeneous Trapping Heterogeneous trapping

The inclusion sampled only a single-phase When pressure drops, more than one fluid
fluid; possible under high pressure when all phases are present. If we consider two fluid
fluid phases coexist as one. phases – one liquid and the other gaseous,
then, a mineral crystallizing will have
Homogeneous entrapment of a
different compositions of fluid inclusions –
heterogeneous fluid is possible if the
can be purely liquid or purely gas or partly
composition of the fluid phase depicts only
liquid and gas.
one fluid phase and not multiple fluid phases.
Some inclusions were purely vapor and some The partly liquid and gas fluid inclusion is the
were purely gaseous – these are the heterogeneous entrapment. They will have
homogeneous entrapments. varied compositions (gas : liquid ratio will
vary) and so they are not useful for micro
thermometric experiments

Heterogeneous entrapments are not possible from homogeneous fluids but homogeneous
entrapments are possible from both homogeneous and heterogeneous fluids.

Micro thermometric experiments are conducted on homogeneous entrapment of fluids. The

most important challenge is that most of the fluid inclusions when viewed under optical
microscopes at room temperature appear heterogeneous.

We need to understand if the fluid entrapped was a heterogeneous entrapment from a

heterogeneous fluid or if the composition of the fluid inclusions changed after entrapment.

Two explanations are possible for a fluid inclusion having both vapor and liquid phase:

- Homogeneous entrapment of a homogeneous fluid occurred but later the vapor phase
exsolved out of the fluid forming two separate phases – liquid and vapor.
- Heterogeneous entrapment of a heterogeneous fluid entrapping both liquid and vapor.

Post-entrapment Changes

➢ Closed System Changes: Refers to phase changes of the fluid.

 SHREYA MUKHERJEE & PRACHI KAR

Schematic diagram representing the

various stability fields of various
phases of water.

In liquid (L) field – only one phase is

present which is liquid. At anywhere
in L field under any P-T conditions,
the entrapped fluid will have only
one phase.

If we take P-T condition at TT, a

single phase is involved during
crystal growth and so entrapped fluid
will be a homogeneous entrapment.
After crystallization, the whole
system is being cooled along the
Isochore (Iso-volume line) line
which essentially represent that there
is no volume change involved. So, if the original volume of
the fluid inclusion needs to be retained during this cooling
process, the internal P-T conditions must follow the isochore
line. As the P-T conditions keep evolving so as to keep the
volume constant, they will touch the liquid-vapor univariant
line and here two phases will now be present.

Now it is possible that the fluid also had dissolved salts, for
example, say NaCl. Now as the P-T conditions follow the isochrore and reach the univariant
line, the P-T conditions of the fluid will begin to
evolve along this line. At lower temperatures,
solubility of dissolved salts will get considerably
reduced and will reach a saturation point where it will
be stable only in the solid form and therefore, NaCl
crystals will be formed within the fluid inclusion.
NaCl will form a cubic crystal and vapor phase will
also be present in this fluid inclusion. This is an
example of complex situation of fluid inclusions.
 SHREYA MUKHERJEE & PRACHI KAR

How the fluid inclusion will look depends

on the composition of the original fluid. In
closed system, phase changes occur via
two processes – unmixing and saturation.

In unmixing, first CO2 liquid exsolves out

from the fluid and on further change in P-T
condition (mainly decrease), a CO2 vapor
phase will form from the CO2 liquid.

How can we distinguish between heterogeneous looking fluid inclusion formed by

homogeneous entrapment of a homogeneous fluid and a heterogeneous entrapment?

Homogeneous entrapment of a homogeneous

fluid: The ratio of the size of cavity to the size of
the vapor bubble will be constant. Larger cavities
will entrap greater fluid and so the vapor phase that
will come out of the dissolved fluid will also be
more. Similarly, smaller cavities will have less
entrapped fluid and thus, diameter of the vapor
bubble will be consequently small.

Similarly, size of the solid crystals forming in a

fluid inclusion present in a larger cavity will be
more compared to that of a smaller cavity as larger
cavities will have greater entrapped fluid and so
greater amount of dissolved salts.

The size of the solid crystals or the vapor bubbles

will be proportional to the size of the cavity.

Homogeneous entrapment of a heterogeneous fluid: Purely liquid inclusions will have

greater (liquid ⁚ vapor) ratio while purely vapor inclusions will have smaller (liquid ⁚ vapor)
ratio.
 SHREYA MUKHERJEE & PRACHI KAR

All fluid cavities having purely liquid will have similar (liquid ⁚ vapor) ratio and all the cavities
containing purely vapor phase will have same (liquid ⁚ vapor) ratio.

Heterogeneous entrapment of a heterogeneous

fluid:

The cavities can entrap the fluids at any (liquid ⁚

vapor) ratio and so size of the cavity and the vapor or
liquid fields will vary.

From the first set of inclusions, identifying if they are

homogeneous entrapments of heterogeneous fluids or
heterogeneous entrapments of heterogeneous fluids is
not entirely possible only by observing two or three
samples as two sets of (liquid ⁚ vapor) ratio is also
possible in homogeneous entrapment from
heterogeneous fluid. If several samples give the same
sets of (liquid ⁚ vapor) ratio then, we can say that
definitely homogeneous entrapment of heterogeneous
fluid has been took place.

The clues lie in the ratio of different phases in a group of co-genetic inclusions.

➢ Open system changes:

• Decrepitation: Destruction/ Bursting of the inclusions

• Stretching and Necking: Minerals stretch to elongate and then get thinned to form a neck
and finally get torn.
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• Diffusion:
- ICC (Isochoric Cooling): This is cavity
volume constant path. P-T conditions
change along the path. The internal
pressure and the external pressure are
equal and so the fluid cavities are stable
and no volume change occurs.
- ITD (Isothermal Decompression):
This is temperature constant path.
Compared to ICC, there is a drop in the
external pressure than what was
required for the fluid cavity to be stable.
The internal pressure exerted by fluids
in the cavity is thus more than the
external lithostatic pressure. Reduction
in external pressure will cause the
inclusion cavity to expand and will
finally burst or explode which is known as explosion decrepitation.
- IBC (Isobaric Cooling): This is pressure constant path. Compared to ICC, there is a rise in
external pressure than normal and so the fluid cavities will shrink which will lead to
implosion.

Class2 (04.02.2021)

Fluid Inclusion Petrography

Investigation of fluid inclusions present in a mineral is generally done under transmitted light
microscope mostly for transparent/ translucent (semi-transparent) minerals like quartz, feldspar,
garnet, gypsum etc. Infrared microscopes are used for investigation of fluid inclusions for
minerals that are opaque under transmitted light microscope (not commonly practiced).

Thickness of thin section is 0.03mm. In normal thin section, fluid inclusions are not present as
thin sections are very thin and so the cavities open up allowing the fluids to escape. Fluid
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inclusions are studied as doubly polished wafers

which are ten times thicker than a thin section.
Thickness of doubly polished wafers is 0.3 to
0.5mm.

Dark minerals like Tourmaline transmit very

less light and identifying fluid inclusions
becomes very difficult and in such case, the
sections need to be thinner than 0.3mm so as to
allow greater penetration of light.

Documentation of sample location, sample

orientation, wafer location and wafer orientation
are very much important for fluid inclusion
study particularly for a structural geologist.

Via heating freezing experiments, the fluid

cavities are frozen first and then temperature is
gradually increased to observe the phase
changes in the cavity.

Different generations of fluid inclusions may be present in a rock. Primary fluid inclusions
formed along growth zones and pseudo secondary fluid inclusions formed along micro-cracks
(later stage deformation) in the mineral.

Microscopic Study of Fluid Inclusions

Microscopic studies of fluid inclusions comprises of -

• Proper classification of inclusions

• Identification of the types and generations of the inclusion
Classification of Fluid Inclusions:

• Descriptive
• Genetic
• Compositional
Descriptive and genetic classifications are done mainly using microscope. These are basically
the petrographic classification. Compositional classification is done by using other analytical
techniques.
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➢ Descriptive Classification: Based solely on the content of fluid cavities at room

temperature. It is observed under transmitted light microscope and depends on the number of
phases present in the fluid cavity.
o Mono-phase: Single phase in fluid cavity – Fig (c)
o Bi-Phase: Two phases present in fluid cavity.
▪ Fig (a) and Fig (d): Vapor phase spherical bubble and liquid phase
▪ Fig (d): Inclusion has greater vapor bubble size ⁚ cavity size ratio than Fig (a)
o Poly-phase: Multiple phases present – Fig (b)
o Top right-most image: Polyphase inclusion - one well rounded bubble containing vapor
phase, two crystal phases – one is well developed cubic crystal and the other one is greenish,
poorly rounded mineral
o Bottom right-most image: Polyphase inclusion - one well rounded bubble containing vapor
phase, two crystal phases – one is prismatic crystal and the other one is greenish, poorly
rounded mineral
o CO2 vapor look brownish or darker than H2O vapor or liquid.

➢ Genetic Classification: Based on the time of formation with respect to the host mineral.
o Primary: Fluids trapped during crystal growth
o Secondary: Fluids trapped at any time after the growth of the host crystal through migration
of fluids along fractures which later got sealed
o Pseudo-Secondary: Appears like secondary but are actually primary
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Criteria for recognizing genetic types:

✓ Single grain:
Primary:

o Inclusions (planar as well as random) parallel to growth zone

or crystal faces
o Inclusions occur in three-dimensional random distribution
o Inclusions are isolated
o Inclusions are large (not a very important distinguishing
criteria)
Secondary:

▪ Occurrence as planar group, outlining healed fractures

▪ Fractures are present up to the grain boundary
▪ Thin flat or irregular shape

Pseudo-secondary: Occurrences same as secondary inclusions, but with fractures terminating at

a growth zone or well inside the host. Secondary inclusions are present along a trail where the
crack is extended up to the grain boundary. Cracks may be developed during crystal growth if
the crystal is under some stress field and deformation occurs or during the constrained growth
of the mineral. If the mineral growth continues after the cessation of deformation then the crack
will not be able to grow up to the boundary of the mineral and the fluid will be entrapped before
crystal growth ceased. So, in this case, though the inclusions are present along a trail, they will
be of primary origin, not secondary.

Primary and pseudo secondary fluid inclusions will provide information on the fluid
composition that was present during the growth of the mineral. Secondary fluid inclusions will
give an idea about the fluid that percolated into the crystal at a later stage.

✓ Massive Rock:
Consist of isolated inclusions, inclusions in trails, trail-bound inclusions, and fluid inclusions
trails.

- Isolated inclusions remain as disseminated fluid cavities in a mineral grain.

- Inclusion trails are fluid inclusions that are aligned in a plane and appear as a line in thin
section. They give us an insight about the multiple generations of fluids that have percolated
through the rock.
Polygonal grains with almost 120o dihedral angle and having straight boundaries showing
recrystallization texture formed by annealing of mineral grains.
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Fig a:

1. Transgranular: Fluid inclusion trails across

grain boundaries – formed after the formation of
entire recrystallized texture – secondary in nature.
2. Intergranular: Fluid inclusion trails along
grain boundaries of same mineral phase – formed
during recrystallization of mineral grains as it follows
the dihedral trace. Fluid source is the mineral itself
and not some external source.
3. Intragranular: Fluid inclusion trails restricted
within single grain – Fluid inclusions occur along a
plane which is visible as a line –pseudosecondary in
nature.
4. Intragranular: Fluid inclusions terminate at
grain boundary and therefore, secondary in nature.
5. Intragranular: Fluid inclusions terminate at
grain boundary and so secondary.
6. Interphase: Fluid inclusion trails occurring
along grain boundary of two different mineral
phases
7. Transphase: Fluid inclusion trails across
boundary of two different phases. Between 7 and 1,
7 is earlier.
Fig b:

1. Fluid inclusion trails along cleavage planes.

2. Fluid inclusion trails along deformation lamellae.
3. Fluid inclusion trails along deformation bands.
4. Fluid inclusion trails along sub-grain boundaries (recrystallized polycrystalline grains –
increase in temperature causes strain accumulation that gets released by formation of sub-
grains by increasing the surface area)
5. Fluid inclusion trails along twin lamellae.
If we have two inclusion trails – one transgranular and the other a combination of transgranular
and transphase, the location where they intersect, if that region is investigated, the inclusion
trail more dominant here is the one which formed at a later stage.
 SHREYA MUKHERJEE & PRACHI KAR

When a mineral gets annealed

via recrystallization, the mineral
expels fluid as metamorphic
fluid as the hydrous phases
become anhydrous due to
dehydration and primary fluid
inclusions may also get expelled
in this process. So, the metamorphic fluid gets mixed with the primary fluid and lead to the
change in primary fluid composition. So, when a rock has undergone metamorphism and
deformation, it is extremely difficult to find the fluid which was responsible for the growth of
the mineral. Quartz often shows this. In that case, we try to look for such minerals that are not
recrystallized during metamorphism and can retain the primary fluid inclusions. For example,
minerals like Tourmaline, Apatite provide us an idea about the primary fluid in a metamorphic
rock.

The fluid that is expelled during recrystallization of mineral grains may concentrate along the
grain boundaries (intragranular fluid
inclusion).

Fluid Inclusion Association (FIA)

FIA incorporates both the primary

disseminated inclusions as well as the
secondary and pseudosecondary
inclusions. The most finely discriminated,
petrographically associated group of
inclusions or groups of inclusions that can
be defined by petrographic means as the
most finely discriminated events of fluid
inclusion entrapment.

Quartz grains are well-rounded; hence they

are mechanically transported and signify a
sedimentary rock with detrital quartz.
Authigenic sediments are present in the
intergranular spaces.

The black fluid inclusions present in the 3

bottom grains are absent in the upper
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grains. Polyphase inclusions are observed in the lower three grains but absent in the upper ones.
This indicates that quartz grains have different provenances.

In the 3 bottom grains, two types of primary inclusions are present that do not occur in any sort
of trail and are isolated. The black fluid inclusions are vapor rich inclusions with a thin liquid
film on their outer rim. The polyphase inclusions have vapor phase as well as halite crystals.
The entrapments are Homogeneous entrapment of a heterogeneous fluid as the size ratios of
cavity and the fluid phases are same for all the inclusions. Such vapor rich and halite bearing
fluid inclusions are formed at shallow silicic magma chamber.

In the upper three grains, the blue circles show

fluid inclusions having a CO2 vapor (central), CO2
liquid surrounding that vapor bubble and a H2O
liquid phase. It indicates that the fluid is H2O-CO2
bearing fluid. Metamorphic fluids are often CO2
bearing but they rarely are saline unless they
interact with some evaporitic (salt) bearing
horizon.

The red arrows show inclusion trails that is

absent in the bottom inclusions and they terminate
at the grain boundaries, indicating a secondary
fluid invasion. Post peak metamorphism related
deformation caused formation of fractures in the
detrital grains and allowed fluids to migrate and
get entrapped. Absence of these inclusion trails in
lower 3 grains indicate they have not gone through later hydrothermal event during regional
deformation in which the inclusion trails have been developed within upper three grains. So,
they were separated in the space.

The yellow arrow shows fluid inclusions having co-existing petroleum (black) and aqueous
solutions and they were formed by petroleum migration through the pores of sediments prior to
cementation (closing of pores by authigenic grains) around the detrital quartz grains within the
overgrowth.

The green arrow shows high salinity aqueous inclusion occurring in the outermost authigenic
quartz overgrowth and indicating post oil migration environment and late-stage cementation
condition.

The crosscutting inclusion trails are formed last in the sequence.

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Methods of Analysis of Fluid Inclusions

Pressure - Composition
Temperature

Micro Qualitative Microscopic

thermometry observation

(Heating – UV-fluorescence
Freezing spectroscopy
Experiments) (identification of
organic compounds)

Semi- Micro thermometry

quantitative

Quantitative Bulk sample analysis Volatiles Gas mass spectroscopy

(Not very useful) Gas chromatography

Volumetric gas absorption

Solute Leachate analysis

analysis
ICP-decrepitation

Single inclusion Micro thermometry

technique
Synchrotron X-ray
(More useful) fluorescence microanalysis

Proton induced X-ray emission

[PIXE]

[Bursting of fluid inclusion

cavity is burst and the fluid is
collected for analysis butt the
problem is cavity composition
and fluid composition may
mix]

Laser ablation analysis (LA-

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ICPMS/LA-ICP-AES)

[Almost same as PIXE]

Laser-Raman spectroscopy

Fourier Transform Infrared

Micro spectroscopy

Fluid Inclusion Micro-thermometry

o This is the most commonly used non-

destructive analytical technique for fluid
inclusions. It doesn’t destroy the fluid
cavity.
o Freezing-heating experiments with fluid
inclusions are done under the microscope.
Wafer sample is kept in the chamber and
the sample is frozen using liquid N2 (below
the eutectic temperature/ solidus) having
temperature -196oC and then heated using
hot gas. We will heat till we get a
homogenized single-phase liquid.
o Assumes constant volume of the inclusion cavity during experiment otherwise if the fluid
inclusion volume expands then it can burst.
o Works with homogenously trapped inclusions.

Some assumptions on fluid inclusion micro thermometry experiments:

o The inclusion cavity has not changed its volume; neither in nature nor during experiment
o The inclusion cavity has remained chemically ‘closed’
o Nothing has been added to or lost from the inclusion after entrapment
o Origin of the inclusions is known (primary/secondary)
o Effect of pressure on inclusion volume is negligible.
Basic components of Linkam THMSG 600 stage –

Using heating-freezing stage equipped with microscope, computer; stages commonly work in
the temperature range of -196 to 6000oC.
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Class 3 (17.04.2021)

Binary System:

A eutectic system is a homogeneous mixture of substances that melts or solidifies at a single

temperature that is lower than the melting point of any of the constituents. Eutectic point is the
point on a phase diagram where the maximum numbers of allowable phases are in equilibrium.
When this point is reached, the temperature must remain constant until one of the phases
disappears. A eutectic is an invariant point.

H2O-KCl System:

▪ Besides ice, sylvite (KCl) crystal may form

▪ Eutectic temperature: 10.6oC
▪ Eutectic composition 19.7 % KCl
Freezing point depression temperature: Decrease in freezing
point of water happens due to presence of dissolved salts.
Alternatively, melting point will be reduced as well. If it
solidifies at 0oC, it implies pure water with no dissolved salts.

Eutectic temperature: It is the first melting temperature. We

check fluid phase changes during heating. Identifying the last
melting phase is very important because that will give us the composition of the fluid. If the
melting temperature was less, then composition of fluid can be determined by the phase which
melted last.

Eutectic temperature is the solidus temperature for a natural system below which all the
materials get solidified but in laboratory since cooling is done much more rapidly as compared
 SHREYA MUKHERJEE & PRACHI KAR

to natural systems, not all materials may get solidified at once below the eutectic temperature
and may be metastable. Hence, cooling is done to a temperature much lower than the eutectic
temperature to ensure homogenous freezing of all materials.

H2O-NaCl System:

▪ In addition to ice, two more solid phases can appear – Hydro-halite (NaCl.2H2O) and halite
(NaCl)
▪ Eutectic temperature is -21.2oC
▪ Eutectic Composition: 23.2 wt%
Peritectic point: The point on a phase diagram where a reaction takes place between a
previously precipitated phase and the liquid to produce a new solid phase is called peritictic
point. When this point is reached, the temperature must remain constant until the reaction has
run to completion. A peritectic is also an invariant point.

Finding the final melting temperature and the final phase which melted is an important criterion
to find out the fluid composition.

There are 3 cases:

1. Fluid containing < 23.2 wt% NaCl: Melting starts at eutectic temperature and Hydro-halite
phase disappears first and ice is the last solid to melt; Salinity (fluid composition) is
measured from ice melting temperature (Eutectic Point).
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2. Fluid containing 23.2-26.3 wt% NaCl: Melting starts at eutectic temperature and ice will
disappear first and then Hydro-halite is the last solid to melt; Salinity is measured from
hydro-halite melting temperature. No solid phase is stable at room temperature in this case.
3. Fluid containing > 26.3 wt% NaCl: We’ll get halite crystal at room temperature; salinity in
this case may be measured from halite dissolution temperature (inclusions are to be heated)
(Peritectic Point).
The NaCl stability field is very steep and almost parallel to the temperature axis which means
the final melting of NaCl takes place at a very high temperature. Thus, NaCl crystals will be
present in the room temperature if fluid composition has > 26.3 wt% NaCl as it will touch the
stability field of NaCl. When we get NaCl crystals in the room temperature while heating, we
won’t stop the experiment as the presence of halite crystal depends on the amount of dissolved
salts (if the amount of dissolved salt is high, then NaCl will remain saturated even at the high
temperature) and finally we have to find out the temperature at which the salt melt.

H2O-NaCl-CaCl2 System:

▪ H2O-NaCl-CaCl2 eutectic: -52oC

▪ H2O-CaCl2 eutectic: - 49.4oC
▪ H2O-NaCl eutectic: - 21.2oC
▪ H2O-NaCl peritectic: 0.1oC
The gray area indicates stability field of hydro-halite.
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Initial fluid composition having < 25.6 wt% NaCl:

If we have the fluid composition close to the H2O
apex, suppose 80% H2O, 10% NaCl and 10% CaCl2
and we cool the system (up to 100oC) then initially
NaCl and CaCl2 will be dissolved in the water and
they will form crystal after being saturated at lower
temperature. Then if we heat the system, the first
melting will begin at ternary eutectic (-52oC).
Antarcticite (CaCl2.6H2O) will disappear first. Then
composition will change along the H2O-NaCl liquidus
line (upper line of the hydrohalite stability field) and
hydrohalite will be the second phase to melt out. Then
the composition will move towards H2O apex and finally ice will melt and melting will be
completed.

Initial fluid composition having > 25.6 wt% NaCl: Melting will start at ternary eutectic and
Antarcticite will be the first phase to melt out then composition will move along the H2O-NaCl
liquidus line and hydrohalite will be the second phase to melt out. And lastly halite crystals will
melt (following the line joining the initial composition and the NaCl apex within NaCl stability
field). We will get halite crystals in room temperature and it will melt at higher temperature
than the room temperature (25oC).

Phase changes will occur according to the initial fluid composition. We need to note the first
melting temperature that is the eutectic temperature very carefully because that will guide us
that what phase diagram we should use.

In the experiment we do extremely rapid cooling compared to the natural system. Due to rapid
cooling solid phases become metastable and phases like halite or hydrohalite may not form. So,
we have to cool the system up to -100oC or more to overcome the problem of metastability.

Eutectic temperatures of common H2O-salt systems:

H2O-NaCl-CaCl2-MgCl2 -57oC
H2O-NaCl-CaCl2 -52oC
H2O-CaCl2 -49.5oC
H2O-FeCl2 -35oC
H2O-MgCl2 -33.6oC
H2O-NaCl-KCl -23oC
H2O-NaCl -21.2oC
H2O-KCl -10.6oC
 SHREYA MUKHERJEE & PRACHI KAR

P-T Estimation from Fluid Inclusion Micro-thermometry:

There are 3 common processes –

1. For Boiling Fluid: Homogenization temperaure is the temperature of entrapment

On the liquid-vapor line, both liquid and vapor are stable. Fluid will start boiling on reaching a
P-T condition at any point that lies on this line and gas dissolved in the fluid will start to form a
bubble and separate out from the liquid. The red point here coincides to the temperature of
homogenization, above which all the fluids are homogeneous, i.e., gases remain dissolved
within the liquid and occur as one single phase.

If homogeneous entrapment of fluid on the liquid-vapor line occurs, we will get two cases –
purely liquid or purely vapor. So statistically, we will get more or less equal abundance of
liquid and vapor rich fluid inclusions here. Homogenization temperature will be the same for all
fluid inclusions (both pure vapor inclusion and pre liquid inclusion) present as they were
entrapped at the same temperature.

If homogeneous entrapment of fluid occurs at some point on the isochore line, then we’ll get the
homogenization temperature during heating experiment, but that essentially doesn’t indicate the
entrapment temperature of fluid as there will be no further phase change beyond the
homogenization temperature.
 SHREYA MUKHERJEE & PRACHI KAR

If the homogeneous fluid entrapment occurs during boiling, then the homogenization
temperature can represent the entrapment temperature (at the point where isochore line touches
the liquid-vapor line).

2. Isochore Intersection Method: Fluid isochores used in conjunction with independent

thermometer (mineralogical or stable isotope)
Reaction curves that run parallel to the pressure
axis are good geothermometer because of their
temperature dependence nature. For example,
biotite-garnet reaction curve (univariant line)
gives steep slope and act as a geothermometer.

In this image, the independent geothermometer

(garnet-biotite) is almost perpendicular to the T
axis (ideal case). Now fluid inclusion is present
within garnet and via heating-freezing experiment
we can find out the salinity and density of the
fluid and isochore of that fluid inclusion is drawn.
The intersection point between the isochore and
the independent geothermometer gives the actual temperature and pressure of fluid entrapment.
This intersection point is the common point when the garnet has crystallized and the fluid
became entrapped within garnet grains.

3. Intersection of fluid isochores for coeval fluids:

Isochore line is density dependant. If in a
mineral, fluid inclusions of different
densities are present, then they’ll show
different isochors depending upon their
density.

Suppose if there are two types of fluid

inclusions in a mineral grain – one is
H2O-NaCl bearing and the other one is
H2O-CO2 bearing. Now, from the figure
below, we can see that NaCl bearing
inclusions give steeper isochors than CO2
bearing fluid inclusion. The intersection
point between these two isochors will also give the temperature and pressure of the fluid
entrapment.
 SHREYA MUKHERJEE & PRACHI KAR

Fluid Inclusion in Exploration:

Fluid inclusions can only be used in exploration for those deposits where fluid was involved.
We should have idea about solubility of metals in fluids of different compositions and
complexing mechanism, precipitation mechanism of different metals from fluids for that study.
For example, high saline fluid (NaCl-F) carries more metals than pure H2O fluid.

Case 1:

Fluid inclusion studies in deciphering the extension of known deposits:

Fluid inclusions are studied for both the mineralized rock and the non-mineralized rock and
their differences are noted. Then nearby places are explored where no exploration have taken
placed yet and after fluid inclusion study of the rocks of that area if we get similarity with the
results we got in fluid inclusion studies of the mineralized rock, then deposit area can be
extended.

For mineralized and non-mineralized host rocks the things that we study and compare are as
following:

▪ The inclusion types

▪ The P-T of entrapment of fluid
▪ Composition of fluid
▪ Fluid evolution trends
Many deposits will show some fundamental differences in one or more of the above which can
potentially be used for exploration

Case Study:
 SHREYA MUKHERJEE & PRACHI KAR

In these two diagrams, salinity is plotted against the number of inclusions present in the crystal
from a mineralized pegmatitic vein. Figure (a) is showing two sets of salinity – one is low
salinity (5-10%) set and the other one is high salinity (25-30%) set. Figure (b) shows a wide
range of salinity of fluids present as inclusions ranging from 0.5 to 30%.

In case of non-mineralized pegmatite, there is either one high salinity fluid [figure (b)] or one
low salinity fluid [figure (a)].

If we plot temperature vs. salinity diagram for the mineralized pegmatites, we can see in the
figure (a) that for both low salinity and high salinity sets, temperature is restricted within a
narrow zone (150-250oC). In figure (b) where there is a long range of salinity, temperature is
mostly restricted below 250oC.
 SHREYA MUKHERJEE & PRACHI KAR

For non-mineralized pegmatites, figure (a) is showing a wide range of temperature for low
salinity fluid inclusions and figure (b) also shows a long range of temperature for high salinity
fluid.

Interpretation:

There are significant differences in the fluid inclusions present in the mineralized and non-
mineralized pegmatites. In the adjoining area, if we get no visible mineralization in pegmatites,
then we’ll go for the fluid inclusion study. If we get two sets of fluid (low salinity and high
salinity) and very restricted temperature, then that pegmatite will be considered as potential
source for mineral exploration. And pegmatites where we’ll get only one type of fluid with long
temperature range, that will definitely be non-mineralized zone.

- Presence of high salinity and low salinity fluid in the mineralized pegmatite indicates mixing
of two different fluids and due to mixing there was be some rapid changes of salinity and
temperature that leads to the precipitation of metals.
- In case of non-mineralized pegmatites low salinity and high salinity fluid didn’t mix and
temperature change was gradual. As a result metals dissolved in the fluid failed to reach
saturation point and there is no precipitation and mineralization.

Case 2:

Fluid Inclusion Stratigraphy (FIS) in petroleum exploration:

Fluid inclusion stratigraphy is stratigraphic succession based on composition of organic and

inorganic fluid species present within samples as fluid inclusions. In other words it is the
mapping of subsurface fluid.
 SHREYA MUKHERJEE & PRACHI KAR

Fluid inclusions generally do not subject to alteration or devolatilization during sampling from
depth or storage; hence they are chemically representative of the pore fluid at depth.

Fluid samples collected from the different horizon from a bore are collected to find out a overall
composition of fluid by using mass-spectrometer.

Samples kept on the chamber and are crushed. Fluid inclusion cavities are opened up due to
crushing and the gaseous fluid phases are collected and sent to the mass-spectrometer which
gives signals. Those signals are analyzed and give whether the fluid content CH 4, CO2 or H2S
etc. depending on the ratio of different compounds.

On the basis of different organic compound present in the fluid are used to make a log. If fluid
is dominated by CO2 or any reduced phase of carbon, then those horizons must not contain any
petroleum. Horizons where we’ll get methane or acetic acid will be potential for petroleum
exploration.
 SHREYA MUKHERJEE & PRACHI KAR

If borehole logs are made from different locations, then via FIS petroleum migration direction
can be determined. Suppose, an organic compound that is the indicator of potential petroleum
source is found at the lower level of the left hand side borehole and the same compound is fount
at the upper part on the right hand side borehole then, we can say up-dip migration of
petroleum on the right side in the petroliferous basin.

So, FIS helps in the recognition of potential horizons of petroleum as well as the migration
direction of the oil.