UNIVERSIDADE DE SÃO PAULO

INSTITUTO DE GEOCIÊNCIAS

MAGMATIC EVOLUTION, IGNEOUS PETROGENESIS AND

METALLOGENETIC IMPLICATIONS OF THE OROSIRIAN MAGMATISM AT
THE TAPAJÓS MINERAL PROVINCE, AMAZONIAN CRATON

LUCAS VILLELA CASSINI

Orientador: Caetano Juliani

Co-orientador: Jean-François Moyen

Tese de Doutoramento

Programa de Pós-Graduação em Recursos Minerais e Hidrogeologia

São Paulo

2021
Resumo

Muito tem se debatido nos últimos anos quanto ao ritmo de crescimento da crosta
continental ao longo das eras geológicas, sendo os modelos existentes variáveis entre
crescimento episódico (com picos de produção), ou então de caráter mais contínuo
com papel mais relevante do Arqueano. No contexto da Plataforma Sul-Americana, o
Cráton Amazônico consiste em uma boa área de estudo quando se refere à crosta Pré-
Cambriana, com boas exposições de rochas Arquenas e Proterozóicas parcialmente
cobertas por sedimentos siliciclásticos associados às bacias hidrológicas fanerozóicas.
Curiosamente, em um contexto global, as associações rochosas e a geodinâmica
arqueana, apesar de serem mais raras, têm chamado mais a atenção dos
pesquisadores, e o número de publicações referentes ao Arqueano são muito maiores
do que as referentes ao Proterozóico. Olhando para a porção centro-sul do Cráton
Amazônico, a Província Mineral do Tapajós (PMT) consiste em uma excelente área de
estudo, onde predominam intrusões orosirianas (2.0 e 1.87 Ga) muitas das quais
associadas à ocorrências e depósitos minerais de metais base e preciosos. Nesse
sentido, esse estudo traz considerações petrogenéticas referente às suítes ígneas
presentes na PMT bem como as respectivas implicações tectônicas e metalogenéticas
para a região. Os resultados permitiram a separação das rochas presentes no Tapajós
em dois conjuntos: a sequência magmática antiga (2.0 – 1.95 Ga) e a sequência
magmática nova (1.89 – 1.86 Ga). A sequência antiga (OMS na sigla em inglês) é
dividida em três subgrupos de acordo com os resultados obtidos.

O grupo I representa os primeiros pulsos de magmatismo na PMT e caracteriza-se por

granitos e granodioritos peraluminosos, ferroanos e cálcio-alcalinos, datados em 2011
Ma, caracterizados por εNd(t) evoluído (–8.36) e alta temperatura de saturação em
zircão (798°C), características que indicam a contribuição de crosta continental para a
formação desses magmas, marcando o início do arco magmático. Os dados de
modelamento geoquímico mostram que as rochas do grupo I evoluíram em um trend
anidro e oxidado em direção a altas razões La/Yb e Sr/Y através da extração de
plagioclásio, piroxênio, biotita, magnetita e titanita. Adicionalmente, a fO2 dos magmas
abaixo de ΔFMQ e a evolução anidra conferem às rochas do grupo I umas baixa
favorabilidade para a formação de depósitos magmático hidrotermais de Cu–Au.

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As rochas do grupo II são mais variáveis em termos composicionais e representam a
evolução do arco magmático. O grupo é marcado por sieno- e monzogranitos,
magnesianos a ferroanos, álcali-cálcicos à cálcio-alcalinos, metaluminosos a félsico-
peraluminosos, com idade em 1986 Ma e caracterizados por εNd(t) moderadamente
negativos (de –1 a –3). Modelamento geoquímico mostra que essas rochas evoluíram
sob a presença de anfibólio, responsável pela baixa razão Dy/Yb nas bordas dos
zircões, e magnetita, que explica a fO2 até ΔFMQ +4. Esses atributos geoquímicos
permitem classificar as rochas do grupo II (e as equivalentes extrusivas) como férteis
do ponto de vista metalogenético. De fato, e não surpreendentemente, a maior parte
dos depósitos na PMT está hospedado nessas rochas (Tocantinzinho, Chapéu do Sol,
São Jorge, Coringa e Patrocínio) onde o minério consiste principalmente em veios e
vênulas de pirita e quartzo ±ouro nas alterações sericíticas, potássica e/ou propilítica
(com sulfetos disseminados mais raramente).

O grupo III é comparativamente mais raro na PMT, e é composto por quartzo-sienitos

e quartzo-monzonitos de alto potássio, ferroanos, alcalinos, metaluminosos a
fracamente peraluminosos, de idades que variam de 1993 à 1974 Ma. Modelamento
geoquímico mostra uma evolução compatível com K-feldspato, plagioclásios, biotita,
apatita, piroxênio e ilmenita, com anomalias negativas de Eu e baixas razões Sr/Y e
La/Yb. A evolução reduzida é coerente com os valores de fO2 abaixo de ΔFMQ +1.
Apesar de ser síncrona com as rochas do grupo II, os mecanismos geradores da
sequência de alto potássio não é de fácil entendimento. Com base na característica
reduzida e anidra dos magmas, a petrogênese das rochas do grupo III possivelmente
envolve fusão por descompressão de manto litosférico metassomatizado,
possivelmente induzida por corner-flow associado à subducção. Complementarmente,
essas rochas em teoria não apresentam as características de magmas formadores de
depósitos magmático hidrotermais, entretanto, em campo foi constatado que essas
rochas são afetadas por alteração hidrotermal e apresentam mineralização
disseminada representada por pirrotita ±ouro presente nas alterações sericítica,
potássica e/ou carbonática. Sendo assim, as rochas do grupo III podem ser
consideradas férteis devido à interação com os magmas mais hidratados e oxidados do
grupo II.

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A sequência magmática nova (YMS na sigla em inglês) é representada pelas vulcânicas
do Grupo Iriri e pelas rochas graníticas das suítes intrusivas Parauari (PAR) e
Maloquinha (MLQ) (e foram descritas nos depósitos V3, Palito e Batalha). As rochas da
YMS são mais frequentes na porção leste da PMT. PAR e as vulcânicas do Grupo Iriri
representam os primeiros pulsos de magmatismo da YMS, e as rochas são
magnesianas a ferroanas, cálcio-alcalinas à álcali-cálcicas e alcalinas, metaluminosas a
félsica-peraluminosas. As vulcânicas intermediárias evoluem em direção a altas razões
Dy/Yb, Sr/Y e La/Yb através da cristalização de K-feldspato, anfibólio, plagioclásio e
biotita. A parte ácida do Grupo Iriri e as rochas graníticas da PAR evoluíram em um
trend similar compatível com plagioclásio, K-feldspato, piroxênio, titanita e apatita, em
direção a baixas razões Sr/Y, La/Yb e Eu/Eu*, compatível com fontes máficas reduzidas
e anidras. As rochas da suíte PAR apresentam εNd(t) mais fortemente negativos (média
de -4.85) quando comparado às rochas do Grupo Iriri, sugerindo um maior tempo de
residência em reservatórios crustais. A assinatura geoquímica dos granitos PAR é
interpretada como o resultado da fusão de manto metassomatizado em um ambiente
tardi- a pós-orogênico. Apesar da característica anidra e reduzida, o contexto tectônico
da YMS é adequado para a formação de depósitos magmático hidrotermais ricos em
ouro, uma vez que esses magmas eficientemente mobilizam sulfetos previamente
formados ricos em elementos siderófilos e calcófilos. MLQ representa os últimos
pulsos de magmatismo orosiriano da YMS e é composta essencialmente por álcali
feldspato granitos ferroanos, álcali-cálcicos, moderadamente peraluminosos,
compatíveis com uma evolução com piroxênio e ilmenita. Esses atributos e os εNd(T)
perto de zero ou fracamente negativos (entre -2.64 and -0.28) indicam fusão de manto
litosférico metassomatizado. Do ponto de vista metalogenético, MLQ apresentam
baixa favorabilidade para a formação de depósitos magmático hidrotermais de cobre e
ouro.

Palavras-chave: depósitos magmático hidrotermais, Cráton Amazônico, Província

Mineral do Tapajós, arco magmático, geoquímica, zircão, geocronologia

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Abstract

Continental crust growth ratio has been challenging researchers significantly over the
past decades, and the existing models vary from episodic to continuous growth
ratios, the latter with a more significant role of the Archean Eon. In the South
American Platform, the Amazonian Craton (AC) provides an excellent window into
Precambrian continental crust, with many exposure of Archean and Paleoproterozoic
continental crust. Interestingly, on a global perspective, Archean tectonics and rock-
associations has been targeted more frequently and the number of papers
overcomes significantly Paleoproterozoic-related publications. Looking closely to
south-central AC, the Tapajós Mineral Province (TMP) consists on an excellent area of
study as it comprises multiple Orosirian igneous suites within the 2.0 – 1.87 Ga
interval with associated mineral deposits and occurrences of both base and precious
metals. Within this aspect, this study provides new petrogenetic constraints on the
TMP’s igneous suites based on whole-rock and zircon-geochemistry, with the
respective tectonic and metallogenetic implications. The results allow the separation
of two main age groups within the TMP: the older- (2.0 – 1.95 Ga) and younger
magmatic sequences (1.89 – 1 .86 Ga). The older magmatic sequence (OMS) is
divided into groups I, II and III granitoids that according to the results acquired
evolved through fractional crystallization and represents the first batches and
evolution of the magmatic arc.

Group I marks the onset of OMS and encompasses ferroan, calc-alkalic and
peraluminous granites and granodiorites dated in 2011 Ma, characterized by evolved
εNd(T) and high zircon saturation temperature (798°C), all compatible with a strong
crustal component on magmatic arc magmas. Geochemical modelling shows a dry
and oxidized evolution towards high La/Yb and Sr/Y ratios through extraction of
plagioclase, pyroxene, biotite, magnetite and titanite. In addition, zircon-based fO2
estimates below ΔFMQ combined with their pyroxene-bearing evolution renders
group I magmas a low metallogenetic favorability for the formation of magmatic
hydrothermal (Cu – Au) mineral deposits.

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 Group II rocks are compositionally more variable, represent the evolution of the arc
magmatism, and comprises magnesian to ferroan, alkali-calcic to calc-alkalic,
metaluminous to felsic-peraluminous granodiorites, monzo- and syenogranites of ca.
1986 Ma, characterized by moderately negative εNd(T) (from -1 to -3). Geochemical
modelling shows an evolution compatible with amphibole and magnetite extraction,
which is also corroborated by low Dy/Yb zircon rims and fO2 between ΔFMQ +0 and
+4. These set of attributes allow group II granites (and its volcanic equivalents) to be
considered as metallogenetic fertile for the formation of magmatic-hydrothermal Cu
– Au mineral systems. In fact, most rocks from the Tocantinzinho, Chapéu do Sol, São
Jorge, Coringa and Patrocínio deposits belong to group II rocks, where mineralization
is defined by disseminated gold-bearing sulfides or by pyrite-quartz ±gold
±chalcopyrite veins and veinlets most often found in the sericitic and, less frequently,
in the potassic and propylitic alteration zones.

Group III rocks are rarer in the TMP and are defined by high-K, ferroan, alkalic,
metaluminous to slightly peraluminous quartz-monzonites and quartz-syenites with
ages that vary from 1993 and 1974 Ma. Whole-rock geochemistry shows an evolution
coherent with K-feldspar, plagioclase, biotite, apatite, clinopyroxene and ilmenite
fractionation, which is accompanied by stronger negative Eu anomalies, Sr and Ba
depletion, and low Sr/Y and La/Yb ratios. Its anhydrous and reduced petrologic trend is
supported by fO2 values below ΔFMQ +1. Despite its synchronicity with group II, group
III’s petrogenesis is harder to be constrained. In view of their reducing and anhydrous
evolution, decompression melting of metasomatized mantle is proposed as the main
mechanism for generating group III magmas. Moreover, these rocks should be
considered as metallogenetically unfertile (pyroxene- and ilmenite-bearing evolution),
yet, on the field syenites and monzonites are often affected by hydrothermal
alteration and show disseminated and gold-bearing pyrite and pyrrhotite crysts on the
sericitic, potassic and/or carbonatic alteration halos. As a consequence, group III rocks
are mineralized as the result of the interaction with the more hydrous, oxidized and
fertile group II magmas.

The younger magmatic sequence (YMS) is represented by the Iriri Group volcanics and
by the Parauari (PAR) and Maloquinha (MLQ) Intrusive Suites (described on the V3,

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Palito and Batalha deposits). Despite their spread on TMP’s geologic maps, these rocks
are more often spotted on the eastern part of the province. The first pulses of YMS are
represented by the PAR granitoids and coeval Iriri volcanics. Both comprise magnesian
to ferroan, calc-alkalic to alkali-calcic and alkalic, metaluminous to felsic-peraluminous
rocks. Intermediate Iriri rocks evolved towards higher Dy/Yb, Sr/Y and La/Yb ratios
through K-feldspar, amphibole, anorthite-rich plagioclase and biotite extraction. Acid
Iriri and PAR granitoids evolved on a similar petrologic trend compatible with albitic-
plagioclase, K-feldspar, pyroxene, titanite and apatite fractionation, that drives the
evolving magmas towards lower Sr/Y, La/Yb and Eu/Eu* ratios and suggest anhydrous
and reduced mafic sources. PAR granitoids show more strongly negative εNd(t)
(average of -4.85) when compared with Iriri rocks, indicating a longer period of
residence in crustal hot zones. Its geochemistry signature is interpreted as the result of
metasomatized mantle melting on a late- or post-orogenic tectonic setting. Despite the
anhydrous and reduced characteristic of the magmas, the geologic framework of YMS
is adequate for the formation of gold-rich (or gold only) magmatic-hydrothermal
mineral deposits, as these magmas efficiently mobilize previously formed, chalcophile-
and siderophile-rich sulfides. MLQ marks the last pulses of the Orosirian magmatism in
the TMP and is characterized by ferroan, alkali-calcic and moderately-peraluminous
alkali-granites that evolved on a pyroxene- and ilmenite-bearing trend. These
characteristics and the close to 0 or slightly negative εNd(T) (between -2.64 and -0.28)
indicates metasomatized mantle melting, likely involving the directly underthrusted
SCLM. From a metallogenetic perspective, MLQ magmatism show a low favorability for
the formation of magmatic-hydrothermal mineral systems.

Keywords: magmatic-hydrothermal mineral deposits, Amazonian Craton, Tapajós

Mineral Province, magmatic arc, geochemistry, zircon, geochronology

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Summary

PART I

Summary .......................................................................................................................... 8
1. Introduction............................................................................................................. 15
1.1. Location and Access ......................................................................................... 18
1.2. Problematic and thesis’ goals .......................................................................... 19
1.3. Analytical methods .......................................................................................... 20
1.4. Geologic Framework, Tectonic Division and Evolution of the Amazonian
Craton22
1.4.1. Carajás Province ....................................................................................... 23
1.4.2. Central Amazon Province ......................................................................... 24
1.4.3. Transamazonian Province ........................................................................ 24
1.4.4. Tapajós-Parima Province .......................................................................... 25
1.4.5. Rondônia–Juruena Province ..................................................................... 26
1.4.6. Rio Negro Province ................................................................................... 27
1.4.7. Sunsás and K’Mudku Provinces ................................................................ 27
2. Results (Lithos publication available as supplementary material, DOI:
10.1016/[Link].2019.105350) ....................................................................................... 29
Orosirian Magmatism in The Tapajós Mineral Province (Amazonian Craton): The
Missing Link to Understand the Onset of Paleoproterozoic Tectonics .......................... 29
3. Results (submitted to Ore Geology Reviews) ......................................................... 31
3.1. Introduction ..................................................................................................... 33
3.2. Geologic Framework of the Tapajós Mineral Province ................................... 35
3.2.1. Lithostratigraphy ...................................................................................... 35
3.2.2. Typology and General Features of the Mineralizing Systems at the TMP 36
[Link]. Deposits Within the Older Magmatic Sequence (OMS).................... 37
[Link]. Deposits Within the Younger Magmatic Sequence (YMS) ................ 38
3.3. Methods ........................................................................................................... 43
3.4. Results .............................................................................................................. 45
3.4.1. Whole-Rock Geochemistry ....................................................................... 45
[Link]. Classification Diagrams ..................................................................... 46
[Link]. Major-element contents ................................................................... 50

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 [Link]. Trace Element Contents .................................................................... 54
3.4.2. Zircon geochemistry ................................................................................. 58
[Link]. Morphology and textural description ............................................... 58
[Link]. U-Pb Dating (LA-ICP-MS) ................................................................... 61
[Link]. Trace element contents .................................................................... 62
[Link]. Ti-in-zircon thermometry .................................................................. 65
[Link]. Magmatic fO2 estimates .................................................................... 66
3.5. Discussion ........................................................................................................ 68
3.5.1. A petrogenesis perspective: generating the older and younger magmatic
sequences ................................................................................................................ 68
3.5.2. Insights from zircon geochemistry: examples from the Patrocínio gold
mineralization.......................................................................................................... 71
3.5.3. Fertile or not-fertile: the million dollar question ..................................... 73
[Link]. What the Sr/Y ratio tell us? ............................................................... 76
3.6. Conclusions ...................................................................................................... 78
4. Discussion ................................................................................................................ 81
4.1. Topics and Considerations on Classification Diagrams.................................... 81
4.2. Genesis of TMP Magmas (the older and younger magmatic sequences) ....... 83
4.3. Metallogenetic Potential of the Igneous Suites .............................................. 91
5. Conclusions.............................................................................................................. 93

BIBLIOGRAPHY……………………………………………………………………………………………………………96

SUPPLEMENTARY MATERIAL I (Zircon trace element contents)………………………………..109

SUPPLEMENTARY MATERIAL II (Zircon U-Pb Dating)…………………………………………………129

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List of Figures
Fig. 1. Amazonian Craton and its tectonic subdivision (Santos et al., 2000, 2006). The
Tapajós Mineral Province (TMP) geologic map, adapted from Klein et al. (2001), brings
the main Orosirian igneous suites and the selected mineral deposits involved in this
contribution. Mafic bodies and Phanerozoic units are not colored. ............................. 17
Fig. 2. Typology of the different OMS (a – o) and YMS rocks (p – u). (a) Massive,
leucocratic, granodiorite drill core sample. (b) Massive, partially altered (potassic
alteration), granodioritic porphyry; (c) Porphyritic and massive syenogranite with
compositionally zoned plagioclase phenocrysts; (d) Syenogranitic porphyry with
plagioclase phenocrysts (outcrop near the Patrocínio area); (e) Equigranular, massive
monzogranite; (f) Strongly altered (potassic alteration) granite, with gold bearing pyrite
in chlorite-sericite veinlets; (g) Sulfide bearing, chlorite-sericite alteration in K-
metasomatized granitoid; (h) Gold bearing, quartz sulfide vein injected near the
granite-syenite contact. Rocks have previously experienced pervasive potassic and
subsequent chlorite-sericite alteration; (i) Granite drill-core sample with multi-phasic
hydrothermal events. early potassic alteration (reddish feldspar crysts) is followed by
fissural and interstitial chlorite-sericite alteration (gray-greenish color). The last
hydrothermal event is represented by the white-silica infilled breccia; (j) Drill core
sample with contact between monzonite (left) and monzogranite (right) with a
reaction rim (central) and small opaque (sulfide?) crysts; (k) Potassic and chlorite-
sericite altered syenite; (l) Chlorite-sericite and potassic altered monzonite with
disseminated, gold bearing sulfide (pyrite and pyrrhotite), and less frequent sulfide
veinlets; (m) Aplitic syenite found as synplutonic dykes in OMS granites. (n) Rhyolite
with feldspar phenocrysts and potassic alteration form the Coringa deposit; (o) Coringa
deposit ore example, with strongly sericitic altered volcanic rock (rhyolite?) cross-cut
by a chalcopyrite + sphalerite + galena vein, brecciated by sericitic + white silica
alteration. (p – t) Palito deposit samples (examples from Echeverri Misas, 2015; (p)
potassic altered granite with secondary K-feldspar; (q) potassic and propylitic
alteration with K-feldspar, chlorite, epidote and carbonate (Cal); (r) Sericitic alteration
with quartz (Qtz), sericite (Ser) and pyrite (Py); (s) Sulfide vein in strongly
hydrothermalized granite (5), with (1) chalcopyrite, (2) pyrite, (3) breccia zone and (4)
quartz veins; (t) Strongly hydrothermalized granite with fluorite (6) and white silica
veining (7). (u) OMS granite injected by YMS dacite dyke with white silica, gold bearing
sulfide pocket and smaller veinlets along the dyke contact. ......................................... 42
Fig. 3. FMW ternary diagram after Ohta and Arai (2007) for the whole-rock
geochemistry database. Samples that plot on the shaded area indicate higher degree
of weathering and were not considered for the results and discussion sections. ........ 46
Fig. 4. De la Roche et al. (1980) classification diagram for the OMS (a), with coeval
volcanics from the Coringa deposit at the top-left. (b) Classification diagram for the
YMS with the V3 volcanics plotted at the smaller top-left diagram. ............................. 47

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Fig. 5. Frost’s classification diagrams for OMS and YMS, with SiO2 vs. Fe-index (a), SiO2
vs. MALI (b), and A-B diagram after Villaseca et al. (1998) (c), where A = Al - (K + Na +
2Ca) and B = Fe + Mg + Ti, calculated for millications. Extrusive rocks from the Coringa
and V3 deposits are plotted for comparison purposes. Groups I, II and III rocks from
OMS are pinpointed on the smaller diagrams. .............................................................. 49
Fig. 6. Silica vs. major oxides diagrams for OMS rocks (symbols are the same as in the
previous figures). Red, green and gray arrays mark the petrologic trends modeled with
the respective minerals involved. The accuracy of the models is given by the R²
parameter, which is defined by the sum of the differences between the theoretical and
real differentiated melts for each element squared. Abbreviations: Am (amphibole), Pl
(plagioclase), Bt (biotite), Px (pyroxene), Mag (magnetite), Ttn (titanite), Ap (apatite),
Ilm (ilmenite). ................................................................................................................. 51
Fig. 7. Silica vs. major oxides for YMS rocks. Yellow and black arrays mark the
petrologic trends modeled, with the minerals involved and the R² parameter indicated
at the top. Symbols are the same as in the previous figures. Abbreviations: Kfs (K-
feldspar), Am (amphibole), Pl (plagioclase), Bt (biotite), Px (pyroxene), Mag
(magnetite), Ttn (titanite)............................................................................................... 53
Fig. 8. Chondrite normalized (Boynton, 1984) REE spidergrams for the OMS (a – e),
YMS (f – h) and trace-element spidergrams normalized by the primitive mantle (Sun
and McDonough, 1989) for both sequences. The respective colored fields represent
the entire range covered by each deposit/unit. Eu anomaly calculated as Eu/Eu* =
EuN/(𝐒𝐦𝐍. 𝐆𝐝𝐍). ........................................................................................................... 55
Fig. 9. Maficity vs. Dy/Yb (a), Eu/Eu* vs. Sr/Y (b) and Eu/Eu* vs. La/Yb (c) plots for OMS
and YMS. Dy/Yb ratio is strongly influenced by amphibole as the mineral shows high
Kd’s for both elements. Sr/Y and La/Yb might also be influenced by amphibole,
however, plagioclase and pyroxene on a lesser extent might also shift the ratios
towards higher or lower values. ..................................................................................... 57
Fig. 10. Cathodoluminescence images from selected zircon grains and the respective
concordia-discordia diagrams from the samples analyzed in this study. Spots are 20 μm
wide. 1-3, 10, 11, 17-19 (partially dissolved) and 30-32 show inherited xenocrystic
cores (grain 32 is partially resorbed); 4, 5, 14, 20, 25, 26 and 35 show oscillatory
zoning; 6 and 7 are broad zoned grains; 8, 9, 15 and 27 show patchy zoned zircon
grains; 12, 13, 33 and 34 show autocrystic cores; 16, 22, 23, 28, 29, 36 and 37 show
sector zoning; 21 and 24 are homogeneous zoned. ...................................................... 60
Fig. 11. Zircon geochemistry with Zr/Hf vs. Eu/Eu* (a) and Th/U vs. Dy/Yb plots (b),
where both Zr/Hf and Th/U ratios were used as proxies for differentiation. Bottom
right smaller graph in (b) shows the polynomial regressions with the general trend for
each sample. (c) Light REE index (LREE-i) as proposed by Bell et al. (2016) vs. Ti plot.
The index is calculated as LREE-i = (Dy/Nd + Dy/Sm), in order to constrain the

11
proportion between middle and light-REE in zircon grains. Grains with low LREE-i show
high LREE content, which might indicate hydrothermal alteration (or LREE rich
inclusions such as apatite or monazite on the ablated spot). ........................................ 64
Fig. 12. Zircon saturation temperature (Watson and Harrison 1983) vs. Ti-in-zircon
temperature (Ferry and Watson 2007) plot. The plot separates fields where zircon
saturation is not achieved by the hosting magmas (top of the diagram) and, conversely,
fields where zircon might be extracted from the magmas (center and bottom parts).
Inherited grains might plot in all fields, whereas autocrystic grains will plot on the
center and bottom parts. (b) Magmatic fO2 treated as log units above or below the
fayalite-magnetite-quartz oxygen buffer plotted against magmatic temperature (T
[Link]). ............................................................................................................................ 67
Fig. 13. MWF plot (13a) (Ohta and Arai, 2007) and classification diagrams after Cox et
al. (1979) (13b); Middlemost (1994) (13c); and De la Roche et al. (1980) (13d) for
weathered and hydrothermally altered rocks. .............................................................. 82

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Thesis structure

Rather than the classic thesis format, this volume is organized with basis on published-
and submitted-papers. Accordingly, the following sections and sub-sections are
presented:

Part I – Introduction, Goals, Methods and Geologic Setting

This first part of the thesis comprises an opening section with a brief introduction to
magmatic-hydrothermal mineral deposits, with emphasis on the porphyry epithermal
class and how important and relevant is the metallogenetic research on ancient and
cratonized Pre-Cambrian terrains. The thesis goals, methods and systematic applied
and the geologic framework are presented in Part I as well.

Part II – Results

 Part II of the thesis comprises the results acquired during the development of
this research, which are presented on published and submitted paper format.
Accordingly, Chapter 2 comprises the paper “Orosirian magmatism in the
Tapajós Mineral Province (Amazonian Craton): the missing link to understand
the onset of Paleoproterozoic tectonics”, published on Lithos in January 2020.
This paper is based on petrography, whole-rock geochemistry and U-Pb zircon
dating. It focuses on constraining the petrogenetic mechanisms behind the 2.0
– 1.87 Ga igneous suites present in the Tapajós Mineral Province, south-central
Amazonian Craton.
 The second part of the results refer to zircon geochemistry data, where in-situ
trace-element measurements were used with whole-rock geochemistry
database in order to constrain the petrologic evolution of the host-rocks of
main mineral deposits within the Tapajós. In addition, the results were also
used as proxies of the oxidation state of the hosting magmas, which has

13
 important metallogenetic implications. These results were organized on the
paper “Towards the fertility trend: unraveling the economic potential of igneous
suites through whole-rock and zircon geochemistry (example from the Tapajós
Mineral Province, Northern Brazil)” submitted to Ore Geology Reviews on
March 2021.

Part III – Discussion and Conclusions

The final part of the thesis reviews the results acquired and summarizes the main
discussion and concluding remarks presented on this research. Additionally, raw zircon
trace-element analyses results are provided as supplementary material in the end of
this volume.

14
 Part I – Introduction, Methods and Geologic Framework

1. Introduction

Magmatic-hydrothermal mineral deposits are the ultimate result of the

interaction between igneous derived fluids and its country rocks. Porphyry Cu ±Au
±Mo deposits in particular, are genetically related with intermediate to acid, oxidized
(ΔFMQ > 0) and hydrous intrusions (2 – 6 wt.% H2O) found in crustal levels no deeper
than 5 Km (Sinclair, 2007; Pirajno, 2009; Sillitoe, 2010; Richards, 2011a; Cooke et al.,
2013; Loucks, 2014; Sun et al., 2015). The evolution of the system towards shallower
stratigraphic levels will generate Au ±Ag high-sulfidation epithermal systems (with
eventually more distal intermediate- and low-sulfidation deposits). On a tectonic
perspective, these mineralizing systems are more commonly identified in modern
magmatic arcs such as in the Andean Cordillera in South-America and, less frequently,
in collisional tectonic settings such as southern Tibet. Axiomatically, the tectonic
setting and its associated petrogenetic mechanisms will dictate the geochemical
characteristic of the igneous suites and, as a consequence, the typology of the
genetically associated magmatic hydrothermal mineral system (e.g. Chen et al., 2015).
In essence, in order to fully constrain the metallogenetic potential of a given geologic
context for the formation of these types of deposits, it is imperative to previously
constrain the tectonic setting and magmatic evolution of the igneous suites so
potentially ore-forming plutons can be individualized. Certainly, Phanerozoic arcs are
much more inviting to explore for porphyry and epithermal deposits than their older
(Precambrian) correspondences, considering variables such as level of erosion,
weathering profile and superposed metamorphism. Unsurprisingly, world-class
porphyry deposits such as Escondida (Cu), Chuquicamata (Cu–Mo), El Teniente (Cu–
Mo), Bingham Canyon (Cu–Au–Mo) are found in Phanerozoic arcs or collisional settings
(Ballard et al., 2001; Landtwing et al., 2010; Hervé et al., 2012; Muñoz et al., 2012). The
increasing demand for copper (and molybdenum) and its importance towards a
greener industry, drives the search for new deposits in Precambrian and cratonized
terrains mutually promising and challenging (reader is referred to “Copper is the New
Oil” report by Goldman Sachs available at [Link]/insights/podcasts/
episodes/[Link]).

15
 Part I – Introduction, Methods and Geologic Framework
A first order problem involves the framework displayed by ancient terrains,
where the arc-related units appear juxtaposed with the collisional, post-collisional,
anorogenic and metamorphic sequences, often superposed by strong and deep
weathering profiles. In addition, plate tectonics went through significant changes over
the geologic record as Earth progressively cooled (e.g. Bédard, 2006, 2018; Condie,
2018), implying in different petrogenetic mechanisms, rock associations and
metallogenetic processes. Not surprisingly, orogenic gold deposits are hosted by
granite greenstone–belts terrains, are predominantly Archean and found in ancient
cratons (Goldfarb and Groves, 2015); Iron-Oxide-Gold-Copper (IOCG) deposits are
usually Pre-Cambrian and found close to shear zones and granitoid bodies (Richards
and Mumin, 2013); and porphyry Cu–Au–Mo prefer modern subduction zones and
magmatic arcs settings, and are usually hosted by intermediate to acid intrusions.

In terms of igneous petrogenesis within the South American Platform (Almeida

et al., 2000), the Paleoproterozoic Era is the most expressive regarding new
continental crust addition, with one event at 2.3 – 2.1 Ga (Rhyacian); and another at
2.1 – 1.8 Ga (Orosirian) ( Sato and Siga Junior, 2002; Giustina et al., 2009). The younger
event is well represented in the Amazonian Craton (AC) (Fig. 1) and comprises calc-
alkaline, high-K calc-alkaline and shoshonitic intrusive and extrusive suites, with the
typically Proterozoic anorthosite–mangerite–charnockite–granite (AMCG) rock
association (Dall’Agnol et al., 1999; Tassinari and Macambira, 1999; Santos et al., 2000;
Alfredo et al., 2010; Valério et al., 2018). The precise tectonic setting and related
interpretations vary among the researchers, and a summary is provided in Table 1.

In south-central AC, in an area known as Tapajós Mineral Province (TMP) (Fig.

1), the Orosirian sequence is intimately related with many gold deposits (with lesser
copper and molybdenum occurrences) (Santos et al., 2001; Juliani et al., 2002, 2005;
Assunção and Klein, 2014; Bettencourt et al., 2016; Borgo et al., 2017;). Most recent
publications describe TMP’s mineralizations as porphyry-epithermal mineral systems
(Juliani et al., 2005; Echeverri Misas, 2015; Tokashiki, 2015; Cassini, 2016; Lopes and
Moura, 2019), yet, Intrusion-Related-Gold-Systems (IRGS) (Santos et al., 2001; Villas et
al., 2013) and hybrid porphyry–IRGS models have also been proposed (Juliani et al.,
2002; Borges et al., 2009; Biondi et al., 2018). Despite the effort over the past years,

16
 Part I – Introduction, Methods and Geologic Framework

Fig. 1. Amazonian Craton and its tectonic subdivision (Santos et al., 2000, 2006). The
Tapajós Mineral Province (TMP) geologic map, adapted from Klein et al. (2001), brings
the main Orosirian igneous suites and the selected mineral deposits involved in this
contribution. Mafic bodies and Phanerozoic units are not colored.

17
 Part I – Introduction, Methods and Geologic Framework
there are still important knowledge gaps that need to be filled so we can constrain the
TMP’s true economic potential.

In order to enlighten the debate, the central point of this thesis is to constrain
the petrogenesis and magmatic evolution of the 2.0 – 1.87 Ga igneous suites within
the TMP, and ultimately define which plutons/units and periods should be considered
metallogenetic fertile. Within this regard, we use two different datasets, one of these
comprises whole-rock geochemistry data, and another with in situ zircon trace-
element and U–Pb measurements.

Whole-rock geochemistry provides relevant information on the magmatic

evolution of the igneous suites and allows petrogenetic constraints, particularly for
granitic rocks. Typical Cu (±Au) porphyry and high-sulfidation epithermal deposits are
genetically connected with hydrous and oxidized plutons that are often amphibole-
and magnetite bearing. Hence, major elements and REE patterns are key tools to
assess the evolution of the targeted plutons. Zircon analyses are extremely relevant in
this study not only for revealing the precise timing and tempo behind the Orosirian
units, but also for assessing magmatic fO2 through the Ce4+/Ce3+ proportion, which has
important metallogenetic implications (Ballard et al., 2002; Trail et al., 2012). Up to this
moment, zircon-based fO2 constraints have not been published for the TMP and its
mineral deposits-hosting plutons. The results, discussion and conclusions presented in
this thesis provide a petrogenetic overview on the 2.0 – 1.87 Ga window, with the
respective petrologic evolution, tectonic setting and economic potential of the igneous
suites.

1.1. Location and Access

The Tapajós Mineral Province is located at the southwestern part of the Pará
state and may be accessed through the north or through the south. From north, the
biggest city on the region is Itaituba, where it is possible to access the BR-230 road
towards south and, afterwards, the BR-163. The BR-163 runs on the NW–SE direction
(black dashed line on Fig. 1) and extends through the entire TMP. Cities and smaller

18
 Part I – Introduction, Methods and Geologic Framework
villages on the BR-163 (Novo Progresso, Moraes de Almeida and Castelo dos Sonhos)
were used as base for the fieldtrips, where smaller country roads may be accessed.
From the south, the biggest city is Alta Floresta, located on northern Mato Grosso
state. From this city, the MT-208 road is accessed on the east direction, towards the
Guarantã do Norte city. Once in Guarantã, it is possible to access the BR-163 on the
north direction towards the Pará state and the TMP.

1.2. Problematic and thesis’ goals

In summary, this study investigates how the igneous suites in the TMP formed,
how they evolved, their respective tectonic setting and the given metallogenetic
implications. By combining whole-rock geochemistry with in-situ zircon trace element
measurements and U–Pb dating, it is possible to constrain the sources, the timing and
processes (assimilation and/or fractional crystallization) involved on the formation of
the igneous suites. The TMP comprises an area greater than 130.000 km², with dense
rainforest cover and rare outcrops. Hence, establishing magmatic correlations is a key
step prior to petrogenetic constraints. Tokashiki (2015), for example, identified ca. 1.97
Ga rhyolites in southern TMP that so far have not been correlated with other
lithostratigraphic unit. Geochemical modelling plays an important role in this case, as it
allows assessing the minerals involved on the evolution of the suites, and whether
different samples, outcrops and/or plutons are likely to be cogenetic.

Ultimately, this study elucidates how igneous petrogenesis, magmatic evolution

and tectonic context translates into metallogenetic potential for the formation of
magmatic hydrothermal mineral deposits. As a result, this contribution could be
understood as an important step towards a more robust, unified and holistic
metallogenetic model for the base and precious metals mineralizations described in
the TMP, south-central Amazonian Craton.

19
 Part I – Introduction, Methods and Geologic Framework

1.3. Analytical methods

The methods involved on the elaboration of this thesis involved, at first,

extensive bibliographic review on the Amazonian Craton, TMP’s mineralizing systems,
magmatic hydrothermal mineral deposits, crustal evolution, Paleoproterozoic
magmatism, tectonics, rock association, petrogenesis and geochemistry. A significant
part of this study involved the organization of a whole-rock geochemistry database
with representative samples from most units identified in the TMP. The data was
treated on a quantitative approach in order to avoid misleading interpretations and, a
first filtering criteria was based on the MFW diagram after Ohta and Arai (2007). The
diagram was idealized with basis on a dataset of igneous rocks and their respective
weathered products, where principal component analysis allows the M and F vertices
to capture mafic to felsic differentiation sequence, whereas the W apex relates with
the degree of weathering. Accordingly, the samples that plot on the center of the
diagram and scatter towards the W vertice present a degree of weathering that might
disturb their original geochemical signature and, consequently, these samples were
excluded from the database. Whole-rock geochemistry was treated with GCDKit
(Janoušek et al., 2006) and later used for the geochemical modelling routines.

Geochemical modelling was carried out using GCDKit and further R

programming. The method follows the universal mass balance equation:

1) 𝐶 = 𝐹𝐶 + (1 − 𝐹)𝐶

where C0 is the initial system composition, F is the fraction of liquid, CL composition of

liquid and CS the composition of the solids. The methodology consists on the definition
of one parental and one differentiated magma. Mass balance equation checks if the
chosen samples are compatible with a petrologic evolution trend. It is possible to
obtain the composition of differentiated liquids (equation 2) and crystallized minerals
or cumulate (equation 3) by rearranging equation 1). This process can be done for any
element (el) at any given mineral (min).

20
 Part I – Introduction, Methods and Geologic Framework
𝐶 − 𝐶 𝐹
2) 𝐶 = (1 − 𝐹 )

𝐶 − 𝐹𝐶
3) 𝐶 = (1 − 𝐹)

For these cases FC is the degree of crystallization or proportion of solids. The accuracy
of a given model is given by the R² parameter, which by definition is the sum of the
differences between the theoretical and real differentiated melts for each element
squared, as it follows:

𝑅 = (𝐶 ( ) − 𝐶 ( ) )²

The R² values closer to 0 imply in models with a better numerical fit. The
partition coefficients (KD) used for calculation of trace elements were taken from
Rollinson (1993) and more details and information on the modelling are available at
Janoušek et al. (2016).

Trace elements and U–Pb geochronology analyses in zircon grains were

performed at the Department of Earth Sciences (ETH – Zürich) using a Thermo Element
XR, sector field, single collector ICP-MS coupled to a 193-nm Resolution S155 (ASI)
laser ablation system. The later counts with a two-volume Laurin Technic ablation cell
fluxed by high-purity He at 0.5 l min-1 rate. The 20 μm spots were ablated for 30
seconds with a repetition rate of 3 Hz and a laser energy of 2 J cm-2. Argon was
admixed to the aerosol within the ablation funnel (0.96 l min-1) to carry the ablated
material for ionization. The integration time per point was 0.662 seconds, and
elemental concentration was calculated using the software Iolite (Paton et al., 2011).
The stoichiometric Si content of zircon (15.2 wt.%) was used as internal standard for
trace element quantification and U–Pb data reproducibility was assured by analyses of
reference zircon grains (AUSZ7-1, OG-1, Plešovice and 91500). U-Pb and trace element
measurements were acquired at the same spot and fractured or metamict domains
were avoided or discarded. Zircon trace element results were treated with GCDKit and
U–Pb data with IsoplotR (Vermeesch, 2018), results are also available as
supplementary material.

21
 Part I – Introduction, Methods and Geologic Framework

1.4. Geologic Framework, Tectonic Division and Evolution of the

Amazonian Craton

The Amazonian Craton, hereinafter AC, comprises approximately 4.6 x106 km2
within the South American Platform (Almeida et al., 1981, 2000) and defines one of the
largest Precambrian terrains on Earth. The AC is delimited by Neoproterozoic mobile
belts (Paraguai–Araguaia and Tucavaca) and show thick Phanerozoic sedimentary
cover related with the Amazonian drainage system. The first attempts for subdivision,
in the early 70’s, divided the craton in western, central and eastern blocks (Amaral,
1974). A few years later Cordani et al. (1979) suggested that the AC evolved from an
ancient nuclei against which Proterozoic orogens were juxtaposed. According to
Cordani’s proposal, the AC would comprise the Maroni–Itacaiunas (2.1 – 1.8 Ga),
Central Amazonian (>2.1 Ga), Rio Negro–Juruena (1.7 – 1.45 Ga) and Rondonian
Provinces (1.4 – 1.1 Ga). However, this model lacks strength as it was essentially based
on Rb–Sr isotopes. On the late 80’s, Gibbs et al. (1986) published Archean U–Pb ages
for the Carajás Province, which afterwards lead Teixeira et al. (1989) to treat it as the
Archean nuclei of the AC. Later, Tassinari and Macambira (1999) proposed the craton’s
subdivision in the Rondonian–San Ignacio, Rio Negro–Juruena, Venturari–Tapajós,
Central Amazon and Maroni–Itacaiunas geochronologic provinces.

Shortly after Tassinari and Macambira’s model, Santos et al. (2000) published a
review on the craton’s subdivision and presented a new proposal based on U–Pb and
Sm–Nd isotopes. In this new proposal, Santos separates the Carajás region from the
Cental Amazon Province, the Maroni–Itacaiunas becomes the Transamazonian
Province, the Venturari–Tapajós is hereinafter referred to as Tapajós–Parima Province,
the Rio Negro–Juruena is divided into the Rio Negro and Rondônia–Juruena Provinces,
and the Sunsás belt is increased on the Brazilian territory. This proposal was updated
on 2006, with subtle modifications that are presented on the map of Figure 1. Perhaps
the point of most significant divergence between the existing models that concerns
this study, refers to the limit between the Tapajós and the Juruena region at southern
AC, where the Alta Floresta Mineral Province is located. Whereas Tassinari and

22
 Part I – Introduction, Methods and Geologic Framework
Macambira’s model positions the limit along the Cachimbo Ridge at southwestern
Pará, Santos’ model extends the Tapajós towards southwest. Juliani et al. (2021) brings
a new discussion on the Tapajós and Juruena Mineral Provinces evolution and the
respective metallogenetic implications.

Recently, Carneiro et al. (2019) based on deep processed magnetic data

proposed a new tectonic setting for the this part of the craton. According to the
authors, the craton would be better divided following E–W lineaments (Paleo-suture
zones) intrinsically related with the AC’s basement. As proposed by the model, the
basement would comprise Archean crust that was previously restricted to the Carajás
Province, and would extend through the Central Amazon and Tapajós–Parima
Provinces. The model was supported by strongly negative εNd results (< –8.36)
coupled with >2.5 Ga TDM model ages within the Tapajós region (e.g. Sato, 1998;
Echeverri Misas, 2015; Cassini, 2016), even though the significance of Sm-Nd model
ages for arc-related rocks is dubious. Yet, direct evidence such as inherited Archean
zircon cores are restricted to one grain acquired by Santos et al. (2004), dated at 2733
±9 Ma. A brief summary and the main features of the tectonic provinces of the
Amazonian Craton is presented on the following subsections.

1.4.1. Carajás Province

The Carajás Province, eastern AC hosts world-class base-metal deposits related

with granitic rocks, ultra-mafic intrusions and metasedimentary sequences with ages
that vary from 2.7 to 1.9 Ga. Among the main examples are the N4-N5 and S11D BIF–
hosted Fe deposits (16 Gt at 63% Fe, Figueiredo e Silva et al., 2013); the Salobo (1,112
Mt at 0.69% Cu and 0.43 g/t Au) and Sossego (335 Mt at 1.1% Cu and 0.28 g/t Au, ref)
IOCG deposits (Schutesky and de Oliveira, 2020); and the Luanga and Lago Grande
mafic complexes with Cr–Ni–PGE deposits (Mansur and Ferreira Filho, 2016). The
province is tectonically divided into the Rio Maria (Mesoarchean) and Carajás domains
(dominantly Neoarchean) structured on the WNW–ESE trend. The Rio Maria domain
comprises ca. 3.05 – 2.85 Ga rocks that belong to the Andorinhas Supergroup
(greenstone belt) and also encompasses the Caracol and Arco Verde and other <1.88

23
 Part I – Introduction, Methods and Geologic Framework
Ga A-type affinity granitoids. The Carajás domain is structured on the Xingu and Pium
Complex (TTG, migmatites and granulites) and on the Sapucaia greenstone belt. The
cover is represented by metavolcano-sedimentary sequences of the Itacaiunas
Supergroup, with interlayed basic to intermediate volcanic rocks, and mafic, ultra-
mafic and <1.8 Ga granitic intrusions. The late Paleoproteorozoic (ca. 1.8 Ga) A-type
magmatism is also present in the Carajás domain (Cigano, Serra dos Carajás and Pojuca
granites).

1.4.2. Central Amazon Province

The province comprises intermediate to acid volcanic rocks (Iriri, Surumu,

Burro-Burro, Caicara and Iricoumé Group); A-type intrusions related with the ca. 1.88
Ga Uatumã magmatism (Maloquinha, Mapuera and Saracura Intrusive Suites); with
later siliciclastic cover (Palmares, Roraima and Urupi groups); and later tholeiitic
affinity sills and dykes. Little is known about the province’s basement, and Santos et al.
(2000) consider it to be essentially Archean. Interestingly, the province truncates the
NW trending structures from the Carajás region, implying in slightly younger ages for
the Central Amazon Province.

1.4.3. Transamazonian Province

It comprises granite-greenstone belt terrains with collisional and post-

collisional granites related with the Transamazonian orogen (2.3 – 2.0 Ga). Isotopic
data point to at least four cicles: i) 2.26 – 2.2 Ga; ii) 2.18 – 2.12 Ga; iii) 2.09 – 2.05 Ga;
iv) 2.01 – 2.0 Ga. The first two events involve accretion of greenstone sequences and
juvenile continental crust. The last two events involve the formation of magmatic-arc
and collisional granitoids. The oldest blocks reported in the province are found in the
central part of Amapá, and are represented by ca. 2.5 Ga granulites (Santos et al.,
2000).

24
 Part I – Introduction, Methods and Geologic Framework

1.4.4. Tapajós-Parima Province

On Santo’s and on Tassinari and Macambira’s models, the Tapajós-Parima (or

Ventuari-Tapajós Province) represents a series of orogenic-belts accreted to the
Central Amazon Province. The accretion process would be responsible for the
formation of several magmatic-arcs on the 2.0 – 1.89 Ga interval, with <1.88 Ga post-
orogenic units (Maloquinha and Iriri Group volcanics).

More recent U-Pb dating suggests two age-groups on the TMP region, both
characterized by intrusive and extrusive sequences: 2.0 – 1.95 Ga rocks, hereinafter
older-magmatic-sequence (OMS); and 1.89 – 1.86 Ga rocks, hereinafter younger-
magmatic-sequence (YMS) (Lamarão et al., 2002; Aguja-Bocanegra, 2013; Echeverri
Misas, 2015; Tokashiki, 2015; Cassini, 2016; Gutiérrez, 2018). Regardless of the
tectonic model and evolution, TMP is vastly dominated by granitic rocks. The main
lithostratigraphic units are represented by the: Cuiú-Cuiú Complex (metatonalites and
metabasalts); the Creporizão Intrusive Suite (monzo- and sienogranites); Tropas
Intrusive Suite (tonalites and granodiorites); Parauari Intrusive Suite (granitic); and the
Maloquinha Intrusive Suites (alkali-feldspar and syenogranites) (Santos et al., 2000,
2001, 2004). A few gold deposits and many occurrences described in the TMP, such as
the Tocantinzinho, Patrocínio, Batalha and Palito gold deposits are related with the
OMS and YMS rocks (Juliani et al., 2002; Echeverri Misas, 2015; Cassini, 2016; Borgo et
al., 2017).

Volcanic rocks were reported by Tokashiki (2015) in southern TMP (ca. 1.97 Ga
rhyolites), but the majority of the extrusive manifestation in the region belongs to the
ca. 1.88 – 1.87 Ga Iriri Group. The later is divided into the Bom Jardim, Salustiano, Aruri
and Moraes Almeida formations. The first comprises basalts, andesites, dacites and
rhyolites (BADR), with associated pyroclastic deposits representing the pre-caldera
rocks association (Juliani et al., 2005). The Salustiano and Aruri formations represent
the caldera dynamic, with rhyolitic to dacitic pyroclastic deposits and volcanic breccias.
The high- and low-sulfidation epithermal deposits described in the TMP are related
with these rocks (e.g. Aguja-Bocanegra, 2013; Juliani et al., 2005). The Moraes Almeida

25
 Part I – Introduction, Methods and Geologic Framework
Formation comprises rhyolites and trachytic sequences with pyroclastic deposits with
A-type geochemical affinity that resembles the Maloquinha signature. Depending on
the geographic position, particularly towards the Central Amazon Province, the
volcanic rocks from the Iriri Group are also individualized on the Sobreiro, Iriri and
Santa Rosa formations. The first comprises high-K calc-alkaline to shoshonitic BADR
rock association with pyroclastic deposits. The Iriri Formation is represented by dacites
and rhyolites flows and the Santo Rosa Formation comprises fissure controlled
volcanism with extensive effusive association and minor coeval, A-type granitic stocks
(Juliani and Fernandes, 2010). A summary of the main lithostratigraphic units identified
in the TMP, with the respective tectonic setting and associated mineral deposits is
presented on Table 1.

1.4.5. Rondônia–Juruena Province

The province is divided into the Jamari and Roosevelt–Juruena domains. The
first comprises medium to strongly metamorphosed sedimentary cover and rapakivi
granites that represent arc-related and subsequent anorogenic magmatism of ca. 1606
e 1532 Ma (Bettencourt et al., 1999). The Roosevelt–Juruena domain is poorly known,
but in summary it comprises arc-related granitoids, volcanic cover (Beneficente,
Roosevelt and Colíder groups) and anorogenic magmatism (Teles Pires Suite) within
the 1.84 –1.74 Ga age interval. The region guards important metallogenetic relevance
as it holds the tin and gold producing Rondonian and Alta Floresta Provinces
respectively. The first shows mineralization related with metaluminous and
peraluminous, A-type, late-Paleo to Neproterozoic granites, that other than Sn show
recoverable resources of W, Ta and Nb (Bettencourt et al., 2016, 1999). The Alta
Floresta Province shows Au–Ag magmatic hydrothermal mineral deposits related with
calc-alkaline, I-type, metaluminous to peraluminous granitic intrusions of 1.98 – 1.7 Ga
(Assis, 2015).

26
 Part I – Introduction, Methods and Geologic Framework

1.4.6. Rio Negro Province

The Rio Negro Province is delimited to the east by the Tapajós–Parima Province
and its boundary with the Sunsás belt isn’t well established yet. The province is built on
the tonalites and granodiorites from the Cauaburi Complex dated at 1798 ±3 Ma e
1796 ±7 Ma (Santos et al., 2006, 2000). The province encompasses different granitic
intrusions of 1700 Ma (Marauiá Suite) and the ca. 1540–1510 Ma (Icana and Uaupés
suites), interpreted as magmatic arcs (Santos et al., 2000). Collisional to late-collisional
magmatism has also been reported and was responsible for lower crust reworking
Tiquié and Marié-Mirim suites (Almeida et al., 1977). Mafic to ultramafic intrusions are
grouped on the Tapuruquara Suite and is represented by NW–SE trending dyke
swarms and late metasedimentary cover belong to the Tunuí Group.

1.4.7. Sunsás and K’Mudku Provinces

The Sunsás Province is located at the southwestern part of the AC and the
K’Mudku belt is located at northern AC, both representing the effects of the
Greenvillian Orogeny upon the coalescence of the Amazônica and Laurentia
paleoplates. Differently than Sunsás, that is represented by at least four orogenic
cycles, the K’Mudku belt is understood as an intracratonic shearing zone (Santos et al.,
2006, 2000). Among the four orogenic cycles that are encompassed within the Sunsás
Province are the Santa Helena, Candeias, San Javier and Nova Brasilândia orogens,
each one characterized by granitic magmatism with ages that vary from 1.4 to 1.1 Ga
(Geraldes et al., 2001).

27
Table 1
Summary of the main igneous suites that encompasses TMP’s older and younger magmatic sequences
Geotectonic Context (references Hosted mineral
Lithostratigraphic Unit Description
between brackets) deposits (*)

Maloquinha Intrusive
Biotite syenogranite and alkali-granite Post-orogenic (1;2;3) -
Suite (1.87 – 1.86 Ga)(2;3;5)
 Rhyolite and trachyte (Moraes Almeida fm)  Post-collisional/anorogenic (5;6) V3 (Au)
(4)
 Tuff, ignimbrite and volcanic breccias (Aruri fm) 
Magmatic-arc/post-orogenic
Iriri Group
Younger  Rhyolite and ignimbrite (Salustiano fm) Chapéu do Sol
1.89 - 1.87 Ga (2)  Magmatic-arc (4)
Magmatic  Andesite, dacite, trachyandesite, latite, rhyolite (Cu-Mo-Au)**
Sequence  Magmatic-arc (4)
and ignimbrite (Bom Jardim fm)
(YMS)
Parauari Intrusive Suite Biotite-hornblende monzo- and syenogranite, Magmatic-arc (2;3); Post- Batalha (Au)
1.89 - 1.87 Ga (2;3;6) tonalite, granodiorite collisional (6) Palito (Au-Cu)
Tropas Suite
Tonalite and granodiorites Island-arc (2;3) -
1.90 - 1.88 Ga (2)
Creporizão Intrusive Suite Patrocínio (Au)
Older Monzo-, syenogranite, granodiorite and tonalite Magmatic-arc (2;3)
1.98 - 1.95 Ga (2;3) Tocantinzinho (Au)
Magmatic
Sequence Vila Riozinho Formation
Basaltic-andesite, trachyte, rhyolite Magmatic-arc (5) -
(OMS) 2.00 Ga (5)
Cuiú-Cuiú Complex
Gneiss, migmatite, granitoids, amphibolite Island-arc (1;2;3); Magmatic-arc (6) -
2.04 - 1.99 Ga (1;2)
Quartzites, metapelites, metavolcanics,
Jacareacanga Group Back-arc and trench derived sediments/oceanic crust (1;3)
metachert
(*) The São Jorge and Coringa deposits haven’t been correlated with any TMP lithostratigraphic unit; **The Chapéu do Sol deposit is associated with both
older and younger magmatic sequences. (1) Santos et al. (2000); (2) Santos et al. (2001); (3) Santos et al. (2004); (4) Juliani et al. (2005); (5) Lamarão et al.
(2002); (6) Juliani et al. (2002).
 Part II – Results (Cassini et al. 2020)

2. Results (Lithos publication available as supplementary material, DOI:

10.1016/[Link].2019.105350)

Orosirian Magmatism in The Tapajós Mineral Province (Amazonian Craton): The

Missing Link to Understand the Onset of Paleoproterozoic Tectonics

Lucas Villela Cassini¹, Jean-François Moyen², Caetano Juliani¹

¹ Universidade de São Paulo, Instituto de Geociências, Programa de Pós-Graduação em

Recursos Minerais e Hidrogeologia

² Université de Lyon, UJM-UCBL-ENSL-CNRS, LGL-TPE, 23 rue Dr. Paul Michelon,

42023, Saint Etienne, France

Abstract

The Tapajós Mineral Province (TMP) located at south-central Amazonian Craton is

dominated by igneous suites that show geochemical and petrologic evidence of a long-
lived subduction process accounting for continental crust generation. The process
lasted for approximately 100 Ma and yielded in different intrusive and extrusive
manifestations within the 1.99 – 1.89 Ga interval. At its initial stage, arc magmatism is
characterized by a strong crustal component on the magmas possibly due to
subcrustal-erosion upon the onset of subduction. After this phase, metaluminous
primary melts provided by the subduction zone gradually differentiate to
peraluminous compositions, the case for the ca. 1.98 - 1.95 Ga Creporizão Intrusive
Suite (CRP) and its extrusive correspondences. Geochemical modelling reveals that the
first bursts of magmatism at the TMP (at ca. 1.99 Ga) evolved through pyroxene
fractionation, whereas the following pulses are amphibole-bearing. As the arc evolves,
the mantle wedge gets progressively metasomatized and hydrated, eventually melting
to generate the high-K metaluminous to mildly peraluminous granitoids of the ca. 1.89
Ga Parauari Intrusive Suite (PAR), accompanied by more evolved εNd(1.88). The first
pulses of the Iriri Group volcanism are synchronous with PAR, nevertheless, Nd
isotopes point to different sources. Around 1.87 Ga, slab break off provokes

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 Part II – Results (Cassini et al. 2020)

asthenospheric upwelling, which is responsible for destabilizing and melting of the

subcontinental lithospheric mantle severely metasomatized by the previous magmatic
events, generating shoshonitic and metaluminous melts with variable degrees of crust
assimilation, translated into mildly negative εNd(1.86) of the Maloquinha Intrusive Suite
(MLQ) and Iriri volcanic rocks at an early-anorogenic tectonic setting. Geochemical
modelling and the depletion in Ba, Sr and Eu of MLQ and part of Iriri are compatible
with early extraction of plagioclase and support the relatively dry evolution of these
units. In addition, fractional crystallization alone cannot account for the geochemistry
variability of MLQ and Iriri, reinforcing crust assimilation on their petrogenesis. In
terms of metallogenetic potential, CRP and PAR have petrologic evolutions consistent
with amphibole and magnetite crystallization, pointing to hydrated and oxidized
magmas that might be considered as favorable for the formation of magmatic
hydrothermal mineral deposits (porphyry Au–Cu–(Mo) and epithermal systems).
Lastly, the magmatic events younger than 1.89 Ga might act incorporating residual Au-
rich sulfide from the mantle, explaining the Au-only characteristic of many mineral
deposits described at the TMP.

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 Part II – Results (submitted to Ore Geology Reviews)

3. Results (submitted to Ore Geology Reviews)

Towards the fertility trend: unraveling the economic potential of igneous

suites through whole-rock and zircon geochemistry (example from the
Tapajós Mineral Province, Northern Brazil)

Lucas Villela Cassini1, Jean-François Moyen², Gabriel Cellier¹, Bruna de Freitas¹, Caetano
Juliani¹, Oscar Laurent³

¹ Universidade de São Paulo, Instituto de Geociências, Programa de Pós-Graduação em

Recursos Minerais e Hidrogeologia

² Université de Lyon, UJM-UCBL-ENSL-CNRS, LGL-TPE, 23 rue Dr. Paul Michelon,

42023, Saint Etienne, France
4
Department of Earth Sciences, Institute for Geochemistry and Petrology, ETH Zürich,
Clausiusstrasse, 25, Zürich 8092, Switzerland

Abstract

Magmatic hydrothermal mineral deposits axiomatically frame the hosting pluton and
the given tectonic setting in which they are inserted. Unsurprisingly, Precambrian
porphyry deposits appear to be different than Phanerozoic examples, as collisional or
post-collisional deposits are different than arc-related mineralizing systems. As such,
this contribution assesses the tectonic framework and the magmatic evolution of the
igneous suites present in south-central Amazonian Craton (Tapajós Mineral Province,
TMP), and how these parameters translate into metallogenetic potential for the
formation of magmatic-hydrothermal copper, molybdenum and gold deposits. For this
purpose we gathered whole-rock geochemistry data from selected TMP copper and
gold deposits and present new in situ trace-element and U–Pb analyses in zircon.

The host rocks of the selected mineralizing systems belong either to the older
magmatic sequence (OMS, 2.00 – 1.95 Ga), or to the younger magmatic sequence
(YMS, 1.90 – 1.86 Ga). Whereas OMS presents characteristics of arc-related rocks, YMS

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 Part II – Results (submitted to Ore Geology Reviews)

represents the evolution towards post-orogenic or collisional setting. OMS might be

divided into groups i, ii and iii granitoids. Group i comprises granites and granodiorites
that mark the onset of the arc-magmatism in the TMP at ca. 2011 Ma. In this stage
rocks are peraluminous, ferroan, anhydrous, show a strong crustal component and fO2
values close to or below the fayalite–magnetite–quartz buffer (ΔFMQ), yielding
metallogenetic unfertile pluton. These rocks correlate with the Cuiú-Cuiú Complex and
comprise samples from the Patrocínio and Tocantinzinho deposits. Group ii granitoids
correlate with the Creporizão Suite and comprise Tocantinzinho, São Jorge, Chapéu do
Sol and Patrocínio deposit samples (with extrusive equivalents in the Coringa deposit).
Rocks are metaluminous to peraluminous, magnesian to ferroan and mark the
evolution of the magmatism towards more oxidizing (0 ≤ ΔFMQ ≤ + 4), hydrous and
metallogenetically fertile conditions at ca. 1986 Ma. Mineralized zones are defined by
gold bearing sulfide veins and veinlets within the potassic or sericitic alteration halos.
Group iii comprises rarer high-K, metaluminous, ferroan, anhydrous and reduced
syenites and monzonites dated at 1993 and 1974 Ma, generated by decompression
melting of metasomatized mantle. By itself, group iii rocks should be considered as
unfertile batches of magma, however, its interaction with the coeval, more hydrous
and oxidized group ii melts, confer these magmas their metallogenetic potential.
Mineralization in group iii rocks is defined by disseminated pyrrhotite–pyrite ±gold
within the sericitic, chloritic and/or carbonate alteration zones.

YMS comprises intermediate and acid rocks that belong to the Parauari Intrusive Suite
and to the Iriri Group. Whereas, intermediate volcanics from YMS evolved on a
hydrous and reduced petrologic trend, acid volcanics and the Batalha and Palito
granitoids evolved on a dry and reduced trend, reflecting a change on TMP’s tectonic
context, from magmatic-arc to a post-orogenic or collisional tectonic setting. Despite
the reduced and anhydrous characteristic of the magmas, YMS’s metallogenetic
potential is related with remobilization or melting of SCLM or lower crustal Au-rich
sulfides formed on the previous magmatic events. Hence, the first pulses of the YMS
might be considered as potentially fertile for the formation of Au-rich magmatic-
hydrothermal deposits.

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 Part II – Results (submitted to Ore Geology Reviews)

3.1. Introduction

The metallogenic process requires the presence of fertile rocks that provide not
only metals but also ligands, fluids and the volatile contents necessary to form an
anomalous concentration and define a mineral deposit. Magmatic-hydrothermal
mineral systems, particularly the copper and gold porphyry-epithermal class, are
genetically connected with oxidized (ΔFMQ > 0), hydrous (2 – 6 wt.% H2O), subduction-
related, intermediate to acid igneous suites, intruded at shallow depths (Cooke et al.,
2013; Loucks, 2014; Pirajno, 2009; Richards, 2015a, 2011a; Sillitoe, 2010; Sinclair,
2007; Sun et al., 2015). Despite the occurrence of porphyry deposits at collisional and
at extensional settings (Chen et al., 2015; Richards, 2015b, 2014, 2009; Wang et al.,
2018), it is unquestionable that these deposits occur preferentially at destructive plate
margins. Therefore, at a given geologic context, it is important in terms of prospective
criteria, to identify which igneous suites are directly related with the magmatic-arc.
This separation is straightforward in Phanerozoic subduction zones such as seen in the
Andean Cordillera or in the west Pacific rim. The problem arises when we look at
ancient and cratonized terrains, where the arc-related sequence appears juxtaposed
with the collisional, post-collisional and anorogenic units. A first order problem in this
case, is that not all arc-magmas are prone to form magmatic-hydrothermal mineral
deposits, even though the reason, processes and features that render a given
magmatic system fertile or not are still unclear (e.g. Zhang and Audétat, 2017). The
physiology of ancient subduction-zones is not particularly helpful and characteristics
such as the absence or diffuse suture zone and ambiguous geochemical signature due
to metamorphism and/or weathering are common caveats. Additionally, whereas
fluid-flux mantle melting is easily achieved in modern subduction zones, yielding
hydrous and metallogenetic fertile magmas, the tectonic and petrogenetic
mechanisms behind Paleoproterozoic (or older) rocks are still dubious. Despite these
peculiarities, the Archean Spinifex Ridge (Mo–Cu) located at eastern Pilbara Craton
(Huston et al., 2007), the Paleoproterozoic Malanjkhand deposit (Cu–Mo–Au) at
central India (Stein et al., 2004) and the Aitik Cu–Au–Ag deposit in northern Sweden
(Wanhainen et al., 2012) are good examples of high-tonnage Precambrian porphyry
deposits.

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 Part II – Results (submitted to Ore Geology Reviews)

Within this topic, the south–central portion of the Amazonian Craton, a region
known as Tapajós Mineral Province (TMP) consists on a promising area (Fig. 1). It
comprises arc-related, collisional and post-collisional igneous suites, that distribute
within the 2.0 – 1.86 Ga age interval and host gold (copper and molybdenum in a
lesser extent) mineral deposits (Borgo et al., 2017; Juliani et al., 2005; Lamarão et al.,
2002; Santos et al., 2004, 2001). Most recent papers describe TMP’s mineralizations as
porphyry–epithermal mineral systems (e.g. Cassini, 2016; Echeverri Misas, 2015; Juliani
et al., 2005; Lopes and Moura, 2019; Tokashiki, 2015), yet, Intrusion-Related-Gold-
Systems (IRGS) (Santos et al., 2001; Villas et al., 2013) and hybrid porphyry–IRGS
models have also been proposed (Biondi et al., 2018; Borges et al., 2009; Juliani et al.,
2002). Despite the effort over the past years, there are still important knowledge gaps
that need to be filled so we can constrain the TMP’s true economic potential.

Ergo, the central point of this study is to investigate how the host rocks of
different mineral deposits at the TMP evolved, examine their general geochemistry
characteristics, pinpoint the main differences and similarities and elucidate how and
why these magmas became fertile. The data approach given by Loucks (2014), for
example, where the author constrains the fertility of plutons by looking at their
geochemical signature (i.e. copper-producing plutons show higher whole-rock Sr/Y and
V/Sc ratios, used as proxies to the hydrous condition of the magmas) is rather
pertinent for our purpose. In this regard, we gathered information and organized a
geochemistry database for selected Au–Cu–Mo mineral deposits and occurrences
identified in the TMP. In addition, we provide new U–Pb and trace-element analyses in
zircon grains from samples collected at central TMP to assess the magmatic evolution
of the intrusions. Cerium content in zircon is used to estimate the oxygen fugacity of
the rocks and consequently their metallogenetic potential (i.e. typical porphyry
deposits are genetically related with plutons with fO2 greater than the fayalite–
magnetite–quartz oxygen buffer (Richards, 2015a). Ultimately, by combining both
empirical and theoretical approaches, our purpose is to establish a prospective criteria
and a systematic capable of constraining the metallogenetic potential of different
igneous suites not only from the TMP, but also from other cratonic terrains.

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 Part II – Results (submitted to Ore Geology Reviews)

3.2. Geologic Framework of the Tapajós Mineral Province

The Tapajós Mineral Province (TMP) is part of the south-central Amazonian

Craton (AC), on the limit between the Ventuari-Tapajós or Tapajós-Parima and Central
Amazonian tectonic provinces (Santos et al., 2000; Tassinari and Macambira, 1999).
According to Santos’ tectonic model (Fig. 1), the Tapajós-Parima Province is the result
of a Paleoproterozoic collisional-orogen that, among other consequences, was
responsible for the expressive orogenic and post-orogenic magmatism that
predominates in the region. This model has been revisited by many authors over the
past years. More recently, Carneiro et al. (2019), supported by high-resolution
magnetometry data, claim that the magmatic-arc sequence was built on Archean
basement, previously restricted to the Central Amazonian and Carajás Provinces.
According to the authors, NNW-SSE lineaments that agrees with Santos’ model are
intrinsically related with the shallower crustal levels, whereas deeper (>15 km) E-W
trending lineaments are related with the Archean basement, which led the authors to
suggest an alternative crustal framework for this part of the AC.

3.2.1. Lithostratigraphy

In general, the older units described at the TMP represent different stages of
the arc magmatism, whereas the tectonic affinity of the younger sequence remains
less consensual (Table 1 presents a summary of TMP’s lithostratigraphic units). The
igneous suites within the 2.0 – 1.95 Ga age interval, addressed hereafter as the older
magmatic sequence (OMS), encompasses: the Cuiú-Cuiú Complex (tonalites and
granodiorites of ca. 2.04 - 1.99 Ga); the Vila Riozinho Formation (basaltic-andesite,
trachyte, rhyolite of 2.0 Ga); and the Creporizão Intrusive Suite (granitoids of ca. 1.98 -
1.95 Ga, ages after Lamarão et al. 2002; Santos et al., 2004, 2001, 2000).

Approximately 50 million years separate the OMS from the younger magmatic
sequence (hereafter YMS). The Tropas and Parauari Intrusive Suites (1.90 – 1.87 Ga)
mark the onset of the younger magmatism, characterized by tonalite and
granodiorites, with syeno-, monzogranites and acid volcanics for the later. These are

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 Part II – Results (submitted to Ore Geology Reviews)

followed by the volcanic rocks of the Iriri Group and its subdivisions, accordingly: Bom
Jardim Formation (intermediate to acid volcanics with subordinate ignimbrites of 1.89
– 1.88 Ga); Salustiano and Aruri Formations (rhyolites, ignimbrites of dacitic
composition and volcanic breccias of 1.88 – 1.87 Ga); and Moraes Almeida Formation
(rhyolites and trachytes of ca. 1.88 Ga, ages and descriptions after Dall’Agnol et al.,
1999; Juliani et al., 2005; Lamarão et al., 2002; Santos et al., 2000)). Often, YMS
volcanics define dykes or lava flows covering OMS plutons. The Maloquinha Intrusive
Suite represents the last stage of YMS and comprises syeno- and alkali-feldspar
granites of ca. 1.87 Ga (Lamarão et al., 2002; Santos et al., 2002) that define round
shaped plutons.

3.2.2. Typology and General Features of the Mineralizing Systems

at the TMP

The results presented in this contribution refer to selected mineral deposits

chosen in order to cover most part of the TMP. Accordingly, the Batalha, V3 and
Chapéu do Sol gold deposits are found in northern TMP; central TMP is represented by
the Tocantinzinho, Palito and São Jorge gold mineralizations; and the Patrocínio and
Coringa gold deposits are found in southern TMP. The Patrocínio, Tocantinzinho and
Coringa deposits are hosted by the OMS, the first two by ca. 1.97 Ga granitoids that
correlate with the Creporizão Intrusive Suite, and the latter is found within coeval
volcanics. The Batalha, Palito and V3 deposits are hosted by YMS granitoids and
volcanic breccias (the case for the later), whereas the São Jorge and Chapéu do Sol
deposits are uniquely associated with both magmatic sequences (Echeverri Misas,
2015; Lamarão et al., 2002). Table 2 summarizes the main features of the mineral
deposits selected at this study.

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 Part II – Results (submitted to Ore Geology Reviews)

[Link]. Deposits Within the Older Magmatic Sequence

(OMS)

The Patrocínio gold mineralization (southern TMP) is found in strongly

hydrothermalized (K-metasomatism and sericitic alteration), calc-alkalic,
metaluminous to peraluminous, syeno- and monzogranites of ca. 1.97 Ga (Figs. 2a –
2i), into which gold bearing sulfide veins and veinlets are injected (Cassini, 2016). A
disseminated type of mineralization was also identified and is associated with syenites
and monzonites (Figs. 2j – 2m) affected by sericitic, chloritic and carbonate
hydrothermal alterations, where the mineralization is characterized by the assemblage
pyrrhotite-pyrite ±gold, with traces of chalcopyrite. On the distal zones, barren
propylitic alteration was identified and commonly overprints the potassic and sericitic
alterations. Even though the Patrocínio mineralization has many attributes of porphyry
systems, the magmatic-hydrothermal system still requires additional efforts for a
better understanding and a more detailed comprehension.

The Tocantinzinho gold deposit (central TMP), the largest at the TMP with 1.7
million oz. of gold (Borgo et al. 2017), presents a similar geologic framework. It is
hosted by metaluminous to peraluminous monzogranites, granitic breccias, aplite and
pegmatites of ca. 1.98 Ga, that are affected by an early stage of K-metasomatism,
followed by sericitic, chloritic and carbonatic alterations (Biondi et al., 2018; Lopes and
Moura, 2019). In this context the mineralization is intimately related with the sericitic
alteration and is represented by disseminated gold or quartz-sulfide, gold bearing
veinlets. The most common sulfide is pyrite, however, late forming chalcopyrite,
sphalerite and galena have also been reported. Biondi et al. (2018) claim that the
Tocantinzinho’s magmatic-hydrothermal system shows features that resemble both
intrusion-related-gold-systems (IRGS) and gold-rich porphyry deposits. Lopes and
Moura (2019), on the other hand, are more emphatic and describe the deposit as a
“porphyry-style” mineralization since it lacks typical features of Phanerozoic (stricto
sensu) porphyries.

The Coringa deposit (southern TMP) is hosted by volcanic rocks of ca. 1.97 Ga
(Fig. 2n), with minor intrusive bodies that are coeval with the Creporizão Intrusive

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 Part II – Results (submitted to Ore Geology Reviews)

Suite. According to Tokashiki (2015) the volcanic units are dominantly rhyolites and the
volcanoclastic sequence is represented by volcanic-breccias, lithic-, lapilli- and crystal-
tuffs, with subordinated ignimbrites. The mineralization is hosted by sericitic altered
rhyolites, that define topographic domes, and is focused on brittle structures
represented by quartz bearing veins and veinlets with galena, pyrite, chalcopyrite and
gold (Fig. 2o). Due the presence of adularia and Mn-carbonates on the mineralized
vein, the author describes the Coringa deposit as a low-sulfidation system that evolves
to an intermediate-sulfidation, and don’t discard the potential of a deeper and
genetically connected porphyry system. Measured and indicated reserves sum a total
of 516.000 oz. of gold (Tokashiki, 2015).

The Chapéu do Sol (copper, molybdenum and gold) mineralization (northern

TMP) is genetically related with volcanic and volcanoclastic sequences, with coeval
porphyry and granitic stocks, formed in two age intervals: one at 1.99 – 1.97 Ga and a
100 Ma younger one, at 1.88 – 1.86 Ga (Echeverri Misas, 2015). The high-K affinity of
the igneous suites led the author to suggest a mature arc tectonic context. The
mineralization is represented by disseminated sulfide (pyrite, chalcopyrite,
molybdenite and sphalerite), or gold bearing sulfide veins and veinlets, more
frequently found on the sericitic alteration halos with adularia. Echeverri Misas (2015)
describes the Chapéu do Sol mineralization as a low-sulfidation system.

[Link]. Deposits Within the Younger Magmatic Sequence

(YMS)

Among the deposits hosted by the YMS, the Batalha, Palito and São Jorge are
hosted by biotite and amphibole bearing syeno- and monzogranites, whereas the V3 is
hosted by intermediate to acid volcanic rocks.

The Batalha gold deposit (northern TMP) is a magmatic-hydrothermal system

hosted by granitoids of 1.88 Ga that correlate with the Parauari Intrusive Suite (Juliani
et al., 2002). The hydrothermal system is characterized by early Na-metasomatism,
followed by potassic, propylitic and late sericitic alterations (the latter two the most

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 Part II – Results (submitted to Ore Geology Reviews)

important for the mineralization). Within the propylitic zone, ore consists in
disseminated pyrite with gold inclusions, or gold bearing quartz veins with carbonate,
fluorite, pyrite, chalcopyrite and chlorite. On the sericitic zone, gold mineralization is
found either on fissures or in pervasive style with quartz, sericite, pyrite, chalcopyrite
and galena. As proposed by Juliani et al. (2002) the Batalha hydrothermal system is
compatible with a porphyry Au-Cu deposit, with some features of IRGS.

The Palito gold and copper deposit (central TMP) is hosted by ca. 1.88 Ga
granitoids that according to Echeverri Misas (2015) correlates with the late stages of
the Parauari Intrusive Suite, on a collisional or post-collisional tectonic setting. It
presents potassic, propylitic and sericitic hydrothermal alteration zones and
mineralization consists mainly on sulfide bearing, NW-SE and E-W trending quartz
veins and veinlets within the sericitic alteration halo, with less frequent disseminated
sulfides (Figs. 2p – 2t). Chalcopyrite is the main sulfide associated with the gold
mineralization, but pyrite, galena, pyrrhotite and Bi bearing minerals were also
identified. Echeverri Misas (2015) describes this magmatic-hydrothermal system as a
porphyry Au-(Cu) deposit.

The São Jorge gold deposit (central TMP) is hosted by the homonymous granite
that was divided by Lamarão et al. (2002) on the older and younger São Jorge granites
(1.98 and 1.89 Ga respectively), the latter more closely related with the mineralization.
Similarly to the Batalha deposit, it shows mineralization focused on the propylitic and
sericitic alteration halos, where gold is usually associated with pyrite veins and
veinlets. A disseminated type of mineralization is also identified but is comparatively
rarer. Other than pyrite chalcopyrite, sphalerite, molybdenite and galena were also
described (Borges et al., 2009; Lamarão et al., 2002). Borges et al. (2009) claim that the
deposit has geological attributes of both IRGS and porphyry systems.

Differently than the other YMS hosted deposits, the V3 gold mineralization
(northern TMP) is associated with hydrothermal breccias developed on the volcanic
and volcanoclastic sequence of the Iriri Group (1.89 - 1.87 Ga), with coeval shallow
level granitic stocks. The hydrothermal system comprises pervasive and fissural
potassic, silicic, propylitic, sericitic, argilic and advanced argilic alunite bearing

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 Part II – Results (submitted to Ore Geology Reviews)

alterations. The latter hosts the highest gold contents, however, the potassic,
propylitic and sericitic alteration zones also show considerable sulfide contents.
40
Ar/39Ar dating in alunite crystals acquired by Echeverri Misas (2015) yielded 1.86 –
1.84 Ga, which is interpreted as the age of mineralization. The author describes the
deposit as a high-sulfidation epithermal system.

In fact, YMS volcanic rocks are often found as dykes in OMS granitoids (the
association has been reported in the Tocantinzinho, Patrocínio and Palito deposits) and
potentially define an additional type of mineralization, characterize by gold bearing
pyrite veins and veinlets injected along the contact between the intrusive and
subvolcanic units (Fig. 2u).

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Table 2
Host rocks, mineralizing style and hydrothermal alteration evolution of the selected TMP mineral deposits.
Deposit/ Hydrothermal Alteration
Mineralization
Mineral Host Rocks References
Style Sodic Potassic Propylitic Sericitic Argilic Adv. Argilic
occurrence
Pyr, Alu, Dsp,
1.89 - 1.87
Hydrothermal Pl, Kfs, Qz, Ser, Rt, And, Sul,
V3 Ga volcanic Kfs, Amp, Bt, Qz, Dk, Ser, Chl, Dk, Kao, Ser,
breccias and Pl Chl, Ep, Cab Cu, Ag, Au, Echeverri Misas (2015)
(Au) rocks (Iriri
veins
Qz, ±Hm ±Sul
±Amp ±Sul
±Alu ±Sul Chl, ±Pl ±Kfs
±Hm ±Dk
Group)
±Kao
Kfs, Qz, ±Pl
Palito 1.88 Ga Veins and Pl, Bt, ±Kfs Pl, Ser, Chl, Ep, Pl, Kfs, Qz, Ser, Pyr, Kao, Ser,
±Amp ±Bt - Echeverri Misas (2015)
(Au - Cu) granitoids disseminated ±Amp ±Qz
±Hm
Ttn, Cab ±Sul Sul ±Au ±Cu Sul ±Pl ±Kfs

Batalha 1.88 Ga Veins and Pl, Chl, Ep, Cab, Qz, Ser, Sul, Au,
Pl Kfs, Bt, Qz - - Juliani et al. (2002)
(Au) granitoids disseminated Sul, ±Qz ±Au Fl ±Cab
Pl, Bt, Chl, ±Ep
São Jorge OMS and Veins and Qz, Cab, Sul, Lamarão et al. (2002); Borges et
Qz, Pl, Kfs, Bt, Ttn, Mag ±Cab ±Ser ±Sul - -
(Au) YMS granites disseminated
±Mag ±Qz ±Kfs
Ser ±Pl ±Kfs ±Bt al. (2009)

OMS and
Chapéu do Disseminated, Pl, Qz, Chl, Ep, Qz, Ser, Adu,
YMS Qz, ill, Kao
Sol veins and Pl Pl, Bt, Kfs, Qz Rt, Ttn, Sul, Cab, Sul, Au, ±Ttn - Echeverri Misas (2015)
volcanics and ±Hm
(Cu - Mo - Au) veinlets ±Hm ±Amp ±Cab ±Bt
subvolcanics
1.99 - 1.95
Veins and
Patrocínio Ga granites,
veinlets Pl Kfs, Qz Chl, Ep, sodic-Pl Ser, Py, Po, ±Au Chl, ±Ccp - Cassini (2016)
(Au) syenites and
±disseminated
monzonites

Ser, Py, Au, Qz, Borgo et al. (2017); Lopes and

Tocantinzinho 1.98 Ga Disseminated Kfs, Qz, Pl, Ep, Chl, Py, Ccp, Au
- Ccp, Gn, Sp, - - Moura (2019); Biondi et al.
(Au) granites and veinlets ±Hm
±Hm ±Pl (2018)

Coringa Veins and Chl, Ep, Qz, Pl, Qz, Ser, Ccp,
1.97 rhyolites - Kfs, Bt, ±Qz ill - Tokashiki (2015)
(Au) veinlets ±Cab ±Py Sp, Gn, ±Adu

Adu: adularia; Alu: alunite; Amp: amphibole; And: andalusite; Bt: biotite; Cab: carbonate; Ccp: chalcopyrite; Chl: chlorite; Dk: dickite; Dsp: diaspore; Ep: epidote; Fl:
fluorite; Gn: galena; Hm: hematite; ill: illite; Kao: kaolinite; Kfs: K-feldspar; Mag: magnetite; Pl: plagioclase; Po: pyrrhotite; Py: pyrite; Qz: quartz; Rt: rutile; Ser:
sericite; Sp: sphalerite; Sul: sulfide; Ttn: Titanite.

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Fig. 2. Typology of the different OMS (a – o) and YMS rocks (p – u). (a) Massive,
leucocratic, granodiorite drill core sample. (b) Massive, partially altered (potassic
alteration), granodioritic porphyry; (c) Porphyritic and massive syenogranite with
compositionally zoned plagioclase phenocrysts; (d) Syenogranitic porphyry with
plagioclase phenocrysts (outcrop near the Patrocínio area); (e) Equigranular, massive
monzogranite; (f) Strongly altered (potassic alteration) granite, with gold bearing pyrite
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in chlorite-sericite veinlets; (g) Sulfide bearing, chlorite-sericite alteration in K-

metasomatized granitoid; (h) Gold bearing, quartz sulfide vein injected near the
granite-syenite contact. Rocks have previously experienced pervasive potassic and
subsequent chlorite-sericite alteration; (i) Granite drill-core sample with multi-phasic
hydrothermal events. early potassic alteration (reddish feldspar crysts) is followed by
fissural and interstitial chlorite-sericite alteration (gray-greenish color). The last
hydrothermal event is represented by the white-silica infilled breccia; (j) Drill core
sample with contact between monzonite (left) and monzogranite (right) with a
reaction rim (central) and small opaque (sulfide?) crysts; (k) Potassic and chlorite-
sericite altered syenite; (l) Chlorite-sericite and potassic altered monzonite with
disseminated, gold bearing sulfide (pyrite and pyrrhotite), and less frequent sulfide
veinlets; (m) Aplitic syenite found as synplutonic dykes in OMS granites. (n) Rhyolite
with feldspar phenocrysts and potassic alteration form the Coringa deposit; (o) Coringa
deposit ore example, with strongly sericitic altered volcanic rock (rhyolite?) cross-cut
by a chalcopyrite + sphalerite + galena vein, brecciated by sericitic + white silica
alteration. (p – t) Palito deposit samples (examples from Echeverri Misas, 2015; (p)
potassic altered granite with secondary K-feldspar; (q) potassic and propylitic
alteration with K-feldspar, chlorite, epidote and carbonate (Cal); (r) Sericitic alteration
with quartz (Qtz), sericite (Ser) and pyrite (Py); (s) Sulfide vein in strongly
hydrothermalized granite (5), with (1) chalcopyrite, (2) pyrite, (3) breccia zone and (4)
quartz veins; (t) Strongly hydrothermalized granite with fluorite (6) and white silica
veining (7). (u) OMS granite injected by YMS dacite dyke with white silica, gold bearing
sulfide pocket and smaller veinlets along the dyke contact.

3.3. Methods

The results presented in this contribution refer to whole-rock and zircon

geochemistry/isotopic analyses. The whole-rock geochemistry database counts with
published and unpublished results from selected deposits in order to cover most part
of the TMP, and involves results from Biondi et al. (2018), Cassini (2016), Echeverri
Misas (2015), Gutiérrez (2018), Juliani et al. (2002), Lamarão et al. (2002), Lopes and
Moura (2019) and Tokashiki (2015) (geochemistry database is available as
supplementary material).

Whole-rock geochemistry data was treated with GCDKit (Janoušek et al., 2006)
and modelling routines of fractional crystallization were performed using further R
programming (Janoušek et al., 2016). Major elements were modeled through simple

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mass-balance and trace-elements through Rayleigh crystallization using partition

coefficients from Rollinson (1993) and GERM database (available at
[Link]

Trace-elements and U-Pb geochronology analyses in zircon grains were

performed at the Department of Earth Sciences (ETH - Zürich) using a Thermo Element
XR, sector field, single collector ICP-MS coupled to a 193-nm Resolution S155 (ASI)
laser ablation system. The later counts with a two-volume Laurin Technic ablation cell
fluxed by high-purity He at 0.5 l min-1 rate. The 20 μm spots were ablated for 30
seconds with a repetition rate of 3 Hz and a laser energy of 2 J cm-2. Ar was admixed to
the aerossol within the ablation funnel (0.96 l min-1) to carry the ablated material for
ionization. The integration time per point was 0.662 seconds, and elemental
concentration was calculated using the software Iolite (Paton et al., 2011). The
stoichiometric Si content of zircon (15.2 wt.%) was used as internal standard for trace
element quantification and U-Pb data reproducibility was assured by analyses of
reference zircon grains (AUSZ7-1, OG-1, Plešovice and 91500). U-Pb and trace element
measurements were acquired at the same spot, and fractured or metamict domains
were avoided. Zircon trace element results were treated with GCDKit and U-Pb data
with IsoplotR (Vermeesch, 2018), results are also available as supplementary material.

We use the 𝑋 𝑋 index (Smythe and Brenan, 2016), to constrain the fO2
of the magmas from central TMP (equations 1 and 2). Most zircon based oxy-
barometers available in the bibliography (Ballard et al., 2002; Chelle-Michou et al.,
2014; Smythe and Brenan, 2016; Trail et al., 2012) rely on the lattice strain model
(Blundy and Wood, 1994) and are strongly influenced by the LREE content of zircon.
The lattice strain model satisfactorily explains the behavior and HREE, but LREE, on the
other hand, commonly deviates from the model predictions, compromising the
robustness of most oxy-barometers. As demonstrated by Zou et al. (2019), Smythe and
Brenan’s 𝑋 𝑋 index might be considered as REE independent and magmatic
fO2 is estimated with basis on the temperature of the magmas (Ti-in-zircon
thermometer from Ferry and Watson (2007), assuming SiO2 and TiO2 activities of 1.0
and 0.65 respectively), non-bridging oxygens (NBO, Virgo et al., 1980) and mole

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fraction of water (estimated with the hygrometer from Waters and Lange, 2015) as it
follows:

⁄
∑ ∑ ∗
1) = ⁄ * 1.04877;
(∑ ∗ ) ∑

(± )
2) 𝑙𝑛 = ln 𝑓𝑂 + − 2.064(±0.011). −

8.878(±0.112). 𝑥𝐻 𝑂 − 8.955(±0.091)

3.4. Results

3.4.1. Whole-Rock Geochemistry

In this section we directly compare whole-rock geochemistry analyses from the

different TMP deposits. As a first selection criteria and in view of the thick weathering
profile at the Amazonian region, the whole-rock geochemical data were plotted on the
MFW diagram after Ohta and Arai (2007) (Fig. 3). The diagram was idealized with basis
on a dataset of igneous rocks and their respective weathered products, where
principal component analysis allows the M and F vertices to capture mafic to felsic
differentiation sequence, whereas the W apex relates with the degree of weathering.
Accordingly, the samples that plot on the center of the diagram and scatter towards
the W vertice likely present some degree of weathering that might disturb their
original geochemical signature and, consequently, these samples were excluded from
the database.

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Fig. 3. FMW ternary diagram after Ohta and Arai (2007) for the whole-rock
geochemistry database. Samples that plot on the shaded area indicate higher degree
of weathering and were not considered for the results and discussion sections.

[Link]. Classification Diagrams

With respect to their geochemical classification, the most prominent difference

between the older and younger igneous suites is the much wider compositional range
covered by the former, in particular for the intrusive sequence (Fig. 4a). The
Tocantinzinho, São Jorge and Patrocínio deposit rocks show a significant variation on
the diagram and vary between diorites, monzonites, quartz-monzonite, granodiorites,
tonalites and granites. The later also shows lower silica syenites, quartz-syenites and
monzodiorites. The Chapéu do Sol rocks show a smaller variation and plot on the
quartz-syenite, granite and alkali-granite fields. Equivalent compositions are verified
for the Coringa deposit, with the extrusive sequence essentially rhyolitic or alkali-
rhyolitic.

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Fig. 4. De la Roche et al. (1980) classification diagram for the OMS (a), with coeval
volcanics from the Coringa deposit at the top-left. (b) Classification diagram for the
YMS with the V3 volcanics plotted at the smaller top-left diagram.

The intrusive sequence of YMS (Palito, São Jorge and Batalha deposits) shows a
much narrower geochemical variation (Fig. 4b). The three deposits host rocks vary
between granite and alkali-granite with a single granodiorite sample for the Batallha
deposit. The V3 deposit is hosted by a volcanic sequence that is dominated by
rhyolites, dacites, lati-andesites and, more rarely, quartz-trachyte.

The diagrams from Figure 5 brings SiO2 vs. Fe-index, SiO2 vs. MALI and an A-B
plot for constraining the sample’s aluminosity (Frost et al., 2001; Villaseca et al., 1998).
In this study we gave preference to use Villaseca’s A-B diagram instead of the classic
A/CNK vs. A/NK plot (Shand, 1943). The former brings aluminosity as a function of
maficity, hence petrologic trends are more promptly identified. In general, OMS
deposit rocks might be separated into three categories: group I comprises ferroan (Fig.
5a), calc-alkalic (Fig. 5b) and preferentially peraluminous granites (s.l.) described in the
Patrocínio and Tocantinzinho deposits (Fig. 5c); group II is defined by magnesian to
ferroan, alkali-calcic to calc-akalic, metaluminous to felsic peraluminous rocks from the
Tocantinzinho, São Jorge, Chapéu do Sol and Patrocínio deposits; and group III is
characterized by ferroan, alkalic and metaluminous to low-peraluminous granitoids
found in the Patrocínio, Tocantinzinho, Coringa and São Jorge deposits.

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Fig. 5. Frost’s classification diagrams for OMS and YMS, with SiO2 vs. Fe-index (a), SiO2
vs. MALI (b), and A-B diagram after Villaseca et al. (1998) (c), where A = Al - (K + Na +
2Ca) and B = Fe + Mg + Ti, calculated for millications. Extrusive rocks from the Coringa
and V3 deposits are plotted for comparison purposes. Groups I, II and III rocks from
OMS are pinpointed on the smaller diagrams.

Within the YMS, the Palito and Batalha samples are ferroan, alkali-calcic and
metaluminous to moderately-peraluminous. On the A-B diagram, the Batalha
granitoids do not define any noticeable trend and instead, samples cluster around the
same value of maficity (at approximately B = 40) and spread towards the low-
peraluminous and moderately-peraluminous fields. The V3 volcanics resemble the
trend identified for the OMS, with magnesian intermediate samples and ferroan acid
members that vary from alkalic to calc-alkalic and define a clear negative slope on the
A-B diagram from metaluminous to felsic-peraluminous.

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[Link]. Major-element contents

As previously mentioned, the São Jorge and the Chapéu do Sol deposits are
associated with both magmatic sequences, however, due to the lack of younger
samples, our models for both deposits will concern only OMS. Harker diagrams for the
OMS show that intermediate samples tend to scatter more strongly than the acid
members and, for silica values over 65%, the trend is linear. Geochemical modelling
shows that fractional crystallization accounts for the geochemical variability within
OMS, which is characterized by three main petrologic trends. Within the higher silica
side (SiO2 > 65 wt. %), one of trends accounts for part of the Patrocínio and
Tocantinzinho samples (group I granites). It starts from a granodioritic melt that
fractionates plagioclase, pyroxene, biotite, magnetite and titanite, with a monzo-
diorite cumulate (green array in Figure 6). The other silica richer trend (group II rocks)
is characterized by a tonalitic initial composition and involves fractionation of albitic
plagioclase, amphibole, biotite, magnetite and titanite (red array in Fig. 6), and is also
compatible with a monzo-diorite cumulate. This trend encompasses most of the OMS,
including the Tocantinzinho, Coringa, Chapéu do Sol, São Jorge (older) granite and part
of the Patrocínio samples. The lower silica spectrum, or group III rocks, involves
syenites and monzonites from the Patrocínio deposit and a few Tocantinzinho, and
Coringa samples that evolved through fractionation of K-feldspar, plagioclase, biotite,
apatite, clinopyroxene and ilmenite (gray array in Fig. 6).

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Fig. 6. Silica vs. major oxides diagrams for OMS rocks (symbols are the same as in the
previous figures). Red, green and gray arrays mark the petrologic trends modeled with
the respective minerals involved. The accuracy of the models is given by the R²
parameter, which is defined by the sum of the differences between the theoretical and
real differentiated melts for each element squared. Abbreviations: Am (amphibole), Pl
(plagioclase), Bt (biotite), Px (pyroxene), Mag (magnetite), Ttn (titanite), Ap (apatite),
Ilm (ilmenite).

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Samples from the YMS, particularly the intermediate rocks, scatter more
strongly than the OMS on the Harker diagrams (Fig. 7). Three trends accounts for the
petrologic evolution of the YMS. Intermediate V3 volcanics show an evolution
coherent with a lati-andesite initial liquid that fractionates K-feldspar, amphibole,
anorthitic-plagioclase and biotite (yellow array in Fig. 7) and generates a quartz-latite
liquid and a diorite cumulate.

The acid members of the V3 deposit define a trend compatible with a rhyolitic
initial composition that differentiates to alkali-rhyolite through fractionation of albitic-
plagioclase, K-feldspar, pyroxene and titanite, with a syenite cumulate (yellow array in
Fig. 7). A relatively similar trend comprises the Batalha and Palito granitoids (black
array in Fig. 7). This evolution starts from a granitic composition and is consistent with
extraction of albitic-plagioclase (44%), K-feldspar (42%), pyroxene (7%), titanite (3%)
and apatite (4%), generating an alkali-granitic liquid and a syenite cumulate.

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Fig. 7. Silica vs. major oxides for YMS rocks. Yellow and black arrays mark the
petrologic trends modeled, with the minerals involved and the R² parameter indicated
at the top. Symbols are the same as in the previous figures. Abbreviations: Kfs (K-
feldspar), Am (amphibole), Pl (plagioclase), Bt (biotite), Px (pyroxene), Mag
(magnetite), Ttn (titanite).

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[Link]. Trace Element Contents

REE spidergrams reveal similar patterns for OMS samples, characterized by a

moderate level of HREE depletion (average La/YbN ≥ 12.1, Figs. 8a – 8e). The steepest
pattern was identified for the São Jorge deposit, in both older and younger granites
(Fig. 8a) with averages La/YbN of 35.4 and 81.5 respectively that are accompanied by
positive to mildly negative Eu anomalies. The Patrocínio samples (Fig. 8b) also define a
steep slope, yet more subtle than the older São Jorge granite, and are accompanied by
null or moderately negative Eu anomalies. The Chapéu do Sol, Coringa and
Tocantinzinho deposits (Figs. 8c – 8e) are characterized by less fractionated trends
(average (La/Yb)N ratios of 19.5, 18.8 and 12.1 respectively) and slight to moderately
negative Eu anomalies.

REE spidergrams for the YMS (Figs. 8f – 8h) show a much more subtle
fractionation between light and HREE when compared with the older sequence (except
for the younger São Jorge granite, Fig. 8a). The Eu anomalies are more restrict and vary
from moderately negative to strongly positive. The V3 volcanic rocks show a moderate
degree of fractionation (Fig. 8f, with average (La/Yb)N of 17.4) and moderately negative
to negligible Eu anomalies. The Palito and Batalha deposit rocks behave similarly (Figs.
8g and 8h, average (La/Yb)N ratios of 10.9 and 8.1 respectively) and define smoother
trends towards lower HREE contents, with moderate to strongly negative Eu
anomalies. The trace-element spidergram (Fig. 8i) shows that YMS is slightly enriched
in HFSE (Ti, Dy, Y, Zr, Sm) and show lower Sr contents.

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Fig. 8. Chondrite normalized (Boynton, 1984) REE spidergrams for the OMS (a – e),
YMS (f – h) and trace-element spidergrams normalized by the primitive mantle (Sun
and McDonough, 1989) for both sequences. The respective colored fields represent
the entire range covered by each deposit/unit. Eu anomaly calculated as Eu/Eu* =
EuN/ (𝐒𝐦𝐍. 𝐆𝐝𝐍).

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Figure 9 shows trace-element ratios plotted against maficity (Fe + Ti + Mg

calculated for millications) or Eu anomaly calculated as EuN/Eu* (EuN = concentration

of Eu normalized by the chondrite after Boynton (1984); Eu* = Sm . Gd ). On the

Dy/Yb vs. maficity plot for the older sequence (Fig. 9a) it’s clear that the older São
Jorge granite is the unit with the largest range of Dy/Yb, and is followed by the
Tocantinzinho and Chapéu do Sol samples that show a minor spread between 1 ≤
Dy/Yb ≤ 2.

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Fig. 9. Maficity vs. Dy/Yb (a), Eu/Eu* vs. Sr/Y (b) and Eu/Eu* vs. La/Yb (c) plots for OMS
and YMS. Dy/Yb ratio is strongly influenced by amphibole as the mineral shows high
Kd’s for both elements. Sr/Y and La/Yb might also be influenced by amphibole,
however, plagioclase and pyroxene on a lesser extent might also shift the ratios
towards higher or lower values.

The Patrocínio and Coringa samples don’t vary significantly and show Dy/Yb
ratio around 2. The younger sequence shows a similar trend and spread horizontally on
the plot, with maficity values between 10 and 200 for a Dy/Yb ratio around 2. The
younger São Jorge granite stands as an outlier and shows Dy/Yb ratio from 2 to 4. The
Sr/Y vs. EuN/Eu* diagram (Fig. 9b) shows a positive correlation between the two
parameters. In general terms, the Patrocínio, Coringa, São Jorge and Chapéu do Sol
show predominantly moderate Sr/Y values that fall between 5 and 50. The only sample
cluster was identified for the Tocantinzinho deposit, that shows predominantly low
ratio (Sr/Y ≤ 5), with scarce exceptions. A similar behavior was identified for the
younger Batalha and Palito granitoids, with Sr/Y ratio ≤ 5. On the other hand, V3
volcanics and the younger São Jorge granite samples show moderate to high ratios
(Sr/Y ≥ 50) followed by null or positive Eu anomalies.

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Both older and younger igneous sequences can be separated into low,
moderate and rarer high La/Yb rocks. On average, the La/Yb and EuN/Eu* correlate
positively. For the OMS, Figure 9c shows that the São Jorge samples vary from
moderate to high ratios (30 ≤ La/Yb ≤ 100). The Coringa, Patrocínio and Chapéu do Sol
samples show predominantly moderate values (20 ≤ La/Yb ≤ 50), whereas the
Tocantinzinho deposit shows mainly low La/Yb rocks (≤ 20). For the younger sequence,
the São Jorge granite shows the highest La/Yb ratios (> 100), which is accompanied by
the highest EuN/Eu*. Moderate values (20 ≤ La/Yb ≤ 50) were acquired for the V3
volcanic units, whereas the Batalha and Palito granitoids show the lowest ratios (La/Yb
≤ 20).

In summary, OMS shows a wide compositional range and rocks vary from
magnesian to slightly ferroan, alkali-calcic to calc-alkalic, metaluminous to moderately
peraluminous and show steep REE patterns. Three trends accounts for the OMS
evolution: a magnetite and pyroxene bearing one involving granodiorites and granites;
an amphibole and magnetite one that comprises most OMS-hosted deposits; and a
third one involving pyroxene and ilmenite fractionation on K-rich magmas. YMS shows
similar MALI and aluminosity, however with a more restrict compositional range and
more subtle REE patterns on essentially ferroan samples (excepted for intermediate
V3). Our models show that these rocks evolved on an reduced and predominantly
anhydrous trend.

3.4.2. Zircon geochemistry

[Link]. Morphology and textural description

At this study we present three new geochronology results from samples

collected at central TMP and reexamine two samples (USP14-136 and USP14-160)
presented by Cassini et al. (2020) for inheritance. Sample USP14-160 (granodiorite) is
characterized by subhedral grains, with rounded or partially corroded edges, 2:1
elongation ratio, with predominantly oscillatory but also broad and patchy zonings.
Round shaped xenocrystic cores displaying both dissolution and resorption textures

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are also common (Fig. 10a). Sample USP14-144 (granodioritic porphyry) is dominated
by euhedral to subhedral, elongated grains (between 2:1 and 3:1), with oscillatory and
less frequent patchy and sector zonings. Two types of cores are observed on this
sample: one comprises rounded, partially resorbed xenocrystic cores (Fig. 10b),

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Fig. 10. Cathodoluminescence images from selected zircon grains and the respective
concordia-discordia diagrams from the samples analyzed in this study. Spots are 20 μm
wide. 1-3, 10, 11, 17-19 (partially dissolved) and 30-32 show inherited xenocrystic
cores (grain 32 is partially resorbed); 4, 5, 14, 20, 25, 26 and 35 show oscillatory
zoning; 6 and 7 are broad zoned grains; 8, 9, 15 and 27 show patchy zoned zircon
grains; 12, 13, 33 and 34 show autocrystic cores; 16, 22, 23, 28, 29, 36 and 37 show
sector zoning; 21 and 24 are homogeneous zoned.

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commonly fractured and metamictic; and the other, comparatively more frequent, is
characterized by oscillatory or homogenously zoned nuclei and lacks dissolution or
resorption textures. Sample USP14-83, an aplite dyke of syenitic composition (R1-R2
classification), comprises euhedral and subhedral zircon grains, with 2:1 elongation
and well preserved oscillatory zoning (Fig. 10c). Round-shaped, partially resorbed
xenocrystic cores with homogeneous, patchy or sector zonings are also observed.
Sample USP14-91 represent a coarser-grained syenite and is characterized by
subhedral to anhedral grains, with elongation that varies between 1:1 and 2:1 (rarer
3:1 grains), predominance of oscillatory zoning with minor examples of sector and
patchy zonings. Cores show predominantly oscillatory and, less frequently,
homogenous zonings with rarer xenocrystic and metamictic domains (Fig. 10d). Sample
USP14-136 (monzonite) is composed by euhedral to subhedral grains, with elongation
between 2:1 and 3:1, with well preserved oscillatory and sector zonings. A detailed
evaluation and description of the grains allowed the identification of two types of
cores: rounded xenocrystic cores that commonly display dissolution textures and
zoning patterns that truncates the rim (Fig. 10e); and comparatively homogenous
rounded cores that show concordant zoning patterns.

[Link]. U-Pb Dating (LA-ICP-MS)

The granodiorite sample (USP14-160) presents a continuous distribution of

207
Pb/206Pb ages between 2000 and 2100 Ma, as demonstrated by the frequency
histograms from Figure 10a, with a more pronounced peak at ca. 2020 Ma. Autocrystic
cores were evaluated and yielded concordant ages of 2031.2 ± 2.0 Ma (n = 15),
whereas 6 xenocrystic cores revealed ages higher than 2050 Ma. Rims analyses yielded
2011.7 ± 4.5 Ma (n = 13) understood as the sample’s magmatic age.

207
The granodioritic porphyry (USP14-144) presents Pb/206Pb ages that spread
from 1800 to 2040 Ma, with a more pronounced peak at ca. 1980 Ma (Fig. 10b). Five
xenocrystic cores were analyzed and yielded concordant results that converge to
2010.9 ± 8.1 Ma. Autocrystic cores and rims point to similar ages, and 22 grains align

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on a discordia with upper intercept at 1986.9 ± 5.9 Ma, considered as the samples
magmatic age.

207
For the aplitic syenite sample (USP14-83) Pb/206Pb age histograms (Fig. 10c)
shows that results concentrate at ca. 1990 Ma, with minor older and younger
examples. A total of 15 xenocrystic cores were evaluated and defined a discordia with
upper intercept at 2012.7 ± 6.7 Ma. Core and rim analyses yielded discordant results
and 16 grains align on a discordia with upper intercept at 1987.3 ± 7.1 Ma, interpreted
as the magmatic age.

207
The syenite sample (USP14-91) also shows Pb/206Pb ages clustered at ca.
1990 Ma (Fig. 10d). Cores and rims analyses converge to a concordia age of 1993.7 ±
2.7 Ma (n = 11). Xenocrystic cores are rare in this sample and were not evaluated.

207
The monzonite sample (USP14-136) shows Pb/206Pb ages that spread
between 1900 and 2060 Ma, with a clear cluster at ca. 1980 Ma (Fig. 10e). Twelve
xenocrystic cores were analyzed and yielded discordant ages that roughly align on a
discordia with upper intercept at 2055.5 ± 8.7 Ma. Cores and rims analyses revealed 18
grains that converge to a concordia age of 1974.6 ± 1.9 Ma, understood as its
magmatic age.

[Link]. Trace element contents

Zircon Eu anomalies are constrained on the diagram from Figure 11a, where
Eu/Eu* is plotted against Zr/Hf (as a proxy for differentiation). At a first glance, all
samples show predominantly Eu/Eu* < 0.5, with a few exceptions for USP14-136, 144
and 160. Accordingly, samples USP14-91 and 144 cover a similar range and Eu/Eu*
varies from 0.1 to 0.5, with a few values closer to unity or higher. Sample USP14-136
defines a gentle negative trend on the diagram, with core Eu/Eu* between 0.1 and 0.5,
and 0.25 to 0.7 for the rims, with minor values greater than 1. USP14-83 also defines a
subtle negative trend, with Eu/Eu* varying from 0.25 on the cores to 0.5 on the rims as
Zr/Hf decreases. Grains from sample USP14-160 scatter on the plot and Eu/Eu* ratio

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varies from 0.1 to 2.0, without any noticeable trend. The most prominent feature
regards the higher Zr/Hf ratio acquired for zircon cores.

The Th/U vs. Dy/Yb plot marks how the zircon grains from all samples evolved
regarding middle- and HREE fractionation and, accordingly, all samples define a
positive trend (Fig. 11b) and zircon cores show higher Dy/Yb and Th/U than the rims.
Sample USP14-83, despite having the most scattered pattern, shows the highest values
for both ratios and grains plot on the upper right part of the graph (Dy/Yb varies from
0.4 to 1.0 and Th/U from 0.5 to 10). Samples USP14- 91 and 144 distribute similarly
and Dy/Yb varies from 0.4 on the cores to 0.2 on the rims as Th/U falls from 1.2 to 0.4
(steeper pattern for USP14-144). Samples USP14-136 and 160 define sub parallel
trends, the later characterized by lower Th/U ratios as Dy/Yb decreases from 0.4 on
the cores to 0.2 on the rims.

The plot from Figure 11c shows the LREE-index (LREE-I = Dy/Nd + Dy/Sm), as
proposed by Bell et al. (2016), plotted against Ti. The parameters correlate negatively
and, for LREE-I values greater than 20, the trend shows a clearer linearity. Roughly all
grains from sample USP14-83, and significant proportion of samples USP14-160, 144
and 136 plots on the scattered part of the graph (LREE-I < 20). Zircon grains from
sample USP14-91, on the other hand, behave more linearly and plot predominantly on
the right side of the graph (LREE-I > 20).

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Fig. 11. Zircon geochemistry with Zr/Hf vs. Eu/Eu* (a) and Th/U vs. Dy/Yb plots (b),
where both Zr/Hf and Th/U ratios were used as proxies for differentiation. Bottom
right smaller graph in (b) shows the polynomial regressions with the general trend for
each sample. (c) Light REE index (LREE-i) as proposed by Bell et al. (2016) vs. Ti plot.
The index is calculated as LREE-i = (Dy/Nd + Dy/Sm), in order to constrain the
proportion between middle and light-REE in zircon grains. Grains with low LREE-i show
high LREE content, which might indicate hydrothermal alteration (or LREE rich
inclusions such as apatite or monazite on the ablated spot).

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[Link]. Ti-in-zircon thermometry

The Ti-in-zircon ([Link]) thermometer after Ferry and Watson (2007) was
applied to constrain magmatic temperatures and the results are summarized on Table
3 (values below 620°C and above 970°C were discarded and not considered on our
database). The plot from Figure 12a shows how [Link] and zircon saturation
temperature ([Link]) (Watson and Harrison, 1983) relate for each sample/grain
analyzed and, accordingly, results distribute in three fields: i) upper part of the plot
where [Link] > [Link] +100, hence zircon-undersaturated field; ii) shaded area
between 1:1 and 1:100 ; and iii) bottom part of the plot with [Link] < [Link], zircon-
oversaturated field. Whereas autocrystic zircons will plot on the bottom and
eventually on field ii, inherited grains (ante- and xenocrysts) spread through all fields.

Table 3
Summary of zircon saturation temperature ([Link]), Ti-in-zircon thermometer ([Link]) and
magmatic fO2 values acquired for OMS.
[Link] (1) [Link] (2) (°C) log fO2 (3)
Samples
(°C) Min Q1 Q2 Q3 Max Min Q1 Q2 Q3 Max
USP14-160 798 674 717 734 783 818 -20.9 -18.1 -17.1 -15.6 -14.4
USP14-144 794 715 749 760 767 796 -16.2 -15.9 -15.1 -13.9 -12.2
USP14-83 754 705 762 794 813 864 -13.4 -12.0 -10.8 -9.5 -5.1
USP14-91 793 700 732 767 775 787 -17.3 -16.3 -15.2 -14.7 -14.0
USP14-136 819 725 763 787 807 820 -16.9 -15.6 -15.1 -14.3 -13.5
(1) Watson and Harrison (1983); (2) Ferry and Watson (2007), absolute error of ±30°C; (3)
Smythe and Brenan (2016), propagated uncertainty of ±1.2 log units.

Samples USP14-144 and 160 show the lowest magmatic temperatures (medians
of 768 °C and 782 °C respectively) with a broader distribution for the later, and are
characterized by intermediate [Link] (794 °C and 798 °C respectively). Zircon grains
distribute between fields ii and iii, with greater concentrations for the [Link] <
[Link] field. Samples USP14-91, 136 and 83 show progressively higher magmatic
temperatures, and median [Link] are respectively 786 °C, 811 °C and 818 °C. The first

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two show grains that equally distributed between fields ii and iii, with intermediate
and high [Link] (793 °C and 819 °C respectively). Sample USP14-83 differs from the
others and its zircon grains distribute essentially on fields i and ii, and are accompanied
by the lowest [Link] (754 °C).

[Link]. Magmatic fO2 estimates

In order to make the data easier to read and comparable with other paper’s
datasets, we treat magmatic fO2 in log units above or below the fayalite-magnetite-
quartz (FMQ) oxygen buffer (results are summarized on Table 3). The graph from
Figure 12b shows magmatic temperature ([Link]) plotted against ΔFMQ (xenocrysts,
high La and low LREE-i zircon grains were ruled out). Sample USP14-83 shows the
highest fO2 values and zircon grains plot on the top part of the graph (values higher
than ΔFMQ + 4). However, these results should be treated cautiously, as the sample
shows predominantly low LREE-i zircon grains.

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Fig. 12. Zircon saturation temperature (Watson and Harrison 1983) vs. Ti-in-zircon
temperature (Ferry and Watson 2007) plot. The plot separates fields where zircon
saturation is not achieved by the hosting magmas (top of the diagram) and, conversely,
fields where zircon might be extracted from the magmas (center and bottom parts).
Inherited grains might plot in all fields, whereas autocrystic grains will plot on the
center and bottom parts. (b) Magmatic fO2 treated as log units above or below the
fayalite-magnetite-quartz oxygen buffer plotted against magmatic temperature (T
[Link]).

The granodioritic porphyry (sample USP14-144) shows the second highest fO2
values, with ΔFMQ from 0 to + 4. Samples USP14-91 and 136 cover a similar and
narrower fO2 range, with ΔFMQ between 0 and + 1. Sample USP14-160 is characterized
by the widest fO2 range and samples tend to scatter more strongly (ΔFMQ varies from
– 4 to 0).

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3.5. Discussion

3.5.1. A petrogenesis perspective: generating the older and

younger magmatic sequences

In the Tapajós Mineral Province, a clear feature of the OMS (igneous suites of
2.00 – 1.95 Ga) is its wider compositional range when compared with the YMS (igneous
suites of 1.90 – 1.86 Ga, Figs. 4a and 4b). Yet, an interesting and relevant common
ground for both magmatic sequences is the presence of metaluminous samples with
higher maficity values (with exception of the Batalha granitoids as shown in Fig. 5c).
The balance between Al and Na, Ca and K is particularly important in granitic rocks
geochemistry as it efficiently constrains their petrogenesis (Clemens et al., 2011;
Clemens and Stevens, 2012; Frost et al., 2001; Frost and Frost, 2013, 2011; Moyen et
al., 2017; Villaseca et al., 1998) and, as such, it indicates metaluminous mafic sources
for both OMS and YMS. Differences between the magmatic sequences are better
evidenced on the Fe-index and MALI vs. silica diagrams (Figs. 5a and 5b) and major-
oxides plots (Figs. 6 and 7), which suggests contrasting melting conditions and
magmatic evolution, in spite of similar sources.

OMS rocks might be divided into three categories. Group i granitoids correlates
with the Cuiú-Cuiú Complex, are found on the Patrocínio and Tocantinzinho deposits
(southern and central TMP respectively), show slightly higher silica contents, are
peraluminous, magnesian to ferroan, calc-alkalic to calcic and comprises granites and
granodiorites compatible with mafic and oxidizing sources, with moderate to strong
continental crust contribution. The group comprises the oldest granodiorite (sample
USP14-160) dated in this contribution at 2011 Ma, characterized by a magnetite
bearing and amphibole-free evolution (green array in Fig. 6) generating the horizontal
distribution of samples on the Dy/Yb plot the moderate to low Sr/Y and La/Yb ratios
(Fig. 9). These rocks represent the first batches of magmatism upon the onset of
subduction on the TMP at ca. 2.0 Ga, that according to Cassini et al. (2020) is
characterized by a strong crustal component due to incorporation of trench derived
sediments and/or subcrustal-erosion of the subducted plate (εNd(T) of -8.36 acquired
by the authors).

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Group ii granitites (s.l.) predominates at the TMP as a whole and correlates

with the Creporizão Intrusive Suite. It comprises samples from the Tocantinzinho, São
Jorge (older granite) and Chapéu do Sol gold deposits (northern and central TMP), with
a few examples from the Patrocínio deposit (sample USP14-144 dated at 1986 Ma).
The rocks are metaluminous to mildly peraluminous, magnesian to slightly ferroan,
calc-alkalic to alkali-calcic and suggest mafic to intermediate, oxidizing sources typical
of subduction-related, I-type granites. Geochemical modelling demonstrates fractional
crystallization as the main differentiation mechanism and a hydrous and oxidized trend
consistent with plagioclase, amphibole, biotite, magnetite and titanite (red array in Fig.
6). Middle-REE depletion (clearer for the Tocantinzinho samples, Fig. 8) and the
distribution on the Dy/Yb, Sr/Y and La/Yb plots (Fig. 9) reinforce the role of amphibole.
Samples from the Coringa deposit (southern TMP) plot on the magnesian-ferroan
transition and are predominantly alkalic, compatible with highly differentiated I-type
granites (Frost et al., 2001; Frost and Frost, 2011). In addition, these samples cover the
higher silica spectrum of group ii’s trend (red array in Fig. 6), suggesting a similar
petrologic evolution. Considering the more discrete variation on the Dy/Yb, Sr/Y and
La/Yb ratios, amphibole most likely played a lesser role on the evolution of the Coringa
rocks. As a whole, group ii rocks might be might be understood as differentiated, I-type
granites that represent the evolution of the arc-magmatism.

Group iii comprises lower silica, K-rich (K2O > 5 wt.%), metaluminous to
peraluminous, ferroan and alkalic syenites (quartz-syenites) and monzonites with ages
between 1974 and 1993 Ma. Major and trace element patterns show that group iii
derives from anhydrous, metasomatized, mafic and reducing parental magmas with
restrict crustal contribution (εNd(T) from -1.64 to +1.69 acquired by Cassini et al., 2020).
The authors also demonstrated how these rocks evolved on an anhydrous and reduced
petrologic trend (pyroxene and ilmenite bearing) as a consequence of corner flow
induced, decompression mantle melting. Early extraction of plagioclase is symptomatic
of anhydrous melts and explains the Eu anomalies (negative), Sr and Ba depletions,
and low Sr/Y and La/Yb ratios. This group of rocks, that accounts for about 15% of our
database and encompasses Patrocínio, Tocantinzinho, Coringa and São Jorge samples,
is not constrained on the S-I-M-A classification (Chappell and White, 2001) and it is

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often treated as K-rich calc-alkaline granitoids (Bonin, 2004, 1990; Bonin et al., 2020)
or as Fe-K granitoids (Laurent et al., 2014) that are typical of post-orogenic or
collisional tectonic settings (Bonin, 2004; Frost et al., 2001; Liégeois et al., 1998).
Despite their abundance in Proterozoic terrains throughout the world (Bogaerts et al.,
2006; Ferré et al., 1998; Ferreira et al., 1998; Kouankap Nono et al., 2010; Laurent et
al., 2014; Vander Auwera et al., 2011), the precise petrogenetic mechanism behind
high-K, metaluminous and ferroan granitoids is still debatable.

Within the YMS, V3 volcanics (Iriri Group) vary from metaluminous to

peraluminous, alkalic to calc-alkalic and are magnesian on the lower silica side and
ferroan on the more acid members, geochemical attributes that suggest oxidizing to
reducing mafic parental magmas with contribution of preexisting crust. Geochemical
modelling indicates that intermediate V3 (and the few younger São Jorge granite
samples) evolved through K-feldspar, amphibole, anorthite-rich plagioclase and biotite
extraction (yellow array in Fig. 7), yielding higher Dy/Yb, Sr/Y and La/Yb ratios (Fig. 9).
More prominent differences between the older and younger sequences are evidenced
by the acid V3 volcanics and by the Palito and Batalha granitoids (that correlate with
the Parauari Intrusive Suite). The rocks show similar aluminosity with the OMS but are
alkali-calcic, essentially ferroan, show a much narrower compositional range and
evolved on a pyroxene and magnetite-free trend (black array in Fig. 7), characterized
by lower Sr/Y, La/Yb and Eu/Eu* ratios. These geochemical attributes mark a transition
from hydrous and oxidizing, to anhydrous and reducing mafic sources.

As a whole, OMS and YMS show subtle geochemical differences and contrasting
petrologic trends and these differences lend support to a changing tectonic framework
on the TMP at ca. 1.88 Ga, from a magmatic-arc context to a post-orogenic or
collisional setting (Juliani et al., 2005; Lamarão et al., 2005, 2002; Santos et al., 2004,
2001, 2000). The suppression of subduction and the absence (or low activity) of slab-
derived fluids positions SCLM as the main magmatic source and explains the higher
HFSE content of YMS.

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3.5.2. Insights from zircon geochemistry: examples from the

Patrocínio gold mineralization

Whole-rock geochemistry shows that the OMS might be grouped into three
categories: group i involves higher-silica granites and granodiorites that evolved on a
dryer trend through fractionation of pyroxene, magnetite and titanite; group ii involves
granites (s.l.) and are compatible with extraction of amphibole, magnetite and titanite;
and group iii accounts for the low-silica, high-K syenites and monzonites that evolved
on a pyroxene- and ilmenite-bearing trend. Zircon textural description and
geochemical analyses for groups I, ii and iii reveal a protracted petrologic history of
approximately 40 Ma.

Sample USP14-160 (granodiorite) belongs to group i, shows the oldest age

among the rocks dated in this study (2011 Ma), autocrystic cores of 2031 Ma and
xenocrystic cores of 2052 Ma, both characterized by higher Zr/Hf and Th/U than the
rims (Figs. 10a, 11a and 11b). The abundance of inherited cores combined with the
whole-rock εNd(T) = - 8.36 (Cassini et al., 2020) and the high [Link] (798 °C) supports
the contribution of preexisting crust for the formation of group i magmas. A few grains
stand as exceptions and show Hf-enriched cores, reflecting episodic injections of new
magma batches as zircon crystallize. Partially corroded and rounded edges and the low
whole-rock Zr content of this sample (179.6 ppm) suggest early zircon extraction.
According to our models, this sample belongs to a magmatic series that evolved
through profound extraction of plagioclase (~71% of the cumulate composition), and a
strong negative Eu anomaly would be ubiquitous on the evolving melt. Loader et al.
(2017) demonstrated how titanite fractionation might potentially drive the melt
towards positive (or only subtly negative) Eu anomalies, as the mineral incorporates
preferentially the other trivalent REE (Kd > 100, Bachmann et al., 2005). Hence,
the chemical effects of plagioclase extraction in group i granites is apparently
counterbalanced by synchronous extraction of titanite (and less importantly
pyroxene), which assigns the evolving magma and subsequently crystallizing zircon
grains (or rims) their Eu/Eu* ≥ 0.5 and lower Dy/Yb ratios (Figs. 11a and 11b).
Additionally, the preferential incorporation of Th by titanite explains the evolution

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towards lower Th/U (Harrison et al., 2007a; Lee et al., 2020). Despite the compatibility
with magnetite, the plot from Figure 12b shows fO2 values close to or a few log units
below the FMQ buffer, just enough to stabilize the mineral.

The granodioritic porphyry (sample USP14-144) belongs to group ii granitoids

and is characterized by magnetite, titanite and amphibole fractionation, a magmatic
age of 1986 Ma and rounded, partially corroded inherited xenocrystic cores dated at
2010 Ma (Fig. 10b), compatible with group i ages. Zircon morphology (3:1 elongation)
and the synchronicity of core and rims suggest a rapid crystallization history for this
sample, which is compatible with the shallower crustal level expected for a porphyry
intrusion. Profound extraction of plagioclase (~73% of the cumulate) explains the
evolution towards lower Eu/Eu* as Zr/Hf decreases and, the few samples with higher
Eu/Eu* likely reflects competing titanite extraction. However, differently than sample’s
USP14-160 case, titanite is approximately 4 times rarer within group ii’s petrologic
trend, fact that diminishes significantly its geochemical effects on the evolving melt.
Combined fractionation of titanite and amphibole modeled for group ii yields the
steepest array on the Th/U vs Dy/Yb plot and the lowest magmatic temperature (768
°C) acquired in this study. In addition, the oxidizing condition of this sample is
sustained by geochemical modelling and by fO2 values between ΔFMQ + 0 and ΔFMQ +
4.

Samples USP14-83, 136 and 91 (quartz-syenites and quartz-monzonites) belong

to the high-K series (group iii) that is characterized by a dry, reduced and protracted
magmatic history. USP14-91 marks the onset of the high-K magmatism at ca. 1993 Ma
(Fig. 10c). This sample presents low silica contents (~60 wt.%) and zircon stabilization is
likely due to the high whole-rock Zr (357.7 ppm) (Fig. 12a indicates the predominance
of autocrystic grains). Sample USP14-136 shares similar characteristics, yet, much
younger magmatic age (1974 Ma, Fig. 10d), representing a late stage pulse of the high-
K magmatism. Inherited zircon grains dated at 2055 Ma reflects a longer period of
residence on deeper hot zones by these primary magmas (Annen et al., 2006),
adequately explaining the positive to slightly negative εNd(T) acquired for group iii rocks
(Cassini et al., 2020). Sample USP14-83 intrudes as synmagmatic aplitic dykes and

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represents the evolution of the high-K magmatism. Its low whole-rock Zr content
(127.4 ppm) suggests that the magma underwent previous zircon extraction and,
consequently, the 1987 Ma age (Fig. 10e) should be understood as inherited (Fig. 12a
indicates the predominance of antecrystic zircon grains). This idea is supported by the
incompatibility between our geochemical modelling results (that indicates a reduced
petrologic trend) and the extreme high fO2 values acquired for group iii (Fig. 12b). The
LREE index vs. Ti plot (Fig. 11c) indicates that USP14-83 and 136 in a lesser extent, are
anomalously LREE enriched, reflecting either hydrothermal alteration or mineral
inclusions on the ablated spot (Bell et al., 2019, 2016), which might compromise the
reliability of the results. As a consequence, zircon trace-element contents for these
rocks should be looked at cautiously. The Eu/Eu* values predominantly below 0.5
denies fractionation of titanite and the smoother drop on the Dy/Yb ratio as Th/U
decreases negates amphibole extraction, supporting the dry, ilmenite- and pyroxene-
bearing evolution modeled for group iii. Its reducing affinity, as pinpointed by
geochemical modeling, is also supported by the fO2 values below ΔFMQ +1.
Additionally, the higher magmatic temperatures acquired for group iii syenites and
monzonites (786° to 811° C) attest the dry characteristic of the high-K magmatism.

3.5.3. Fertile or not-fertile: the million dollar question

On a tectonic perspective, typical Cu–Au porphyry deposits form preferentially

(but not only) in destructive plate margins where they genetically relate with hydrous
(up to 6 wt. % H2O), oxidized (ΔFMQ + 0 to + 2), intermediate to acid, shallow, arc-
related intrusions that upon decompression exsolves fluids and volatile phases
responsible for mobilizing siderophile and chalcophile elements under chlorine- or
sulfate-bearing complexes and, ultimately, for their precipitation as ore metals
(Richards, 2015a, 2011a; Sillitoe, 2010; Sobolev and Chaussidon, 1996; Sun et al.,
2015). Interestingly, not all arc rocks are adequate for the formation of porphyry
deposits and, in this regard, hypotheses involving the depth of intrusion, size of the
pluton, redox state and water, sulfur and metallic contents of the magmas have been
raised as potential players that might influence whether or not a given magmatic

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system is fertile (a good summary might be found in Zhang and Audétat, 2017). Sulfur
speciation, as a consequence of magmatic fO2, stands as one of the most critical
variable that dictates the characteristics of the porphyry mineralization (Sun et al.,
2015). According to Richards (2015a), mantle melting in subduction zones under fO2 ≥
ΔFMQ + 1 destabilizes residual sulfides and transfer their metallic content into the
evolving melt. The optimal oxidation state, around ΔFMQ + 0 to + 2, may only be
achieved through several million years of steady subduction. In essence, timing and
tectonic context are crucial points to fully assess the metallogenetic potential of the
igneous suites in the TMP.

The different igneous suites that encompass the OMS are interpreted as
subduction related (e.g. Cassini et al., 2020; Juliani et al., 2002; Lamarão et al., 2005,
2002), and group i granitoids of ca. 2011 Ma represent the first batches of the arc-
magmatism. These rocks are characterized by fO2 values close to or below ΔFMQ,
which are lower than the typical range for arc rocks (ΔFMQ + 0 to + 2). By combining its
redox state with the pyroxene-bearing petrologic evolution, group i granites and
granodiorites represent an unfertile stage of the arc-magmatism for the formation of
typical Cu – Au magmatic-hydrothermal mineral deposits. In fact, group i rocks show
negligible hydrothermal alteration (minor and localized K-metasomatism) and lack any
trace of mineralization (Cassini, 2016).

Group ii granitoids, identified in the Tocantinzinho, Chapéu do Sol, Coringa, São

Jorge and Patrocínio deposits, show higher fO2 (ΔFMQ + 0 to + 4) and a petrologic
trend compatible with amphibole fractionation, characteristics that indicate the
evolution of the arc-magmatism towards more hydrous, oxidized and metallogenetic
fertile conditions. The granodioritic porphyry (USP14-144) dated at 1986 Ma is also
accompanied by younger granitoids, evidencing a protracted magmatic history behind
group ii rocks (i.e. 1958 Ma for amphibole-bearing monzogranite from the Patrocínio
deposit by Cassini (2016); 1979 Ma for the Tocantinzinho deposit syenogranites by
Borgo et al. (2017); 1975 Ma for the Coringa deposit rhyolites by Tokashiki (2015)), a
typical feature of porphyry forming plutons (Chelle-Michou et al., 2017; Large et al.,
2018; Pirajno, 2009; Richards, 2015a). Group ii-hosted mineralizations are defined by

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disseminated gold bearing sulfides or by pyrite-quartz ±gold ±chalcopyrite veins and

veinlets most often found in the sericitic and, less frequently, in the potassic and
propylitic alteration zones. Early and late-stage hydrothermal alterations (sodic and
argilic respectively), when present, are barren.

The high-K magmatism of group iii covers an age interval of approximately 20

Ma (1993 – 1974 Ma) and represents decompression melting of metasomatized
mantle. Group iii rocks are rarer in the TMP, yet syenites and monzonites have been
reported in the Patrocínio, Tocantinzinho, Coringa and São Jorge gold deposits. Our fO2
estimates around ΔFMQ + 0 to + 2, combined with the pyroxene-bearing petrologic
trend, assigns this group a low favorability for the formation of Cu – Au magmatic-
hydrothermal systems. Interestingly, group iii rocks often show sericitic, potassic and
carbonate hydrothermal alteration with disseminated, gold bearing, pyrite and
pyrrhotite, features that we interpret as diagnostic of an interaction between the
reduced, anhydrous and unfertile high-K magmas with the synchronous, hydrous,
oxidized and metallogenetic fertile group ii melts.

There is a lack of data when it comes to mineralization age in the TMP and, in
spite of the theoretical fertility of group ii granites (and group iii on a minor extent), Ar-
Ar dating of alunite crystals points to mineralization age of 1.86 – 1.84 Ga, which is
compatible with the YMS (ages from the V3 and Batalha deposits by Echeverri Misas
(2015) and Juliani et al. (2005)). Whereas OMS represents the magmatic-arc sequence
with oxidized and hydrous melts, YMS is compatible with the evolution of the system
towards late-orogenic and collisional tectonic settings, a consequence of the
progressive flattening of the subducting-slab, resulting in progressively anhydrous and
reduced magmas (Fernandes et al., 2011; Fernandes and Juliani, 2019). During active
subduction, the continuous sulfur influx through the mantle enables a high fS2, which
stabilizes gold- and copper-rich residual sulfides. When subduction stalls, subsequent
mantle melting (likely involving metasomatized SCLM), triggered due to astenospheric
upwelling or orogenically thickened crust, will efficiently destabilize the previously
formed sulfides and mobilize their metallic content into the generating melt (Richards,
2015a, 2011a). Hence the association of gold-rich porphyry deposits with late-orogenic

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or collisional magmatism such as the YMS (Chen et al., 2015; Hou et al., 2013; Richards,
2015b). The Batalha and Palito deposit (and possibly the younger São Jorge granite)
are hosted by the Parauari Intrusive Suite that coupled with the volcanics of the V3
deposit (Iriri Group) represent the first batches of the YMS (ca. 1.89 Ga). The first two
deposits show the greatest concentration of disseminated gold and gold bearing
sulfide veinlets in the sericitic alteration zone and, secondarily, on the propylitic and
argilic zones. The associated granitoids show features (metaluminous to mildly
peraluminous, high-K to shoshonitic, more evolved Nd isotopes than OMS and > 2.0 Ga
inherited zircon grains) that suggest a mutual role of metasomatized mafic and crustal
sources (Cassini et al., 2020; Echeverri Misas, 2015; Santos et al., 2004). The V3 deposit
is hosted by rhyolites compatible with a stronger crustal contribution in primary SCLM
magmas (ferroan, peraluminous, alkali-calcic to calc-alkalic). Mineralization is found in
hydrothermal breccias in a shallower stratigraphic level of the system, and consists on
alunite- and gold bearing sulfide veinlets distributed on the advanced argilic alteration,
with lower sulfide concentrations on the potassic, propylitic and sericitic alterations.

In summary, despite their predominantly anhydrous characteristic, the first

pulses of YMS are intimately related with gold-rich (gold-only?) magmatic-
hydrothermal mineral deposits as a result of remobilization of SCLM and/or lower
crust residual sulfides. Hence, the Parauari Intrusive Suite and the initial pulses of the
Iriri volcanism may be considered as potentially fertile for the generation of gold-rich
magmatic-hydrothermal mineral systems.

[Link]. What the Sr/Y ratio tell us?

Over the past decade much attention has been driven to the relation between
high Sr/Y rocks and porphyry Cu – Au deposits (i.e. most calc-alkaline, arc- and
porphyry related magmas found in Andean-type subduction zones show high Sr/Y
ratio), even though the origin of such relation remains in dispute. Some authors (e.g.
Mungall, 2002; Sun et al., 2015) defend that high Sr/Y arc-rocks are genetically related
with slab-melting and should be understood as high-silica adakites (Moyen 2009).

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However, thermal modelling of subduction zones (e.g. Bouilhol et al., 2015) reveals
that slab melting is rare and unlikely to be a major contributor for arc-magmatism,
neither is garnet an abundant restitic phase upon mantle melting. An alternative
explanation suggests that the adakitic signature of arc-magmas relates with the
magmatic evolution itself and relies primarily on the timing of amphibole and
plagioclase fractionation (Chiaradia et al., 2012; Loucks, 2014; Richards, 2011b). High
Sr/Y rocks experienced early amphibole extraction and is typical of magmas with ≥ 4
wt. % H2O that evolved at mid-crustal depths. On the other hand, if plagioclase
precedes amphibole extraction, the case for less hydrous and shallower developed
magmas, the system will be Sr depleted and the result will be low Sr/Y magmas.

More recently, special attention has been driven to alkaline, high-K to

shoshonitic, low Sr/Y magmas, intruded in late- to post-subduction environments, the
geologic scenario that frames TMP’s context. World-known deposits such as Cadia Au –
Cu porphyry (eastern Australia), the Bingham Canyon Cu – Mo – Au porphyry (eastern
USA) and the Ok-Tedi Au – Cu porphyry (Papua New Guinea) are found in such geologic
and tectonic contexts (Cloos et al., 2005; Cooke et al., 2013; Grondahl and Zajacz,
2017; Holliday et al., 2002; Richards, 2009). Chiaradia (2012) explains the Sr/Y ratio of
a given magma with basis on the depth of evolution. Accordingly, intermediate
composition magmas evolving at depths greater than 0.2 GPa will stabilize amphibole
prior to plagioclase and magnetite, which yields high Sr/Y. Such magmas might
eventually ascend through the crust and reach shallower depths, ultimately exsolving
fluids and volatiles necessary to form magmatic-hydrothermal mineral systems. On the
other hand, if the same magma undergoes a rapid decompression, plagioclase and
magnetite will precede amphibole crystallization, yielding low Sr/Y and less hydrous
magmas. In addition, magnetite-induced sulfide saturation will deplete the system in
chalcophile elements prior to fluid exsolution, resulting in economically barren
magmas. Chiaradia’s model adequately explains the low Sr/Y of OMS’s group ii
granitoids, that still show reasonable fO2 for the formation of porphyry Au – Cu
deposits and is compatible with amphibole, more likely on a late stage of the
crystallizing sequence. The YMS marks a transition from evolved-arc to post-orogenic
or collisional tectonic settings and, with the exception of intermediate V3 volcanics,

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amphibole is absent in all units, implying in anhydrous magmas with low Sr/Y.
However, as mentioned on the previous section, YMS’s petrogenesis involves
remobilization of subduction-modified mantle and possibly lower crust, which confers
this magmatic sequence its metallogenetic potential for gold-rich magmatic-
hydrothermal mineral deposits.

3.6. Conclusions

The relevance of this study regards how the tectonic context translates into
metallogenetic potential for base and precious metal occurrences in south-central
Amazonian Craton. Results acquired allowed a better understanding on the magmatic
evolution and on the tectonic context of the host rocks from selected mineral deposits
in the Tapajós Mineral Province (TMP). Discussion and conclusions might be
understood as a first step towards a unified metallogenetic model for the magmatic-
hydrothermal mineralizations in the TMP. The different mineralizing systems are
hosted either by igneous suites of 2.00 – 1.95 Ga, designated as the older magmatic
sequence (OMS), or by igneous suites of 1.90 – 1.86 Ga, treated as the younger
magmatic sequence (YMS).

OMS rocks might be divided into three groups. Group i correlate with the Cuiú-
Cuiú Complex and comprises peraluminous granites and granodiorites that represent
the first batches of arc-magmatism on the TMP (granodiorite sample dated at 2011
Ma), which is characterized by a strong crustal component and an oxidizing and dry
petrologic evolution. The 𝑋 𝑋 zircon-based oxy-barometer indicate fO2 values
close to the FMQ buffer (– 4 ≤ ΔFMQ ≤ + 0). However, due to its anhydrous trend these
rocks show a low favorability for the formation of magmatic-hydrothermal mineral
systems.

Group ii rocks are common and widespread in the TMP, correspond to the
Creporizão Intrusive Suite, comprises metaluminous to peraluminous granites (s.l) that
evolved on an amphibole and magnetite bearing trend, and represents the evolution
of the arc-magmatism. The granodioritic porphyry dated at 1986 Ma represents this

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stage, which is characterized by the lowest magmatic temperature 768 °C. fO2
constraints corroborate the more oxidized trend for these rocks (0 ≤ ΔFMQ ≤ + 4),
rendering their potential fertility for the formation of porphyry Cu – Au
mineralizations. The low Sr/Y ratio reflects a rapid decompression, enabling plagioclase
fractionation prior to amphibole extraction in spite of hydrous magmas. On the field,
group ii rocks are commonly affected by hydrothermal alteration, with disseminated
gold or gold and chalcopyrite bearing veins and veinlets most commonly found on the
sericitic zone, with potassic and propylitic alterations also economically relevant and
barren sodic and argilic alterations.

Group iii comprises lower silica, high-K, metaluminous, ferroan, reduced and
anhydrous quartz-syenites and monzonites of 1993 and 1974 Ma, generated through
decompression melting of metasomatized mantle, which yields high magmatic
temperatures ([Link] from 786 to 811 °C). These rocks are rarer and have only been
reported in the Patrocínio and Coringa deposits (southern TMP) on drill core sampling.
fO2 between ΔFMQ = 0 and + 1 positions these rocks on an intermediate redox state
within OMS. Its reducing petrologic trend indicates that, by itself, group iii should not
be considered economically fertile. Nevertheless, the group’s metallogenetic potential
lies on its interaction with the coeval, more hydrous and oxidizing group ii melts. The
end products are syenites and monzonites affected by sericitic, chloritic and carbonate
alterations with disseminated pyrrhotite-pyrite ±gold with less frequent gold bearing
pyrite veinlets.

YMS comprises rocks from the Parauari Intrusive Suite and from the Iriri Group,
and is represented in the Batalha, Palito, São Jorge and V3 deposits. Field relationships
between the older and younger sequences are rare, but Iriri volcanics are found as
dykes within OMS granitoids or define lava-flows, whereas the intrusive units define
round-shaped plutons. Whereas intermediate V3 volcanics share similar geochemical
features with the OMS, acid V3 and the Batalha and Palito granitoids are essentially
ferroan and evolved on a magnetite- and amphibole-free trend, suggesting anhydrous
and reduced parental magmas. We interpret such differences as symptomatic of a
changing tectonic framework within the TMP, from magmatic-arc (OMS) to a post-

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orogenic or collisional setting. As subduction stalls (or upon the progressive flattening
of the slab) magmatism gets dryer, comparatively reduced and, in theory, less
favorable for the formation of magmatic-hydrothermal mineral deposits. However,
YMS’ metallogenetic potential is related with remobilization or melting of SCLM and/or
lower crustal, gold-rich sulfides formed on the previous magmatic events. The
outcome is identified in the Batalha and Palito deposits, with disseminated gold and
gold bearing sulfide veinlets preferentially distributed in the sericitic zone, and in the
V3 mineralization, with alunite and gold bearing sulfide veinlets hosted by
hydrothermal breccias on the advanced argilic alteration. Therefore, YMS should be
treated as metallogenetic fertile for the formation of gold-rich magmatic-hydrothermal
systems, since it efficiently mobilizes previously formed sulfides.

Acknowledgements

The results presented in this research were funded by the National Council for
Scientific and Technological Development (CNPq) through the processes 550342/2011-
7 and 573733/2008-2, and by the Society of Economic Geologists (SEG) through its
McKinstry fund. The authors are also thankful for the ETH’s Department of Earth
Sciences for the in-situ zircon analyses. Scholarships for Lucas V. Cassini were provided
by the Coordination for the Improvement of Higher Education Personnel (CAPES) and
CNPq from Brazil, and by the French agency Campus France through its Eiffel Bourse
d’excellence. Merci beaucoup!

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4. Discussion

4.1. Topics and Considerations on Classification Diagrams

A few problems arise when dealing with classification of igneous rocks in the
TMP. Both thick weathering profile and widespread hydrothermal alteration might
hinder a reliable petrographic- or whole-rock geochemistry-based classification (Fig. 13
exemplifies the empirical effects of both processes). Samples J-35 and J-36 are
intermediate and undifferentiated intrusive rocks described by Tokashiki (2015) at
southern TMP that show a considerable degree of weathering likely due to leaching of
soluble major oxides as Na2O, K2O and CaO (Fig. 13a). As a result, plotting these
samples on Total Alkali vs. Silica (TAS) diagrams (Cox et al., 1979; Middlemost, 1994)
might render unrealistic or unreliable classifications (Figs. 13b and 13c). This effect
tends to be soothed on the R1-R2 plot by De la Roche et al. (1980), which comprises all
major rock-forming elements in millications (highly mobile Na and K are balanced
against other major elements). As a result, De la Roche’s classification diagram should
be preferentially used since it yields a more reliable discrimination of intrusive and
extrusive rocks. The weathering effects on granites are also represented on the plots
from Figure 13 (samples Fbt-3/7b and CJ-33 from the Batalha and Palito deposits plot
close to the W vertice, out of range on Cox’s and De la Roche’s plots and close to the
granodiorite-granite boundary on Middlemost’s TAS.

Ideally, and despite its caveats (Bonin et al., 2020), the modal QAP classification
(Streckeisen, 1976) should be applied in order to unbias the effects of hydrothermal
alteration (i.e. secondary minerals originated due to K or Na-Ca metasomatism should
not be considered on modal classification). Samples DT-07b and Fbt-2/7b demonstrate
the effects of hydrothermal alteration on granitic rocks on the TMP. Both lack the
weathering geochemistry signature (Fig. 13a) and are described as granites affected by
Na- and/or K-metasomatism (Echeverri Misas, 2010; Juliani et al., 2002) which
translates into granodiorite and granite on the TAS diagram after Cox et al. (1979) (Fig.
13a), or quartz-monzonites on the TAS diagram after Middlemost (1994) (Fig. 13b), or
tonalite and syenite on R1-R2 plot after De la Roche et al. (1980) (Fig. 13c).

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Part III – Discussion and Conclusions

Fig. 13. MWF plot (13a) (Ohta and Arai, 2007) and classification diagrams after Cox et
al. (1979) (13b); Middlemost (1994) (13c); and De la Roche et al. (1980) (13d) for
weathered and hydrothermally altered rocks.

Cassini (2016) also demonstrated how monzo- and syenogranites described on

petrography might be geochemically classified as K-richer granitoids, yielding fake- or
episyenites (Suikkanen and Rämö, 2019). However, the QAP classification may not be
the best option when dealing with a robust database, which could render the task
practically unrealistic. As demonstrated by Bonin et al. (2020) modal and chemical
composition of igneous rocks are not easily overlapped and, for this reason, De la
Roche’s R1-R2 diagram is used in this study with a mere descriptive objective.
Petrogenetic constraints were based on aluminosity and radiogenic isotopes as will be
demonstrated on the following sub-sections.

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As for aluminosity, preference was gave to the A-B plot after Debon and Le Fort
(1983), revisited by Villaseca et al. (1998). The classic A/CNK vs. A/NK plot (mol%
oxides) introduced by Shand (1943) adequately mirrors the excess or deficit of the
system in Al after feldspar extraction. However, since it is the intention of this
contribution to access the petrologic evolution of the rocks and how they relate to
each other, it is convenient to plot aluminosity against a differentiation index,
adequately mirrored by maficity on the B axis. On the B-A plot, the A > 0 domain is
divided with basis on the intensity of peraluminosity, which brings relevant
petrogenetic implications as will be demonstrated.

Moreover, the widely used Pearce diagrams for discriminating tectonic setting
based on trace-element content (Y, Nb, Rb, Yb and Ta) of granitic rocks might render
important discussion but it lack robustness by itself since these element abundances
are intimately related with the accessory mineral content (zircon, apatite, monazite,
allanite etc). Granitic rocks or magmas might undergo innumerous modification
processes after mantle and/or crustal melting (i.e. differentiation, assimilation,
hybridization etc) ultimately resulting in newer and evolved compositions that no
longer mirrors their parental magmas nor the original tectonic context (Annen et al.,
2015, 2006; Bonin et al., 2020; Moyen et al., 2017). Hence, tectonic-setting diagrams
should be used with caution and, ideally, supported by additional data.

4.2. Genesis of TMP Magmas (the older and younger magmatic

sequences)

The results acquired in this study, coupled with whole-rock geochemistry data
available in the bibliography, allowed the separation of the Orosirian units in the
Tapajós Mineral Province (TMP) into the older- (OMS) and younger magmatic
sequences (YMS), respectively 2.0 – 1.95 Ga and <1.89 Ga. The older magmatic
sequence is divided in group I, II and III granitoids, with rhyolites associated, whereas
YMS is represented by the Iriri volcanics, Parauari (PAR) and Maloquinha Intrusive
Suites (MLQ).

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Part III – Discussion and Conclusions

The first bursts of magmatism in the Tapajós Mineral Province (TMP) refer to
the ca. 2.0 Ga granitoids of the Cuiú-Cuiú Complex that belong to group I granitoids,
represented by the 2011 Ma granodiorite (sample USP14-160). This sample shows
evolved εNd(t) = -8.36 (similar results were also reported by Echeverri Misas, 2015 and
Sato, 1998), high [Link] (798 °C), belongs to a series characterized by preferentially
peraluminous samples and by a great proportion of inherited zircon cores, indicating a
strong crustal component for the formation of these magmas. These data appear to
support the tectonic model proposed for the Amazonian Craton by Carneiro et al.
(2019) and by Juliani et al. (2015), that defend the existence of Archean basement on
the Tapajós region. Yet, direct evidence of > 2.5 Ga crust on the TMP region is
restricted to one zircon grain (Santos et al., 2004). Geochemical modelling for group I
shows an evolution compatible with plagioclase (68%), biotite (16%), magnetite (7%),
titanite (3%) and clinopyroxene (6%) fractionation, which defines an anhydrous
petrologic evolution towards high Sr/Y and La/Yb. Zircon petrochronology enlightens in
more detail the evolution of these rocks. Hf-enriched zircon cores reflect episodic
injections of new magma batches within the magmatic chamber, and partially
corroded, rounded edges and the low whole-rock Zr content of this sample (179.6
ppm) suggest early extraction of the mineral. Titanite fractionation render the positive
to subtly negative Eu anomalies and the low Th/U ratio observed on the zircon grains
(Fig. 11) (Harrison et al., 2007b; Lee et al., 2020; Loader et al., 2017). The fO2 estimates
point to values close to or a few log units below the FMQ buffer (–4 ≤ ΔFMQ ≤ +0), just
enough to stabilize magnetite (Fig. 12b). These geochemical attributes mark the onset
of the subduction process on the TMP region at ca. 2.0 Ga, where oxidizing
components were introduced on mantle wedge melts that got subsequently
contaminated by overlaying crust on deep-seating hot-zones and/or by subcrustal-
erosion material (Fernandes and Juliani, 2019; Juliani et al., 2015).

The secondary pulses of the arc magmatism (or group II granites, dated at 1986
Ma) are markedly different and cover a vaster area on the TMP. After its first phase,
arc-magmatism got less contaminated by continental crust, fact that translates into
moderately negative εNd(t) acquired for CRP granites and synchronous volcanics of ca.
1.97 Ga (averages of -2.77 and -1.87 respectively). Aluminosity also individualizes the

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first phase (or group I granites) from its evolution, suggesting the role of different
melting sources (Clemens et al., 2011; Clemens and Stevens, 2012; Villaseca et al.,
1998). Whereas group I comprises peraluminous samples, group II rocks define a
negative slope on the A-B diagram (Fig. 5c), with samples that vary from metaluminous
to mildly peraluminous on the more evolved members. The trend is typical of
subduction-related granitoids and is compatible with the presence of mafic parental
magmas, understood as a mantelic heritage. Geochemical modelling shows an
evolution compatible with a granodioritic liquid that evolved to alkali-granite
composition. Such petrologic evolution is consistent with fractionation of plagioclase
as the most abundant phase (up to 55% of the cumulate composition), which is
accompanied by K-feldspar (10%), amphibole (30%), titanite (3%) and magnetite (2%),
for a Fc of 0.43 to 0.57, a monzonitic cumulate and R² = 0.083 (Cassini et al., 2020).
Geochemical and timing equivalencies, allowed the interpretation of the volcanic
sequence described by Tokashiki (2015) in southern TMP as the extrusive
manifestation of the CRP magmatism. As demonstrated by Chiaradia et al. (2012),
Grove et al. (2012) and Loucks (2014), in H2O-rich arc-related magmas (≥ 4 wt. % H2O),
amphibole precedes plagioclase extraction, resulting on high Sr/Y (and La/Yb) rocks
(Fig. 9). On the other hand, if plagioclase precedes amphibole extraction, the case for
less hydrous and shallower developed magmas, the system will be Sr depleted and the
result will be low Sr/Y magmas. According to Annen et al. (2015), the main
differentiation mechanism that controls granitic magma generation is fractionation of
the primary mafic magma. This process is usually erratic and occurs in many stages,
where a batch of more primitive andesitic magma is injected into a more differentiated
dacitic crystal mush at shallower hot zones. This concept and model accounts for many
of the field relations described in the TMP such as mutually intrusive bodies, diffusive
or unclear contact, ubiquitous mafic enclaves and rarer rapakivi textures.

Zircon petrochronology also allows important petrologic constraints on group II

rocks. Sample USP14-144 (granodioritic porphyry) is characterized by elongated zircon
grains and a synchronicity between core and rims U-Pb dating, suggesting rapid zircon
crystallization which is compatible with a shallow crustal level intrusion (<4 km depth).
Plagioclase fractionation explains the evolution towards lower zircon Eu/Eu* as Zr/Hf

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Part III – Discussion and Conclusions

decreases and, the few samples with higher Eu/Eu* reflects competing titanite
extraction. Amphibole and titanite fractionation explains the steeper array on the Th/U
vs. Dy/Yb plot (Fig. 11) and low magmatic temperature ([Link] = 768 °C).
Furthermore, the oxidized condition of group II magmas is supported by geochemical
modelling and fO2 values between ΔFMQ +0 and ΔFMQ +4 (Fig. 12).

The high-K and low silica facies of CRP (syenites and monzonites dated at 1993
and 1974 Ma) defines group III granitoids. They are comparatively rarer in the TMP,
but have been reported in the Patrocínio, Tocantinzinho, Coringa and São Jorge
deposits. The rocks are metaluminous to peraluminous, ferroan, alkalic (Fig. 5), are
characterized by εNd(t) from -1.64 to +1.69 and are understood as differentiated
batches of juvenile material with negligible crustal contribution. Geochemical
modelling reveals a petrologic evolution compatible with crystallization of K-feldspar
as the major phase (up to 64% of mineral proportion on the cumulate), followed by
plagioclase (20%), biotite (7%), apatite (4%), clinopyroxene (3%) and ilmenite (2%), for
a Fc within the range 0.33 – 0.37, and a K-feldspar rich cumulate. Such evolution is
dryer when compared with group II granites, where the cumulate has approximately
30% of amphibole. This suggests that group III rocks evolved through early extraction
of plagioclase which is symptomatic of anhydrous melts and explains the Eu anomalies
(negative), Sr and Ba depletions, and low Sr/Y and La/Yb ratios. Another important
difference between groups II and III granitoids regard their iron-oxide mineral phase.
Geochemical modelling shows that magnetite is incompatible on the petrologic
evolution of group III and is only suitable on the evolution modeled for the group II
granites. Despite their equivalent alumina saturation index (metaluminous to mildly
peraluminous), syenites are characterized by positive εNd(t) which represents early
differentiated batches of magma provided by the corner flow induced,
metassomatized mantle wedge melting with practically no crustal contamination. On
the bibliography, these rocks are treated as K-rich calc-alkaline granitoids (Bonin, 2004,
1990; Bonin et al., 2020) or as Fe-K granitoids (Laurent et al., 2014). Despite their
abundance in Proterozoic terrains throughout the world (Ferré et al., 1998; Ferreira et
al., 1998; Bogaerts et al., 2006; Kouankap Nono et al., 2010; Vander Auwera et al.,

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2011; Laurent et al., 2014), the precise petrogenetic mechanism behind group III
granitoids remains unclear debatable.

Zircon geochemistry for samples USP14-83, 136 and 91 enlightened the

petrologic trend for group III’s syenites and monzonites. USP14-91 (syenite) marks the
onset of the high-K magmatism at ca. 1993 Ma (Fig. 10). This sample presents low silica
content (60 wt.%) and zircon saturation is due to the high whole-rock Zr (357.7 ppm).
In fact, Figure 12a indicates the predominance of autocrystic grains. Sample USP14-136
(monzonite) shares similar characteristics, yet, much younger magmatic age (1974 Ma)
representing a late stage pulse of the high-K magmatism. Inherited zircon grains dated
at 2055 Ma reflect a protracted residence period on deep hot zones by the primary
magmas, which explains the positive to slightly negative εNd(T) acquired for group iii
rocks (Tab. 3 on Lithos paper available as supplementary material). Sample USP14-83
represents aplitic dykes that mark the evolution of the high-K magmatism. Its low
whole-rock Zr content (127.4 ppm) suggests previous zircon extraction and,
consequently, the 1987 Ma age (Fig. 10e) should be understood as inherited (Fig. 12a
suggests the predominance of antecrystic zircon grains). Unrealistic fO2 constraints of
ΔFMQ +2 or greater (Fig. 12b) for this sample are the product of inherited zircon
grains, hydrothermal alteration and/or mineral inclusions on the ablated spot
(anomalous LREE enrichment is evidenced on the LREE index vs. Ti plot from Fig. 11c)
(Bell et al., 2019, 2016). Low Eu/Eu* negates titanite fractionation and the subtle drop
on Dy/Yb as Th/U decreases supports a dry, amphibole-absent, ilmenite- and
pyroxene-bearing evolution modeled for group iii. Its reducing affinity, as pinpointed
by geochemical modeling, is also supported by the fO2 estimates of ΔFMQ +0 to +1.
Additionally, the higher magmatic temperatures acquired for group iii syenites and
monzonites (786° to 811° C) attest the dry characteristic of the high-K magmatism.

These findings also enlighten the debate on the tectonic mechanisms that
operated during the Paleoproterozoic. As pointed out, OMS rocks are different the
typical Archean and TTG dominated continental crust. Group I and II granitoids show
geochemical evidence of arc-related rocks (vary from metaluminous to peraluminous,
calc-alkalic, magnesian to ferroan and show evolved Nd isotopes). Group I evolved
through pyroxene and magnetite extraction at ca. 2.0 Ga, and evolves to more hydrous

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and oxidized magmas (group II) as the arc matures at ca. 1.98 Ga. These characteristics
indicate that on the Rhyacian-Orosirian transition, oxidizing agents were being
progressively recycled and transferred into the generated magmas, making magnetite
a more abundant phase (with magmatic fO2 up to ΔFMQ +4), which strongly suggests
similar tectonic and petrogenetic mechanisms as seen in modern Phanerozoic
magmatic arcs. Similar results and tectonic implications have been recently published
by Meng et al. (2021) for the ca. 1.88 Ga, Haib porphyry Cu deposit in southern
Namibia. Interestingly, the results presented in this thesis are slightly older and allow
the connection between OMS and the ultimate cycles of atmospheric oxygen buildup
known as the great-oxidation-event (e.g. Gumsley et al., 2017) that affected the planet
from early- to mid-Paleoproterozoic. These findings coupled with the results and ideas
from Evans and Tomkins (2011), Meng et al. (2021) and Richards and Mumin (2013)
provide relevant and robust data that tectonic and metallogenetic processes as seen
on Phanerozoic terrains also operated on the Paleoproterozoic.

The first batches of YMS magmatism is represented by the ca. 1.90 granites of
the Parauari Intrusive Suite (PAR), approximately 70 million years younger than CRP.
PAR guards similarities with OMS rocks (e.g. metaluminous to mildly peraluminous
rocks), yet, most prominent differences regard PAR’s alkali-calcic, essentially ferroan
and much narrower compositional range (Fig. 4). Geochemical modelling shows an
evolution compatible with albitic-plagioclase (44%), K-feldspar (42%), pyroxene (7%),
titanite (3%) and apatite (4%) extraction, generating an alkali-granitic liquid and a
syenite cumulate, characterizing an anhydrous and reducing evolution. This trend
drives the evolving magma towards lower Sr/Y, La/Yb and Eu/Eu* ratios (Fig. 9).
Moreover, the suite shows more strongly negative εNd(t) (average of -4.85) when
compared with OMS’ group II and III granitoids, which could be the result of crust-
contaminated or metasomatized mantle melting. PAR’s precise tectonic setting,
however, is hard to interpret based on its geochemistry signature. Its high-K to
shoshonitic, ferroan, alkalic-calcic affinity and the presence of metaluminous samples
on the least evolved spectra is compatible with reduced mafic parental magmas on a
late-, post-orogenic or collisional tectonic setting, where igneous petrogenesis involves
previously metasomatized mantle melting. According to Bonin (1990), a typical

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orogenic rock association will comprise igneous suites directly involved with hydrated
mantle-wedge melting that transitions to alkaline magmatism through collision-related
high-K magmatism on an age span usually shorter than 100 Ma. Within this context the
alkaline suites (divided into post-orogenic and early-anorogenic alkaline granites)
commonly overlap in age the last pulses of the arc-related sequence. Regardless of its
precise tectonic scenario, PAR’s geochemical attests a transition from hydrous and
oxidizing (amphibole and magnetite bearing granites) to anhydrous and reducing
magmas.

The volcanic rocks of the Iriri Group (1.89 – 1.87 Ga) show geochemistry
characteristics that partially resemble the PAR granitoids. In fact these rocks overlap in
age and represent the onset of the YMS. The rocks vary from metaluminous to
peraluminous, alkalic to calc-alkalic and are magnesian on the lower silica side and
ferroan on the more acid members, geochemical attributes that suggest oxidized to
reduced mafic parental magmas with contribution of preexisting crust. Mildly negative
εNd(T), however, indicate a greater contribution from juvenile sources (Cassini et al.,
2020). Geochemical modelling shows a discontinuous petrologic trend within the Iriri
Group. Accordingly, intermediate facies of Iriri evolved through K-feldspar, amphibole,
anorthite-rich plagioclase and biotite extraction, which drives the evolving magma
towards higher Dy/Yb, Sr/Y and La/Yb ratios. The acid spectra of Iriri, on the other
hand, defines a trend compatible with a rhyolitic initial composition that differentiates
to alkali-rhyolite through fractionation of albitic-plagioclase, K-feldspar, pyroxene and
titanite, with a syenite cumulate (an evolution similar to the one modeled for PAR
granites, Fig. 7). Besides the magnetite-free evolution, acid Iriri and PAR evolved on an
amphibole–absent trend, which reinforces a change on the tectonic framework of the
TMP. The predominantly hydrous and oxidized melts from OMS were possible due to
an active subduction-zone that provided slab-derived fluids and oxidizing agents to the
mantle wedge. The geochemistry features of PAR and Iriri contrasts with OMS and
suggests that subduction-modified mantle is the most likely source for the ca. 1.88 Ga
magmatism on the TMP region.

The Maloquinha Intrusive Suite (MLQ, ca. 1.87 Ga) represents the final pulses of
YMS. It is compositionally homogeneous and varies from metaluminous to highly

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peraluminous alkali-granites that indicate a greater proportion of incorporated lower

crust components and peritectic minerals (possibly garnet?) by primary magmas.
Geochemical modelling shows an evolution that starts from a granitic initial
composition that evolves to alkali-granite through extraction of plagioclase (36%), K-
feldspar (36%), clinopyroxene (25%) and ilmenite (3%). According to the geotectonic
model proposed by Fernandes et al. (2011), around 1.88 Ga the TMP was affected by
flat-subduction event that metasomatized the lithospheric mantle. Magma generation
in this context would involve the directly underthrusted subcontinental-lithospheric-
mantle (SCLM), severely metasomatized by the previous events. This tectonic setting
would generate high-K and metaluminous primary magmas that shift to higher
aluminosity upon crustal contamination. The ultimate result translates into the close to
zero or slightly negative εNd(T) (between -2.64 and -0.28) acquired for MLQ. As
proposed by Bonin (2004), high-K igneous suites are genetically related with
phlogopite-bearing and metasomatized lithospheric mantle melting, that will
commonly present crustal contamination as it ascends. MLQ shows similar
geochemical and petrologic characteristics with the Fe-K igneous suites of the Matok
pluton located at northern Kapvaal Craton (Laurent et al., 2014). The authors
understand the pluton’s composition as an intermediate member between Mg-K
sanukitoids and A-types granites that would be the result of differentiation of a
parental mafic magma whose petrogenesis would involve melting of both
metasomatized SCLM and asthenosphere. With the suppression of the subduction
process, on a continent-continent collisional setting, either slab-breakoff, slab-retreat
or SCLM delamination could result in asthenospheric mantle inflow and, in this case,
SCLM melting would be a consequence of the increasing thermal anomaly, a tectonic
scenario that is an analogue for MLQ petrogenesis. Ascension of magma for the
formation of both MLQ and late pulses of Iriri magmatism is particularly enhanced by
the continental-crust extension due to astenospheric upwelling (Fig. 10d). In fact, it is
exactly at this tectonic stage that the São Gabriel AMCG association (central
Amazonian Craton) is formed (Valério et al., 2018). Even though the precise
petrogenetic processes that involve MLQ still require further investigation, the tectonic
implication of its geochemistry signature is invariable. It marks the shift of the tectonic

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setting from a post-collisional or post-orogenic to an early-anorogenic tectonic setting,

with increasing degrees of crustal signature on originally metaluminous SCLM melts.

4.3. Metallogenetic Potential of the Igneous Suites

Both whole-rock and zircon geochemistry allowed constraining the most and
least fertile suites for the formation of Cu – Au magmatic-hydrothermal mineral
systems. The first pulses of OMS magmatism at ca. 2.0 Ga are included on group I
granitoids. These are characterized by a strong crustal component and a magnetite-
and pyroxene-bearing petrologic trend that coupled with fO2 estimates close to or
below ΔFMQ positions group I slightly below the optimal oxidizing window for typical
porphyry Cu – Au deposits (ΔFMQ +0 to +2, Sun et al., 2015). This indicates that
despite the presence of small amounts of magnetite, the subduction process still
needed to reach its maturity in order to generate more hydrous and higher fO2
magmas. As a consequence, these rocks lack the geochemistry attributes of typical
ore-forming plutons and should be understood as metallogenetic unfavorable.

As stated by Richards (2015a) it may take tens of million years after the onset
of subduction so arc-related magmas can acquire their characteristic oxidized
signature (≥ ΔFMQ +0.5). OMS’s group II granitoids represent the evolution of the
magmatic-arc (granodioritic porphyry dated at 1986 Ma), that according to the
modeling results evolved through amphibole and magnetite fractionation. The fO2
estimates of ΔFMQ +0 to +4 lends support to the oxidized conditions of group II
magmas, that consequently should be understood as metallogenetic fertile. Not
surprisingly, the Patrocínio (Cassini, 2016), Tocantinzinho (Borgo et al., 2017) and the
Coringa deposits (Tokashiki, 2015) are hosted by OMS rocks, where mineralization is
defined by disseminated gold bearing sulfides or by pyrite-quartz ±gold ±chalcopyrite
veins and veinlets most often found in the sericitic and, less frequently, in the
potassic and propylitic alteration zones.

The high-K and low silica rocks of group III (quartz-syenites and monzonite of
1993 – 1974 Ma) represent metasomatized mantle melts that evolved on a pyroxene-

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and ilmenite-bearing trend. Zircon-based fO2 estimates around ΔFMQ +0 to +2

position these rocks on the reduced spectra of the magmatic-arc which, in theory,
represent unfertile plutons. On the field, however, group III rocks often display
hydrothermal alteration (sericitic, potassic and/or carbonatic) with disseminated,
gold bearing, pyrite and pyrrhotite, despite its reduced characteristic. Such features
suggests that group III magmas interacted with the more oxidized, hydrous and
metallogenetic fertile group II melts, ultimately generating the textural relations,
hydrothermal alteration and mineralized syenites and monzonites.

Despite the theoretical potential of group II and III granitoids for the formation
of magmatic-hydrothermal mineral deposits, the available data point to mineralization
age of 1.86 – 1.84 Ga (Ar-Ar dating of alunite crystals by Echeverri Misas (2015) and
Juliani et al. (2005), that macthes YMS timing.

Whereas OMS represents the magmatic-arc sequence, with oxidized and

hydrous melts, YMS represents the evolution of the tectonic framework towards late-
orogenic and collisional tectonic settings. During active subduction, the continuous
sulfur influx through the mantle enables a high fS2, which stabilizes gold- and copper-
rich residual sulfides. When subduction stalls, subsequent mantle melting will
destabilize previously formed sulfides and mobilize their metallic content into the
generating melt (Richards, 2011a, 2015a). For this reason, late-orogenic or collisional
magmatism such as part of the YMS, are prone for the formation of gold-rich porphyry
deposits (Hou et al., 2013; Chen et al., 2015; Richards, 2015b). In fact, both the Batalha
and Palito deposits (and possibly the younger São Jorge granite) are hosted by the PAR
granites that represent the first batches of YMS (ca. 1.89 Ga). The hosting granites are
metaluminous to mildly peraluminous, high-K to shoshonitic, show more evolved Nd
isotopes than OMS and > 2.0 Ga inherited zircon grains, all suggesting a mutual role of
metasomatized mantle and crustal sources on a post-orogenic or collisional tectonic
setting (Santos et al., 2004; Echeverri Misas, 2015; Cassini et al., 2020). Iriri volcanics
host the epithermal (high-sulfidation) V3 gold deposit. The rocks are ferroan,
peraluminous, alkali-calcic to calc-alkalic compatible with a stronger crustal
contribution in primary SCLM-derived magmas, also compatible with a post-orogenic
or collisional tectonic setting.

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Part III – Discussion and Conclusions

5. Conclusions

The efforts applied in this study focused on unrevealing how the Orosirian
suites evolved on the Tapajós Mineral Province (TMP), the given tectonic setting
behind the suites and how these parameters translate into metallogenetic fertility.
Two methods were applied: whole-rock geochemistry, which includes unpublished
data and results available on the bibliography; and new in-situ trace-element
measurements and U-Pb dating in zircon grains, which allowed further petrogenetic
and geochronology constraints.

The results allowed the individualization of two main age groups in the TMP,
the older-(OMS, 2.0 – 1.95 Ga) and younger magmatic sequences (YMS, 1.89 – 1.86
Ga). Within the OMS, three group of granitic rocks (with minor extrusive equivalents)
are individualized:

 Group I marks the onset of subduction-related magmatism

(granodiorite sample dated at 2011 Ma) and comprises peraluminous
granites (s.s.) and granodiorites, characterized by highly evolved εNd(T),
and an anhydrous and slightly oxidized petrologic evolution (– 4 ≤ ΔFMQ
≤ + 0).
 Group II comprises metaluminous to peraluminous granites and
rhyolites inserted on the 1.98 – 1.95 Ga interval (the granodioritic
porphyry dated at 1986 Ma represents this stage of the arc-
magmatism). These rocks evolved on an amphibole- and magnetite-
bearing trend (0 ≤ ΔFMQ ≤ + 4) which indicates the presence of hydrous
and oxidized mafic parental magmas and, consequently, the evolution
and maturity of the arc-magmatism. Furthermore, group II granites are
the units that cover the most area within OMS.
 Group III involves high-K, low-silica, ferroan and metaluminous quartz-
syenites and monzonites (dated at 1993 – 1974 Ma) characterized by
juvenile εNd(T). Geochemical modelling reveals a reduced and
anhydrous evolution compatible with pyroxene and ilmenite

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Part III – Discussion and Conclusions

fractionation. Despite its synchronicity with group II, group III rocks
represent juvenile batches of magma as a consequence of
decompression melting of metasomatized mantle.

Despite the heterogeneities and geochemistry variability involved in subduction

related magmatism, the results acquired adequately explains (and predicts) the
petrologic evolution and the composition of the evolving melts through fractional
crystallization. Interestingly, the worst correlation for the fractional crystallization
models (or highest R²) belongs to group I granitoids, that accordingly show the greatest
evidence of crustal assimilation.

The YMS comprises rocks from the Iriri Group (1.89 – 1.87 Ga) and granitoids
from the Parauari (PAR, ca. 1.89 Ga) and Maloquinha Intrusive Suites (MLQ, ca. 1.87
Ga).

 Iriri volcanic rocks are metaluminous to peraluminous, magnesian to

ferroan and cover a vast compositional range (from andesites to alkali-
rhyolites). The intermediate facies evolved on an amphibole-bearing
and magnetite-free trend. Acid volcanics, on the other hand, lacks
amphibole and evolved a reduced trend, suggesting reduced and
anhydrous parental magmas that significantly differ from OMS’s source.
 PAR is synchronous with the first pulses of Iriri and comprises
metaluminous to peraluminous, high-K to shoshonitic and ferroan
granites that are characterized by evolved εNd(T) (average of -4.85).
These rocks evolved on a reduced and anhydrous trend that supports
different sources for YMS magmas (most likely metasomatized mantle)
as a result of a changing tectonic framework on the TMP, from
subduction to a post-orogenic setting.
 MLQ defines the final pulses of YMS, represented by metaluminous to
highly peraluminous alkali-granites that show slightly negative or close
to 0 εNd(T) and a reduced and anhydrous trend. These features are
interpreted as the consequence of metasomatized SCLM melting after
the flat-subduction event on ca. 1.88 Ga.

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Part III – Discussion and Conclusions

By looking in detail to the acquired results, OMS’s group II granites gathers the
required features to be considered as metallogenetic fertile (i.e. metaluminous to
peraluminous, magnesian to ferroan, hydrous and oxidized rocks), fact that is attested
by the Patrocínio, Tocantinzinho and Coringa deposits. The YMS rocks evolved on a
reduced and anhydrous petrologic trend that in theory would be economical
metallogenetic unfertile plutons. Perhaps the most crucial point to be taken into
account regarding the metallogenetic potential of the igneous suites in the TMP
involves remobilization of previously formed gold-rich sulfides. As demonstrated, YMS
petrogenesis invariably involves melting of subduction modified mantle sources and,
consequently, the first pulses of the younger sequence (Parauari and Iriri volcanics)
might be responsible for remobilization of residual sulfides and their metallic content,
ultimately resulting in gold-rich magmatic-hydrothermal mineral deposits as
exemplified by the Palito, Batalha, V3 and São Jorge gold deposits.

95
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Supplementary material I - Zircon Geochemistry

109
LA-ICP-MS trace-element measurements in zircon grains for sample USP14-83 (aplitic syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
486 128. 198. 107
83 - 1 Core 7.77 2.00 2030 530 7300 1.63 0.91 69.0 28.0 18.0 33.0 21.0 5.9 4.2 76.0 493 56 92 9 250 398 31 473 18
800 0 0 70
12.0 440 1100 808
83 - 3 Core 0.67 713 17 0.29 0.13 19.4 0.5 2.3 0.3 3.4 0.2 0.7 0.1 66.1 1.4 215 4 42 1 180 65 2 62 3
4 000 0 0
455 1200 24.8 310. 183. 961
83 - 11 Core 7.75 0.64 1623 60 6.20 48.0 56.5 6.3 42.4 4.1 6.1 0.6 11.0 373 10 68 2 220 342 16 257 7
000 0 0 0 0 0
10.2 485 1400 228. 921
83 - 16 Core 1.20 2271 52 0.41 0.12 48.1 6.2 15.0 2.0 22.3 2.4 2.9 0.3 6.9 536 22 95 3 290 345 15 193 14
0 000 0 0 0
12.3 501 1300 149. 128. 995
83 - 21 Core 1.00 1471 49 0.77 0.10 16.0 13.5 1.6 17.2 1.5 2.4 0.2 3.9 359 12 66 2 320 554 25 493 18
9 000 0 0 8 0
11.0 435 214. 243. 828
83 - 29 Core 0.99 2527 90 9500 1.00 0.16 23.0 22.5 2.2 28.7 3.8 3.8 0.5 8.8 552 15 100 2 180 534 24 367 13
3 900 0 2 0
47
83 - 16. 1.4 1500 0.8 0.0 17 14. 19. 11 24 93 25 23 17
Core 1024 56 40 6.7 1.0 0.9 3.3 0.3 3.9 7 44 1 8 5
37 88 0 0 4 5 0.8 7 1 5.5 4 50 0 0 5
00
451 112. 102. 981
83 - 50 Core 7.29 1.10 860 110 9300 0.80 0.28 30.0 11.5 2.8 15.5 3.7 2.4 0.6 14.0 224 14 41 3 210 184 12 173 5
100 0 0 0
428 1100 958
83 - 62 Core 4.02 0.57 972 27 1.18 0.77 91.0 7.4 7.6 1.7 9.4 1.2 1.2 0.2 88.3 3.8 277 7 54 2 320 309 8 401 10
000 0 0
Rim 411 906
83 - 7 6.39 0.86 746 36 9100 6.20 2.70 39.0 6.5 10.4 3.8 4.8 1.0 0.4 0.1 65.4 3.8 231 9 44 1 300 225 12 223 10
(i2) 400 0
19.4 490 161 150. 107. 456. 112
83 - 13 Rim 1.40 3490 220 7400 5.50 0.49 78.5 5.7 9.8 20.9 1.8 47.0 589 54 97 7 340 844 48 322 12
4 800 0.0 0 9 0 10
10.3 469 1600 274. 211. 988
83 - 17 Rim 0.87 1680 130 3.69 0.53 32.0 63.0 5.8 68.5 6.4 11.2 1.1 17.0 329 17 56 3 270 681 77 321 12
2 000 0 0 0 0
486 1500 145. 111
83 - 30 Rim 6.32 0.89 1694 67 2.65 0.24 70.3 9.8 19.8 1.2 17.1 1.4 2.9 0.3 7.7 538 19 102 3 340 421 23 795 30
000 0 0 30
450 1400 118. 107. 102
83 - 44 Rim 7.23 0.67 970 130 0.72 0.22 37.0 13.7 4.3 18.4 5.3 3.3 1.1 20.0 250 21 45 3 220 195 16 308 21
000 0 0 0 30
12.5 536 1600 303. 179. 109
83 - 46 Rim (i) 1.80 1780 100 3.85 0.23 20.0 41.1 6.0 44.9 6.4 7.7 1.1 7.8 358 16 64 4 690 248 21 502 26
1 000 0 0 4 90

110
LA-ICP-MS trace-element measurements in zircon grains for sample USP14-83 (aplitic syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
5040 1800
83 - 41 Core 9.91 0.98 2495 77 5.58 0.41 328.0 13.0 63.1 4.2 57.0 3.1 9.4 0.9 238.9 5.1 512 11 90 3 9350 360 545 24 419 16
00 0
5131 1082
83 - 72 Core 8.75 1.00 1187 54 9700 0.80 0.08 296.0 8.2 15.6 1.3 19.9 1.2 3.7 0.4 121.3 7.8 266 12 49 3 320 238 10 139 5
00 0
4962 1550. 1115
83 - 73 Core 33.53 3.50 5420 530 6700 10.39 0.86 160.0 148.0 13.0 161.0 16.0 27.5 3.0 603.0 52.0 1226 66 210 10 320 768 45 1952 67
00 0 0
114. 127 451 740 29.5 528 370. 433. 507. 181 150. 223 101 326 184
83 - 5 Core 5.90 800 2.30 31.0 34.0 91.2 6.9 160 361 22 180 240 80
79 30 300 0 0 0.0 0 0 0 0.0 0 0 80 0 3
4890 1300
83 - 8 Core 7.05 1.10 1122 54 0.21 0.02 112.9 8.7 5.3 0.3 8.3 0.6 1.4 0.1 110.5 7.7 284 10 52 2 9250 340 286 13 112 5
00 0
1310 4650 1000 5870. 1770. 1193
83 - 9 Core 37.41 1.70 1500 27.60 3.20 770.0 410.0 37.0 507.0 52.0 99.0 10.0 200.0 1740 170 267 29 330 1840 170 1390 68
0 00 0 0 0 0
1120 4950 1400 2910. 1700.
83 - 12 Core 39.60 3.70 1100 16.00 1.90 440.0 227.0 22.0 317.0 29.0 61.0 6.2 170.0 1810 140 270 18 8400 340 695 58 1640 160
0 00 0 0 0
4640 1600 1291
83 - 18 Core 9.85 0.64 4950 110 17.46 0.79 726.0 69.0 162.0 5.8 165.4 8.8 28.5 1.5 577.0 22.0 1169 31 215 6 380 988 39 2750 110
00 0 0
4883 2950. 1262. 1020
83 - 23 Core 15.21 0.90 9260 330 7700 26.20 1.30 160.0 441.0 34.0 466.0 20.0 88.2 4.1 45.0 1275 39 197 5 230 1272 78 1060 110
00 0 0 0
4730 1021
83 - 27 Core 19.80 7.50 2600 200 8300 10.60 2.10 276.0 20.0 95.0 12.0 93.0 12.0 16.1 2.2 300.0 23.0 492 63 84 10 290 430 64 697 69
00 0
4769 2300. 1200. 1060
83 - 31 Core 12.95 0.75 9000 1100 8000 20.50 2.60 460.0 294.0 39.0 346.0 50.0 60.3 9.2 190.0 1530 130 246 19 230 3020 320 2077 41
00 0 0 0
4550 1400 2250. 1001
83 - 33 Core 25.14 1.70 6480 310 13.29 0.66 130.0 190.4 9.5 217.0 11.0 37.5 1.9 788.0 45.0 1320 47 221 10 260 1820 170 1355 85
00 0 0 0
4330 1700
83 - 39 Core 30.97 1.20 3520 130 7.65 0.25 141.8 4.7 82.4 3.5 72.1 2.7 14.6 0.6 373.0 14.0 661 18 122 4 8190 440 315 9 567 13
00 0
4110 1100
83 - 43 Core 8.50 0.71 1150 120 0.55 0.05 99.8 4.1 11.6 1.0 18.2 3.0 3.1 0.2 120.1 6.7 262 19 47 2 8110 270 253 12 213 7
00 0
4360 1300
83 - 48 Core 11.54 1.10 3910 120 5.72 0.60 246.0 20.0 93.3 8.5 85.8 6.9 14.6 1.3 395.0 15.0 950 31 164 6 9600 250 1303 73 1220 110
00 0

111
LA-ICP-MS trace-element measurements in zircon grains for sample USP14-83 (aplitic syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4367
83 - 52 Core 21.99 1.30 3620 170 9000 8.04 0.47 793.0 46.0 123.4 8.0 148.1 8.5 26.7 1.8 525.0 31.0 675 32 105 4 9430 210 3020 140 551 20
00
4920 1400 1065
83 - 58 Core 5.00 0.43 2965 98 2.61 0.37 122.0 11.0 35.7 3.6 40.9 3.3 6.7 0.5 284.0 10.0 845 32 149 6 350 870 37 1521 68
00 0 0
4990 1100 1139
83 - 54 Core 13.73 1.10 3530 160 7.80 1.10 749.0 92.0 97.0 7.4 104.5 7.3 18.4 1.5 369.0 17.0 772 43 132 6 430 1390 100 900 100
00 0 0
2460 4210 1200 3730. 1054
83 - 60 Core 18.23 0.92 1200 25.90 1.30 743.0 48.0 334.0 18.0 512.0 25.0 121.4 6.8 220.0 3310 150 483 20 240 6670 840 774 84
0 00 0 0 0
4490 1400
83 - 63 Core 39.96 3.00 4260 180 8.43 0.43 821.0 23.0 143.2 7.5 157.8 6.4 27.3 1.2 535.0 30.0 810 45 143 7 8610 270 687 34 750 31
00 0
4920 1400 1086
83 - 68 Core 5.31 0.53 2823 53 4.76 0.16 280.0 11.0 40.8 2.5 42.5 1.7 6.5 0.3 284.7 9.0 813 23 145 4 340 671 23 1418 47
00 0 0
4940 1400 2421. 1004. 1027
83 - 70 Core 42.15 2.30 6790 240 16.17 0.58 65.0 250.0 10.0 310.0 11.0 56.2 2.8 47.0 1115 52 166 6 230 1976 88 930 31
00 0 0 0 0
4680 1300 1145
83 - 2 Rim 16.76 1.60 6490 580 33.90 2.10 990.0 130.0 219.0 19.0 226.0 27.0 44.3 5.4 827.0 96.0 1270 60 210 10 260 1622 82 2759 65
00 0 0
4580 1300 1089
83 - 4 Rim 8.95 0.74 3080 120 23.80 0.74 252.0 17.0 102.8 5.1 78.0 4.1 16.0 0.7 325.0 15.0 787 37 141 5 270 1019 26 2183 56
00 0 0
4730 1600 1910. 1074
83 - 6 Rim (i1) 36.20 2.90 4350 180 8.67 0.61 130.0 145.0 13.0 179.0 15.0 32.0 3.1 633.0 33.0 828 47 137 10 840 1242 86 559 26
00 0 0 0
4819 1112
83 - 10 Rim 17.49 1.70 4690 240 7500 29.50 1.00 920.0 120.0 169.0 13.0 125.0 15.0 23.0 3.0 478.0 43.0 1155 38 202 5 220 1542 46 3135 66
00 0
4666 2160. 1120
83 - 15 Rim 35.47 2.90 4960 300 6500 15.30 2.30 230.0 209.0 28.0 243.0 32.0 38.0 5.0 649.0 63.0 1040 49 173 7 180 2070 110 1292 37
00 0 0
4450 1000 1054
83 - 19 Rim 4.63 0.54 1572 91 3.25 0.46 128.0 34.0 26.3 3.2 27.6 4.5 5.2 0.8 146.0 14.0 465 12 89 2 170 546 18 829 30
00 0 0
4850 1500 1184
83 - 22 Rim 48.34 6.60 4430 180 32.30 2.20 672.0 56.0 169.0 14.0 135.7 9.9 25.6 1.5 459.0 20.0 1088 32 193 4 280 1430 72 2905 80
00 0 0
162.7 4610 1800
83 - 26 Rim 28.00 2431 90 4.50 0.49 148.0 17.0 29.1 2.7 31.5 2.5 5.4 0.4 214.7 9.3 752 28 144 4 9970 340 595 26 1901 50
7 00 0

112
LA-ICP-MS trace-element measurements in zircon grains for sample USP14-83 (aplitic syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4623 1164
83 - 28 Rim 19.50 0.94 4490 150 8800 22.20 1.60 620.0 55.0 136.9 4.9 133.0 8.0 23.5 1.4 537.0 24.0 998 31 170 5 240 1582 71 1927 54
00 0
4910 1100 1237
83 - 36 Rim 9.91 0.96 3230 99 5.82 0.32 532.0 48.0 71.5 5.7 76.0 4.6 13.2 0.7 321.0 19.0 816 36 149 9 300 770 44 2104 85
00 0 0
126.3 4710 1200 1176
83 - 38 Rim 20.00 3172 83 33.10 1.80 312.0 24.0 83.7 6.3 65.6 3.3 12.6 0.5 320.9 9.2 853 23 160 3 310 1271 51 2834 66
3 00 0 0
4720 1400 1076
83 - 51 Rim 21.99 2.50 3730 330 12.90 1.10 545.0 98.0 114.0 14.0 112.0 15.0 20.0 2.8 397.0 35.0 799 38 143 7 370 1342 78 2209 54
00 0 0
4911 1354
83 - 61 Rim 21.14 1.80 5400 420 8500 13.10 1.00 269.0 32.0 98.0 9.7 96.0 11.0 22.0 2.7 572.0 53.0 1335 59 242 7 310 1297 82 2571 77
00 0
4446
83 - 66 Rim 22.11 1.50 4900 370 7700 3.91 0.85 130.0 17.0 48.6 6.4 76.2 9.4 17.8 1.9 625.0 54.0 781 55 114 7 9970 160 1080 150 648 28
00

113
LA-ICP-MS trace-element measurements in zircon grains for sample USP14-91 (syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4436
91 - 10 Rim 8.28 0.63 915 16 4400 0.61 0.06 20.3 0.4 2.9 0.3 3.7 0.2 0.4 0.0 77.2 1.4 279 5 53 1 9570 200 144 3 168 4
00
4805
91 - 14 Rim (i) 9.62 0.70 820 17 8400 0.02 0.01 28.1 0.5 1.1 0.1 2.7 0.2 0.3 0.1 66.8 2.7 246 7 47 1 9040 210 210 5 216 6
00
4232
91 - 21 Rim 8.99 1.00 728 33 8700 0.69 0.11 17.1 0.5 2.8 0.3 3.3 0.4 0.4 0.1 60.5 2.6 253 14 50 2 9580 220 207 4 328 13
00
4230 1300
91 - 35 Rim 14.70 1.80 636 14 5.60 4.70 35.0 12.0 7.1 5.2 3.4 1.0 0.4 0.1 59.6 1.7 207 5 40 1 9230 210 160 3 197 4
00 0
4302
91 - 37 Rim 5.82 0.52 825 20 8800 7.06 0.85 41.3 1.8 13.5 1.1 5.8 0.4 0.7 0.1 72.9 2.3 255 6 49 1 9390 220 197 5 251 5
00
4434
91 - 46 Rim 5.64 0.42 829 23 8100 0.11 0.03 22.5 0.5 1.3 0.2 2.7 0.2 0.2 0.0 68.8 2.5 257 10 50 2 9750 230 263 7 317 12
00
4850 2200 1017
91 - 64 Rim 8.81 0.68 806 35 0.08 0.02 23.6 1.0 1.4 0.3 3.3 0.3 0.3 0.1 69.1 3.8 246 8 47 2 300 210 10 248 11
00 0 0
4757
91 - 28 Rim 7.88 0.73 677 13 8300 0.02 0.00 18.0 0.3 1.0 0.1 2.3 0.2 0.2 0.0 55.6 1.3 208 6 40 1 9310 270 110 2 119 3
00
4620 1100
91 - 24 Core 14.61 0.57 1559 50 9.53 0.57 36.6 1.5 19.7 1.3 11.3 0.6 1.1 0.1 135.5 4.6 348 11 66 2 8120 260 161 8 134 6
00 0
4531
91 - 43 Core 12.51 1.20 621 67 6900 14.70 6.30 43.0 15.0 21.9 8.9 6.9 2.0 0.5 0.1 56.2 7.0 172 18 33 3 8010 140 47 5 63 5
00
5000 1200
91 - 47 Core 14.41 0.90 1852 60 1.30 0.54 22.0 1.5 9.8 1.0 10.8 0.8 1.5 0.1 160.8 8.5 432 25 79 4 8530 200 201 11 181 6
00 0
4682
91 - 49 Core 7.34 0.69 1685 33 8200 0.62 0.12 30.4 0.7 5.0 0.4 6.9 0.3 0.7 0.1 136.8 3.3 459 12 86 2 9670 220 343 12 324 11
00
4450 1300
91 - 54 Core 4.35 0.80 606 39 0.04 0.01 15.4 0.6 0.8 0.1 1.8 0.3 0.1 0.0 48.2 3.4 196 13 39 3 9530 250 144 11 213 10
00 0
4373
91 - 63 Core 8.28 0.61 790 22 8100 0.01 0.00 10.7 0.3 1.5 0.2 3.1 0.2 0.3 0.0 68.1 2.0 237 5 46 1 8900 170 79 3 94 3
00
4810 1004
91 - 65 Core 3.78 0.47 555 15 8000 0.18 0.05 9.9 0.3 1.3 0.2 2.1 0.2 0.2 0.0 45.9 1.4 173 8 34 1 150 57 2 191 8
00 0

114
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-91 (syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4800 1400 1002
91 - 4 Rim 6.45 0.54 766 33 0.01 0.01 25.8 0.8 1.0 0.1 2.6 0.2 0.2 0.0 65.3 2.5 232 7 44 1 220 216 6 254 9
00 0 0
4160 1000 1017
91 - 8 Rim 3.89 0.46 411 14 0.01 0.00 10.8 0.4 0.4 0.1 0.9 0.1 0.1 0.0 33.1 1.6 159 4 33 1 260 102 4 180 7
00 0 0
4710 1400
91 - 15 Rim (o) 6.88 0.98 854 39 9.50 3.60 46.6 8.0 14.3 5.4 5.2 1.5 0.3 0.1 67.2 3.7 250 6 48 2 9730 240 250 7 301 7
00 0
4400 1400
91 - 23 Rim 6.15 0.51 624 47 0.30 0.12 17.5 1.1 1.7 0.4 2.4 0.3 0.4 0.1 54.9 4.1 201 12 39 2 9540 230 103 6 146 7
00 0
4440 1100
91 - 25 Rim (i) 8.33 0.89 1183 32 0.36 0.10 22.1 1.2 3.1 0.5 5.0 0.5 0.5 0.1 105.1 5.4 339 12 65 2 9430 230 230 11 235 9
00 0
4100 1000
91 - 30 Rim 4.64 0.51 646 18 0.01 0.01 12.2 0.3 0.4 0.1 1.7 0.2 0.2 0.0 63.6 2.8 184 8 37 1 8780 220 58 3 166 6
00 0
4470 1000 1020
91 - 48 Rim 5.13 0.47 800 21 0.06 0.03 21.6 1.4 1.4 0.2 2.7 0.3 0.2 0.0 67.2 2.7 283 8 53 1 120 270 9 373 12
00 0 0
4390 1100
91 - 66 Rim 6.67 0.85 1108 49 0.88 0.14 14.4 1.1 6.7 0.7 7.1 0.6 1.0 0.1 110.7 6.7 293 12 55 2 9200 200 125 7 255 6
00 0
4314 1016
91 - 29 Core 5.19 0.47 982 37 8800 0.02 0.01 11.6 0.4 1.2 0.1 3.1 0.3 0.2 0.0 86.4 3.5 276 11 52 2 200 106 5 339 9
00 0
3970 1400
91 - 40 Core 15.91 1.10 3480 230 0.86 0.19 21.8 0.9 11.9 0.6 18.5 2.1 2.6 0.3 316.0 18.0 819 60 149 9 6670 280 599 47 361 22
00 0
4690 1100
91 - 22 Core 15.79 1.30 3400 130 14.70 4.10 98.0 12.0 48.0 8.2 30.9 3.6 7.3 0.6 302.0 19.0 1065 28 204 5 9780 280 1337 89 2598 68
00 0
4120 1100
91 - 68 Core 6.62 0.68 592 17 0.20 0.02 16.0 0.6 1.5 0.2 2.0 0.3 0.1 0.0 51.8 2.2 201 4 40 2 8940 270 108 3 152 4
00 0
4090 1000
91 - 69 Core 19.92 2.10 1397 46 1.85 0.13 30.6 1.6 8.8 1.0 8.6 0.6 1.2 0.1 129.7 5.9 414 20 75 2 9180 290 264 15 235 7
00 0
35.7 238 482 160 247. 108
91 - 70 Rim 2.80 52 9.20 0.68 71.7 2.7 34.0 2.0 22.2 2.0 4.5 0.3 16.0 792 38 133 6 600 494 52 594 42
1 3 000 00 0 80
4660 2400 1066
91 - 1 Core 7.41 1.70 892 15 0.09 0.03 25.1 1.2 1.7 0.3 3.6 0.2 0.2 0.1 84.4 5.1 275 14 51 3 730 239 11 293 17
00 0 0

115
LA-ICP-MS trace-element measurements in zircon grains for sample USP14-91 (syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4583
91 - 2 Rim 19.92 1.30 1055 29 7800 1.72 0.21 29.5 1.2 7.1 0.7 6.3 0.4 1.0 0.1 100.0 4.1 339 13 62 2 8970 160 223 10 210 7
00
4520 1100
91 - 6 Rim 9.81 0.85 1129 48 1.50 0.25 36.2 1.7 6.4 0.9 6.0 0.5 0.9 0.1 99.9 4.4 337 13 63 2 9770 210 439 15 458 9
00 0
4100 1100
91 - 7 Core 11.54 1.20 1180 77 2.96 0.20 20.9 0.9 8.7 0.7 5.0 0.6 0.8 0.1 77.9 7.2 513 21 105 4 6420 160 244 5 324 9
00 0
4220 1000
91 - 9 Core 39.11 3.30 1910 510 1.04 0.09 11.9 0.5 9.2 2.4 18.6 6.5 7.8 3.1 237.0 85.0 359 68 66 10 8210 250 80 7 129 7
00 0
4496
91 - 11 Core 17.37 1.20 511 17 8500 9.80 0.61 52.0 1.5 32.0 1.9 10.0 0.7 3.1 0.2 50.0 1.5 142 4 27 1 9160 220 40 1 73 3
00
4311
91 - 13 Core 10.20 1.80 1265 64 4200 1.21 0.53 19.9 2.4 6.1 1.9 6.6 1.3 1.1 0.2 120.1 6.2 366 20 68 2 9900 340 154 5 355 25
00
4580 2000
91 - 19 Rim 24.05 1.20 1033 37 2.60 0.11 31.7 1.2 10.9 0.5 8.2 0.4 1.4 0.1 103.7 2.7 325 22 59 4 9250 700 204 27 214 28
00 0
4490 1500
91 - 20 Core 16.64 1.10 650 49 0.53 0.15 12.8 1.1 2.8 0.5 3.8 0.5 0.7 0.1 62.7 3.8 205 13 38 2 7850 210 79 5 103 7
00 0
4610 1100 1016
91 - 27 Core 6.83 0.51 565 13 0.89 0.10 19.2 0.6 3.1 0.4 2.7 0.3 0.5 0.0 49.1 1.4 181 6 35 1 330 114 3 165 5
00 0 0
4940 2200 1094
91 - 31 Core 52.84 3.30 3392 82 11.25 0.55 82.5 4.1 46.5 3.0 32.1 1.2 5.6 0.3 349.0 12.0 1085 59 187 2 600 996 43 1106 80
00 0 0
4349
91 - 32 Rim (i) 28.79 1.60 1740 57 7400 6.81 0.50 55.4 3.1 27.4 1.8 16.3 0.9 3.8 0.2 177.9 7.3 632 25 120 4 9430 190 288 9 443 9
00
4300 1100
91 - 33 Rim (o) 13.26 0.71 916 42 1.25 0.12 30.2 1.5 5.8 0.5 5.0 0.4 0.6 0.1 85.7 4.6 307 13 56 2 9270 160 207 11 247 12
00 0
4116
91 - 34 Core 11.95 0.91 373 18 9500 0.48 0.04 11.4 0.3 1.6 0.2 1.4 0.2 0.2 0.0 30.8 1.3 131 5 26 1 8320 240 58 1 62 2
00
4148
91 - 36 Core 12.88 1.40 1300 130 6600 1.47 0.22 16.7 1.1 9.2 1.0 9.5 1.0 2.0 0.3 118.0 12.0 360 47 77 12 8910 260 127 12 178 8
00
5140 2000
91 - 38 Core 17.73 1.60 1541 64 1.36 0.18 11.3 0.7 6.9 0.5 8.4 0.7 0.9 0.1 129.1 6.3 408 15 78 2 8560 290 125 11 321 15
00 0

116
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-91 (syenite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
30.0 129 464 840 124. 107
91 - 39 Rim 2.10 37 3.39 0.17 40.8 1.3 14.7 0.8 9.6 0.6 1.9 0.1 6.0 424 8 76 3 340 288 8 412 15
0 1 700 0 9 70
4375 1002
91 - 42 Rim (o) 12.51 1.40 887 58 7900 2.37 0.30 23.3 2.4 9.1 1.4 6.6 0.9 1.3 0.2 83.8 7.7 338 21 62 3 150 145 4 265 7
00 0
4520 1400
91 - 44 Rim 27.69 2.10 665 23 1.27 0.13 22.9 1.5 5.9 0.5 6.5 0.8 1.5 0.3 75.5 3.9 206 11 38 2 9750 330 145 11 177 13
00 0
4600 1000
91 - 45 Core 8.84 0.77 562 13 0.99 0.09 18.9 0.6 3.6 0.3 2.7 0.3 0.4 0.0 46.4 1.3 187 6 38 1 9330 230 95 2 136 3
00 0
4460 1000
91 - 52 Core 25.39 1.30 1371 90 2.16 0.22 29.2 1.5 11.3 1.3 9.3 0.9 1.5 0.2 140.0 10.0 394 21 72 3 8550 180 193 11 221 13
00 0
4050
91 - 53 Rim 9.40 0.70 433 11 7500 2.35 0.80 16.6 1.6 2.6 0.7 1.8 0.2 0.2 0.0 37.5 1.3 141 4 28 1 8500 150 68 2 86 2
00
4430 1100 1105
91 - 55 Rim 25.51 2.60 844 35 2.63 0.23 23.4 1.1 9.7 0.9 5.9 0.5 1.5 0.1 74.8 3.6 350 16 74 3 280 258 7 596 17
00 0 0
4758 1144
91 - 56 Core 13.00 1.30 4080 190 8500 13.52 0.87 37.6 3.3 16.1 2.2 12.5 1.0 2.1 0.3 328.0 17.0 1352 65 233 12 310 1530 110 3290 220
00 0
4390 1400 1004
91 - 57 Rim 17.86 1.70 1530 190 5.80 1.30 44.2 6.1 17.6 3.3 12.4 2.0 2.9 0.7 144.0 18.0 448 38 82 6 240 446 54 633 51
00 0 0

117
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-136 (monzonite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
5180 2600 1003
136 - 1 Core 12.03 1.30 1438 40 1.04 0.09 53.4 3.4 13.2 1.2 11.8 0.7 2.9 0.3 143.6 6.2 415 10 76 3 280 332 18 253 9
00 0 0
4790 1300
136 - 6 Core 5.45 0.58 629 14 0.02 0.01 15.3 0.5 0.9 0.1 2.5 0.2 0.1 0.0 61.4 2.0 219 7 42 1 9970 280 126 6 172 9
00 0
4924
136 - 11 Core 9.12 0.79 754 47 9200 0.08 0.02 22.1 1.6 2.1 0.4 3.6 0.4 0.4 0.1 70.5 5.0 245 12 47 3 9130 230 167 13 182 11
00
4380 1800
136 - 13 Core 13.12 1.20 1596 78 1.51 0.14 46.1 1.7 13.1 1.4 11.6 1.3 2.4 0.4 143.3 7.4 432 14 81 3 8540 250 524 31 449 15
00 0
4520
136 - 24 Core 11.42 1.50 3410 230 6700 0.85 0.23 49.3 1.9 18.8 1.6 22.7 1.2 2.5 0.4 310.0 18.0 814 56 145 9 7820 260 729 75 347 25
00
5290 1300 1143
136 - 26 Core 9.11 0.71 928 29 2.78 0.30 26.7 1.1 6.3 0.5 6.1 0.6 1.1 0.1 83.5 3.3 268 10 49 2 420 296 10 341 9
00 0 0
4758
136 - 30 Core 19.19 1.10 1610 180 8100 2.75 0.24 50.4 6.2 20.4 1.9 17.4 1.8 3.4 0.3 161.0 17.0 499 51 93 11 9300 170 427 80 421 46
00
4620 1700
136 - 40 Core 9.60 0.72 1084 76 16.60 5.90 58.0 14.0 25.6 8.3 9.3 1.7 0.6 0.1 103.9 5.4 309 14 61 3 9720 200 169 8 191 5
00 0
4520 1300
136 - 42 Core 9.86 0.72 3240 95 0.14 0.03 37.2 1.0 15.5 0.5 23.9 1.0 1.6 0.1 331.0 12.0 745 26 132 5 8050 170 708 34 458 13
00 0
4954
136 - 44 Core 20.04 1.50 3690 220 8100 3.92 0.35 142.5 9.1 31.9 3.0 30.7 2.2 4.8 0.6 353.0 24.0 970 57 164 10 8370 170 2650 220 1110 54
00
4320 1200 1005
136 - 46 Core 11.42 1.40 1370 110 1.86 0.37 31.9 3.3 13.8 2.5 12.6 1.9 3.9 0.7 138.0 14.0 387 19 68 3 230 301 10 419 12
00 0 0
4540 1400 1027
136 - 56 Rim 5.04 0.57 403 17 0.40 0.09 14.5 0.9 1.7 0.4 2.1 0.3 0.3 0.1 39.6 2.4 143 5 28 1 200 102 5 157 4
00 0 0
5240 1300 1037
136 - 2 Rim (i) 11.66 1.20 1068 48 1.37 0.32 45.4 4.0 14.0 3.4 12.1 2.2 3.2 0.7 100.9 7.1 270 9 49 1 380 294 13 320 15
00 0 0
108 510 120 102. 137
136 - 3 Rim (o) 8.62 1.10 44 1.52 0.23 43.6 2.6 16.1 2.7 12.8 2.3 4.1 0.7 5.9 372 13 81 4 540 408 53 636 61
9 000 00 5 60
26.6 143 450 890 10.4 156. 109
136 - 5 Rim 4.40 100 2.20 57.0 7.5 29.8 5.1 18.2 2.8 5.2 0.9 15.0 476 34 79 5 270 336 13 623 30
0 0 800 0 0 0 90

118
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-136 (monzonite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4620
136 - 7 Rim 12.05 0.96 1459 43 8900 1.79 0.11 39.0 1.0 17.2 1.1 16.2 0.8 4.7 0.2 152.2 4.7 345 9 61 2 9600 280 289 7 279 5
00
4798 1232
136 - 17 Rim (o) 20.16 1.60 648 21 8900 0.70 0.10 11.8 0.8 3.4 0.6 2.7 0.4 0.6 0.1 47.6 2.6 280 9 63 2 270 208 6 553 14
00 0
4550 1324
136 - 21 Rim 11.05 1.30 1580 150 9900 11.60 2.30 62.3 9.6 37.5 5.7 20.5 2.8 17.9 3.2 151.0 16.0 633 55 120 10 360 298 18 1020 120
00 0
4150 1100
136 - 23 Rim 11.78 1.10 567 15 0.47 0.05 22.0 0.6 4.3 0.8 4.1 0.4 0.9 0.1 57.3 2.3 179 5 34 1 8730 230 172 10 184 8
00 0
4807 1104
136 - 27 Rim 6.22 0.60 631 43 8200 2.11 0.25 18.7 1.3 4.5 0.8 3.8 0.6 0.7 0.1 56.4 4.0 212 14 41 3 220 146 8 247 8
00 0
4640 1300 1168
136 - 29 Rim 2.94 0.45 772 23 0.04 0.02 13.7 0.3 0.7 0.1 1.9 0.2 0.1 0.0 59.8 2.4 308 12 62 3 420 318 11 524 27
00 0 0
4657
136 - 31 Rim 9.58 0.69 629 19 8900 0.25 0.03 19.6 0.6 3.0 0.3 3.4 0.3 0.6 0.1 61.9 2.1 215 6 40 1 9960 250 148 6 186 6
00
4724 1012
136 - 36 Rim 15.31 1.10 1170 22 8200 1.64 0.08 37.7 0.7 14.5 0.8 11.4 0.5 2.7 0.2 107.4 2.5 363 7 67 1 190 269 8 341 7
00 0
5380 2200
136 - 38 Rim (i) 27.94 3.20 3397 94 4.46 0.30 80.8 1.7 44.8 2.9 42.3 2.2 8.8 0.6 340.1 6.9 797 22 139 7 9630 440 764 30 490 12
00 0
4539
136 - 39 Rim (o) 8.21 0.63 600 9 6300 0.54 0.28 22.0 0.6 1.5 0.3 2.3 0.2 0.2 0.0 53.4 1.3 192 4 37 1 9150 210 141 3 158 3
00
4810 1500
136 - 43 Rim 6.92 0.66 635 25 0.02 0.01 23.0 0.6 1.0 0.1 2.2 0.2 0.2 0.0 60.0 2.1 217 6 42 1 9810 260 144 4 169 4
00 0
4800 1000 1073
136 - 52 Rim (o) 7.09 0.69 1029 46 10.20 3.50 52.5 6.0 19.3 4.0 9.3 0.5 1.2 0.2 98.1 6.8 330 17 60 2 290 257 11 309 10
00 0 0
4510 1200
136 - 57 Rim 5.37 0.64 730 27 25.00 19.00 79.0 43.0 34.0 25.0 8.1 4.2 0.3 0.1 60.6 2.7 216 7 44 1 9450 260 196 6 245 7
00 0
4557 1009
136 - 60 Rim 16.52 1.50 1957 45 5300 3.09 0.16 41.4 1.7 19.9 1.2 17.0 1.1 4.3 0.3 184.1 7.7 556 16 100 3 190 417 11 473 14
00 0
4153
136 - 62 Rim 6.88 0.96 854 43 9700 14.70 9.90 59.0 27.0 28.0 16.0 9.7 3.4 1.0 0.2 83.2 5.5 279 11 53 2 9580 210 262 7 335 7
00

119
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-136 (monzonite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4181
136 - 64 Rim 10.20 1.00 871 49 7100 16.30 2.60 62.3 6.8 24.7 4.5 10.0 1.5 1.1 0.2 81.9 6.5 259 12 50 2 8840 150 204 7 219 6
00
4386
136 - 66 Rim 9.47 0.74 897 21 7700 0.92 0.05 26.9 0.9 7.4 0.6 7.7 0.4 1.5 0.1 96.7 3.4 271 9 49 1 9760 210 250 9 212 8
00
4960 1000
136 - 10 Core 12.40 0.83 1280 140 3.30 2.30 34.2 7.6 13.1 4.6 11.5 2.0 2.4 0.2 119.0 15.0 354 37 63 6 9990 270 241 26 188 7
00 0
4477
136 - 20 Core 21.38 1.10 1869 65 7100 2.93 0.30 47.3 2.5 23.3 2.3 18.4 1.4 3.9 0.5 182.6 9.2 535 25 98 3 9740 200 518 22 520 16
00
4576
136 - 25 Rim 30.97 1.90 2403 98 9000 15.11 0.80 115.5 3.0 57.2 2.4 35.8 2.4 24.2 1.4 257.0 12.0 631 17 105 3 9310 230 1084 46 786 21
00
3910 2300
136 - 33 Rim 28.18 4.10 1690 190 10.10 1.40 79.3 9.7 52.9 8.6 33.3 5.1 21.0 2.5 186.0 24.0 564 63 114 11 9290 440 226 27 780 82
00 0
4930 2200
136 - 53 Core 33.65 5.50 2060 610 3.90 1.80 57.0 22.0 40.0 18.0 31.0 13.0 6.9 3.0 230.0 74.0 580 170 99 28 9330 400 380 150 308 97
00 0
4480 1200
136 - 54 Rim (i) 13.36 1.00 1169 44 0.77 0.08 22.3 0.5 7.3 0.5 8.5 0.4 1.6 0.1 113.2 4.5 323 10 61 2 8420 360 177 8 142 6
00 0
51.8 376 458 160 17.4 145. 101. 454. 111 100 130 106
136 - 4 Core 4.40 400 2.00 19.0 13.0 71.4 9.5 18.7 2.6 49.0 82 186 14 210 220 120
7 0 000 00 0 0 0 0 9 20 0 0
4970 1400
136 - 28 Core 90.62 4.30 1506 50 2.74 0.16 29.7 0.9 15.5 0.5 14.3 1.0 3.0 0.2 145.6 4.6 393 12 72 2 7620 250 227 7 183 4
00 0
119.0 4450 1000
136 - 34 Core (i) 25.00 1000 120 1.23 0.38 24.4 1.5 9.8 1.3 9.6 1.4 2.5 0.4 99.0 14.0 282 33 52 6 8160 200 93 11 82 8
4 00 0
4001
136 - 50 Core 32.80 2.80 3310 230 9200 7.22 0.65 81.8 7.7 61.3 6.6 51.6 5.4 12.0 1.1 377.0 36.0 815 87 133 13 7660 220 296 40 275 26
00
4600 1200
136 - 61 Core 47.13 3.70 3850 240 12.90 1.50 105.0 9.2 53.4 6.3 40.3 4.4 17.7 2.1 379.0 31.0 1072 77 175 11 9490 360 1262 54 1322 39
00 0
4730 1300 1143
136 - 9 Rim 33.04 4.30 2840 300 16.00 8.30 85.0 20.0 48.8 9.8 37.0 6.1 7.4 1.0 303.0 35.0 930 110 152 16 310 860 100 1240 130
00 0 0
218.6 3020 2800
136 - 19 Rim 55.00 958 83 2.80 0.30 21.1 1.6 14.8 1.6 9.9 1.1 3.3 0.4 85.1 8.7 452 41 94 9 9080 880 165 19 709 59
4 00 0

120
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-136 (monzonite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4520 1200 1350
136 - 47 Rim 46.77 2.80 2703 64 25.40 1.10 144.0 5.4 102.2 3.9 51.3 2.2 31.7 1.4 284.4 8.8 684 13 129 3 250 439 13 1108 44
00 0 0
4540 1300
136 - 37 Core 8.64 0.77 1409 84 0.35 0.07 27.2 1.4 6.2 0.7 8.7 0.9 1.0 0.1 130.7 9.0 340 20 65 3 8510 190 201 12 181 11
00 0
4680 1400
136 - 18 Core 18.77 0.90 2510 230 2.60 0.23 86.4 9.2 23.8 1.6 22.3 1.1 4.2 0.4 258.0 24.0 690 49 120 8 8610 140 960 160 615 65
00 0
5010 1500
136 - 32 Core 12.63 0.91 738 47 0.34 0.06 16.1 0.7 3.1 0.4 4.8 0.4 0.8 0.1 69.7 4.3 216 10 41 2 9770 240 102 3 137 4
00 0
5210 1400
136 - 35 Core (o) 22.23 1.60 918 57 0.88 0.11 33.0 1.6 8.2 0.8 7.8 0.6 2.1 0.2 87.1 4.6 266 11 50 2 8350 180 111 3 101 4
00 0
4470 1500
136 - 65 Core 16.52 2.40 3190 950 2.52 0.34 78.0 23.0 26.6 6.8 29.4 8.8 5.9 1.9 330.0 100.0 820 220 146 37 7440 370 980 330 460 100
00 0

121
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-144 (granodioritic porphyry)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4400 1100
144 - 5 Core 8.02 0.99 1152 84 36.20 2.40 124.9 7.0 63.9 3.0 17.3 1.3 5.9 0.4 104.4 6.7 278 14 54 3 8450 230 161 11 135 10
00 0
4930 1600 1264
144 - 21 Core 13.36 1.50 5930 170 5.64 0.64 132.0 11.0 36.8 3.1 25.1 1.5 1.4 0.2 519.0 16.0 1891 36 331 6 380 4681 91 7260 200
00 0 0
4780 1300
144 - 26 Core 9.47 1.60 750 33 4.60 2.20 127.0 42.0 7.1 1.2 1.7 0.2 0.1 0.0 38.5 1.3 441 32 106 6 9630 310 232 37 1343 82
00 0
4632 1042
144 - 35 Core 6.44 0.66 1203 22 5700 21.00 10.00 60.0 16.0 11.1 4.6 5.1 0.7 0.7 0.3 96.2 2.3 344 9 66 1 190 404 8 476 8
00 0
4360 1100 1026
144 - 42 Core 7.34 0.73 1461 50 3.02 0.91 28.3 2.6 11.4 2.2 8.8 0.9 0.5 0.1 124.5 5.1 425 16 80 2 220 383 16 437 15
00 0 0
4110 1300
144 - 46 Core 8.14 1.10 1650 130 17.90 6.90 42.0 8.7 11.4 4.9 6.3 1.2 0.7 0.4 130.3 7.8 491 39 90 6 9620 510 920 110 1710 150
00 0
4830 1500 1143
144 - 51 Core 11.64 0.97 2092 94 40.40 2.80 152.0 10.0 87.0 11.0 29.8 2.7 4.0 0.5 207.0 11.0 578 34 97 4 320 1253 99 1110 66
00 0 0
4781 1060
144 - 57 Core 6.30 0.65 611 27 7500 2.31 0.30 22.6 0.7 8.7 0.6 4.3 0.2 0.7 0.1 52.5 2.8 187 5 36 1 270 133 5 185 3
00 0
4610 1332
144 - 64 Core 15.18 2.80 4670 170 8200 39.00 11.00 78.0 30.0 33.0 16.0 12.5 3.6 0.5 0.2 361.0 24.0 1654 60 301 8 430 2990 530 5570 430
00 0
4380 1013
144 - 67 Core 9.21 0.74 353 8 7700 18.50 1.70 35.2 2.3 18.6 1.3 6.2 0.4 6.8 0.7 31.4 1.2 117 4 24 1 240 68 1 120 2
00 0
4790 1600 1133
144 - 69 Core 3.04 1.10 2950 140 20.10 7.90 39.4 7.6 3.9 0.9 7.5 0.5 0.3 0.1 217.0 15.0 837 79 146 11 290 1190 110 1420 150
00 0 0
4660 1700 1115
144 - 71 Core 7.62 0.97 1295 52 29.30 8.00 89.0 19.0 33.9 7.4 8.7 0.9 1.1 0.2 114.2 5.7 391 19 75 3 330 347 21 490 26
00 0 0
4570 1100 1115 1120
144 - 79 Core 20.41 3.00 3430 660 34.00 10.00 136.0 38.0 74.0 27.0 25.5 8.1 0.8 0.2 259.0 55.0 1010 100 196 19 220 3300 9200 2200
00 0 0 0
4910 1100 1129
144 - 6 Rim 5.58 0.89 1954 70 43.00 11.00 100.0 13.0 24.2 2.7 8.9 0.6 5.7 1.4 148.8 6.3 652 35 123 5 230 716 48 1033 28
00 0 0
4650 1700 1357
144 - 8 Rim 14.70 1.20 1294 45 26.00 4.70 65.5 8.1 35.1 7.4 11.4 1.8 2.0 0.4 94.7 3.3 531 19 110 4 430 337 9 1600 44
00 0 0

122
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-144 (granodioritic porphyry)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4812 1012
144 - 10 Rim 14.09 1.60 848 55 7900 16.70 5.50 67.0 16.0 41.0 12.0 17.0 4.3 1.3 0.3 73.8 6.1 254 15 49 2 250 172 10 224 10
00 0
4495 1202
144 - 13 Rim (o) 2.43 0.33 1298 30 8900 10.00 4.60 25.9 5.3 3.7 1.5 3.2 0.3 0.2 0.1 98.1 3.3 479 14 92 3 310 549 10 1045 46
00 0
4449 1000
144 - 24 Rim 6.50 0.49 688 12 7300 0.01 0.01 23.6 0.5 1.0 0.1 2.4 0.2 0.2 0.0 59.9 1.6 216 6 42 1 210 173 4 206 4
00 0
4980 2000 1009
144 - 25 Rim 9.47 1.10 730 26 0.04 0.01 24.1 1.2 1.6 0.2 3.2 0.4 0.5 0.1 72.5 3.8 232 13 44 2 470 134 9 156 10
00 0 0
4490 1300 1051
144 - 30 Rim 4.30 0.41 1059 29 12.80 3.60 36.9 4.3 4.6 0.6 4.2 0.3 0.4 0.0 86.0 2.7 370 10 74 2 280 518 17 625 27
00 0 0
4220 1100
144 - 34 Rim 7.48 0.62 682 28 12.50 2.70 92.0 14.0 67.0 11.0 17.7 2.9 10.9 1.5 67.3 3.7 211 8 42 1 9110 220 168 10 203 14
00 0
3992
144 - 38 Rim (i) 12.63 1.70 722 11 7300 29.60 1.50 95.1 3.1 49.7 1.9 12.6 0.7 4.2 0.4 67.7 2.6 223 6 43 2 8640 300 183 4 202 5
00
4500 1300 1087
144 - 41 Rim 4.51 0.47 1010 31 12.30 3.70 50.0 10.0 16.6 5.4 4.7 0.8 2.2 0.8 80.6 2.3 365 9 72 1 200 356 13 595 20
00 0 0
4406
144 - 52 Rim 7.32 0.48 796 13 8200 2.70 1.80 31.1 5.8 8.9 4.3 5.2 1.0 0.5 0.1 71.5 2.1 245 5 48 1 9120 180 193 3 204 3
00
4470 1000 1188
144 - 54 Rim 3.75 0.68 824 23 9.10 4.60 30.4 9.1 11.7 5.3 4.8 1.5 0.6 0.3 62.6 2.9 329 11 68 2 300 316 9 675 21
00 0 0
4690 1200 1019
144 - 58 Rim 5.51 0.55 967 22 1.66 0.77 31.8 1.7 3.4 0.7 4.1 0.3 0.5 0.1 87.3 3.0 304 9 57 1 310 321 10 348 10
00 0 0
4671 1367
144 - 68 Rim 2.75 0.51 2513 77 6300 6.50 1.70 27.2 4.3 14.9 4.4 7.2 1.4 0.3 0.1 183.5 9.4 832 39 153 7 360 875 54 2460 100
00 0
4780 1400 1072
144 - 72 Rim (i) 6.68 1.00 936 30 2.80 1.50 32.7 4.5 4.9 2.0 4.4 0.6 0.3 0.0 85.0 3.8 301 12 57 2 360 269 12 352 20
00 0 0
4440 1100
144 - 78 Rim 7.29 0.50 674 21 0.01 0.01 23.3 0.9 1.1 0.1 2.8 0.2 0.2 0.0 62.8 2.9 219 8 42 1 9450 220 167 6 185 7
00 0
4431
144 - 80 Rim 10.52 0.68 728 16 8900 5.33 0.78 38.8 2.2 12.2 1.1 5.2 0.4 0.6 0.1 67.3 2.0 225 5 44 1 9380 180 176 5 181 6
00

123
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-144 (granodioritic porphyry)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4210 1600
144 - 3 Core 48.59 13.00 621 16 48.00 16.00 131.0 35.0 72.0 21.0 21.2 6.6 1.8 0.6 60.6 4.5 188 6 39 1 9330 420 178 7 221 8
00 0
108.1 4507 1003
144 - 27 Core 60.00 2240 110 8800 12.30 3.20 145.0 27.0 47.0 11.0 19.0 3.3 0.5 0.1 208.0 15.0 612 24 112 3 250 1255 59 1354 40
1 00 0
4600 1122
144 - 37 Core 51.26 4.00 1601 41 6800 34.50 5.70 95.0 14.0 58.0 11.0 15.4 2.9 1.4 0.3 132.6 6.8 463 19 90 3 250 2700 1100 1530 230
00 0
4947 1128
144 - 75 Rim 30.37 7.60 406 7 9700 3.74 0.89 28.8 2.9 18.8 2.2 5.8 0.7 5.0 0.8 31.4 1.2 142 6 28 1 420 89 3 175 7
00 0
4080 1300 1031
144 - 7 Core 25.87 5.40 306 32 38.50 8.30 149.0 44.0 98.0 43.0 24.1 9.0 6.6 2.9 32.8 4.0 101 8 21 2 570 60 2 167 16
00 0 0
4249
144 - 20 Rim 13.60 2.70 706 16 8900 26.80 1.90 87.0 4.6 51.1 2.7 15.7 1.1 5.2 0.3 64.5 1.6 221 5 43 1 9580 180 176 3 221 5
00
4570 1200 1002
144 - 28 Rim 7.28 0.63 880 57 49.00 16.00 62.0 12.0 38.0 11.0 11.8 2.4 2.7 0.7 74.5 6.3 270 20 50 3 240 189 18 357 27
00 0 0
3070 1300
144 - 29 Core 3.52 0.85 1000 180 19.90 4.60 43.7 7.9 17.4 3.6 10.9 1.6 1.0 0.2 97.0 16.0 322 38 68 6 4970 170 179 37 227 15
00 0
4170 1600
144 - 44 Core 7.80 0.86 489 25 16.70 1.90 96.0 9.8 61.6 7.2 14.7 1.6 5.8 0.6 45.9 2.5 155 8 33 1 9310 270 85 5 145 9
00 0
5310 1700 1132
144 - 48 Core 8.14 1.10 657 29 14.00 1.00 54.8 1.5 30.0 1.5 9.8 0.6 2.4 0.2 55.5 2.3 206 12 40 2 460 108 3 163 6
00 0 0
4988 1023
144 - 49 Rim (i) 9.91 0.73 793 18 8200 13.10 1.60 62.2 4.1 35.5 3.0 12.8 1.0 2.5 0.2 67.9 2.3 230 9 44 1 290 199 6 240 8
00 0
4800 1600
144 - 53 Core 17.86 1.30 1839 41 7.47 0.30 34.3 0.7 26.3 1.2 16.6 0.8 2.4 0.2 170.7 4.2 450 15 84 2 7830 240 174 4 159 3
00 0
5240 1100 1045
144 - 62 Rim (i) 8.31 0.74 701 17 0.47 0.76 27.3 1.9 1.6 1.2 2.9 0.5 0.2 0.0 60.5 1.0 223 5 42 1 320 162 4 188 5
00 0 0

124
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-160 (granodiorite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4965
160 - 1 Core 11.78 0.89 932 40 9700 0.38 0.18 11.1 0.5 3.3 0.5 5.8 0.5 0.7 0.1 85.1 3.5 222 5 44 1 9200 250 79 3 105 2
00
4285 1046
160 - 2 Core 12.63 2.70 1270 120 9800 29.40 7.60 135.0 35.0 134.0 37.0 31.3 7.7 13.8 3.8 108.0 10.0 392 28 72 4 270 103 18 528 18
00 0
4780 1100 1209
160 - 3 Core 8.87 1.10 835 40 3.56 0.32 23.8 2.1 33.4 3.8 12.1 1.2 4.2 0.4 67.6 5.9 288 15 55 2 520 41 3 322 12
00 0 0
4700 1900
160 - 5 Core 20.89 1.70 1371 28 2.20 1.00 29.3 4.9 19.5 4.2 16.0 2.1 4.3 0.7 137.3 4.6 338 7 64 1 8420 160 151 3 178 7
00 0
4140 1200
160 - 7 Core 6.79 0.99 1594 50 0.06 0.02 19.7 0.7 7.4 0.6 10.6 0.8 4.1 0.3 153.5 7.7 411 19 82 2 7400 170 157 9 96 6
00 0
4350 1200 1015
160 - 11 Core 3.72 0.37 1327 80 3.33 0.78 38.7 2.3 8.2 1.7 4.8 0.5 0.4 0.0 109.8 6.9 414 23 85 4 270 243 19 517 45
00 0 0
4590 1200
160 - 12 Core 7.37 0.73 1643 33 2.49 0.28 29.4 1.4 11.1 1.2 9.3 0.6 1.2 0.1 132.2 2.5 399 8 79 2 7700 280 219 7 316 7
00 0
4598
160 - 14 Core 8.49 0.82 1447 40 9300 0.09 0.06 37.7 1.0 3.5 0.4 6.2 0.5 1.5 0.1 117.0 6.2 454 15 90 2 8410 200 281 9 340 10
00
4650 1700 1286
160 - 21 Core 8.66 0.84 3460 390 10.50 6.20 59.0 28.0 60.0 45.0 37.0 26.0 7.4 6.2 303.0 58.0 965 43 182 5 470 1640 150 3884 93
00 0 0
4920 1800 1214
160 - 24 Core 8.14 1.30 1350 260 12.50 1.80 28.2 2.7 14.7 2.2 5.7 1.4 0.4 0.1 135.0 29.0 250 70 42 12 450 38 6 321 25
00 0 0
4460 1400
160 - 26 Core 23.20 2.60 1443 61 4.90 1.30 59.5 5.8 36.2 7.7 21.6 3.0 4.9 0.5 131.1 5.6 405 16 83 2 7580 160 214 15 245 7
00 0
4450 1300
160 - 28 Core 7.03 0.53 562 22 0.02 0.01 11.3 0.5 0.9 0.1 2.1 0.2 0.3 0.0 54.4 2.4 180 6 35 1 9570 180 73 2 141 4
00 0
4300 1000
160 - 30 Core 12.88 1.30 566 16 0.05 0.04 13.1 0.5 1.5 0.2 3.1 0.2 0.6 0.1 55.1 3.0 169 5 34 1 8070 180 62 2 79 2
00 0
4770 1500
160 - 32 Core 9.40 0.72 523 43 0.01 0.01 10.8 0.8 0.9 0.1 2.3 0.2 0.1 0.0 48.1 3.6 152 11 29 2 8770 220 67 6 136 9
00 0
4337
160 - 34 Core 9.12 0.57 938 20 9000 23.40 1.30 135.7 7.7 129.1 8.3 33.7 1.9 14.1 0.8 94.0 2.4 209 6 40 1 8540 190 76 3 118 4
00

125
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-160 (granodiorite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4640 1600
160 - 36 Core 4.88 0.43 2606 75 0.93 0.36 24.7 1.9 8.8 1.2 14.0 0.6 1.9 0.5 247.7 5.0 585 18 109 3 8920 250 388 11 566 16
00 0
4340 1600 1031
160 - 39 Core 6.11 0.89 1042 38 6.93 0.46 47.7 2.9 42.4 3.1 10.5 0.6 11.4 1.3 98.6 2.8 269 7 53 2 300 43 5 365 13
00 0 0
4110 1100
160 - 44 Core 12.75 1.10 1299 79 26.50 4.10 34.5 4.8 10.6 1.5 6.3 1.0 1.9 0.3 120.2 6.3 368 15 74 3 7760 250 96 10 250 17
00 0
4070 1300
160 - 49 Core 14.82 1.40 2714 81 36.50 1.50 186.2 4.4 178.3 5.7 62.7 1.7 8.5 0.5 300.0 11.0 600 24 109 4 7660 190 470 15 424 15
00 0
4770 1900 1107
160 - 53 Core 23.08 18.00 1375 49 24.00 13.00 136.0 52.0 121.0 70.0 51.0 25.0 8.5 5.1 124.6 6.1 436 8 86 2 460 420 13 660 33
00 0 0
4300 1200
160 - 56 Core 5.03 0.68 505 8 0.04 0.01 12.4 0.4 1.0 0.1 2.6 0.2 0.3 0.0 51.5 1.2 151 4 30 1 8620 230 79 1 139 3
00 0
4352 1101
160 - 58 Core 7.65 1.60 3211 54 8400 7.40 3.10 42.9 9.2 21.5 6.1 13.4 1.6 0.9 0.2 317.0 13.0 756 23 133 3 260 1149 62 2276 75
00 0
4670 1400 1039
160 - 62 Core 20.29 1.70 1703 34 13.80 1.50 125.0 4.6 65.6 3.6 29.4 2.5 23.5 1.6 179.1 6.8 479 12 89 3 280 385 12 346 9
00 0 0
4750 1100
160 - 64 Core 16.52 1.10 1487 39 2.82 0.12 20.1 0.8 22.1 1.1 20.0 1.1 2.4 0.2 161.9 8.8 330 13 60 2 8180 170 106 3 125 7
00 0
4570 1800
160 - 66 Core 5.66 0.63 4080 150 0.64 0.62 59.9 3.1 16.9 1.2 27.0 1.1 4.9 0.2 401.0 10.0 959 29 177 5 7880 230 1227 57 897 29
00 0
4350 1400
160 - 68 Core 18.22 1.60 1325 55 24.90 5.10 102.0 14.0 71.0 11.0 27.3 2.2 13.2 0.6 149.3 6.7 329 8 61 2 7450 150 137 6 216 6
00 0
4920 1500 1079
160 - 70 Core 18.46 2.70 2116 93 30.60 6.00 143.0 24.0 112.0 19.0 35.4 4.8 8.4 1.6 226.6 9.6 530 11 96 4 390 338 12 523 21
00 0 0
4530 1600
160 - 72 Core 9.07 0.58 552 7 0.02 0.01 6.8 0.2 1.8 0.2 3.5 0.2 0.6 0.0 59.7 1.2 159 4 31 1 8140 250 59 1 94 2
00 0
4850 1200 1094
160 - 78 Core 7.22 0.67 1890 180 0.42 0.10 10.8 0.6 9.7 0.7 13.0 1.2 1.0 0.1 179.0 18.0 436 36 81 6 390 302 41 727 50
00 0 0
5090 1200
160 - 86 Core 5.47 0.58 939 40 0.36 0.02 23.1 0.4 2.0 0.2 4.3 0.3 0.5 0.1 81.4 2.2 269 8 53 1 9830 260 131 4 187 4
00 0

126
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-160 (granodiorite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4900 1900 1296
160 - 90 Core 9.47 1.90 3100 150 9.10 4.00 68.0 15.0 43.0 14.0 19.3 2.1 4.9 1.5 304.0 18.0 881 57 155 8 270 874 59 1700 110
00 0 0
4680 1100
160 - 92 Core 10.26 0.84 1742 41 5.92 0.89 44.8 5.9 43.5 7.0 30.3 3.7 10.1 1.7 172.3 4.3 349 9 64 2 8010 160 165 5 256 7
00 0
5120 1300 1321
160 - 4 Rim 8.75 3.00 3373 99 26.20 8.10 117.0 38.0 98.0 46.0 23.8 9.2 12.6 5.4 238.3 6.6 1013 45 186 9 250 206 9 845 26
00 0 0
4113 1146
160 - 20 Rim 5.34 1.10 947 31 9100 2.00 1.00 21.0 4.3 7.5 3.4 6.3 2.1 1.7 0.9 82.9 3.5 422 23 88 5 230 97 2 823 43
00 0
5160 1700 1007
160 - 22 Rim (i) 5.04 0.81 873 27 0.02 0.01 16.2 0.5 1.1 0.2 3.3 0.2 0.3 0.1 77.0 1.6 237 10 46 1 410 122 3 218 5
00 0 0
4570 1000
160 - 33 Rim 4.54 0.97 727 16 0.01 0.01 22.4 0.6 1.1 0.2 2.2 0.2 0.2 0.0 61.7 1.7 220 6 43 1 9850 220 198 6 322 6
00 0
4970 1500 1105
160 - 40 Rim (i) 10.80 0.62 1896 51 7.06 0.56 36.1 2.3 42.8 2.6 12.0 0.9 11.7 0.8 162.3 3.3 519 17 99 3 340 121 3 768 23
00 0 0
4087 1047
160 - 47 Rim 2.92 0.52 1742 52 8900 0.13 0.06 5.9 0.3 0.8 0.2 3.5 0.4 0.3 0.0 146.1 7.4 516 17 100 3 260 150 8 502 17
00 0
4280 1500 1091
160 - 57 Rim 13.00 1.80 838 26 6.75 0.83 47.6 3.5 34.8 3.9 17.5 2.2 4.6 0.4 81.9 3.7 266 10 57 2 310 188 8 529 23
00 0 0
4168 1006
160 - 59 Rim 2.96 0.46 1168 35 8600 0.17 0.05 12.9 0.4 1.5 0.2 4.4 0.4 0.2 0.0 108.6 2.7 324 8 61 1 210 355 8 711 19
00 0
4460 1000
160 - 63 Rim 21.99 1.70 579 13 3.56 0.30 36.9 2.2 20.9 1.8 9.7 1.2 7.3 0.5 53.1 1.7 168 7 37 1 8060 220 45 1 54 3
00 0
4483 1018
160 - 65 Rim 9.60 1.30 749 21 6500 6.40 1.30 21.2 2.2 5.8 1.2 3.3 0.5 1.6 0.3 60.5 2.1 265 5 56 1 300 80 2 240 4
00 0
4640 1500
160 - 77 Rim 11.30 1.40 634 29 0.35 0.18 13.4 1.3 3.7 1.1 4.7 1.0 0.5 0.1 61.3 3.0 169 7 34 1 8250 230 90 4 137 5
00 0
4360 1100 1022
160 - 79 Rim 4.80 0.84 3100 110 3.71 0.73 27.8 2.3 10.1 1.9 7.7 0.8 1.0 0.1 249.5 6.8 968 27 182 6 200 259 5 867 30
00 0 0
4557 1186
160 - 81 Rim 9.13 0.72 347 11 7200 10.60 2.70 53.0 11.0 56.0 11.0 18.5 3.5 4.0 0.9 36.6 2.0 130 5 28 1 290 114 3 426 9
00 0

127
 LA-ICP-MS trace-element measurements in zircon grains for sample USP14-160 (granodiorite)
Obs
Spot # Core/ Ti 2σ Y 2σ Zr 2σ La 2σ Ce 2σ Nd 2σ Sm 2σ Eu 2σ Dy 2σ Yb 2σ Lu 2σ Hf 2σ Th 2σ U 2σ
Rim
4412
160 - 83 Rim 17.13 3.60 676 46 7100 11.00 1.80 62.9 8.0 51.3 9.1 20.1 4.1 7.8 1.6 68.0 7.6 213 10 43 1 9720 250 144 7 301 7
00
4534 1117
160 - 87 Rim 2.78 0.39 1885 90 8700 4.53 0.33 23.5 1.3 5.5 0.6 3.4 0.5 0.7 0.1 132.1 6.6 576 23 111 4 220 226 20 755 33
00 0
4970 1200
160 - 93 Rim 7.41 1.20 1956 50 18.30 5.20 82.0 19.0 31.4 7.8 13.1 2.1 6.8 2.9 165.7 3.3 525 19 100 3 9920 240 329 11 814 29
00 0
4630 1451
160 - 23 Rim (o) 1.72 0.35 3339 58 9500 1.57 0.68 19.2 2.6 4.3 1.7 5.2 0.4 0.8 0.2 262.4 9.3 1124 31 206 5 300 628 25 1957 43
00 0
5015
160 - 37 Rim (i) 43.73 3.40 1048 63 9100 11.33 0.75 81.8 4.0 82.4 5.8 48.9 3.6 7.8 0.7 124.0 7.9 215 10 40 1 9450 240 240 14 237 11
00
4470 1500
160 - 48 Core 7.91 0.54 814 79 0.03 0.01 10.1 0.6 3.8 0.6 6.1 0.7 2.5 0.4 83.7 8.6 232 15 47 3 7220 180 54 7 37 3
00 0
4760 1600 1485
160 - 10 Rim 27.82 6.80 912 39 8.78 0.62 38.2 2.4 26.5 4.4 10.5 2.2 1.9 0.3 73.6 3.5 368 19 77 3 540 161 12 836 37
00 0 0
3910 1600
160 - 16 Core 25.63 9.50 1904 48 10.10 1.90 56.9 5.0 32.0 19.0 15.8 0.8 3.2 0.4 173.9 7.7 433 15 82 4 6380 300 392 22 270 15
00 0
193.1 4180 1100
160 - 43 Rim 80.00 715 30 14.80 2.20 98.3 8.5 52.3 7.6 19.1 2.9 3.5 0.6 71.7 3.2 212 9 42 1 9360 290 223 7 278 7
4 00 0
510.1 4760 1200 1059
160 - 50 Rim 66.00 553 98 30.70 8.90 114.0 27.0 107.0 28.0 37.0 9.9 9.3 2.2 75.0 16.0 140 11 30 2 290 220 30 462 37
7 00 0 0
437.2 100.0 4600 1500
160 - 54 Rim (i) 607 45 5.65 0.81 31.7 4.7 24.0 5.9 12.0 3.2 2.6 0.5 59.4 5.8 184 10 40 2 8770 240 75 17 107 24
9 0 00 0
4439
160 - 82 Core 57.09 12.00 704 49 9100 11.20 2.20 58.7 7.1 63.8 5.9 29.7 2.4 8.8 1.2 78.7 6.6 152 9 30 1 7620 140 72 5 68 3
00

128
Supplementary material II - Zircon U-Pb dating

129
LA-ICP-MS U-Pb measurements for sample USP14-83 (aplitic syenite)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
83 - 1 Core antecryst 6.070 0.130 0.362 0.010 0.123 0.002 0.79 0.50 1986 18 1989 49 1991 35 100
83 - 3 Core antecryst 6.100 0.150 0.361 0.009 0.122 0.003 0.68 0.07 1989 22 1985 43 1995 38 100
83 - 11 Core antecryst 5.650 0.140 0.338 0.009 0.122 0.003 0.56 0.10 1922 21 1878 41 1977 47 98
83 - 14 Core antecryst 4.270 0.120 0.253 0.008 0.122 0.002 0.88 0.00 1684 23 1454 42 1984 34 86
83 - 16 Core antecryst 5.280 0.180 0.316 0.015 0.120 0.003 0.59 0.67 1864 29 1771 75 1950 46 95
83 - 21 Core antecryst 5.540 0.120 0.330 0.011 0.123 0.003 0.68 0.37 1907 19 1835 55 1996 46 96
83 - 29 Core antecryst 5.460 0.190 0.323 0.011 0.122 0.003 0.81 0.16 1892 31 1805 56 1992 43 95
83 - 37 Core antecryst 4.650 0.140 0.268 0.007 0.126 0.003 0.79 0.30 1765 27 1531 34 2036 45 87
83 - 50 Core antecryst 5.780 0.240 0.347 0.017 0.122 0.004 0.79 0.31 1951 40 1918 82 1979 58 98
83 - 62 Core antecryst 5.858 0.099 0.343 0.008 0.122 0.002 0.48 0.39 1954 15 1900 40 2005 32 97
83 - 7 Rim (i2) antecryst 6.140 0.170 0.362 0.012 0.122 0.004 0.54 0.37 1995 24 1992 56 1976 53 100
83 - 13 Rim antecryst 4.110 0.150 0.242 0.008 0.123 0.003 0.72 0.15 1654 30 1396 41 1997 46 84
83 - 17 Rim antecryst 4.304 0.091 0.253 0.006 0.122 0.003 0.66 0.29 1693 18 1455 33 1987 35 86
83 - 30 Rim antecryst 5.240 0.120 0.313 0.011 0.120 0.004 0.57 0.69 1858 20 1753 53 1953 54 94
83 - 44 Rim antecryst 4.890 0.300 0.288 0.019 0.122 0.003 0.96 0.16 1786 53 1641 97 1987 37 92
83 - 46 Rim (i) antecryst 5.540 0.170 0.332 0.019 0.122 0.003 0.75 0.41 1907 26 1846 90 1976 47 97
83 - 5 Core xenocryst 2.003 0.069 0.111 0.005 0.130 0.003 0.94 0.62 1115 23 675 28 2101 37 61
83 - 8 Core xenocryst 5.840 0.200 0.335 0.012 0.126 0.003 0.79 0.15 1952 29 1864 56 2054 47 95
83 - 9 Core xenocryst 2.670 0.160 0.150 0.007 0.129 0.003 0.96 0.46 1312 42 901 41 2075 41 69
83 - 12 Core xenocryst 1.420 0.100 0.078 0.006 0.134 0.004 0.92 0.52 894 43 482 38 2141 58 54
83 - 23 Core xenocryst 3.110 0.300 0.183 0.017 0.123 0.003 0.98 0.17 1416 78 1079 93 1992 40 76

130
LA-ICP-MS U-Pb measurements for sample USP14-83 (aplitic syenite)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
83 - 25 Core xenocryst 2.620 0.130 0.146 0.010 0.133 0.004 0.92 0.62 1324 38 878 54 2136 48 66
83 - 27 Core xenocryst 4.230 0.360 0.238 0.019 0.128 0.003 0.98 0.42 1663 69 1371 98 2069 39 82
83 - 39 Core xenocryst 4.910 0.110 0.276 0.007 0.130 0.002 0.86 0.12 1803 18 1571 35 2092 28 87
83 - 43 Core xenocryst 5.140 0.130 0.305 0.009 0.122 0.002 0.85 0.17 1842 21 1714 42 1988 34 93
83 - 48 Core xenocryst 4.540 0.160 0.270 0.009 0.121 0.004 0.79 0.11 1737 29 1539 45 1969 53 89
83 - 52 Core xenocryst 4.090 0.130 0.239 0.009 0.122 0.002 0.93 0.31 1649 26 1382 47 1977 30 84
83 - 56 Core xenocryst 3.410 0.270 0.203 0.019 0.123 0.003 0.99 0.68 1495 65 1182 100 2000 37 79
83 - 58 Core xenocryst 4.860 0.120 0.289 0.008 0.120 0.003 0.70 0.15 1794 21 1634 39 1958 38 91
83 - 54 Core xenocryst 4.560 0.250 0.265 0.015 0.123 0.002 0.96 0.31 1738 46 1514 75 2002 31 87
83 - 63 Core xenocryst 3.402 0.096 0.200 0.007 0.123 0.002 0.88 0.35 1503 22 1173 37 1998 34 78

131
LA-ICP-MS U-Pb measurements for sample USP14-91 (syenite)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
91 - 10 Rim autocryst 6.112 0.083 0.361 0.008 0.123 0.002 0.54 0.46 1991 12 1986 38 1995 31 100
91 - 14 Rim (i) autocryst 6.130 0.110 0.362 0.009 0.123 0.003 0.55 0.34 1993 15 1990 40 1993 40 100
91 - 21 Rim autocryst 5.940 0.310 0.355 0.015 0.123 0.004 0.85 0.10 1964 46 1960 72 1993 54 100
91 - 26 Rim (o) autocryst 6.050 0.170 0.353 0.008 0.124 0.003 0.68 0.00 1982 24 1947 40 2007 36 98
91 - 35 Rim autocryst 5.880 0.100 0.348 0.008 0.122 0.002 0.52 0.41 1960 15 1924 40 1980 34 98
91 - 37 Rim autocryst 6.080 0.100 0.361 0.008 0.123 0.003 0.49 0.29 1987 14 1984 38 1993 36 100
91 - 46 Rim autocryst 6.110 0.077 0.360 0.008 0.123 0.002 0.70 0.41 1991 11 1981 37 1995 29 99
91 - 64 Rim autocryst 5.824 0.077 0.348 0.011 0.122 0.003 0.40 0.48 1950 12 1924 50 1986 44 99
91 - 28 Rim autocryst 6.030 0.140 0.359 0.010 0.122 0.003 0.46 0.39 1978 20 1977 45 1989 40 100
91 - 24 Core autocryst 5.880 0.100 0.349 0.011 0.122 0.002 0.73 0.48 1958 15 1928 55 1994 38 98
91 - 43 Core autocryst 6.170 0.130 0.365 0.008 0.123 0.003 0.37 0.35 1998 18 2006 39 1997 43 100
91 - 47 Core autocryst 6.100 0.190 0.356 0.009 0.124 0.004 0.06 0.53 1988 27 1962 44 2007 56 99
91 - 49 Core autocryst 6.190 0.130 0.363 0.011 0.123 0.002 0.88 0.36 2001 18 1995 53 1996 28 100
91 - 54 Core autocryst 6.090 0.180 0.365 0.013 0.123 0.003 0.77 0.39 1987 26 2003 63 1996 38 101
91 - 63 Core autocryst 6.120 0.150 0.364 0.009 0.122 0.002 0.76 0.11 1999 20 1999 43 1982 33 100
91 - 65 Core autocryst 6.160 0.130 0.362 0.009 0.124 0.003 0.70 0.25 1997 19 1992 44 2013 34 100

132
LA-ICP-MS U-Pb measurements for sample USP14-136 (monzonite)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
136 - 1 Core autocryst 5.870 0.230 0.358 0.012 0.120 0.003 0.84 0.21 1956 34 1972 58 1955 50 101
136 - 6 Core autocryst 5.890 0.110 0.353 0.010 0.121 0.003 0.68 0.35 1963 17 1947 45 1967 42 99
136 - 11 Core autocryst 5.920 0.130 0.351 0.009 0.124 0.003 0.64 0.23 1969 18 1939 45 2010 39 98
136 - 24 Core autocryst 5.840 0.110 0.349 0.010 0.122 0.003 0.60 0.38 1952 17 1928 49 1983 37 99
136 - 26 Core autocryst 6.050 0.190 0.360 0.010 0.122 0.003 0.61 0.10 1982 27 1984 46 1992 49 100
136 - 46 Core autocryst 6.020 0.160 0.358 0.011 0.122 0.002 0.81 0.22 1981 23 1974 51 1982 32 100
136 - 12 Rim autocryst 6.130 0.100 0.360 0.009 0.123 0.002 0.70 0.50 1994 14 1983 44 1994 31 99
136 - 16 Rim (i) autocryst 5.910 0.130 0.353 0.009 0.123 0.003 0.43 0.55 1962 19 1948 41 2000 38 99
136 - 17 Rim (o) autocryst 6.050 0.150 0.358 0.010 0.122 0.002 0.78 0.10 1987 20 1972 45 1990 34 99
136 - 29 Rim autocryst 6.090 0.110 0.362 0.009 0.121 0.003 0.56 0.48 1988 16 1992 43 1981 39 100
136 - 39 Rim (o) autocryst 5.954 0.097 0.359 0.009 0.121 0.003 0.57 0.46 1968 14 1985 42 1965 41 101
136 - 51 Rim (i) autocryst 6.030 0.130 0.359 0.008 0.121 0.003 0.45 0.31 1979 19 1978 40 1980 38 100
136 - 52 Rim (o) autocryst 5.960 0.120 0.359 0.010 0.121 0.003 0.63 0.60 1970 18 1976 47 1969 40 100
136 - 55 Rim (o) autocryst 5.896 0.098 0.353 0.009 0.120 0.002 0.67 0.38 1960 15 1948 44 1961 37 99
136 - 57 Rim autocryst 6.000 0.150 0.360 0.010 0.121 0.004 0.42 0.51 1975 22 1982 50 1970 64 100
136 - 62 Rim autocryst 5.970 0.120 0.357 0.010 0.120 0.003 0.75 0.21 1971 18 1969 47 1965 38 100
136 - 64 Rim autocryst 6.060 0.120 0.360 0.012 0.123 0.003 0.83 0.63 1984 18 1981 56 1996 39 100
136 - 4 Core antecryst 3.650 0.230 0.219 0.013 0.119 0.002 0.97 0.07 1552 49 1272 67 1943 35 82
136 - 8 Core antecryst 4.981 0.095 0.316 0.008 0.115 0.002 0.72 0.28 1815 16 1770 39 1874 33 98
136 - 28 Core antecryst 4.720 0.150 0.284 0.008 0.123 0.004 0.50 0.14 1777 29 1609 39 2001 57 91
136 - 34 Core (i) antecryst 5.170 0.140 0.310 0.008 0.121 0.003 0.42 0.30 1847 23 1740 41 1968 52 94
136 - 50 Core antecryst 4.350 0.160 0.257 0.012 0.125 0.003 0.84 0.21 1700 31 1473 59 2021 46 87

133
 LA-ICP-MS U-Pb measurements for sample USP14-136 (monzonite)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
136 - 61 Core antecryst 4.050 0.130 0.254 0.009 0.116 0.002 0.86 0.16 1644 26 1460 47 1894 37 89
136 - 9 Rim antecryst 4.390 0.200 0.276 0.011 0.118 0.002 0.92 0.27 1713 39 1569 55 1929 36 92
136 - 19 Rim antecryst 4.674 0.096 0.297 0.009 0.115 0.003 0.55 0.61 1761 17 1675 45 1879 44 95
136 - 47 Rim xenocryst 3.402 0.073 0.212 0.006 0.116 0.002 0.87 0.28 1504 17 1245 33 1889 31 83
136 - 37 Core xenocryst 5.890 0.150 0.341 0.010 0.129 0.003 0.80 0.35 1958 22 1893 49 2082 38 97
136 - 18 Core xenocryst 5.760 0.150 0.330 0.010 0.126 0.002 0.89 0.07 1945 24 1835 46 2049 30 94
136 - 32 Core xenocryst 5.580 0.130 0.321 0.009 0.127 0.002 0.81 0.03 1912 20 1792 43 2059 33 94
136 - 35 Core (o) xenocryst 5.520 0.140 0.321 0.008 0.127 0.003 0.66 0.04 1903 22 1793 39 2048 40 94
136 - 63 Core xenocryst 6.060 0.130 0.361 0.008 0.123 0.003 0.40 0.34 1984 19 1985 39 2002 47 100
136 - 65 Core xenocryst 5.590 0.170 0.320 0.010 0.126 0.003 0.85 0.08 1912 26 1790 51 2036 40 94

134
LA-ICP-MS U-Pb measurements for sample USP14-144 (granodioritic porphyry)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
144 - 5 Core autocryst 5.830 0.180 0.352 0.009 0.121 0.004 0.39 0.30 1963 26 1942 45 1965 59 99
144 - 16 Core autocryst 6.230 0.100 0.367 0.008 0.123 0.002 0.65 0.29 2007 14 2017 39 1995 31 100
144 - 18 Core autocryst 5.790 0.170 0.340 0.013 0.123 0.003 0.85 0.15 1944 26 1887 62 1999 37 97
144 - 19 Core autocryst 4.552 0.083 0.290 0.009 0.115 0.003 0.56 0.48 1740 15 1642 43 1871 41 94
144 - 21 Core autocryst 5.820 0.140 0.349 0.012 0.123 0.003 0.69 0.52 1960 20 1929 58 1990 44 98
144 - 26 Core autocryst 6.000 0.170 0.355 0.011 0.122 0.003 0.86 0.02 1974 25 1959 52 1989 46 99
144 - 35 Core autocryst 6.030 0.110 0.358 0.009 0.122 0.002 0.65 0.16 1980 16 1974 41 1987 35 100
144 - 42 Core autocryst 5.990 0.100 0.357 0.009 0.122 0.002 0.81 0.48 1976 15 1966 42 1984 29 99
144 - 55 Core autocryst 2.070 0.120 0.164 0.007 0.091 0.002 0.93 0.42 1133 38 979 37 1444 46 86
144 - 57 Core autocryst 6.224 0.092 0.373 0.008 0.123 0.003 0.53 0.40 2007 13 2043 40 1991 36 102
144 - 64 Core autocryst 2.540 0.160 0.191 0.011 0.096 0.002 0.96 0.48 1290 44 1126 57 1561 40 87
144 - 67 Core autocryst 5.650 0.130 0.333 0.008 0.122 0.003 0.66 0.01 1922 19 1852 40 1976 38 96
144 - 69 Core autocryst 4.030 0.260 0.263 0.014 0.111 0.004 0.92 0.39 1635 52 1502 70 1819 57 92
144 - 71 Core autocryst 5.190 0.160 0.316 0.009 0.120 0.002 0.82 0.10 1850 26 1769 45 1959 35 96
144 - 4 Rim autocryst 5.960 0.140 0.351 0.008 0.123 0.002 0.80 0.24 1967 20 1937 38 1999 34 98
144 - 10 Rim autocryst 6.290 0.170 0.368 0.010 0.123 0.003 0.71 0.10 2015 24 2017 46 1999 49 100
144 - 22 Rim autocryst 6.170 0.120 0.364 0.008 0.122 0.002 0.66 0.25 1999 16 2002 39 1985 34 100
144 - 24 Rim autocryst 6.090 0.110 0.362 0.008 0.122 0.002 0.59 0.28 1990 16 1990 40 1991 33 100
144 - 34 Rim autocryst 6.040 0.130 0.356 0.009 0.122 0.003 0.59 0.30 1980 18 1963 43 1984 38 99
144 - 38 Rim (i) autocryst 6.050 0.130 0.361 0.009 0.123 0.002 0.75 0.51 1983 19 1987 44 1997 35 100
144 - 41 Rim autocryst 5.878 0.092 0.348 0.008 0.122 0.002 0.76 0.25 1960 13 1927 40 1993 28 98
144 - 47 Rim autocryst 6.140 0.150 0.359 0.008 0.124 0.003 0.80 0.31 1995 22 1978 40 2010 44 99

135
LA-ICP-MS U-Pb measurements for sample USP14-144 (granodioritic porphyry)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
144 - 52 Rim autocryst 6.140 0.110 0.363 0.008 0.122 0.003 0.53 0.38 1994 16 1996 40 1987 36 100
144 - 54 Rim autocryst 6.075 0.099 0.361 0.008 0.121 0.002 0.55 0.30 1986 14 1986 38 1976 33 100
144 - 58 Rim autocryst 6.047 0.074 0.364 0.008 0.122 0.002 0.63 0.35 1982 11 2001 36 1977 30 101
144 - 72 Rim (i) autocryst 5.830 0.120 0.352 0.010 0.121 0.002 0.86 0.74 1950 18 1942 48 1968 34 100
144 - 78 Rim autocryst 5.940 0.110 0.357 0.008 0.122 0.003 0.46 0.29 1969 15 1965 37 1986 38 100
144 - 80 Rim autocryst 6.190 0.110 0.365 0.009 0.122 0.002 0.64 0.22 2002 16 2007 41 1989 33 100
144 - 1 Core xenocryst 6.430 0.170 0.372 0.010 0.126 0.003 0.74 0.01 2035 23 2037 47 2046 39 100
144 - 3 Core xenocryst 6.130 0.130 0.366 0.009 0.122 0.004 0.42 0.67 1993 19 2008 44 1986 55 101
144 - 9 Core xenocryst 2.310 0.180 0.171 0.012 0.097 0.002 0.99 0.41 1204 52 1017 63 1560 36 84
144 - 27 Core xenocryst 5.910 0.110 0.366 0.009 0.118 0.002 0.91 0.30 1962 16 2011 44 1928 27 102
144 - 33 Core xenocryst 6.100 0.130 0.366 0.010 0.121 0.003 0.54 0.47 1990 18 2017 44 1971 48 101
144 - 37 Core xenocryst 5.450 0.250 0.354 0.015 0.112 0.004 0.81 0.17 1884 40 1952 72 1817 60 104
144 - 45 Rim xenocryst 6.040 0.230 0.358 0.014 0.123 0.003 0.81 0.28 1981 33 1971 67 1999 46 99
144 - 74 Core xenocryst 5.420 0.360 0.365 0.024 0.107 0.002 0.97 0.03 1911 57 2030 110 1755 38 106
144 - 75 Rim xenocryst 6.250 0.150 0.364 0.009 0.124 0.004 0.38 0.44 2011 21 2003 41 2012 52 100

136
LA-ICP-MS U-Pb measurements for sample USP14-160 (granodiorite)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
160 - 1 Core autocryst 6.310 0.140 0.369 0.010 0.124 0.003 0.31 0.33 2019 19 2026 45 2023 49 100
160 - 2 Core autocryst 6.320 0.160 0.369 0.012 0.125 0.003 0.78 0.21 2020 22 2023 57 2027 39 100
160 - 3 Core autocryst 6.470 0.150 0.376 0.010 0.125 0.003 0.55 0.32 2041 21 2056 47 2020 39 101
160 - 7 Core autocryst 6.260 0.170 0.370 0.012 0.125 0.004 0.48 0.45 2011 24 2027 54 2024 58 101
160 - 11 Core autocryst 6.320 0.110 0.363 0.009 0.125 0.002 0.68 0.33 2020 15 1995 43 2023 34 99
160 - 12 Core autocryst 6.510 0.120 0.376 0.009 0.126 0.003 0.76 0.40 2047 16 2057 44 2046 39 100
160 - 14 Core autocryst 6.320 0.140 0.372 0.010 0.124 0.003 0.55 0.42 2020 20 2037 46 2020 49 101
160 - 30 Core autocryst 6.330 0.150 0.368 0.009 0.124 0.003 0.20 0.37 2021 21 2020 40 2007 47 100
160 - 32 Core autocryst 6.409 0.097 0.369 0.009 0.126 0.002 0.59 0.29 2033 13 2024 41 2039 33 100
160 - 36 Core autocryst 6.518 0.094 0.370 0.008 0.127 0.002 0.60 0.32 2048 13 2027 39 2057 30 99
160 - 39 Core autocryst 6.450 0.110 0.367 0.009 0.128 0.002 0.42 0.50 2038 15 2015 44 2068 32 99
160 - 44 Core autocryst 6.190 0.150 0.368 0.012 0.124 0.003 0.64 0.47 2002 21 2017 57 2013 35 101
160 - 49 Core autocryst 6.400 0.170 0.370 0.012 0.125 0.002 0.82 0.16 2031 23 2030 55 2025 34 100
160 - 64 Core autocryst 6.510 0.140 0.372 0.009 0.128 0.003 0.66 0.26 2047 19 2037 44 2065 36 100
160 - 66 Core autocryst 6.304 0.096 0.367 0.009 0.125 0.002 0.58 0.46 2020 14 2013 40 2031 33 100
160 - 78 Core autocryst 6.610 0.150 0.382 0.010 0.126 0.002 0.89 0.23 2060 20 2086 44 2047 27 101
160 - 86 Core autocryst 6.490 0.140 0.374 0.011 0.127 0.003 0.68 0.41 2044 19 2048 51 2058 36 100
160 - 4 Rim autocryst 6.370 0.150 0.366 0.011 0.124 0.002 0.74 0.18 2028 20 2009 51 2012 34 99
160 - 20 Rim autocryst 6.200 0.180 0.364 0.010 0.124 0.003 0.88 0.03 2003 26 2002 45 2017 35 100
160 - 22 Rim (i) autocryst 6.300 0.140 0.366 0.010 0.125 0.003 0.55 0.46 2017 20 2011 47 2021 38 100
160 - 29 Rim autocryst 6.220 0.100 0.366 0.009 0.124 0.003 0.61 0.43 2006 15 2010 45 2005 36 100
160 - 33 Rim autocryst 6.360 0.170 0.373 0.009 0.125 0.004 0.48 0.11 2026 24 2042 40 2019 54 101

137
LA-ICP-MS U-Pb measurements for sample USP14-160 (granodiorite)
207Pb 206Pb 207Pb
Obs
207Pb 206Pb 207Pb Rho Rho /235U /238U /206Pb Conc.
Spot # Core/ Obs 2σ 2σ 2σ 2σ 2σ 2σ
/235U /238U /206Pb 75/68 86/76 date date date (%)
Rim (Ma) (Ma) (Ma)
160 - 40 Rim (i) autocryst 6.390 0.150 0.362 0.010 0.128 0.002 0.78 0.22 2034 20 1989 47 2078 35 98
160 - 41 Rim (o) autocryst 6.160 0.130 0.360 0.011 0.123 0.003 0.74 0.36 1998 19 1983 51 2001 38 99
160 - 47 Rim autocryst 6.200 0.160 0.364 0.010 0.124 0.002 0.81 0.03 2003 23 1999 47 2015 35 100
160 - 59 Rim autocryst 6.150 0.120 0.363 0.010 0.124 0.002 0.80 0.34 2001 16 1997 48 2022 32 100
160 - 63 Rim autocryst 6.380 0.450 0.379 0.023 0.124 0.004 0.89 0.04 2040 57 2070 110 2004 62 101
160 - 79 Rim autocryst 6.350 0.120 0.371 0.008 0.124 0.002 0.75 0.04 2024 16 2036 38 2016 33 101
160 - 81 Rim autocryst 6.294 0.086 0.369 0.008 0.124 0.002 0.61 0.37 2017 12 2023 38 2017 33 100
160 - 83 Rim autocryst 6.210 0.110 0.368 0.011 0.123 0.003 0.52 0.62 2005 15 2021 50 1992 43 101
160 - 87 Rim autocryst 6.530 0.170 0.380 0.009 0.124 0.003 0.77 0.08 2049 23 2074 42 2014 37 101
160 - 24 Core xenocryst 6.700 0.190 0.382 0.014 0.128 0.004 0.62 0.59 2072 25 2087 65 2070 59 101
160 - 46 Core xenocryst 6.730 0.160 0.379 0.011 0.130 0.003 0.51 0.35 2081 22 2073 49 2094 46 100
160 - 64 Core xenocryst 6.510 0.140 0.372 0.009 0.128 0.003 0.66 0.26 2047 19 2037 44 2065 36 100
160 - 78 Core xenocryst 6.610 0.150 0.382 0.010 0.126 0.002 0.89 0.23 2060 20 2086 44 2047 27 101
160 - 86 Core xenocryst 6.490 0.140 0.374 0.011 0.127 0.003 0.68 0.41 2044 19 2048 51 2058 36 100
160 - 92 Core xenocryst 6.500 0.130 0.381 0.010 0.126 0.003 0.58 0.45 2045 17 2081 45 2034 37 102

138