©2018 Society of Economic Geologists, Inc.

Economic Geology, v. 113, no. 8, pp. 1–000

Hydrothermal Alteration, Fluid Evolution, and Re-Os Geochronology of the Grota Fun-
da Iron Oxide Copper-Gold (IOCG) Deposit, Carajás Province (Pará State), Brazil
R.B. Hunger,1,† R.P. Xavier,1 C.P.N. Moreto,1 and Jian-Feng Gao2
1 Institute of Geosciences, University of Campinas, 250 Carlos Gomes, Campinas, São Paulo 13083–855, Brazil
2 State
Key Laboratory of Ore Deposit Geochemistry, Institute of Geochemistry,
Chinese Academy of Sciences, 99 Lincheng West Road, Guiyang 550081, China

Abstract
The Grota Funda iron oxide copper-gold (IOCG) deposit is situated within a regional WNW-ESE–striking
shear zone in the northwestern portion of the Carajás domain, an Archean (3.0–2.55 Ga) segment of the Carajás
Province, Brazil. Metavolcano-sedimentary sequences of the Igarapé-Pojuca Group, comprising basalt, dia-
base, gabbro, dacite, and banded iron formations, are the main lithotypes recognized in the deposit area. In
this sequence, mafic igneous rocks represent the main hosts to the copper (-gold) mineralization stages. The
paragenetic evolution of the Grota Funda hydrothermal system encompasses an early high-temperature cal-
cic-sodic alteration (albite-hastingsite-scapolite), followed by intense Fe metasomatism (magnetite-grunerite-
almandine), potassic alteration with biotite, chlorite-quartz-tourmaline assemblage, and late carbonate-quartz
veining. Copper (-gold) mineralization stages are spatially and temporally associated with iron-enriched (min-

T
eralization I), potassically altered (mineralization II), and chlorite-altered zones (mineralization III). Molybde-
nite from grunerite-magnetite veins yielded a Re-Os model age of 2530 ± 60 Ma, which is interpreted as the

F
mineralization I age. The main sulfide ore (mineralization II) predominantly forms breccia bodies characterized
by a chalcopyrite-magnetite-sphalerite-pyrrhotite assemblage. Chalcopyrite δ34S values (0.9 ± 0.9‰) point to
a magmatic source for sulfur, probably leached from the host mafic rocks. Development of early and high-tem-

A
perature (>500°C) alteration assemblages is attributed to regional circulation of deep-seated hypersaline and
metalliferous fluids. Mixing with moderate- to high-salinity (24–29 wt % NaCl + CaCl2 equiv) and cooler fluids

R
may have triggered ore precipitation in the main ore zone of mineralization II, due to a decrease in temperature
and Cl– activity. Postore alteration assemblages resulted from considerable temperature and pH decreases.

D
Introduction controversial, mixing of hot (>500°C), hypersaline (~50 wt %
The Carajás domain, in the southeastern sector of the Amazon NaCl + CaCl2 equiv), metal-bearing fluids with lower-salinity,
craton, is among the world’s best-endowed provinces in metal more diluted fluids (e.g., meteoric water) has been attribu-
deposits formed during the Neoarchean to Paleoproterozoic ted as the main mechanism of copper-gold ore precipitation.
(Xavier et al., 2010, 2012). It contains a significant number of However, the genesis of these systems is also dependent upon
Cu-Au systems, of which world-class (>200 million tons [Mt]) a series of other important factors, such as sulfur availability,
iron oxide copper-gold (IOCG) deposits (e.g., Cristalino, Iga- fluid redox and sulfidation states, and degrees of fluid-rock
rapé-Bahia, Sossego, Salobo; Huhn et al., 1999b; Tallarico et interaction (Xavier et al., 2012). It is noteworthy that the role
al., 2005; Monteiro et al., 2008; Melo et al., 2016) have been of magmatic and nonmagmatic fluids on the genesis of these
the main targets of the mineral exploration industry. Cur- systems has been a matter of debate, which has precluded a
rently, Sossego and Salobo are the two mines in operation by more robust definition of metallogenic models for the Cara-
VALE in the Carajás domain, with remaining ore reserves of jás domain (Chiaradia et al., 2006; Xavier et al., 2008, 2012;
120.1 Mt at 0.68% Cu and 0.2 g/t Au and 1,193.4 Mt at 0.61% Moreto et al., 2011). The importance of Archean (ca. 2.75 or
Cu and 0.3 g/t Au, respectively (VALE, 2017). A third mine, 2.57 Ga) and Paleoproterozoic (ca. 1.88 Ga) granitic intru-
Antas North, initially operated by Avanco Resources Ltd. and sions as potential sources of heat and fluids has been rein-
most recently acquired by Oz Minerals, has total reserves of forced by several authors (Huhn et al., 1999b; Réquia et al.,
2.78 Mt at 2.38% Cu and 0.53 g/t Au within a total resource 2003; Tallarico et al., 2005; Neves, 2006; Pollard, 2006; Villas
of 19.84 Mt at 1.1% Cu and 0.2 g/t Au (Avanco Resources et al., 2006; Grainger et al., 2008). Nonetheless, the partici-
Limited, 2018). The copper reserves in Brazil are in the order pation of evaporative fluids (e.g., bittern fluids generated by
of 11 Mt (1.5% of the world), about 85% of which is concen- seawater evaporation), which may explain the characteristic
trated in the IOCG systems of the Carajás domain. high salinity of the ore fluids, has been shown by boron, chlo-
The present knowledge on the IOCG deposits of the rine, and strontium isotope data and halogen ratios (e.g., Cl/
Carajás domain reveals that these systems are the product Br, Na/Cl) in fluid inclusions (Chiaradia et al., 2006; Xavier et
of multiple hydrothermal episodes of Neoarchean (ca. 2.71 al., 2008, 2009, 2013).
and 2.57 Ga) and Paleoproterozoic (2.0 and 1.88 Ga) ages The Grota Funda IOCG deposit (15–40 Mt at 0.8–1.2%
(Moreto et al., 2015a, b), involving the circulation and mixing Cu; VALE unpub. report, 2016) belongs to the set of IOCG
of multisourced fluids at different crustal levels (Xavier et al., systems sitting in the northern sector of the Carajás domain.
2010, 2012). Although the origin of mineralizing fluids is still Paragenetic evolution marked by early sodic-calcic alteration,
Fe-rich metasomatism, and potassic alteration, followed by
† Corresponding author: e-mail, [email protected] ore precipitation, has been recognized in this deposit, similar
ISSN 0361-0128; doi: 10.5382/econgeo.2018.0000; 25 p. Submitted: April 24, 2018
1 Accepted: November 15, 2018
2 HUNGER ET AL.

to other important IOCG deposits in this sector of the Carajás from sandstones (2681 ± 5 Ma; Trendall et al., 1998) and
domain (e.g., Salobo; Melo et al., 2016), suggesting an analo- metagabbro sills (2645 ± 12 and 2708 ± 37 Ma; Dias et al.,
gous evolution of the hydrothermal system. Nevertheless, 1996; Mougeot et al., 1996).
we further demonstrate in this work that the Grota Funda Widespread felsic to mafic-ultramafic magmatism has been
deposit is the result of contrasting copper mineralizing events reported in the Carajás domain. Archean granitic magmatism
that evolved due to changes in temperature, redox state, and is attributed to ca. 2.76 to 2.73 Ga syntectonic, foliated alka-
sulfur availability of the fluid regimes. Thus, this study aims to line intrusions (e.g., Plaquê, Planalto, Estrela, Serra do Rabo,
present the hydrothermal evolution and related mineralizing Igarapé-Gelado, and Pedra Branca Suites; Avelar et al., 1999;
events at the Grota Funda deposit, focusing on the definition Huhn et al., 1999a; Barros et al., 2004, 2009; Sardinha et al.,
of its host rocks, distribution and types of hydrothermal alte- 2006; Feio et al., 2012, 2013) and to ca. 2.57 Ga peralkaline to
ration, and modes of occurrence of copper (-gold) minera- metaluminous granitoids, represented by the Old Salobo and
lization. Moreover, this paper also presents S isotope, fluid Itacaiúnas granites (Machado et al., 1991; Souza et al., 1996).
inclusion, and geochronological data that contribute to the Paleoproterozoic (ca. 1.88 Ga) A-type alkaline to subalkaline
current knowledge on the origin and composition of the mine- and metaluminous to slightly peraluminous granites (e.g.,
ralizing fluids and the timing of IOCG genesis in the Carajás Central de Carajás, Young Salobo, Cigano, Pojuca, Breves,
domain. and Rio Branco; Machado et al., 1991; Tallarico et al., 2004)
are also broadly recognized in the province. Mafic-ultramafic
The Carajás Province: Geologic Setting intrusions are mainly characterized by the Luanga layered
The Carajás Province, in the southeastern sector of the Ama- complex (2763 ± 6 Ma; Machado et al., 1991) and the Cateté
zon craton (Fig. 1A), is segmented into the Mesoarchean Rio intrusive suite, which includes the Serra da Onça, Serra do
Maria granite-greenstone terrane (3.0–2.86 Ga; Almeida et Puma, Serra do Jacaré-Jacarezinho, Vermelho, and Igarapé
al., 2010) in the south and the Meso- to Neoarchean Cara- Carapanã bodies (Macambira and Vale, 1997; Macambira and
jás domain (3.0–2.55 Ga; Dall’Agnol et al., 2006) in the north Ferreira Filho, 2002; Ferreira Filho et al., 2007).
(Fig. 1B). A major and geophysically constrained east-west The tectonic evolution of the Carajás domain is ascribed to
tectonic discontinuity is interpreted to be the approximate at least three main hypothesis, including the formation during
limit between the Rio Maria and Carajás domains, formerly a dextral transtension, subsequently tectonically inverted to
designated as the transition zone (Feio et al., 2013). positive flower structures by sinistral transpression (Araújo et
The Carajás domain (Fig. 1C), previously known as the al., 1988), during continental rifting related to mantle-plume
Itacaiúnas shear belt (Araújo et al., 1988), comprises Meso- activity (Tallarico, 2003), and in a volcanic arc setting related to
archean (ca. 3.0–2.83 Ga) basement rocks overlain by Neoar- subduction processes (Meirelles, 1986; Dardenne et al., 1988;
chean (ca. 2.76–2.73 Ga) metavolcano-sedimentary sequences Meirelles and Dardenne, 1991; Teixeira, 1994; Lobato et al.,
of the Itacaiúnas Supergroup and Rio Novo Group and meta- 2005; Silva et al., 2005; Teixeira et al., 2010). A more recent
siliciclastic rock units of the Águas Claras Formation (Vasquez model for the Carajás domain invokes a 2.87 to 2.83 Ga colli-
et al., 2008). The basement rocks include tonalitic to trond- sion that resulted in a stable basement substrate upon which
hjemitic gneiss and migmatites (e.g., Xingu Complex, 3066 ± a rift-related system and subsequent volcano-sedimentary
6.6 Ma; Delinardo da Silva, 2014), mafic granulites (e.g., Pium sequences evolved through collisional-extensional events that
Complex or Chicrim-Cateté orthogranulite, 3002 ± 14 Ma; periodically took place from the Neoarchean (2.76–2.52 Ga)
Pidgeon et al., 2000), and granitic units, such as the Bacaba to the Paleoproterozoic (2.09–1.88 Ga) (Tavares, 2015). These
and Campina Verde tonalites, the Rio Verde trondhjemite, events were accompanied by extensive bimodal plutonism in
and the Canaã dos Carajás Cruzadão, Bom Jesus, and Serra the Neoarchean and alkaline A-type granitic intrusions in the
Dourada granites (Moreto et al., 2011; Feio et al., 2013; Paleoproterozoic (ca. 1.88 Ga). Major regional-scale linea-
Rodrigues et al., 2014). ments recognized in the Carajás domain represent the north-
The overlying Neoarchean (2.76–2.74 Ga) metavolcano- ern Cinzento and Carajás transcurrent shear zones and the
sedimentary sequences of the Itacaiúnas Supergroup consist southern Canaã shear zone (Pinheiro et al., 2013), products
of basic to felsic metavolcanic rocks, banded iron formations, of a regional north-northeast–south-southwest shortening
and metavolcaniclastic, amphibolite, and metasedimentary also responsible for the widespread E-W–trending foliation
units, subdivided into the Igarapé Salobo, Grão Pará, Igar- observed in this domain.
apé Bahia, and Pojuca Groups. This supergroup is the host
to several economically important IOCG deposits, including The Grota Funda Iron Oxide Copper-Gold Deposit
Salobo, Igarapé-Bahia/Alemão, and Cristalino (Companhia
Vale do Rio Doce/Caemi Mineração e Metalurgia S.A., 1972; Geologic setting and host rocks
Rio Doce Geologia e Mineração S.A., 1988; Vasquez et al., The Grota Funda deposit is located at the northwestern
2008). The Rio Novo Group comprises amphibolites, schists, part of the Carajás domain. Along with the Pojuca volcanic-
metagraywackes, tholeiitic metavolcanic rocks, and gabbros hosted massive sulfide-type and Gameleira Cu polymetallic
(Hirata et al., 1982). deposits, it lies within a regional WNW-ESE–striking shear
The Águas Claras Formation (Nogueira et al., 1995) dis- zone known as the Pojuca fault system (Fig. 2). The deposit
cordantly overlies the Itacaiúnas Supergroup and mainly is also intersected by NE-SW– and E-W–trending subsidiary
consists of fluvial to shallow marine sandstones, siltstones, faults associated with the Carajás fault system. Mafic igneous
and orthoconglomerates. Minimum deposition ages were rocks (basalt and diabase) correlated with the Igarapé Pojuca
obtained through dating of detrital zircon grains extracted Group represent the main hosts to the Cu-Au mineralization
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 3

50°W

Cinz
ento
Strik
e-sli
p Fa
GT 46 ult S
yste
m

Salobo

Paulo Afonso
Breves Furnas
Cigano
Pojuca Gameleira
6°S

Grota Funda
Igarapé Parauapebas
Bahia/Alemão Serra Curionópolis
Verde
Águas Claras
Antas
Cara
jás Strik
Norte Estrela
e-slip
Central Fault
Syste
de Tarzan m
Carajás Estrela
Alvo
Jatobá Castanha
118 Cristalino
Amazonian Bacuri
Craton Sossego Visconde Borrachudo
Bacaba
Canaã
Santa Lúcia
dos
Canaã Shear
Zone Carajás
Seringa Pedra
Branca

Lateritic Cover Rio Novo Group Geologic Contacts

Cururu Diabase (Alto Tapajós Basin) Itacaiúnas Supergroup (2.76 - 2.73 Ga) Thrust Fault
Igarapé Pojuca Group
Serra Grande Group (Parnaíba Basin) Fault
Igarapé Bahia Group
Transcurrent
Grão Pará Group Shear Zone
Araguaia Belt
Carajás Formation Transpressional
Shear Zone
Parauapebas Formation
A-type Granite (1.88 Ga) IOCG Mines
Igarapé Salobo Group
Bacajá Domain
Aquiri Group IOCG Deposits

Cu-polymetallic Deposits
Águas Claras Formation Serra Dourada Granite (2.85 Ga)
Santa Inês Gabbro Campina Verde Tonalite (2.87 Ga) VMS-type Cu-Zn System

Cateté Intrusive Suite (2.76 Ga) Pium Diopside-Norite

City
Luanga Complex (2.76 Ga) Pium Complex

Granitoids (2.76 - 2.74 Ga) Xingu Complex

Fig. 1. (A) Location of the Carajás Province (black) in the Amazonian craton (light gray). (B) The Rio Maria domain (RMD)
in the south, and the Carajás domain (CD) in the north, as part of the Carajás Province, limited to the north by the Bacajá
domain (BD). (C) Simplified geologic map of the Carajás domain, showing the location of the main copper deposits and
structures (modified from Vasquez et al., 2008). Abbreviations: IOCG = iron oxide copper-gold, VMS = volcanogenic massive
sulfide.
4 HUNGER ET AL.

550000

Paulo Afonso
(Cu-Au)
Cinz
9350000

ento
Shea
r Zon
e

2.76 - 2.73 Ga
1.88 Ga
Breves Pojuca
(Cu-Au) (Cu-Zn)
Gameleira
(Cu-Au) Pojuca Fault Syst
Grota Funda em
(Cu-Au)

Igarapé-Bahia/Alemão
(Cu-Au)
10

Paleoproterozoic Mesoarchean
Xingu Complex
Paleoproterozoic granite (1.88 Ga)
Gneiss, migmatite, granulite and amphibolite
Neoarchean
Neoarchean granite (2.76 - 2.73 Ga) Geologic Symbols
Transcurrent Shear Zone
Águas Claras Formation
Fault
Conglomerate, sandstone, siltstone, shale and pelite
Deposit
Itacaiúnas Supergroup

Igarapé-Pojuca Group Igarapé-Bahia Group

Fig. 2. Geologic map of the northwestern sector of the Carajás domain, displaying the main shear zones and the location of
the Grota Funda iron oxide copper-gold, Pojuca volcanic-hosted massive sulfide-type, and Gameleira Cu polymetallic depos-
its (modified from VALE, unpub. report, 2016).

(Fig. 3). Other lithotypes recognized in the deposit area fine-grained rim of chlorite (Fig. 4A). Least altered diabase
include gabbro, a felsic subvolcanic rock, and banded iron and gabbro display similar compositions and relatively pre-
formations. Original textural and mineralogical features of served subophitic textures, differing only in their grain sizes
the Grota Funda lithotypes have been partially to completely (Fig. 4B-D). Both rocks are dark gray to green in color and
obliterated by intense and widespread hydrothermal altera- predominantly composed of plagioclase and augite, the lat-
tion and brittle-ductile deformation. ter intensively altered to hydrothermal hastingsite and biotite.
The definition of basalt among the mafic rocks in the deposit Least altered plagioclase crystals are generally tabular with
area was inferred based on the presence of amygdaloidal tex- poorly preserved twinning but most commonly converted
tures observed in extremely fine grained rock samples essen- into scapolite and subsequently mantled by biotite and chlo-
tially composed of chlorite and quartz. These amygdaloidal rite. When preserved, augite commonly displays cleaved and
cavities are filled with microcrystalline quartz and lined by a simple twinned basal sections (Fig. 4E).
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 5

PKO-GFUN-FD009 PPG-POJU-FD001
PKO-GFUN-FD003 PKO-GFUN-FD029
PKO-GFUN-FD028 PKO-GFUN-FD037
B
A

40 m

Lithotypes PKO-GFUN-FD029

Águas Claras Formation DRILL CORE

Laterite (conglomerate, sandstone,
siltstone, shale, pelite)

Diabase Dikes Mafic Volcanic Rocks

Au (g/t)

Gabbro Mineralized Zone

Banded Iron Formation

Symbols Cu (%)

Lineament Cross Section

Fault Weathering Surface TOTAL LENGTH

500.75

Fig. 3. Simplified geologic map and cross section of the Grota Funda iron oxide copper-gold deposit, showing the spatial
distribution of the main lithotypes described in the deposit area and the mineralized zones (modified from VALE, unpub.
report, 2016).

The banded iron formation units at Grota Funda belong to G). Contact between microbands is usually diffuse. Magnetite
the oxide facies. Compositional layering is typically marked by is mostly fine grained and generally displays different degrees
the alternation of grayish-white quartz + grunerite and dark of martitization. Grunerite crystals are typically acicular and
magnetite-rich microbands, both up to 0.5 mm thick (Fig. 4F, randomly oriented within quartz-rich microbands.
6 HUNGER ET AL.

A B C D
Pl Hs
Pl
Pl
Qtz

Bt 1 cm

Chl
Bt E
Bt Bt Aug

Cpy
Pl

1 cm 1 cm 1 cm 250 μm

F G H Qtz I Bt
Pl
Qtz + Gru
Cb

Qtz Qtz
Cpy
Mag 250 μm
Mag
Chl J
Qtz

Gru Qtz
1 cm 1 cm 1 cm 1 cm

Fig. 4. Main lithotypes of the Grota Funda deposit. (A) Mafic igneous rock, possibly basalt, showing quartz-filled amygda-
loidal texture. (B) and (C) Partially preserved subophitic texture in diabase and gabbro, both affected by potassic alteration.
(D) Subophitic texture in diabase, showing plagioclase crystals intergrown with hydrothermal hastingsite. (E) Simple twinned
augite crystal along its longitudinal section. (F) Oxide facies banded iron formation displaying the intercalation of quartz-
grunerite and magnetite-rich microbands. (G) Photomicrograph (transmitted light/cross-polarized light [XPL]) with detail of
the banded iron formation with magnetite-rich and quartz-grunerite–rich microbands. (H) Felsic rock of dacitic composition
displaying pervasive chlorite alteration. (I) Photomicrograph (transmitted light/XPL) of dacite showing a fine-grained quartz-
plagioclase–rich matrix. Note the presence of biotite as part of the potassic alteration. (J) Photomicrograph (transmitted light/
XPL) of dacite with bipyramidal quartz phenocrysts surrounded by a fine-grained matrix of quartz. Mineral abbreviations:
Aug = augite, Bt = biotite, Cb = carbonate, Chl = chlorite, Cpy = chalcopyrite, Gru = grunerite, Hs = hastingsite, Mag =
magnetite, Pl = plagioclase, Qtz = quartz.

Felsic subvolcanic rock was only locally recognized within Bulk mineralogy indicates a dacitic composition. Trace amounts
the drill core investigated, but where observed, it has been of zircon and epidote are also recognized within this rock. Chal-
intensely affected by potassic and chlorite alteration (Fig. 4H). copyrite occurs as disseminations and fracture infillings.
It is greenish to grayish in color and has a fine-grained (<1 mm)
matrix composed of quartz and plagioclase (Fig. 4I), with sub- Hydrothermal alteration and mineralization
ordinated potassium feldspar (microcline) that locally includes The Grota Funda IOCG deposit has undergone intense
euhedral (bipyramidal) phenocrysts of bluish quartz (Fig. 4J). and widespread hydrothermal alteration, including stages of
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 7

sodic-calcic alteration, Fe metasomatism, potassic alteration, depicted by massive precipitation of magnetite (I)-grune-
chlorite-quartz-tourmaline formation, and carbonate-quartz rite-almandine ± chlorite (I)-quartz. Veins containing coarse
veins. At least three main episodes of copper (-gold) mineraliza- grunerite, magnetite, and minor molybdenite (1–2 cm in
tion have been recognized in the deposit, respectively associated size) intersect previous zones of sodic-calcic alteration (Figs.
with Fe metasomatism, potassic, and chlorite alteration stages. 6A, B, 7A) and are also associated with the Fe metasoma-
Sodic-calcic alteration: Sodic-calcic alteration zones are tism stage. Grunerite replaces hastingsite (Fig. 7B), forming
represented by two different assemblages. The first is char- a fine-grained mass of frequently twinned prismatic crys-
acterized by fracture-controlled veinlets of fine- to medium- tals, often in diamond-shaped basal sections, which involves
grained albite ± quartz that crosscut the dacitic rock (Fig. 5A). rounded almandine porphyroblasts (up to 5 mm in diam;
Pervasive Na-rich alteration domains containing albite were Fig. 7C).
only locally observed in the mafic igneous rocks, where they Magnetite is perhaps the most important mineral phase
were obliterated by overprinting scapolite (Fig. 5B), biotite, associated with the iron metasomatism stage. Massive magne-
and chlorite (Fig. 5C). Albite crystals are generally xenoblastic tite bodies (Fig. 6C), locally constituting up to 55% of the rock
to subidioblastic and, when limpid, exhibit evidence of stress- mass, can reach thickness up to 10 m along the drill holes.
related deformation processes, including stretching, undulose Magnetite (I) is subidioblastic to idioblastic, commonly exhib-
extinction, twin boundary migration, and tapered deformation iting granular to massive structure.
twins. These crystals usually contain tiny inclusions of hema- Toward iron-enriched zones, almandine content becomes
tite, which impart a reddish color to the altered rocks. progressively higher along the drill holes (Fig. 6D). The Fe-
A distinct assemblage of hastingsite + scapolite overprints rich garnet is generally poikiloblastic, riddled with grunerite,
zones with previously formed albite. This alteration stage is magnetite, and quartz inclusions. Individual crystals are also
better recognized in mafic protoliths, where hastingsite and extremely fractured and selectively replaced by biotite. Elon-
marialitic ([Na,Ca]4[Al3Si9O24]Cl) scapolite replace the igne- gated almandine grains with pressure shadows are observed in
ous clinopyroxene and plagioclase grains, respectively. Hast- intensely deformed zones of the deposit.
ingsite is typically bluish green and forms subidioblastic to A first generation of chalcopyrite formation is also recog-
idioblastic prismatic crystals, frequently displaying diamond- nized within these magnetite-rich zones (mineralization I).
shaped basal sections (Fig. 5D). It apparently reveals a rela- Chalcopyrite (I) is predominantly xenoblastic and typically
tionship of mutual replacement with grunerite (Fig. 5E), intergrown with magnetite, grunerite, and molybdenite (Figs.
which suggests that the latter could have been formed earlier 6E, 7D-F). Light rare earth element-bearing (La-Ce-Nd)
in the hydrothermal system. Scapolite is light yellow in thin monazite, allanite, uraninite (UO2), and Te bismuthite are
section and generally occurs as xenoblastic crystals or as albite common accessory phases associated with this mineralization
pseudomorphs (Fig. 5F). stage (Fig. 7G). They usually form tiny inclusions in magne-
Fe metasomatism: The central zone of the Grota Funda tite and chalcopyrite. Gold occurs essentially as inclusions in
deposit is marked by intense iron-rich metasomatism, magnetite (Fig. 7H).

A B C
Chl

Ab
Scp
Qtz
Ab
250 μm 250 μm 250 μm

D E F
Hs Gru
Hs
Scp
Bt
Hs Hs
Hs
500 μm 250 μm 250 μm

Fig. 5. Photomicrographs showing the main features of the Na-Ca alteration. (A) Albite vein crosscutting dacite matrix. (B).
Scapolite pseudomorph after albite. (C) Xenoblastic crystal of albite mantled by chlorite. (D) Diamond-shaped hastingsite
crystals surrounded by fine-grained biotite. (E) Grunerite crystal replaced by hastingsite along its rims. (F) Marialitic scapo-
lite in association with hastingsite. Mineral abbreviations: Ab = albite, Bt = biotite, Chl = chlorite, Gru = grunerite, Hs =
hastingsite, Qtz = quartz, Scp = scapolite.
8 HUNGER ET AL.

Gru Grt
Gru Mo

Cpy I
Hs

Cpy I
Hs Mag I
Gru

1 cm 1 cm 1 cm 1 cm

G H
Qtz
Qtz
Bt
Cpy I

Gru
Bt
Bt
Mag I

Grt

1 cm 1 cm 1 cm 1 cm

Fig. 6. Drill core samples showing the main features related to the Fe metasomatism and potassic alteration stages. (A)
Grunerite vein crosscutting Na-Ca–altered mafic igneous rock with hastingsite. (B) Coarse-grained molybdenite crystal
within grunerite-rich vein, intersecting Na-Ca–altered mafic rock with hastingsite. (C) Massive magnetite (I) associated with
grunerite in Fe-metasomatized zones. Note chalcopyrite (I) as a late-stage phase. (D) Almandine porphyroblasts immersed
in a grunerite-rich matrix, with chalcopyrite (I) aggregates, marking the transition to massive magnetite zones. (E) Mineral-
ized zone containing chalcopyrite (I) intergrown with magnetite (I) and grunerite. (F) and (G) Strongly mylonitized rock
with biotite, quartz veinlets, and stretched almandine crystals aligned with the foliation. (H) Silicification associated with the
potassic alteration. Mineral abbreviations: Bt = biotite, Cpy = chalcopyrite, Grt = garnet (almandine), Gru = grunerite, Hs =
hastingsite, Mag = magnetite, Mo = molybdenite, Qtz = quartz.

Potassic alteration: Widespread potassic alteration affects brown biotite is commonly observed (Fig. 7L, M). Millime-
all rock types and overprints both sodic-calcic and Fe-rich ter-scale veinlets of fine-grained greenish to brownish biotite
alteration assemblages. Strongly potassically altered zones are flakes are also recognized as fracture infillings in the mafic
well developed in high-strain domains and are represented igneous rocks, frequently as alteration of almandine (Fig. 7N).
essentially by biotite + quartz (Fig. 6F-H), accompanied They also crosscut the coarse grunerite-magnetite veins (Fig.
by subordinate amounts of apatite, tourmaline (I), allanite, 7O). Tourmaline (I) crystals are mainly dark greenish blue
ilmenite, and Ti hematite (Fig. 7I). In this case, biotite usually and display clear internal zonation. In the felsic rocks, biotite
occurs as a fine- to medium-grained groundmass of brown- generally mantles the igneous feldspar (Fig. 7P) and shows
ish tabular crystals intergrown with stretched quartz grains evidence of later replacement by chlorite.
and tourmaline aggregates, defining a mylonitic foliation (Fig. Main sulfide ore: The main sulfide ore (mineralization II)
7J, K). Selective replacement of hastingsite and grunerite by at Grota Funda is chiefly represented by breccia bodies (Fig.
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 9

Hs Cpy I

Gru
Grt Mag I
Gru Gru

500 μm 500 μm 500 μm Gru 500 μm

Te-Bis
Mag I
Mag I
Mag I Cpy I

Cpy I Cpy I Mo Mnz Au

Mag I
250 μm 250 μm 100 μm 100 μm

Qtz Qtz
Bt Bt
Aln Ap Tur I Hs Hs
Bt
Bt
Chl
250 μm 500 μm 500 μm 250 μm

Gru Grt
Grt Pl
Bt
Qtz
Mag I
Bt Bt
Bt
Pl
250 μm 500 μm 500 μm 150 μm

Fig. 7. Photomicrographs showing the main features of the Fe metasomatism and potassic alteration stages. (A) Vein-hosted
twinned coarse-grained grunerite crystal (transmitted light/cross-polarized light [XPL]). (B) Front of acicular grunerite crys-
tals replacing hastingsite (transmitted light/plane-polarized light [PPL]). (C) Almandine porphyroblasts surrounded by fine-
grained grunerite (transmitted light/XPL). (D) (transmitted light/XPL) and (E, F) (reflected light/PPL) Chalcopyrite (I)
mineralization associated with magnetite (I), grunerite, and molybdenite. (G) Monazite and Te bismuthite inclusions in
magnetite (I)(scanning electron microscopy backscattered electron [SEM-BSE]). (H) Native gold inclusion in magnetite (I)
(SEM-BSE). (I) Allanite-quartz-apatite-biotite association in potassically altered rock with biotite (transmitted light/XPL).
(J) Tourmaline (I) aggregates associated with biotite-rich zone (transmitted light/PPL). (K) Pervasive potassic alteration with
biotite, quartz, and hastingsite aligned with the foliation (transmitted light/XPL). (L) Diamond-shaped hastingsite crystal
altered to biotite and surrounded by fine-grained chlorite (transmitted light/XPL). (M) Grunerite crystal partially altered to
biotite (transmitted light/PPL). Note the presence of magnetite (I). (N) Green biotite fracture infillings in almandine (trans-
mitted light/PPL). (O) Coarse grunerite vein crosscut by green biotite veinlet (transmitted light/XPL). (P) Igneous plagioclase
crystals from dacitic rock mantled by biotite (transmitted light/XPL). Mineral abbreviations: Aln = allanite, Ap = apatite, Bt =
biotite, Chl = chlorite, Cpy = chalcopyrite, Grt = garnet, Gru = grunerite, Hs = hastingsite, Mag = magnetite, Mnz = mona-
zite, Mo = molybdenite, Pl = plagioclase, Qtz = quartz, Te-Bis = Te bismuthite, Tur = tourmaline.

8A) that may reach up to 15-m thickness in drill cores. Sub- Unlike iron-enriched zones, in which magnetite is the dom-
ordinately, the mineralization can also occur in veinlets (Fig. inant mineral phase, magnetite (II) represents a secondary
8B) and as disseminations. The breccia ore type is spatially mineral phase when compared to sulfide abundance. It gener-
associated with the potassic alteration and essentially hosted ally occurs as subidioblastic to idioblastic crystals, commonly
by mafic igneous rocks. The ore consists primarily of mas- exhibiting octahedral basal sections (Fig. 8D). Pyrrhotite
sive chalcopyrite (II) (up to 70%), followed by magnetite, usually forms xenoblastic crystals, which may present fine-
pyrrhotite, pentlandite, and sphalerite that fill the breccia grained pentlandite exsolutions along their rims and cores
matrix (Fig. 8C). Apatite, quartz, tourmaline, biotite, chlo- (Fig. 8E). Sphalerite is mainly granular, commonly exhibiting
rite, and allanite are commonly in association with the cop- chalcopyrite inclusions (chalcopyrite disease; Fig. 8F). Under
per ore type. transmitted light, sphalerite grains are typically translucid
10 HUNGER ET AL.

A B Cpy II

Ap
Cpy II Bt
Tur I

0.5 cm 1 cm

C Cpy II
D Cpy II E
Po Pn
Pn Pn
Ap Cpy II
Ap Mag II
Po Po
Mag II
1 mm 250 μm 500 μm

F G H Ti-hem
Cpy II
Sph
Cpy II Ilm
Bn
Ap
Po Ilm
500 μm 500 μm 150 μm

I J K
Cpy II
Py I
Po
Sg
Cpy II
Cpy II Cob

500 μm 250 μm 30 μm

Fig. 8. (A) Drill core sample of mineralized breccia with massive chalcopyrite (II) enclosing fine-grained apatite crystals. (B)
Drill core sample of chalcopyrite (II)-tourmaline (I) veinlets in a biotite-rich groundmass. C to J are photomicrographs under
reflected light and plane-polarized light (PPL). (C) Chalcopyrite (II)-pyrrhotite-magnetite (II)-pentlandite-apatite associa-
tion in breccia ore type sample. Note coarse apatite surrounded by the sulfide-rich matrix. (D) Magnetite (II) crystal along its
octahedral basal section within chalcopyrite (II) and in contact with pyrrhotite and pentlandite. (E) Pentlandite exsolution in
pyrrhotite as inclusions in chalcopyrite (II). (F) Xenoblastic sphalerite with chalcopyrite disease in association with chalcopy-
rite (II), pyrrhotite, and apatite. (G) Bornite replacing chalcopyrite (II) along its rims. Note the presence of ilmenite crystals.
(H) Ti hematite exsolutions in ilmenite crystal. (I) Chalcopyrite (II)-pyrrhotite-pyrite (I) in ore sample. (J) Siegenite crystal as
inclusion in chalcopyrite (II). (K) Backscattered electron image under scanning electron microscopy showing cobaltite crystal
in contact with chalcopyrite (II). Mineral abbreviations: Ap = apatite, Bn = bornite, Bt = biotite, Cob = cobaltite, Cpy = chal-
copyrite, Ilm = ilmenite, Mag = magnetite, Pn = pentlandite, Po = pyrrhotite, Py = pyrite, Sg = siegenite, Sph = sphalerite,
Ti-hem = Ti hematite, Tur = tourmaline.

and orange brown, indicating low iron contents. Among the 8K), and melonite (NiTe2) are also recognized in ore samples,
sulfides, bornite is exceptionally subordinate and generally occurring as inclusions in chalcopyrite.
replaces chalcopyrite along its rims (Fig. 8G). Ilmenite rep- Chlorite alteration: Chlorite alteration is widespread at Grota
resents a common accessory phase, especially in biotite-rich Funda and is better recognized in areas distal to the central
zones, and frequently displays Ti hematite exsolutions (Fig. zone of the deposit. Strongly chloritized domains, in which
8H). Minor pyrite (Fig. 8I), siegenite (Fig. 8J), cobaltite (Fig. biotite and amphiboles are converted into Fe-rich chlorite (I)
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 11

(chamosite), are also accompanied by silicification and tour- Magnetite, tourmaline, and actinolite represent significant
maline (II)-magnetite (III)-carbonate-actinolite precipitation products of the chloritization process. Magnetite (III) is usu-
(Fig. 9A). The mafic igneous rocks are particularly affected ally massive, occurring as fine- to medium-grained subidio-
by this intense chloritization, having their original igneous tex- blastic to idioblastic crystals, intergrown with tourmaline,
ture completely obliterated (Fig. 9B). Veinlets of chlorite (I) ± chlorite, quartz, and actinolite (Fig. 9D). Tourmaline (II)
quartz-carbonate-chalcopyrite (III)-epidote are commonly is black to dark brown and typically occurs as xenoblastic to
observed as fracture infillings within the felsic rocks (Fig. 9C). subidioblastic coarse-grained prismatic crystals (up to 4 mm in

A Act
B

Mag III Qtz

Chl I
Chl I
Tur II 1 cm 1 cm

C D Tur II E
Chl I
Mag III
Qtz Tur II
Cb Chl I

Act Chl I
Cpy III
1 cm 1 cm 1 cm

F G Cpy IV Act H
Act Cpy III
Cb Chl II
Cb Tur II

Chl I

Chl I 1 cm 1 cm 1 cm

I J Cpy IV
Chl I Cb

Cpy IV Cb
Qtz Chl I

1 cm 1 cm

Fig. 9. Main features of the chlorite alteration stage and late carbonate veining. (A) Drill core sample of chlorite (I)-mag-
netite (III)-tourmaline (II)-actinolite association in pervasively chlorite-altered zone. (B) Drill core sample of mafic igneous
rock strongly altered to chlorite (I) and quartz. (C) Photomicrograph under transmitted light of chlorite (I)-chalcopyrite
(III) veinlet crosscutting dacitic rock (plane-polarized light [PPL]). (D) Photomicrograph under transmitted light of idio-
blastic magnetite (III) associated with tourmaline (II), actinolite, chlorite (I), and carbonate (PPL). (E) Drill core sample of
tourmaline-rich domain in chlorite-altered rock. (F) Photomicrograph under transmitted light of actinolite in association with
chlorite (I) and tourmaline (II), partially replaced by carbonate (cross-polarized light [XPL]). (G) Drill core sample of coarse-
grained prismatic actinolite crystals pervasively replaced by carbonate. Note the presence of chalcopyrite (IV) in association
with carbonate. (H) Photomicrograph under transmitted light of Fe-rich (purple, Chl I) and Mg (dark brown, Chl II) chlorites
in mineralized zone with chalcopyrite. (I) Drill core sample of carbonate-quartz-chalcopyrite (IV) veinlets crosscutting mafic
rock. (J) Drill core sample of breccia associated with late carbonate-chalcopyrite (IV) veining. Mineral abbreviations: Act =
actinolite, Cb = carbonate, Chl = chlorite, Cpy = chalcopyrite, Mag = magnetite, Qtz = quartz, Tur = tourmaline.
12 HUNGER ET AL.

length), often crystallized in triangular basal sections. Unlike performed at the State Key Laboratory of Ore Deposit Geo-
tourmaline (I), this second generation of B-rich silicate shows chemistry, Institute of Geochemistry, Chinese Academy of
no evident internal zonation and is generally poikiloblas- Sciences (Guiyang, China), on an ELAN DRC-e inductively
tic, riddled with chlorite, quartz, and carbonate inclusions. coupled plasma-mass spectrometry (ICP-MS) instrument.
Tourmaline-rich domains (up to 70 vol %) are recurrent along Detailed analytical procedures followed those of Andao et al.
strongly chloritized zones (Fig. 9E). Although uncertain, the (1995), Shirey and Walker (1995), Markey et al. (1998), Stein
paragenetic association between chlorite (I), magnetite (III), et al. (1998), and Qi et al. (2007, 2010). Approximately 10 mg
tourmaline (II), and actinolite, observed in thin sections, sug- of concentrated molybdenite was weighed and loaded into a
gest that the actinolite represents a product of the chloritiza- 120-ml reusable Carius tube with known amounts of 185Re
tion process (Fig. 9F). Actinolite generally occurs as prismatic and 190Os spikes. Samples were then digested and equilibrated
coarse-grained crystals (up to 3 cm in length), frequently using 10 ml of concentrated HNO3 and 2 ml HCl. The tube
replaced by carbonate (Fig. 9G). was subsequently placed in a stainless-steel jacket and heated
A third stage of chalcopyrite crystallization is spatially at 200°C for about 12 h. After cooling, Os was separated from
related to chlorite-altered domains (mineralization III). The the matrix as OsO4, using the in situ distillation equipment,
mineralization, in this case, consists of massive chalcopyrite and Re was extracted from the remaining solution utilizing an
(III) (up to 50%) that occurs with quartz, chlorite, epidote, anion exchange resin (Biorad AG 1-X8, 200–400 mesh). Irid-
carbonate, and minor Ti-bearing minerals (e.g., titanite, ium was added to the Re and Os solutions for mass discrimina-
ilmenite, and rutile). Two generations of chlorite were recog- tion correction (Schoenberg et al., 2000; Huang et al., 2013).
nized within these mineralized zones, including an Mg-rich Sulfur isotope analyses of chalcopyrite separates were
phase (anomalous dark-brown birefringent colors; chlorite carried out at the Stable Isotope Laboratory of the Univer-
II), which apparently replaces the early formed chamosite sity of Brasília, Brazil, using a Thermo Scientific MAT253
(Fig. 9H). isotope ratio mass spectrometer (IRMS) instrument. Nine
Late carbonate veins: The latest stage of hydrothermal mineralized drill core samples containing chalcopyrite were
activity recognized at Grota Funda is represented by milli- hand crushed and manually ground in an agate mortar. The
meter-scale veinlets (<4 mm) consisting of calcite-quartz ± samples were then placed in petri dishes, and chalcopyrite
chalcopyrite (IV)-pyrite (II), which overprints previous zones grains were carefully handpicked to ensure maximum purity.
of alteration and crosscuts all host rocks (Fig. 9I). In this con- Approximately 2 mg of each sample were put in individual
text, galena and Ag tellurides occur as inclusions in chalcopy- tin capsules and subsequently loaded into a Thermo Scientific
rite (IV). These calcite-quartz veins are commonly brecciated MAS 200R automatic sampler. They were then dropped into
(Fig. 9J) and evidence open space-filling textures. In perva- a combustion furnace held at 1,020°C and combusted in the
sive carbonate-altered domains, calcite usually replaces both presence of excess oxygen. The gaseous products were swept
igneous and hydrothermal feldspar crystals, Ca amphiboles, in a helium stream through a tin trioxide catalyst and then
and tourmaline. Paragenetic associations at Grota Funda are reduced over high-purity copper wires. Water was removed by
presented in Figure 10. a magnesium perchlorate trap. Sulphur dioxide was separated
by a packed column gas chromatograph held at an isothermal
Materials and Analytical Methods temperature, and the resultant SO2 chromatographic peak
Five drill cores from the Grota Funda deposit (GRFUN_ was introduced into the ion source of the IRMS, where it was
FD028, GRFUN_FD029, GRFUN_FD037, GRFUN_ ionized and accelerated. Gas species of different mass were
FD046, and PKO-09) were studied in detail to determine separated in a magnetic field and simultaneously measured by
the host rocks, spatial distribution and stages of hydrothermal a Faraday cup universal collector array. For SO2, masses 64,
alteration, and modes of occurrence of the copper-gold ore. 65, and 66 were monitored. Sulfur isotope compositions are
Petrographic investigations were undertaken in 32 polished reported in the standard delta notation (δ) relative to Vienna-
thin sections, and accessory mineral phases were additionally Canyon Diablo Troilite (V-CDT). Analytical precision (1σ)
identified by a scanning electron microscope (SEM) coupled was ± 0.2‰. Reference materials IAEA-SO-5, IAEA-S-2,
with an energy-dispersive X-ray spectrometer (EDS). Fluid IAEA-S-3 (Ding et al., 2001), and an in-house standard (CdS)
inclusion analyses of apatite were conducted on a doubly were used to enable comparison against the V-CDT scale.
polished thin section representative of the chalcopyrite + Data were processed using the software package Isodat 3.0.
pyrrhotite ± magnetite ± sphalerite ore zone. Microthermo-
metric data were obtained on a LINKAM THMSG600 heat- Fluid Inclusion Studies
ing-freezing stage attached to a LEICA DMLP petrographic
microscope, equipped with 50, 80, and 100x objectives. Cali- Petrography and inclusion types
bration was performed using the Synflinc set of synthetic fluid Fluid inclusion studies were only performed in two apatite
inclusions and revealed a precision of ±0.1°C for freezing crystals from the main sulfide ore stage (mineralization II).
runs down to –21.2°C and ±2°C for heating runs up to 300°C. Fluid inclusions in quartz and calcite from later-stage miner-
These studies were conducted at the Institute of Geosciences, alization III could not be investigated due to their extremely
University of Campinas, Brazil. small sizes. The investigated apatite grains are semirounded, up
Molybdenite for Re-Os analyses was manually separated to 800 µm in length, and slightly to moderately fractured and
from a drill core sample (GRFUND_FD037/105,40) rep- display a poikilitic texture mainly characterized by smaller chal-
resentative of the grunerite-magnetite veins, using a dia- copyrite inclusions. Two types of fluid inclusions were recog-
mond-tipped, slow-speed, handheld drill. The analyses were nized in the selected samples, based on phases present at room
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 13

Fe- Main Chlorite Late

Calcic-sodic Potassic
metasomatism Sulfide Ore Alteration Carbonate
Alteration Alteration
(Mineralization I) (Mineralization II) (Mineralization III) Veins

Albite
Scapolite
Hastingsite
Quartz
Grunerite
Almandine
Biotite
Tourmaline I
Tourmaline II
Allanite
Apatite
Magnetite I
Magnetite II
Magnetite III
Chalcopyrite I
Chalcopyrite II
Chalcopyrite III
Chalcopyrite IV
Molybdenite
Monazite
Uraninite
Te-bismuthite
Gold
Pyrrhotite
Sphalerite
Pentlandite
Bornite
Pyrite I
Pyrite II
Ilmenite
Ti-hematite
Siegenite
Cobaltite
Melonite
Chlorite I
Chlorite II
Epidote
Altaite
Rutile
Titanite
Zircon
Actinolite
Carbonate
Galena
Ag-telluride
Abundant Common Trace

Fig. 10. Paragenetic sequence of the Grota Funda hydrothermal system.

temperature: multiphase, saline-aqueous inclusions (type 1), intragranular planar arrays containing exceptionally smaller
and aqueous two-phase inclusions (type 2). Both types of inclu- fluid inclusions were locally distinguished (Fig. 11B).
sions display sizes rarely larger than 10 µm and may be faceted, Type 1 inclusions contain a liquid phase (LH2O), one or
rounded, or irregularly shaped. They are usually randomly dis- multiple solid phases (S) and a vapor bubble (VH2O), which
tributed within the apatite crystals (Fig. 11A), although thin together may correspond to more than 50% of the inclusion
14 HUNGER ET AL.

A Cpy

Cpy

Cpy

Cpy

Ap
200 μm
150 μm

B C D
V
L
V S

Op
L
L

50 μm 10 μm V 10 μm

E F G
V S2 V S V

Hem?
S1 L
L

10 μm 10 μm 5 μm

Fig. 11. Fluid inclusion assemblages and types hosted in apatite associated with the main sulfide ore stage (mineralization
II). (A) Sketch depicting the distribution of fluid inclusions within an apatite crystal with chalcopyrite inclusions (see inset in
the lower left corner). (B-G) Photomicrographs under transmitted light and plane polarized light of the main fluid inclusion
types within the above apatite crystal. (B) Intragranular planar array containing extremely small (<2 µm) fluid inclusions.
(C) Coexistence of opaque phase-bearing type 1 (LH2O + VH2O + S) and type 2 (LH2O + VH2O) fluid inclusions. (D) and
(E) Multiphase type 1 fluid inclusions, respectively displaying one and two daughter crystals (S). (F) Type 1 fluid inclusion,
containing an irregularly shaped solid phase of unknown nature and a hematite(?) crystal. (G) Typical negative-shaped type 2
fluid inclusion, the most abundant in apatite crystals. Abbreviations: Ap = apatite, Cpy = chalcopyrite, Hem = hematite, L =
liquid, Op = opaque, S = solid, V = vapor.

volume. Among the solids, opaque phases are by far the most are dominant (>80 vol %) among inclusion types and are
abundant (Fig. 11C), followed by rectangular to irregularly characterized by a liquid phase (LH2O) and a vapor bubble
shaped translucent solids (Fig. 11D, E) and possibly hematite (VH2O) that usually accounts for 10 to 20% of the inclusion
grains, given their reddish color (Fig. 11F). Type 2 inclusions volume (Fig. 11G).
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 15

Microthermometric results inclusions were therefore estimated in terms of wt % NaCl +

The results of the microthermometric measurements are CaCl2 equiv, revealing values ranging from 24 to 29 (Fig.
12C). Concentrations of NaCl (3.30–19.90 wt %) and CaCl2
listed in Table 1. Data have only been recorded from type 2
(3.86–25.87 wt %) were calculated following the method of
fluid inclusions, once the observation of phase changes in type
Steele-MacInnis et al. (2011). It is important to point out
1 inclusions was precluded due to their small size and poor that once the real hydrohalite melting temperatures were
visibility. During low-temperature runs, most of the investi- not considered to calculate the salinity, as well as the total
gated aqueous inclusions froze completely at temperatures NaCl and CaCl2 concentrations for type 2 fluid inclusions,
between –65° to –85°C, displaying either granular or clear Tmice was used as the utmost possible Tmhh value (Tmice =
appearances. Upon heating, first-melting (Te) and ice-melting Tmhh). According to Chi and Ni (2007), this approximation
temperatures (Tmice) were systematically registered. Due to is valid and provides a maximum error in salinity estimation
the metastable behavior of hydrohalite, its melting tempera- of <2 wt %, which is insignificant to most geologic processes.
ture (Tmhh) was not precisely recognized, and therefore dis- Total homogenization temperatures (ThLV-L) for type 2 fluid
carded from the data. inclusions span from 113.2° to 293°C, with most of the val-
The great majority of Te and Tmice values are respectively ues confined within the 120° to 200°C interval (Fig. 12D).
confined within the –80° to –75°C and –35° to –25°C ranges Homogenization, in this case, invariably occurs to the liquid
(Fig. 12A, B). These data suggest the presence of a complex state, via disappearance of the vapor phase.
mixture of metal chlorides—in particular NaCl, CaCl2, and Evidence of metastability among type 2 fluid inclusions
LiCl (Crawford, 1981; Roedder, 1984)—within the trapped was commonly observed during microthermometric runs.
fluids. The bulk salinity results for the aqueous two-phase The most noticeable indications of this metastable behavior

Table 1. Microthermometric Data for Type 2 Fluid Inclusions of the Grota Funda Iron Oxide Copper-Gold Deposit

No. Te (°C) Tmice (°C) ThLV-L (°C) Salinity (wt % NaCl + CaCl2 equiv)1 NaCl (wt %)1 CaCl2 (wt %)1

1 –79.6 –27.3 142.5 25 10.78 14.62

2 –81.8 –28.8 122.9 26 9.08 16.79
3 –76.9 –22.9 197 24 18.65 5.29
4 –79.1 –34 182.6 27 5.30 22.08
5 –76.1 –36.9 185.9 28 4.09 24.08
6 –86.5 –31.3 146.5 27 6.94 19.68
7 –92.7 –30.1 163.5 26 7.87 18.39
8 –78.9 –28.6 205.2 26 9.28 16.52
9 –75 –32.5 186.2 27 6.14 20.82
10 –78.9 –32.3 173.3 27 6.26 20.64
11 –81.1 –30.5 184.9 26 7.54 18.83
12 –81.3 –26 212 25 12.59 12.39
13 –79.1 –33 188.3 27 5.84 21.26
14 –79.6 –31 148.4 27 7.16 19.37
15 –79.8 –29.8 157.4 26 8.13 18.04
16 –84.4 –39.6 113.2 29 3.30 25.54
17 –95.7 –39.1 144.2 29 3.43 25.29
18 –81.8 –35.1 148.9 28 4.79 22.90
19 –76.6 –28.7 140.7 26 9.18 16.65
20 –75.4 –33.9 134.2 27 5.36 22.00
21 –77.3 –22.4 293 24 19.90 3.86
22 –71 –31.5 - 27 6.79 19.88
23 –74.5 –33.8 137.9 27 5.41 21.92
24 –78.8 –30.6 177.1 26 7.46 18.94
25 –74 –27.1 - 25 11.04 14.30
26 –77.7 –28 - 26 9.94 15.68
27 –80.4 –28.5 140.2 26 9.39 16.38
28 –79.5 –23.5 171.1 24 17.26 6.90
29 –78.8 –24.1 178.7 24 15.98 8.38
30 –78.1 –33.6 142.6 27 5.51 21.76
31 –89.8 –40.3 137.6 29 3.14 25.87
32 –83.8 –34.7 - 28 4.97 22.61
33 –77.7 –23.5 145.1 24 17.26 6.90
34 –83.9 –29.2 147.4 26 8.68 17.30
35 –75.8 –23.8 149.8 24 16.60 7.65
36 –74 –23.5 149.7 24 17.26 6.90
37 –93 –38.8 - 29 3.50 25.14
38 –77.2 –35.6 153.9 28 4.58 23.24
39 –94.6 –37.4 137.2 28 3.92 24.37

Abbreviations:- = no data, Te = first melting or eutectic melting, Tmice = ice melting; ThLV-L = homogenization to liquid
1 Estimated following the method of Steele-MacInnis et al. (2011)
16 HUNGER ET AL.

A B
Frequency

Frequency
Te (°C) Tmice (°C)

C D
Frequency

Frequency

Salinity (wt % NaCl + CaCl2 equiv) ThLV-L (°C)

Fig. 12. Microthermometric data obtained from type 2 (LH2O + VH2O) fluid inclusions in apatite crystals. (A) First-melting
temperatures (Te). (B) Ice-melting temperatures (Tmice). (C) Salinities (in wt % NaCl + CaCl2 equiv) estimated considering
Tmice = Tmhh and following the method of Steele-MacInnis et al. (2011). (D) Total homogenization temperatures (ThLV-L).
Abbreviations: L = liquid, Tmhh = hydrohalite-melting temperatures, V = vapor.

include several inclusions that have not undergone freezing Re abundance of 89.11 ppm (σ = ±0.55), 55.78 ppm of 187Re
during supercooling (temperatures below –190°C) and fluid (σ = ±0.35), radiogenic 187Os concentration of 2.40 ppm (σ =
inclusions that could be either single-phase (LH2O) or two- ±0.05), and 2.05 ppb of total common Os (σ = ±0.25). The
phase (LH2O + VH2O) at room temperature (Roedder, 1971). ELAN DRC-e ICP-MS analysis conducted in this study
yielded a Re-Os model age of 2530 ± 60 Ma.
Sulfur Isotopes in Chalcopyrite
Sulfur isotope compositions of chalcopyrite from the Grota Discussion
Funda deposit are shown in Table 2. The highest δ34S val-
ues, from 1.5 to 1.8‰, are from the iron-enriched alteration Evolution of the hydrothermal system
zones that are host to mineralization I. Chalcopyrite from the The evolution of the Grota Funda hydrothermal system is
main sulfide ore (mineralization II) yield δ34S values from marked by multiple episodes of hydrothermal alteration
0.3 to 0.5‰, whereas chalcopyrite associated with chlorite- and copper (-gold) mineralization. Early sodic-calcic altera-
altered domains (mineralization III) display lower δ34S val- tion characterizes the initial stage of hydrothermal activity
ues between 0 and 0.1‰, except for one sample with δ34S = in the deposit, followed by intense Fe metasomatism, potas-
0.6‰. sic alteration, chlorite-quartz-tourmaline formation, and late
carbonate-quartz veining. Sodic-calcic alteration assemblages
Molybdenite Re-Os Dating are very common in IOCG systems worldwide, as well as in
Molybdenite from coarse-grained grunerite-magnetite veins Carajás, especially in those emplaced in deeper crustal levels
representative of the iron-rich alteration zone (Fig. 6B) has (Hitzman et al., 1992; Pollard, 2001; Monteiro et al., 2008;
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 17

Table 2. Sulfur Isotope Analyses in Chalcopyrite from the Grota Funda Iron Oxide Copper-Gold Deposit

Sample Mode of occurrence δ34S (‰ V-CDT)

FD29/397,20 Massive magnetite-chalcopyrite-grunerite (mineralization I) 1.8

FD29/443,00 Massive magnetite-chalcopyrite-grunerite (mineralization I) 1.4
FD29/441,25 Massive magnetite-chalcopyrite-grunerite (mineralization I) 1.5
FD37/339,80 Chalcopyrite-pyrrhotite-sphalerite-magnetite ore (mineralization II) 0.3
FD37/339,70 Chalcopyrite-pyrrhotite-sphalerite-magnetite ore (mineralization II) 0.6
FD37/340,00 Chalcopyrite-pyrrhotite-sphalerite-magnetite ore (mineralization II) 0.5
FD37/309,50 Massive chalcopyrite-chlorite-quartz bodies (mineralization III) 0.1
FD37/309,40 Massive chalcopyrite-chlorite-quartz bodies (mineralization III) 0.0
FD37/309,30 Massive chalcopyrite-chlorite-quartz bodies (mineralization III) 0.6

Abbreviations: V-CDT = Vienna-Canyon Diablo Troilite

Melo et al., 2016). At Grota Funda, this alteration is marked with mineralized zones (mineralization II). According to Lin-
by the precipitation of hydrothermal albite, with subsequent denmayer et al. (2001), the first type represents a Ti-bearing
hastingsite and marialitic scapolite formation, at tempera- biotite in the Gameleira deposit, whereas the second is F rich.
tures probably above 500°C (Oliver et al., 1993; Perring et The main sulfide ore (mineralization II) is represented by
al., 1999). This is corroborated by geothermometry studies in mineralized breccia bodies spatially and temporally associated
hornblende and almandine at the Gameleira deposit, which with potassically altered zones and mainly characterized by a
have yielded an average equilibrium temperature of 540 ± chalcopyrite (II)-magnetite (II)-pyrrhotite-sphalerite associa-
25°C for the sodic-calcic assemblage (Lindenmayer et al., tion. Gold is absent in this stage. This ore assemblage clearly
2001). Moreover, the presence of marialite in Na-Ca altera- formed under lower ƒO2 conditions than the mineralization
tion zones indicates that these high-temperature fluids also associated with Fe-rich alteration domains (mineralization I),
contained high-chlorine contents (Vanko and Bishop, 1982), although at similar ƒS2 (Fig. 13). However, the replacement
which may have enhanced the transport of iron, copper, and of chalcopyrite by bornite, which is expected at temperatures
gold as chloride complexes (Williams-Jones et al., 2009; Pok- below 355°C (Amcoff, 1988), and the late crystallization of
rovski et al., 2013, 2014) in the initial stages of hydrothermal pyrite are evidences of fluid evolution toward higher ƒS2 con-
activity at Grota Funda. ditions (Fig. 13).
The first stage of copper-gold mineralization (mineraliza- A distinct chlorite alteration assemblage, represented by
tion I) recognized in the Grota Funda deposit is coeval with chlorite ± quartz-tourmaline (II)-magnetite (III)-actinolite-
intense Fe metasomatism, which is mainly characterized by carbonate, overprints previous hydrothermally altered zones.
massive precipitation of magnetite (I) ± grunerite-almandine- Experimental data indicate that the incipient replacement
chalcopyrite. In IOCG deposits, these magnetite-rich altera- of biotite by chlorite, observed in this study, requires hydro-
tion assemblages typically form from a relatively oxidized fluid thermal fluids with relatively low pH (Beane, 1994). This is
at temperatures over 400°C (Skirrow and Walshe, 2002; Bas- further corroborated by the replacement of tourmaline (II),
trakov et al., 2007; Rusk et al., 2010; Somarin and Mumin, which is only stable under pH ≥ 6.5 (London et al., 1996), by
2014). The transition between Na-Ca alteration and Fe meta- carbonate in the late stages of hydrothermal activity at Grota
somatism suggests that precipitation of chalcopyrite and gold Funda. However, the presence of magnetite instead of hema-
was possibly facilitated by a decrease in temperature and tite in association with chlorite suggests that the hydrothermal
Cl– activity, the latter due to early destabilization of scapolite, fluids remained under relatively low ƒO2 conditions. Consider-
besides an increase in ƒO2 evidenced by the precipitation of able temperature decreases probably represented the main
magnetite. mechanism that triggered chalcopyrite precipitation in min-
Potassic alteration with biotite is well developed at Grota eralized zones spatially associated with the chlorite alteration
Funda, particularly in high-strain zones marked by the devel- (Liu and McPhail, 2005).
opment of a penetrative mylonitic foliation within the shear The last stage of hydrothermal alteration observed at Grota
zone domain. The high-K+ activity in the hydrothermal flu- Funda is characterized by widespread carbonate veining.
ids in this stage may be due to the consumption of Na and These veins are mainly composed of calcite ± quartz-chalco-
Ca in the preceding alteration stages. This alteration stage pyrite-pyrite and were probably generated in a brittle struc-
is also accompanied by massive quartz precipitation, which tural regime. According to Lindenmayer et al. (2001), similar
may have been controlled by mixing of high- and low-salinity veins recognized in the Gameleira area were formed from an
solutions, as silica solubility tends to decrease with decreas- acidic fluid at temperatures around 190 ± 10°C.
ing salinity, temperature, and pH (Fournier, 1983; Rimstidt, The paragenetic evolution of the Grota Funda deposit
1997). In addition, early destabilization of scapolite may have reflects important changes in the physical-chemical condi-
been promoted by influx of external diluted fluids, favoring tions of the hydrothermal fluids. This is mainly illustrated by
subsequent quartz formation (Rimstidt, 1997). temperature conditions dropping from 540°C (Na-Ca altera-
Similar to what is observed at Gameleira, two types of bio- tion) to below 200°C (late carbonate veins), accompanied by
tite were recognized in the Grota Funda deposit: tabular fine- a decrease in salinity and pH. In this scenario, early and high-
to medium-grained brownish biotite in pervasively altered temperature alteration assemblages (albite, scapolite-hasting-
zones and fine-grained green biotite flakes, directly associated site) were possibly formed due to circulation of metalliferous
18 HUNGER ET AL.

Seawater/Evaporite Sulfate
at ~ 3.5 - 2.5 Ga

Magmatic
Sulfur

Mantle

δ34SVCDT (‰)
Fig. 13. Sulfur isotope compositions of chalcopyrite from the Grota Funda deposit and of sulfides from several iron oxide
copper-gold deposits in the Carajás Province. Sources of data: (1) Silva et al. (2015); (2) Pestilho (2011); (3) Ribeiro (2008);
(4) Torresi et al. (2012); (5) Monteiro et al. (2008); (6) Lindenmayer et al. (2001); (7) Marschik et al. (2002); (8) Dreher et
al. (2008); (9) Galarza et al. (2008); (10) Réquia and Fontboté (2001); (11) this study. Isotopic data for continental basalt and
gabbro are from Seal (2006). Mantle, magmatic sulfur, and seawater/evaporite sulfate fields are from Eldridge et al. (1991),
Ohmoto and Goldhaber (1997), and Canfield (2004), respectively. VCDT = Vienna-Canyon Diablo Troilite.

and hypersaline fluids, whereas the onset of ore precipitation The Grota Funda and Gameleira deposits appear to have
was probably related to fluid mixing processes, with the par- undergone the same hydrothermal alteration stages in a simi-
ticipation of relatively dilute (moderate salinity) and cooler lar chronological order. Apart from some local-scale differ-
fluids. A fluid regime evolution has been proposed for several ences, they apparently shared a similar evolutionary history
IOCG deposits situated in both northern and southern sec- during the late Neoarchean (2.6–2.5 Ga) with multiple epi-
tors of the Carajás domain, including Sossego, Igarapé Bahia/ genetic mineralizing pulses. However, it should be noted that
Alemão, Alvo 118, Bacuri, Salobo, and others (Dreher et al., the Gameleira deposit is not regarded to be an IOCG deposit
2008; Monteiro et al., 2008; Torresi et al., 2012; Melo et al., sensu stricto but is currently interpreted to be a magmatic end
2014, 2016). member of this class of deposits (Lindenmayer et al., 2001;
Additionally, the Grota Funda deposit shares other simi- Pimentel et al., 2003; Chiaradia et al., 2006).
larities with the Carajás IOCG systems. Early sodic-calcic
alteration, succeeded by high-temperature iron-enriched Fluid evolution and ore genesis
assemblages (e.g., grunerite-almandine-magnetite), seems Fluid inclusion analyses conducted on ore-related apatite
to be a ubiquitous feature of IOCG deposits from the north- have revealed that the main sulfide ore zone (mineralization
ern sector of the Carajás domain. This relationship is evi- II) of the Grota Funda deposit possibly developed from the
dent at Salobo (Melo et al., 2016), Igarapé Bahia/Alemão interaction between highly saline fluids, defined by type 1
(Tallarico et al., 2005), and Igarapé Cinzento/GT46 (Silva multiphase, saline-aqueous inclusions, and moderate- to high-
et al., 2005). In contrast, the predominance of potassic and salinity (24–29 wt % NaCl + CaCl2 equiv), low-temperature
chlorite alteration zones seems to be characteristic of shal- (113°–212°C), Ca-Na–rich, CO2-free aqueous fluids, repre-
low-emplaced deposits, such as seen at the Sossego orebody sented by type 2 inclusions. These data seem to be in accor-
(Sossego mine; Monteiro et al., 2008) and Alvo 118 (Torresi dance with what has been registered in other IOCG systems of
et al., 2012). the Carajás domain. The involvement of hot (>500°C), highly
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 19

saline (35−70 wt % NaCl equiv) metalliferous brines in the pyrrhotite, in equilibrium with chalcopyrite, suggests that the
ore-forming processes represents a striking feature of these mineralizing fluid was in the H2S predominant field. There-
systems, as illustrated at Salobo (Réquia et al., 1995), Igar- fore, according to Ohmoto and Goldhaber (1997), the range
apé Bahia/Alemão (Dreher et al., 2008), Sossego (Carvalho, of δ34S values would closely reflect the sulfur isotope compo-
2009), Alvo 118 (Torresi et al., 2012), and others. The origin of sition of the fluid itself (δ34SSS).
these metalliferous brines, however, has been matter of con- The Grota Funda deposit displays δ34S values similar to
siderable debate. A magmatic-hydrothermal affiliation with those of other IOCG systems described in the Carajás domain,
Archean granites has been proposed by several authors (Tal- such as Visconde, Jatobá, Bacuri, Cristalino, and Salobo (Fig.
larico et al., 2005; Grainger et al., 2008). In contrast, indepen- 13). For these deposits, there is a consensus that a large
dent evidence from chlorine and boron isotopes, combined proportion of sulfur must have been leached from the igne-
with Cl/Br-Na/Cl systematics, indicates a major contribution ous country and host rocks to, eventually, form sulfides dur-
from evaporative brines as a source of high salinity in the ing episodes of mineralization (Réquia and Fontboté, 2001;
Carajás IOCG-related fluids (Chiaradia et al., 2006; Xavier et Ribeiro, 2008; Pestilho, 2011; Silva et al., 2015). Analogously,
al., 2008, 2009). Nevertheless, lower-temperature (<250°C), sulfur derivation from leaching of mafic igneous rocks is here
low- to intermediate-salinity aqueous fluids seem to predomi- interpreted as the most reasonable explanation for the range
nate in the mineralizing stages of most of the Carajás IOCG of δ34S values obtained in this study, which also overlap the
deposits (Xavier et al., 2012), with or without interaction of interval commonly attributed to continental basalt and gabbro
aqueous-carbonic (CO2 ± CH4; Réquia and Fontboté, 2001; sources (δ34S = 1.0 ± 3.2‰; Seal, 2006).
Dreher, 2004) fluids. Sulfur contribution from inorganically reduced Archean
The fluid inclusion assemblages at Grota Funda strongly (~3.5–2.5 Ga) seawater/evaporite sulfate sources (δ34S =
suggest that a fluid mixing process could have represented 2.0–10‰; Canfield, 2004), on the other hand, has been pro-
the main mechanism controlling ore formation. Although no posed to explain the heavier δ34S values observed in several
microthermometric or geochemical data has been measured IOCG deposits of the Carajás domain, including Sossego
for type 1 fluids, it is possible that they represent initial highly (Sequeirinho-Pista and Sossego-Curral-Baiano orebodies),
saline hydrothermal fluids responsible for the extensive high- Igarapé Bahia/Alemão, Bacaba, and Alvo 118 (Galarza et al.,
temperature Na-Ca alteration in the deposit area and for the 2008; Monteiro et al., 2008; Pestilho, 2011; Torresi et al.,
transport of Cu(-Au) as chloride complexes during the evolu- 2012). The participation of nonmagmatic fluids in the evo-
tion of the Grota Funda hydrothermal system. The interaction lution of the Carajás IOCG systems has also been corrobo-
of this metalliferous brine with a lower-temperature and rela- rated by chlorine isotope data and halogen ratios (e.g., Cl/
tively diluted fluid (type 2 fluid inclusions) during the potassic Br-Na/Cl) in fluid inclusions (Chiaradia et al., 2006; Xavier
alteration event may have induced temperature and salinity et al., 2009). According to Chiaradia et al. (2006), the high
decrease and, therefore, ore precipitation. However, it should molar Cl/Br (≥4,000) ratios and the near 0‰ δ37Cl values
be noted that the homogenization temperatures obtained for presented by the ore fluids at Gameleira, for example, are
type 2 inclusions are considerably low (mostly <200ºC) to indicative of a prevailing evaporitic Cl contribution in the
reflect proper conditions for magnetite-chalcopyrite precipi- deposit, with a probable participation of magmatic fluids, as
tation from a hydrothermal fluid. Hence, they could hardly supported by other supplementary stable isotope data (S, O,
represent the actual temperature range in which the main and C). Even though the δ34S values for the Grota Funda
sulfide ore was formed, registering instead the entrapment deposit indicate a predominant participation of magmatic
conditions for type 2 inclusions. fluids in the mineralization stages, its spatial proximity to the
Gameleira deposit, as well as its many similarities with other
Sulfur sources IOCG deposits of the Carajás domain, suggests that a con-
Sulfur isotope compositions of chalcopyrite (δ34S = 0.9 ± tribution from nonmagmatic fluids to the evolution of the
0.9‰) from distinct episodes of mineralization recognized deposit cannot be completely ruled out. However, further
in the Grota Funda deposit deviate slightly from the inter- geochemical analyses should be performed to confirm this
val expected for a mantle source (δ34S = 0 ± 1‰; Eldridge hypothesis.
et al., 1991) and are most likely compatible with the range
commonly attributed to magmatic sources (δ34S = 0 ± 5‰; Timing of IOCG mineralization
Ohmoto and Goldhaber, 1997). These data indicate that no Molybdenite from the grunerite-magnetite veins yielded a
significant degree of isotopic fractionation occurred while Re-Os model age of 2530 ± 60 Ma (σ). According to field and
sulfur was being transported by the hydrothermal fluid, oth- petrographic observations, these veins are correlated with the
erwise a larger deviation in the δ34S values, which is charac- Fe-enrichment event defined in the early stages of hydrother-
teristic of fractionation at high oxidation states (Davidson and mal alteration of the Grota Funda deposit. Thus, the intrinsic
Dixon, 1992), would be expected. At Grota Funda, however, relationship between iron-enriched domains and mineralized
a significant amount of oxygen was undoubtedly consumed to zones strongly suggests that the first event of Cu-Au miner-
form massive magnetite-chalcopyrite bodies (mineralization I) alization recognized at Grota Funda (mineralization I) took
during the iron-enrichment stage of hydrothermal alteration. place in the Neoarchean. However, the significance of this
Consequently, the oxygen fugacity of the fluid dropped to lev- mineralizing event and its implications on the current metal-
els that allowed the coprecipitation of pyrrhotite and sphaler- logenic models for the formation of IOCG systems in the
ite during the main sulfide ore formation (mineralization II). Carajás domain, especially those situated in the northern sec-
Under these relatively reduced conditions, the occurrence of tor, need to be interpreted with caution.
20 HUNGER ET AL.

Moreto et al. (2015a, b) have demonstrated that the IOCG available geochronological data for the northern sector of the
systems in the Southern copper belt (Sossego, Cristalino, Carajás domain (Table 3) point to an important metallogenic
Alvo 118, Bacaba, Castanha, Visconde, Bacuri, and Jatobá event at ca. 2.57 Ga, which, notably, has not been recorded
deposits) are the result of multiple episodes of hydrothermal yet in the southern sector. Evidence that supports this event
activity spanning the Neoarchean (ca. 2.71–2.68 Ga) to the includes the mineralization ages obtained for the Salobo
Paleoproterozoic (2.0–1.88 Ga). In contrast, the currently (2576 ± 8 Ma, Re-Os in molybdenite; Réquia et al., 2003)

Table 3. Geochronological Data for Regional Units and IOCG Deposits from the Northern Sector of the Carajás Domain

Sample Age (Ma) Method Reference

Regional units
Migmatite (Xingu Complex) 2859 ± 2 U-Pb in zircon Machado et al. (1991)
Migmatite (Xingu Complex) 3066 ± 6.6 U-Pb in zircon Delinardo da Silva (2014)
Mafic granulites (Pium Complex) 3002 ± 14 U-Pb in zircon Pidgeon et al. (2000)
Itacaiúnas granite 2560 ± 37 Pb-Pb in zircon Souza et al. (1996)
Northern IOCG deposits
Igarapé-Cinzento/GT46
Host rocks Gray granite 2612 ± 2 U-Pb in monazite Silva et al. (2005)
Pink and gray granites 2668 ± 100 Sm-Nd (whole rock) Silva et al. (2005)
Basalts and gabbro 2686 ± 87 Sm-Nd (whole rock) Silva et al. (2005)
Ore Ore breccia and hydrothermal sample 1752 ± 77 Sm-Nd (whole rock) Silva et al. (2005)
   from the Salobo deposit
Biotite (potassic alteration) 1858 ± 7 40Ar/39Ar in biotite Silva et al. (2005)
Molybdenite from pegmatitic granite 2554 ± 8 Re-Os in molybdenite Silva et al. (2005)
Molybdenite from pegmatitic granite 2557 ± 8 Re-Os in molybdenite Silva et al. (2005)
Molybdenite from granite 2600 ± 8 Re-Os in molybdenite Silva et al. (2005)
Molybdenite from amphibolite 2711 ± 9 Re-Os in molybdenite Silva et al. (2005)
Salobo
Host rocks Magnetite-rich rock 2551 ± 2 U-Pb in monazite Machado et al. (1991)
Old Salobo granite 2573 ± 2 U-Pb in zircon Machado et al. (1991)
Granitic vein 2758 U-Pb in zircon Machado et al. (1991)
Foliated amphibolite (metamorphism) 2761 ± 3 U-Pb in zircon Machado et al. (1991)
Rocks with postore alteration 2950 ± 25 U-Pb in zircon Melo et al. (2016)
Cascata gneiss 2763 ± 4.4 U-Pb in zircon Melo et al. (2016)
Old Salobo granite 2547 ± 5.3 U-Pb in zircon Melo et al. (2016)

Ore Molybdenite 2562 ± 8 Re-Os in molybdenite Réquia et al. (2003)

Molybdenite 2576 ± 8 Re-Os in molybdenite Réquia et al. (2003)
Bornite-chalcopyrite leachates 2579 ± 71 Pb-Pb (sulfides) Réquia et al. (2003)
Salobo ore 2535 ± 8.4 U-Pb in zircon Melo et al. (2016)
Salobo ore 2452 ± 14 U-Pb in monazite Melo et al. (2016)
Igarapé-Bahia
Host rocks Mafic metavolcanic rock 2758 ± 75 Sm-Nd (whole rock) Galarza et al. (2003)
Mafic metavolcanic rock 2748 ± 34 U-Pb in zircon Tallarico et al. (2005)
Mafic metavolcanic rock 2745 ± 1 Pb-Pb in zircon Galarza et al. (2008)

Ore Monazite from ore breccia 2575 ± 12 U-Pb in monazite Tallarico et al. (2005)
Chalcopyrite (mafic metavolcanic rock) 2756 ± 24 Pb-Pb in chalcopyrite Galarza et al. (2008)
Chalcopyrite (hydrothermal breccia) 2772 ± 46 Pb-Pb in chalcopyrite Galarza et al. (2008)
Chalcopyrite (mafic intrusive rock) 2777 ± 22 Pb-Pb in chalcopyrite Galarza et al. (2008)
Gameleira
Host rocks Amphibolite (metamorphism) 2732 ± 2 U-Pb in zircon Machado et al. (1991)
Quartz diorite 2705 ± 2 Pb-Pb in zircon Galarza and Macambira (2002)
Meta-andesite1 2719 ± 80 Sm-Nd (whole rock) Pimentel et al. (2003)
Metagabbro and cogenetic meta-andesite1 2757 ± 81 Sm-Nd (whole rock) Pimentel et al. (2003)
Biotite (potassic alteration) from meta-andesite 1734 ± 8 40Ar/39Ar in biotite Pimentel et al. (2003)
Ore Quartz-grunerite-gold vein 1839 ± 15 Sm-Nd (whole rock) Pimentel et al. (2003)
Ore-related molybdenite 2614 ± 14 Re-Os in molybdenite Marschik et al. (2005)
Grota Funda
Ore Molybdenite from grunerite-magnetite veins 2530 ± 60 Re-Os in molybdenite This study
Pojuca2
Host rocks/ore Amphibolite separates 2732 ± 2 U-Pb in zircon Machado et al. (1991)

Abbreviation: IOCG = iron oxide copper-gold

1 Also interpreted as host rocks of the Pojuca deposit
2 Volcanogenic massive sulfide-type Cu-Zn deposit
 THE GROTA FUNDA IOCG DEPOSIT, CARAJÁS, BRAZIL 21

and Igarapé Bahia/Alemão (2575 ± 12 Ma, U-Pb in mona- Igarapé-Pojuca Group represent the main hosts to the copper
zite; Tallarico et al., 2005) deposits, which are contemporane- (-gold) mineralization.
ous with the emplacement of the Old Salobo (2573 ± 2 Ma, The hydrothermal alteration sequence of the Grota Funda
U-Pb in zircon; Machado et al., 1991) and the Itacaiúnas deposit encompasses (1) an early sodic-calcic alteration, rep-
(2560 ± 37 Ma; Pb-Pb in zircon; Souza et al., 1996) granites. resented by albite, hastingsite, and scapolite, followed by
The obtained ca. 2.53 Ga age for the Cu-Au mineralization at (2) intense Fe metasomatism, with massive precipitation of
Grota Funda overlaps within error the mineralization ages for magnetite, grunerite, and almandine, (3) potassic alteration
the Salobo and Igarapé Bahia/Alemão deposits. Moreover, in with biotite, accompanied by quartz formation and spatially
the Igarapé Cinzento/GT46 deposit, pegmatite intrusive bod- associated with the main sulfide ore zone, (4) widespread
ies yielded Re-Os molybdenite ages of 2554 ± 8 and 2557 ± chlorite alteration, associated with quartz, tourmaline, actin-
8 Ma (Silva et al., 2005), whereas ore-related molybdenite olite, and carbonate, and (5) late carbonate-quartz veining
from the Gameleira deposit recorded a slightly older Re-Os developed during brittle deformation. Copper (-gold) min-
age of 2614 ± 14 Ma. eralization events have also been recognized associated with
Collectively, this set of ages points to a temporal link Fe-metasomatized and chlorite-altered zones. Molybdenite
between the ca. 2.5 Ga granitic magmatism and IOCG gen- from grunerite-magnetite veins yielded a Re-Os model age
esis in the northern sector of the Carajás domain. According of 2530 ± 60 Ma, which is interpreted as a mineralization age
to Melo et al. (2016), however, the ca. 2.5 Ga age may reflect coeval with the Fe metasomatism.
an important tectono-thermal event that could be related to The main sulfide ore occurs predominantly as breccia bod-
the reactivation of the Carajás and Cinzento strike-slip fault ies, subordinately recognized in veinlets and fracture infillings
systems at ca. 2.6 Ga (Pinheiro and Holdsworth, 1997). and as disseminations. Ore paragenesis includes primarily
It is noteworthy that Cu-bearing quartz-grunerite veins and chalcopyrite, magnetite, pyrrhotite, pentlandite, and sphaler-
late sulfide-biotite veins from the Gameleira deposit yielded ite with minor ilmenite, Ti hematite, siegenite, cobaltite, and
whole-rock Sm-Nd isochron ages of 1839 ± 15 (mean square melonite. The association of chalcopyrite-magnetite-pyrrho-
of weighted deviates [MSWD] = 0.83) and 1700 ± 31 Ma tite-sphalerite indicates precipitation under low ƒS2 and ƒO2
(MSWD = 2.3), respectively, whereas brown biotite from the conditions, whereas the replacement of chalcopyrite by born-
metavolcanic host rocks recorded a minimum 40Ar/39Ar age of ite and the late crystallization of pyrite are evidence of fluid
1734 ± 8 Ma for the pervasive potassic alteration (Pimentel et evolution toward higher ƒS2 conditions.
al., 2003). According to Pimentel et al. (2003), these ages pro- The paragenetic evolution of the Grota Funda deposit
vide strong evidence that the mineralizing fluids at Gameleira points to significant changes in the physical-chemical condi-
were possibly derived from or intensively interacted with tions of the hydrothermal fluids, such as temperature decrease
Paleoproterozoic (ca. 1.8 Ga) granites analogous to the Pojuca from 540°C (Na-Ca alteration) to below 200°C (late carbon-
granite. A similar style of potassic alteration has been recog- ate veins), accompanied by a decrease in salinity and pH. The
nized at the Grota Funda deposit, suggesting that a regional- early, high-temperature alteration assemblages (albite, scapo-
scale episode of hydrothermal activity could have affected lite-hastingsite) may be intrinsically related to regional circu-
both deposits. Consequently, it would be expected that biotite lation of deep-seated hypersaline and hot metalliferous fluids,
from the Grota Funda deposit might give Paleoproterozoic which transported metals as chloride complexes, whereas the
ages similar to those of Gameleira. In this scenario, the previ- onset of ore precipitation resulted from significant influx of
ously established Neoarchean (ca. 2.5 Ga) system would have relatively dilute (moderate salinity) and cooler fluids.
been overprinted by a Paleoproterozoic hydrothermal event. Overall, the fluid inclusion data for the Grota Funda deposit
However, the emplacement of the Paleoproterozoic Pojuca point to a trend in fluid evolution that apparently involved the
granite (1874 ± 2 Ma, U-Pb in zircon; Machado et al., 1991) in interaction between highly saline hydrothermal fluids and
the Pojuca-Gameleira-Grota Funda trend suggests that a dif- cooler, relatively dilute fluids. This process may have induced
fusion-driven thermal reset, especially in the 40Ar/39Ar system, temperature and salinity decrease and, consequently, the pre-
could have occurred. At temperatures over 300°C, for exam- cipitation of the main sulfide ore. Sulfur isotope compositions
ple, partial or total resetting of the 40Ar/39Ar isotope system in of chalcopyrite (δ34S = 0.9 ± 0.9‰) point to a magmatic sulfur
biotite is expected due to significant thermally activated argon source, which was most probably leached from the mafic igne-
diffusion (Chiaradia et al., 2013). Assuming that biotite from ous host rocks present in the deposit area.
pervasively potassically altered zones of both Gameleira and
Grota Funda deposits formed previously (e.g., Neoarchean?), Acknowledgments
the thermal effect caused by emplacement of the Pojuca gran- We are very grateful to VALE for their continuous support,
ite could have reset the 40Ar/39Ar system. Therefore, the ages especially to geologists Ronan Barbosa and Fernando Mat-
obtained through this method would not represent the tim- tos. We also acknowledge Maria José Mesquita and Luiz Hen-
ing of biotite crystallization itself but instead would reflect the rique Ronchi for their impressions on earlier versions of this
cooling history of the mineral after the granite emplacement. manuscript. Constructive suggestions and comments by Mike
Porter and an anonymous reviewer, combined with careful
Conclusions editing by Adam Simon, significantly improved the qual-
The Grota Funda, Gameleira, and Pojuca deposits all lie ity of this paper. This research was funded by Fundação de
along a regional WNW-ESE–striking shear zone (Pojuca fault Amparo à Pesquisa do Estado de São Paulo (FAPESP; grant
system) in the northwestern portion of the Carajás domain. 2016/131162–7), Conselho Nacional de Desenvolvimento
In the deposit area, mafic igneous rocks attributed to the Científico e Tecnológico (CNPq; grant 457689/2014–-5),
22 HUNGER ET AL.

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and source of salinity of ore-bearing fluids in Cu-Au systems of the Carajás in geology (2015) and a M.Sc. degree (2017) in geo-
mineral province, Brazil: Society for Geology Applied to Mineral Deposits sciences at the University of Campinas, Brazil. He
(SGA) Biennial Meeting, 10th, Townsville, Australia, 2009, Proceedings, is currently pursuing a Ph.D. degree at the same
p. 272–274. university. His Ph.D. research involves the appli-
Xavier, R.P., Monteiro, L.V.S., Souza Filho, C.R., Torresi, I., Carvalho, E.R., cation of rare earth element and nonconventional
Dreher, A.M., Wiedenbeck, M., Trumbull, R.B., Pestilho, A.L.S., and stable isotope geochemistry for the investigation of
Moreto, C.P.N., 2010, The iron oxide copper-gold deposits of the Carajás possible sources of metals and fluids involved in the genesis of Cu-Au systems
mineral province, Brazil: An update and critical review, in Porter, T.M., ed.,
in the Carajás Province (Brazil), including the world-class Salobo iron oxide
Hydrothermal iron oxide copper-gold and related deposits: A global per-
spective, v. 3, Advances in the understanding of IOCG deposits: Adelaide, copper-gold deposit.
PGC Publishing.
Xavier, R.P., Monteiro, L.V.S., Moreto, C.P.N., Pestilho, A.L.S., Melo,
G.H.C., Silva, M.A.D., Aires, B., Ribeiro, C., and Silva, F.H.F., 2012, The
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Economic Geologists, Special Publication 16, p. 433–454.
Xavier, R.P., Trumbull, R.B., Wiedenbeck, M., and Monteiro, L.V.S., 2013,
Sources of mineralizing fluids in Cu-Au systems from the Carajás min-
eral province (Brazil): Constraints from in situ microanalysis of hydrogen
and boron isotopes in tourmaline: Society for Geology Applied to Mineral
Deposits (SGA) Biennial Meeting, 12th, Uppsala, Sweden, 2013, Proceed-
ings, p. 1402–1405.