Biondi Et Al 2012 - The Paleoproterozoic Aripuanã Zn-Pb-Ag (Au, Cu) PDF

2013 Society of Economic Geologists, Inc.
Economic Geology, v. 108, pp. 781811
The Paleoproterozoic Aripuan Zn-Pb-Ag (Au, Cu) Volcanogenic Massive

Sulfide Deposit, Mato Grosso, Brazil: Geology, Geochemistry of Alteration,
Carbon and Oxygen Isotope Modeling, and Implications for Genesis*
JOO CARLOS BIONDI,1, ROBERTO VENTURA SANTOS,2 AND LEONARDO FADEL CURY1
1 Departamento
de Geologia, Universidade Federal do Paran (UFPR), C.P. 19.001, 81531-980 Brazil
2 Laboratory
Istopos Estveis, Universidade de Braslia (UnB) 70910-900 Brazil
Abstract
Aripuan is a Paleoproterozoic (1.761.75 Ga), stratiform, volcanogenic Zn-Pb-Ag-(Au-Cu) massive sulfide
deposit, has an estimated resource of 11.6 million metric tons (Mt) of ore, and is located on the south-southwest border of the Amazon craton (Brazil). Aripuan resides in a caldera composed of strongly fractionated,
felsic metavolcanic rocks, transitional between calc-alkaline and tholeiitic compositions. The entire region was
metamorphosed into lower greenschist facies (1.681.63 Ga) and the deposit was subsequently thermally
metamorphosed and metasomatized (1.561.53 Ga).
The mineralized bodies are lenticular and elongated. They are located at the base of a sequence of turbidites,
which overlie dacitic and rhyolitic ignimbrites. The rocks of the footwall are silicified, sericitized, and chloritized, and the hanging-wall rocks are carbonate rhythmites and turbidites, hydrothermal marbles, carbonate
breccias, and breccia-like rocks, carbonate + talc + tremolite + chlorite rock, talc-, tremolite-, and biotite-rich
rocks, and carbonate- and fluorite-bearing cherts.
The deposit was formed during at least four submarine-exhalative hydrothermal cycles in which siliceous
marbles and marls represent the initial phase of each cycle, followed by the coprecipitation of pyrite +
pyrrhotite + sphalerite + argentiferous galenas chalcopyrite, which were disseminated in clay-carbonate breccias or formed massive lenses. This phase was followed by fluoritic cherts and argillites, which were followed
by carbonate and (fluorite?) rhythmites, and turbidites to close the cycle.
The variation in total rare earth element (REE) contents and in the Eu and Ce anomalies indicates that the
original sediments were mixtures of hydrothermal carbonate and smectitic clay and were deposited below a
redoxcline. Isotopic analysis identified 18OSMOW values between 8 and 13 and 13CPDB values between 7
and 1. Modeling isotopic data showed that mineralizing fluids were distinct based on the proportion of
magmatic fluid that mixed with the seawater. Carbonate rocks and sulfide minerals precipitated while hydrothermal activity and volcanism evolved from an exhalative to an exhalative-explosive character with temperatures increasing between 100 and 200C.
The regional metamorphism of the deposit formed carbonate + talc + tremolite + chlorite rocks, tremolite-,
biotite-, and talc-rich rocks; it recrystallized the minerals, foliated and folded all of the rocks, and caused
limited decarbonation at the sites where carbonate rocks contained silica and smectite. However, the original
isotopic signatures were maintained. The thermal metamorphism erased the metamorphic foliation, and the
metasomatism generated veinlets of chlorite with sulfides.
Introduction
ARIPUAN is a polymetallic Zn-Pb-Ag (Cu, Au) massive sulfide
deposit, located in the Rondnia-Juruena Province, in the
southern part of the Amazon craton (Fig. 1). Discovered in
1998, it is a property owned by Votorantim Metais and
Karmin Exploration Corporation that announced in 2011 the
discovery of resources totaling 11.6 Mt of mineralized rocks
grading 6.29% Zn, 2.25% Pb, 0.07% Cu, 65 g Ag/ton and 0.25
g Au/ton. In 2003, Karmin Exploration Inc. announced 27.7
Mt of indicated resources with a 6.44% Zn equivalent plus 5.8
Mt of possible resources with a 6.52% Zn equivalent in the
deposit.
In this study, we present the results of a regional geologic
mapping of the area around the Aripuan deposit as well as a
detailed mapping of the deposit itself. We also provide a detailed description of the lithologies and facies observed at the
Corresponding author: e-mail, jcbiondi@ufpr.br
*A digital supplement to this paper is available at http://economicgeology.
org/ and at http://econgeol.geoscienceworld.org/.
0361-0128/13/4116/781-31
scale of the deposit including mineralogical, textural, isotopic,

and geochemical data. The present study extends the available published data about this deposit and allows for interpretation of the geologic setting of the deposit and its paragenesis. Aripuan is an unusual volcanogenic submarine deposit
in the sense that it contains a high content of hydrothermal
carbonate rocks, which hosts Zn, Pb, and Ag (Cu, Au) massive
sulfide mineralization, related to a sequence of felsic igneous
rocks.
Previous Studies
Neder (2002) and Neder et al. (2002) dated dacites (U-Pb),
which are located in the southern part of the deposit, at 1.762
6 Ma, and granite, located in the north, at 1.755 6 Ma.
They suggested that the Aripuan deposit, then called Expedito, consists of various lenses, veins, and pipes with pyrite,
pyrrhotite, sphalerite, galena, chalcopyrite, and arsenopyrite,
locally replaced by magnetite, found in unmetamorphosed
rocks. The mineralized bodies were discordant bodies of the
volcanic-hosted massive sulfide type.
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Submitted: March 8, 2011

Accepted: May 18, 2012
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BIONDI ET AL.
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ARIPUAN
CALDERA
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a
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R i ve r
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Amazon
Craton
LEGEND
Manaus
Amazonas
Acre
Shear zones
and faults
Belm
Par
Rondnia
Aripuan main
caldera limits
Mato
Grosso
Aripuan
Aripuan
294000
Cuiab
Braslia
Belo Horizonte
Campo Grande
So Paulo
River
Rio de Janeiro
Aripuan town
MESOPROTEROZOIC
Rio Vermelho Granite
Caiabis Group
Rio do Sangue Suite
Arinos Formation
PALEOPROTEROZOIC
Dardanelos Formation
Z do Torno granite (U-Pb, 1755 5 Ma)
Canam Alkaline rocks

(Rb/Sr, 1216 30 Ma)
Aripuan Granite (U-Pb 15377 Ma
and Pb-Pb 1546 5 Ma)
Roosevelt Group (U-Pb, 1762 6

to 17408 Ma)
So Pedro Suite (U-Pb, 1784 6 Ma)
Vitria Suite (U-Pb, 17856 Ma)
FIG. 1. Summary of the geology of the Aripuan region 1:250,000 (Albuquerque and Oliveira, 2007a). The Aripuan deposit is located in the western part of the Aripuan main caldera (Fig. 5), whose approximate limits are designated in the topleft corner of this figure. Note the location of Aripuan, in the Mato Grosso State, in the southern part of the Amazonas craton (Rondnia-Juruena Province).
Dexheimer Leite et al. (2005) mapped and sampled the

area around the Aripuan deposit and described four drill
holes located in the northern part of the deposit. The
samples were characterized by petrography, bulk geochemistry, including rare earth elements, whole-rock Sm-Nd isotopes, 204Pb/206Pb of massive sulfides, and carbon and oxygen
isotope analysis in carbonate minerals. Zircons from a sample
of tuff of the hanging wall were dated by the 206Pb-207Pb zircon evaporation method, resulting in an age of 1768 28 Ma
(Dexheimer Leite et al., 2005), similar to that obtained by
Neder (2002). They concluded that the deposit is volcanogenic, comprises volcanic and felsic volcaniclastic rocks, with
a lower zone of stringer ore and an upper zone of massive ore
with disseminated sulfides. Fluid inclusions indicated that
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mineralizing fluids had compositions that could be modeled

by the system H2O-MgCl2-FeCl2-NaCl-(KCl) with high CH4
content, salinity between 12 and 25 wt % NaCl equiv, and
homogenization temperatures between 100 and 250C;
however, these fluids were not considered to be those that
originally precipitated the sulfides of the orebodies but
should reflect later stages of hydrothermal or metamorphic
alteration (Dexheimer Leite et al. 2005). According to these
authors, however, the deposit may have been affected by
higher temperatures (380 and 510C) as indicated by temperatures calculated based on chlorite geothermometry.
They further argued that 34S values between 0.7 and
+3.3 for sulfides suggest that the primary mineralizing
fluids were formed by the mixture of evolved and heated
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ARIPUAN Zn-Pb-Ag (Au, Cu) VOLCANOGENIC MASSIVE SULFIDE DEPOSIT, MATO GROSSO, BRAZIL
seawater and magmatic fluid with sulfur from the leached of

volcanic rocks.
Regional Geologic and Tectonic Settings

The Aripuan gold deposit is located in the RondniaJuruena province, within the tectonic context of the Roosevelt
Group (Santos et al., 2000, 2008; Rizzotto et al., 2004). Santos
et al. (2008) dated 81 zircons from six samples collected in the
Rondnia-Juruena province, using the U-Pb by SHRIMP.
Among these ages, 54 were concordant and are shown in Figure
2. These ages, together with geologic mapping and previously
published data, were used to define the geotectonic environment of the Aripuan region.
The deposit was formed between 1762 and 1755 Ma (Fig.
2). During the Quatro Cachoeiras orogeny (1,6891,632 Ma),
the entire sequence was folded, foliated, and metamorphosed
to middle greenschist facies. After a geologic quiescence period of about 70 m.y., the Rondnia-Juruena province was intruded by the Aripuan granites, dated at 1542 2 Ma (Rizzotto et al., 2002), which thermally metamorphosed and
metasomatized rocks related to the deposit. Santos et al.
(2008) also reported ages of 1370 to 1320 Ma, which were
considered to be metamorphic ages related to the deformational regimes of the Grenville orogenic cycle (Ectasian Period) in South America, also known as the Candeias orogeny
of Sunss orogen (Fig. 2). Evidence of this orogeny has not
been identified in rocks of the deposit.
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DEPOSIT RELATED ROCKS

Aripuan granites Z do Torno meta-granites
_ 2Ma
1542 +
_ 6Ma
1755 +
Juruena Orogeny
Hanging wall meta-dacite

_ 6Ma
1762 +
Jamari Orogeny
Quatro Cachoeiras Orogeny
Serra da Providncia Suite
10
Sunss Orogen - Candeias Orogeny
12
Absolute number
Sampling and Analytical Methods

Samples for this study include 96 outcrop samples collected
during the geologic mapping and 186 samples collected from
62 drill holes of the mineralized region. Selected samples
were ground and crushed in tungsten carbide mills and then
quartered and separated into aliquots of 200 g for analysis of
major and trace elements, including REEs, Zn, Pb, Cu, Ag,
and Au, at Acme Analytical Laboratories Ltd., Vancouver,
Canada. Trace element and REE abundances were determined
by inductively coupled plasma mass spectrometry (ICP-MS),
whereas major elements were determined by inductively coupled plasma emission spectroscopy (ICP-OES). Fluorine was
determined by ion specific electrode, and Zn, Pb, Cu, and Ag
were determined by atomic absorption (AA). Gold content
was measured by fire assay and by AA, and the results are reported in Appendix 1. Twenty-three additional analyses were
compiled from the work of Dexheimer Leite et al. (2005).
For determination of the 13C and 18O values, 89 carbonate samples were collected (each sample weighted 0.72.3 g)
and analyzed for major elements by ICP-AES at ACME.
These samples were obtained by drilling carbonate crystals
from drill cores made with a TREMEL microgrinder power
tool. For oxygen and carbon isotopes an aliquot of approximately 300 ug of each sample was placed in glass vials that
were subsequently submitted to an He flush at 72C. After
flushing, the aliquots were reacted with concentrated phosphoric acid, and the CO2 released was analyzed for carbon
and oxygen isotopes in a Delta V Advantage connected to a
Gas Bench II apparatus from the Geochronos Laboratory of
the University of Braslia. Analyses of NBS 18 during the
period of this study yield an average value of 5.1 for
13CVPDB and +23.1 for 18OVPDB.
14
0
1300 1400 1500 1600 1700 1800 1900
207
Pb/
206
2000 2100
Pb age (Ma)
FIG. 2. Distribution of 54 U-Pb SHRIMP radiometric ages from samples

with ages that fit the concordia curve, collected by Santos et al. (2008) in
Rondnia-Juruena province, in the Amazon craton.
During the Mesoproterozoic, the Rio Vermelho porphyritic

syenogranites and the Rio do Sangue granite were emplaced
(Fig. 1), followed by the Aripuan (or Rio Branco) porphyritic
granite and, finally, by syenites, microsyenites, quartz syenites,
and trachytes of the alkaline Canam Complex (1216 Ma).
Later, during an extensional regime, the Dardanelos basin
was opened (1.41.2 Ga) and filled with polymictic conglomerates and arkosic rocks. These rocks were crosscut by dikes
and sills of basic rocks from the Arinos Formation (K-Ar =
14161225 Ma; Silva et al., 1980).
In the area vertical to subvertical, transcurrent brittle structures oriented WNW-ESE are dominant. This sinistral shearing coalesced during the continental collision that caused the
Quatro Cachoeiras orogeny.
Geochemical characteristics, values of Y + Nb close to 50
and Rb above 130 (App. 1), place the granites of the Aripuan
region between the VAG (volcanic arc granite), synCOLG
(syncollisional), and WPG (within-plate) domains, indicating
that the magmatism was postcollisional (Pearce et al., 1984)
and rift related with high K, calc-alkaline rocks predominant.
The Aripuan deposit formed in a back-arc region of the
Jamari and Alto Jauru island arc. Since the continental collision that caused the Quatro Cachoeiras orogeny, the Aripuan
caldera has rested in an accretionary prism, between two
paleocontinents.
The limits of the main Aripuan caldera are shown in the
top-left corner of Figure 1, which summarizes the known geology of the Aripuan region. The main Aripuan caldera is an
elliptical structure (57 28 km) with the major axis oriented
at N 80 E (Fig. 3A), within which four subcalderas were identified (Fig. 3A, B). In the interior of the main caldera,
metarhyolites, rhyodacites, and grayish ignimbrites are predominant, among which occur rhyolitic domes of varied dimensions. The subcalderas are structurally depressed regions
that have metacherts, metaturbidites, and metatuffs in the
central region, and metarhyolites, metadacites, and metaignimbrites at the base and on the edges. All rocks are folded
and metamorphosed, with folds with axial-plane foliation.
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Serraria
SM
Fig. 4
x
90 64
x
65 xx
66 x67
80
x
55
85
Branco River
West
caldera
52
14 x13
57x
x 54
70
Au
59 61
x
60
x x x
55x
34
Au
50
Au xx
x
30
32
52x
40
East
caldera
26 25
x Naqui Indian
51
x
Au
33
12
24
65
11 10
settlement
48x
47x
46
45xxx44
43 x
80
x
x40
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caldera
n
ua it
ip os
Ar dep
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South
caldera
x Fazenda
Pavorosa
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MESOPROTEROZOIC
Caiabis Group
Dardanelos formation.
K-Ar = 1.4 e 1.2 Ga and maximum age 207Pb-206Pb = 1.7 Ga.
Central microgranite
Rio Branco granite
Zircon U-Pb SHRIMP = 15377 Ma e 207Pb-206Pb = 15465
Green schist metamorphism

U-Pb SHRIMP = 1689 - 1632 Ma
PALEOPROTEROZOIC
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PALEOPROTEROZOIC (Cont.)
230000
LEGEND
Gray-vesicular meta-rhyolites interbedded

with bedded meta-chert and metacinerites
(volcanic cinders)
Volcanic and volcanosedimentary units that
contain the Aripuan deposit (Fig. 6)
Caldera undated acid volcanic rocks
8860000
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Fazenda
Britex
R ve r
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x
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BIONDI ET AL.
Faults
Inferred caldera
limits
80
Red meta-dacites and meta-rhyolites

dated zircon U-Pb e 207Pb-206Pb = 1,80-1,74 Ga
Meta-sandstone and conglomerates
Granites with U-Pb and 207Pb-206Pb = 1801-1757 Ma
Fault strike
and dip
Rivers
R oosevelt Group
Red, porphyritic rhyolites
Z do Torno granite
Zircon U-Pb SHRIMP = 17555 Ma
Lithic meta-tuff, meta-welded tuffs and
rhyolites of domes and volcanic chimneys (red)
Gray meta-ignimbrites, meta-tuffs,
meta-rhyolites and dacites
Aripuan
town
ARCHEAN
Xingu Complex
Granites, charnockites and meta-sediments
Au
Au panning
location
FIG. 3. The Aripuan caldera: (A). GDEM (Global Digital Elevation Model) image of the ASTER satellite (source:
www.wist.echo.nasa.gov). (B). Simplified geologic map. Note the location of Figure 4.
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The volcanic rocks of the Aripuan caldera have Zr/Y ratios

between 2 and 20 and Yb/La ratios between 1 and 25, which
indicates that they represent a transitional series between
calc-alkaline and tholeiitic. The Z do Torno granites are
metaluminous to peraluminous, subalkaline with an alkaline
tendency. The Rio Vermelho and Aripuan granites are calcalkaline to alkaline, high K, and can be classified as postcollisional or anorogenic. According to Albuquerque and Oliveira
(2007a, b), the Arinos gabbros (Fig. 1) are tholeiitic, have
high Mg, and are not very differentiated.
When the subcalderas collapsed, they were bounded by
curvilinear normal faults with concentric dips on the order of
40 to 50. After having been metamorphosed, folded, and
sheared from an E-W direction, the entire region was intruded by the Aripuan granite that released fluids that locally
mineralized the concentric faults bordering the east subcaldera. Later, the entire region was covered by sandy and
arkosic sediments of the Dardanelos and Arinos Formations.
During the extensional phase that opened the Caiabis basin,
E-W shear zones were reactivated as normal faults, causing
the fragmentation of the Aripuan deposit into the following
three blocks (Fig. 4): AREX to the NW, where a single mineralized body is known; AMBREX in the center, with at least
four mineralized bodies; and Babau and Massaranduba to
the SE, where there are two mineralized bodies. In the stratigraphic sections of the central part of the deposit, from the
top down to the base, the stratigraphy is as follow described:
1. UVS(A): Volcanosedimentary unit with 400 to 430 m of
a massive and laminated metatuff layers, with a crystalline
lithic tuff intercalated with metarhyolites.
2. USV(B): A 20- to 160-m-thick unit of metaturbidites and
metarhythmites that are carbonated in the mineralized locations, with meter-scale lenses of metachert that are interlayered with epiclastic metassediments.
3. UV: Volcanic unit with a 60- to 80-m-thick, grayish
massive layer of metadacites, deposited on at least 40 m of
metaignimbrite rhyolites.
In contrast to the Aripuan mineralized USV(B) unit, carbonate rocks were never found during regional and caldera
mapping.
Rocks related to mineralization
The mineralized zone of the Aripuan deposit stretches for
nearly 5 km on the western border of the eastern subcaldera
(Figs. 3, 4). The stratiform mineralized bodies are located at
the base of the USV(B) unit (Fig. 4). Metamorphism (Figs.
5E, F, 6B) did not obliterate the primary subaquatic structures in rocks of the main caldera (Fig. 5A-C), which is filled
with volcanoclastic sediments and red porphyritic rhyolites
characterized by partly resorbed quartz phenocrysts (Fig.
6A). Volcanoclastic rocks, grayish metadacites, and metarhyolites occur in the interior of the subcalderas.
The deposit is hosted by carbonate metaturbidites and
metarhythmites (CTRh) with typical subaqueous sedimentary
structures, such as the very fine, alternated layers of carbonate and silica (Fig. 5B), with or without fluorite, in convoluted
folds (Fig. 5C), and flame structures delineated by crystals of
sphalerite and pyrite (Fig. 5A). These structures indicate a
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clastic-chemical sedimentary subaqueous origin for the majority of rocks that host the deposit as well as for those directly
related to mineralized bodies. The mineralized bodies are
hosted by marbles and carbonate breccia with carbonate,
tremolite, talc, and chlorite (CTTC), fluorite tremolite-rich(TRR), fluorite talc-rich- (TAR), biotite-rich- (BR), and chlorite-rich rocks (CR). All these rocks are unfoliated, contact
metamorphic rocks with characteristics that identify them genetically as recrystallized clastic-chemical sedimentary rocks.
Laminated metaturbidites and metarhythmites overlay the
deposit. These low-grade metaturbidites (Fig. 5E) were derived from ash-sized pyroclastic rock fragments and volcanic
tuffs that were transported as epiclastic sediments. These
rocks are characterized by an alternation of millimetric layers
of clastic sediments and carbonate because of their deposition
by turbiditic currents during the precipitation of carbonates
(Fig. 5B). Carbonate rhythmites (Fig. 5E) differ genetically
from turbidites because their clastic bands are derived from
volcanic ash falls sedimented also while carbonate precipitated. Locally they are interstratified with massive lens of epiclastic metasediments and cherts that locally have isolated
carbonate blebs (Fig. 5N). These blebs may coalesce into
larger blebs that were deposited parallel to the local stratification, thus forming a carbonate layer that can be interbeded
with epiclastic sediments or chert.
The ore zone was affected mainly by a pervasive silicification process that extends for more than 5 km west of the
deposit. Besides silicification, other important hydrothermal
alteration assemblages are observed mainly below the mineralized bodies. In order of importance, these alteration types
include sericitization, chloritization, and pyritization. The
rocks of the footwall contrast in their composition and in the
presence of metamorphic foliation with the rocks of the deposit, which are generally devoid of foliation (Figs. 5G-M,
6D-L) and have poikilitic porphyroblasts of biotite (Fig. 6C).
The mineralized bodies and the associated rocks have a
large amount of carbonate. Due to intense metasomatism,
there are facies changes within 50 m from the drill cores,
making facies correlation difficult within this scale. Metasomatism may have driven recrystallization because there is no
metamorphic orientation of silicates (Fig. 6F-I) and carbonates are zoned (Fig. 6D). Among the recrystallized rocks,
there are late metasomatic veinlets of massive chlorite with
pyrrhotite, chalcopyrite, and magnetite (Fig. 5Q) that extend
from the basal volcanic unit UV(A) to the stratigraphically
higher mineralized body.
Close to the mineralized bodies, carbonate-rich rocks
(CTTC or marbles) are important and they grade laterally to
carbonate-chert followed by massive chert and/or argillitic
chert. Locally, CTRh rocks have black bands composed of microcrystalline pyrite and magnetite that are always serrated by
regional metamorphic foliation (Fig. 6B).
Massive and banded marbles with thicknesses of up to 6 m
occur in the core of the mineralized zones, generally enveloped
beside or below the orebodies. These are white colored rocks
(Fig. 5G, App. 1), generally with greenish clusters of talc
chlorite tremolite. Carbonate breccias, usually related to
mineralization, are composed of angular marble fragments
with a matrix of chlorite, tremolite, talc, microcrystalline carbonate, sphalerite (Fig. 5P), galena, pyrite and rare pyrrhotite,
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A
AR
EX
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34
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B
AM
BR
E
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C
X
D
U
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SA
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BA
S
MA
55
55x
RA
ND
A
UB
Au
Au
50x
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NW
A-B section
1000 m
C-D section
SE
meters
+100 Volcaniclastic
S.L. meta-turbidites
-100 and rhythmites
-300
Felsic volcanics
AREX
Volcaniclastic meta-turbidites
and rhythmites
Felsic volcanics
Felsic volcanics
AMBREX
BABAU
MASSARANDUBA
RECENT
Gossan with pyrite - chalcopyrite - pyrrhotite - galena - sphalerite
PALEOPROTEROZOIC
Z do Torno granite: Hornblende-biotite monzoand syenogranites, isotropic or foliated
Gray, vesicular meta-rhyolite and
volcaniclastic meta-rhythmites
Volcanosedimentary unit: silicified and sericitized
meta-tuff, massive and banded silicified and
sericitized epiclastic metasediments
with meta-ignimbrite and meta-rhyolite lenses
on top, and silicified and carbonatized
meta-turbidites and metachert at base
Volcanic unit: Gray, silicified and
sericitized meta-rhyolites and
meta-dacite with meta-tuff lenses
Gray, silicified meta-ignimbrites,
rhyolitic and dacitic meta-tuffs and
welded meta-tuffs
Chloritized and tremolitized meta-tuffs,

massive and banded epiclastic
metasediments and breccias
Silicicified and sericitized banded
meta-turbidites and epiclastic
metasediments
Marbles, carbonate breccias and
chlorite-tremolite-carbonate rocks
Meta-basic sill
FIG. 4. Geologic map of the Aripuan deposit (see location in Fig. 3). Due to weathering, there are only a few outcrops
where there is mineralization, and the information for this area comes mainly from the descriptions of 61 drill holes. In the
lower part of the map, there is a longitudinal section of the main orebodies, and the locations of the A-B cross section (AREX,
Fig. 7) and the B-C cross section (AMBREX, Fig. 8) are shown. Locations where gold was panned are also indicated.
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FPAR-69 (54,30)
FPAR -10 ( 164,35)
Volcanogenic
quartz-chlorite
schist
sph
Sphalerite
R
FPAR-09 (278,70)
Sphalerite
FPAR-04 ( 389,70)
Sphalerite
F24(402,50)
S
FPAR-09 (424,70)
1 cm
O P
787
F PAR -06 ( 261,65)
F -27 (512,55)
F-24 ( 467,90)
FPAR-05 (296,80)
Carbonate
flakes
Ga lena
Sphalerite
( 419,00)
F PAR-09
PYRIT E
FPAR-06 ( 434,10)
sph
F PAR -14 (250,80)
FPAR -08 (765,60)
L
F-24 (466,90)
FPAR-09 (277,20)
sph + py
metasomatic
chloritite
sph + py
FPAR-12 (190,00)
FPAR-20 (31,00)
FPAR -11 (330,60)
B
F-27 ( 555,70)
F PAR-14 (147,00)
Metasomatic
biotite and
tremolite
Recrystallized
metasomatic
massive
sphalerite
FIG. 5. Photographs of cut and polished drill cores. On the left side of each photo, the text reports the drill hole identification and the distance to the collar. In all of the figures, the length of the horizontal bar is 1 cm. (A). Mineralized epiclastic
metasediment with flame structures delineated by fragments of sphalerite and pyrite. (B). Laminated carbonate metaturbidite. (C). Convolute folds of metachert. (D). Carbonate-rich CTTC rock. (E) Carbonate metarhythmites. (F). Axial-plane
metamorphic foliation in layered epiclastic metasediment. (G). Hydrothermal micritic marble with talc + chlorite nodules.
(H). Carbonate breccia with a chlorite matrix. (I). CTTC rock with little carbonate. (J). Breccia with twisted carbonate fragments in a biotite matrix. (K). Pseudofragmental hydrothermal rock with zoned, concentric, and carbonate spheroids. (L).
Pseudofragmental hydrothermal rock with rhombohedral carbonates in a biotite matrix. (M). Fluoritic chert with clusters of
tremolite and chlorite. (N). Massive epiclastic metasediment with carbonate blebs. (O). Massive ore with microcrystalline
sphalerite and galena. (P). Breccia with carbonate fragments cemented by sphalerite. (Q). Breccia with fragments of metamorphosed silicified and chloritized pyroclastic rock cemented by unmetamorphosed massive chlorite. (R). Thermally metamorphosed talc-tremolite-rich rock (TRR). (S). Ore with pockets of recrystallized sphalerite in biotite-tremolite-rich rock.
chalcopyrite, and magnetite. These breccias occur in the

outer parts of the marbles where they are mixed with CTTC
rocks.
Pseudofragmental CTTC rocks are composed of heterogeneous mixtures of carbonate-tremolite-talc-chlorite, in places
with fluorite, biotite, and spheroid structures (Fig. 5K). They
are also commonly mineralized and occur enveloping other
breccias, marbles, and mineralized rocks. The main mineralogy of these rocks varies from being silicate (Fig. 5 I) to carbonate (Fig. 5D) dominated.
0361-0128/98/000/000-00 $6.00
Twisted-fragment carbonate breccias (Fig. 5J) and breccias

with carbonate rhombohedra, which have cloudy core and
transparent edges (Figs. 5L, 6G), occur associated with CTTC
rocks and massive marble. The matrix of these breccias is
composed of microscopic crystals of chlorite (Fig. 6G), carbonate, talc, and tremolite (Fig. 6F) and, less commonly, of
euhedral porphyroblasts biotite and radial talc.
Some rocks contain carbonate spheroids, 0.2 to 12.0 mm in
diameter (Fig. 5K), and rhombohedral carbonate crystals
(Fig. 5L). The carbonate spheroids are rare structures hosted
787
788
BIONDI ET AL.
FPAR-09 (144,60)
ARI-26
AA
C
C
BB
qz
FPAR-15 (444,00)
bio
qz+sct+fel
glass
F-50 (625,25)
cbt
DD
trm
cbt
cbt
cbt
clt
cbt
FPAR-09 (248,40)
FPAR-09 (359,70)
FPAR-06 (182,50)
FPAR-04 (389,70)
trm
clt
cbt
sph
I
cbt
trm
bio
cbt
FPAR-09 (370,75)
FPAR-09 (331,05)
FPAR-09 (342,70)
gal
sph
gal
sph
FEX-12 (161,05)
sph
sph
py
py
sph
po
sph
po
cpy
sph
po
gal
cpy
ccpy
FIG. 6. Photomicrographs of thin sections of rocks, obtained with plane-polarized transmitted light. In each photograph
the text reports the drill hole and the distance to the collar. (A). Partly resorbed phenocrysts of quartz and of feldspar in red
rhyolite. (B). Millimeter-scale detail of microcrystalline-pyrite band folded and foliated by regional metamorphic foliation.
(C). Porphyroblast of contact-metamorphic biotite in silicified and sericitized rhyolite. (D). Rhombohedra of recrystallized
carbonate in a breccia with twisted carbonate fragments with a massive chlorite matrix. (E). Microcrystals of pyrite aligned
with the axis of a carbonate fragment from a breccia with twisted fragments. (F). Rhombohedral carbonate in unmetamorphosed talc-tremolite matrix. (G). Rhombohedra of carbonate in a matrix of metasomatic massive chlorite. (H). Centimeterscale detail of crystallized tremolite (trm) in a biotite medium (bio) and in a carbonate matrix (cbt). (I). Tremolite cemented
by sphalerite. Photomicrographs of polished sections of mineralized rocks, obtained with reflected light. (J). Metasomatic
mineralization with talc and tremolite, with sphalerite (sph), magnetite and pyrrhotite (po) cemented by galena (gal). (K).
Clusters of pyrite (py), associated with pyrrhotite (po), sphalerite (sph), and galena (gal) in a carbonate breccia with a tremolite matrix. (L). Sphalerite (sph) with punctual contents (blebs) of chalcopyrite (ccpy) (chalcopyrite disease) next to euhedral
crystals of metamorphic pyrite.
in TRR and CTTC rocks, which are composed of carbonate

(7085%), chlorite (520%), talc (14%), and tremolite (1
2%) and at least 2% pyrite + sphalerite. They are zoned and
made of radially crystallized carbonate layers separated by
narrow bands of microcrystalline chlorite.
TRR and TAR rocks consist of millimeter- to centimeterlong crystals of tremolite and radial talc aggregates (Figs. 5I,
0361-0128/98/000/000-00 $6.00
6F, H) mixed with carbonate and biotite. They are always

associated marbles or carbonate breccias (App. 2) and are
mineralized (Fig. 6I).
Fluorite-bearing cherts with nodules of tremolite-talc and
carbonate (Fig. 5M) are characterized by irregular centimeterwidth banding and are composed of quartz (+feldspar) (50
70%), microcrystalline fluorite (0.110%), carbonate (115%),
788
FEX-45
FEX-37
FEX-25
300SW
100SW
+200
of fluorite-bearing chert in the AMBREX area, each one on

the top of a mineralized zone (Fig. 8), indicates that the deposit was formed by at least four distinct sedimentary
exhalative episodes. BR rocks with quartz, carbonate, and
200SW
chlorite (530%), and talc + tremolite (210%; App. 2). They

occur associated with BR rocks and are placed stratigraphically on the top of the mineralized zones and below the carbonate turbidites (Figs. 7, 8). The presence of four horizons
B
+200
FEX-13
?
+100
+100
?
FEX-13(75,50)
FEX-13(86,70)
SL
SL
?
-100
-100
-200
-200
NW ARIPUAN
AR-05
100m
-300
-300
Brecciated fault zone

Acid volcanics - Metamorphosed
altered dacite, rhyolite and tuffs
with quartz and sericite
Metamorphosed quartz-feldspar
turbidites and rhythmites, quartzfeldspar volcaniclastics and chert
Metamorphosed chert and
carbonate turbidite and rhythmite
Fluoritic chert and meta-cinerite
with tremolite, talc and carbonate
nodules
Tremolite-carbonate sulfide ore
with 5-40% pyrite, 5-85% sphalerite,
2-10% galena, 0-2% chalcopyrite
Chloritite with phenoblasts of biotite,
(sphalerite, chalcopyrite)
Tremolitic sulfide ore with

10-80% pyrite, 5-30% pyrrhotite,
2-5% magnetite, 0-5% chalcopyrite
and 0-5% sphalerite + galena (>Ag)
Twisted carbonate breccia with tremolite

and talc groundmass, 0-5% pyrite,
0-2% sphalerite, 0-2% magnetite
Chloritic (tremolite, biotite) sulfide

ore with 10-80% pyrite, 2-10% ccpy,
2-10% magnetite, 0-5% pyrrhotite
and 0 - 2% sphalerite
Carbonate breccias and mixed
carbonate - talc - tremolite - chlorite
(CTTC) rock with 0-10% sphalerite,
0-5% galena and 0-3% chalcopyrite
Pyrrhotite, pyrite, chalcopyrite,

sphalerite (magnetite) stringer
zone, with quartz, sericite and chlorite
Moderately altered metamorphosed dacites
and rhyolitic ignimbrite with quartz, feldspar,
sericite, biotite porphyroblasts and pyrite
Least altered metamorphosed dacites
and ignimbrites with quartz, feldspar
and sericite
Massive pyrite
(Biotite) - talc tremolite-rich rock
with carbonate, 5-15% pyrrhotite,
Chlorite-talc marble with 0-5% pyrite,
0-2% sphalerite and 0-2% pyrrhotite
LEGEND
FEX-45
Drillhole identification, collar and trace
Circle - Collar in the section zone
FIG. 7. Simplified section AR-5 of the mineralized AREX region in the NW part of the deposit. Note the presence of a
mineralized zone with three lenses of ore hosted among carbonate rocks and topped by a horizon of fluoritic chert (the thickness of this horizon has been magnified to make it visible in the scale of the figure).
0361-0128/98/000/000-00 $6.00
789
789
790
BIONDI ET AL.
100N
50N
100S
50S
FPAR-05
Gossan Hill
150S
FPAR-70
FPAR-60
+150
+150
F-17
0
R -9
F PA
R -11
F PA
FPAR-06
FPAR-36
Mineralized
zone n 3
?
+100
FP
AR
-68
+100
?
+50
+50
F-24
SL
F-49
SL
Mineralized
zone n 2
-50
?
?
-50
?
FPAR-72
?
-100
Mineralized
zone n 4
F-34
?
-150
-100
Mineralized
zone n 1
-150
?
?
-200
100N
?
50N
Brecciated fault zone

Acid volcanics - Metamorphosed
altered dacite, rhyolite and tuffs
with quartz and sericite
Metamorphosed quartz-feldspar
turbidites and rhythmites, quartzfeldspar volcaniclastics and chert
Metamorphosed chert and
carbonate turbidite and rhythmite
Fluoritic chert and meta-cinerite
with tremolite, talc and carbonate
nodules
Tremolite-carbonate sulfide ore
with 5-40% pyrite, 5-85% sphalerite,
2-10% galena, 0-2% chalcopyrite
Chloritite with phenoblasts of biotite,
(sphalerite, chalcopyrite)
-200
0 ?
50S
100S
150S
Tremolitic sulfide ore with

10-80% pyrite, 5-30% pyrrhotite,
2-5% magnetite, 0-5% chalcopyrite
and 0-5% sphalerite + galena (>Ag)
Twisted carbonate breccia with tremolite

and talc groundmass, 0-5% pyrite,
Chloritic (tremolite, biotite) sulfide

ore with 10-80% pyrite, 2-10% ccpy,
2-10% magnetite, 0-5% pyrrhotite
and 0 - 2% sphalerite
Carbonate breccias and mixed
carbonate - talc - tremolite - chlorite
(CTTC) rock with 0-10% sphalerite,
0-5% galena and 0-3% chalcopyrite
Pyrrhotite, pyrite, chalcopyrite,

sphalerite (magnetite) stringer
zone, with quartz, sericite and chlorite
Moderately altered metamorphosed dacites
and rhyolitic ignimbrite with quartz, feldspar,
sericite, biotite porphyroblasts and pyrite
Least altered metamorphosed dacites
and ignimbrites with quartz, feldspar
and sericite
Massive pyrite
(Biotite) - talc tremolite-rich rock
with carbonate, 5-15% pyrrhotite,
Chlorite-talc marble with 0-5% pyrite,
0-2% sphalerite and 0-2% pyrrhotite
LEGEND
FEX-45
Drillhole identification, collar and trace
Circle - Collar in the section zone
Double arrow - Collar behind or in front of
the section zone
FIG. 8. Simplified AM-30 section of the mineralized AMBREX region, located in the central part of the deposit. Same
legend as Figure 7. Note the presence of four mineralized zones, emphasizing zone 2, which contains various massive orebodies with different compositions. The FPAR-72 drill hole, which is the only one that sectioned mineralized zone 4, is located around at 100 m to the southeast of this section and was projected horizontally to show the position of zone 4 in relationship to the other mineralized zones.
0361-0128/98/000/000-00 $6.00
790
tremolite are uncommon and the fluorine contents of 0.2 to

0.9% (App. 2) are due mostly to substitution into biotite,
rather than to the presence of fluorite.
Sulfide mineralization
The highest concentration of sulfides (more than 60 vol %)
occurs associated with the CTTC rocks, TRR and TAR rocks
and carbonate breccias. Mineralized rocks are composed of
varying proportions of sphalerite, galena, pyrite, pyrrhotite,
and chalcopyrite and minor fluorite. Sulfides were crystallized in irregular and curvilinear shapes (Fig. 6J, K), suggesting sedimentary coprecipitation. Pyrite is the most common
sulfide, followed by sphalerite, galena, pyrrhotite, and chalcopyrite. Sphalerite is dark, reddish brown (Figs. 5P, S, 6I)
and is generally homogeneous. Zoned sphalerite crystals,
however, are also found and are characterized by inclusions of
pyrrhotite, galena, and chalcopyrite and by substitutions by
chalcopyrite (chalcopyrite disease, Fig. 6L), which are common features among Kuroko-type deposits (Barton and
Bethke, 1987; Eldridge et al., 1988; Bortnikov et al., 1991).
Chalcopyrite generally occurs in association with pyrrhotite
or on the edges of sphalerite crystals, which suggests reequilibrium due to metamorphism, as described by Craig (1983)
for Appalachian metamorphosed Kuroko-type deposits. Magnetite occurs with pyrrhotite and chalcopyrite, as well as in
chlorite- and chlorite-tremolitite-rich rocks.
The mineralized zone has a pronounced vertical zonation
that has been related to different volcanogenic hydrothermal
episodes. The base of the deposit is dominated by Fe (Cu,
Zn)-rich minerals including sphalerite (02%), pyrite (10
80%), magnetite (210%), pyrrhotite (15%), and chalcopyrite (02%). In the middle portion of the deposit (50100 m
above the base), Fe-Cu-Zn minerals such as sphalerite (1
5%), pyrite (1080%), pyrrhotite (530%), magnetite (25%),
and chalcopyrite (25%) dominate. In the upper portion microcrystalline ores of Zn-Pb-Fe, along with sphalerite (585%),
pyrite (540%), galena (210%), and chalcopyrite (12%),
mixed with recrystallized tremolite microscopic crystals are
most important. Massive and disseminated sulfides (pyrite
chalcopyrite sphalerite) that occur within normal faults and
fractures were formed during the collapse of the subcalderas.
They are interpreted as late metasomatic remobilization of
sulfides, such as those in the Gossan Hill fault (Fig. 8), among
others.
Morphology and composition of the mineralized bodies
The only mineralized zone of the AREX area consists of
one lens of Zn-Pb-Fe massive sulfide on the top and two
lenses of Zn-Pb-Fe massive sulfide at the base. This ore zone
is located on the southeastern flank of a syncline that is parallel to a N 4555 W/5060 NE fault (Fig. 7) filled with brecciated quartz, with sericite and pyrite (Fig. 7, section A-B, Fig.
4). Below the mineralized zone, there are quartz-chloritesericite metadacites and rhyolitic metaignimbrites with disseminated pyrite, chalcopyrite, and sphalerite oriented parallel
to the metamorphic foliation. They are cut by veinlets of massive chlorite (biotite) rock. Below, metadacites and metaignimbrites of the footwall grade into quartz-feldspar metadacites
with sericite and porphyroblasts of biotite and pyrite, and
then, into metadacites without pyrite, with little silicification.
0361-0128/98/000/000-00 $6.00
791
The main mineralized bodies are located in four zones in the

center of the deposit (Fig. 8, section C-D, Fig. 4) in the AMBREX area. They have greater thicknesses above marbles or
carbonate breccias and are all capped by fluorite-bearing chert.
The substrate of the mineralized bodies immediately below the
mineralized zone 1 is the same as that of the AREX area. Mineralized zones 1, 2, and 4 (Fig. 8) in the Gossan Hill region are
separated from zone 3 by the same fault described in the AREX
zone and are filled at depth by massive pyrite, chalcopyrite,
and sphalerite, and by massive pyrite close to the surface.
In mineralized zone 1, Fe (Cu, Zn)-type ore is hosted in
marble, in carbonate breccias, and in CTTC rocks. It is stratiform, with a minimum strike length of 400 m, width between
50 and 80 m, and thickness between 2 to 40 m. Zone 2 contains Fe (Cu, Zn)-type ore at the stratigraphic base, Fe-CuZn-type ore in middle, and Zn-Pb-Fe-type ore at the top, in
three lenticular mineralized bodies. The two lenses of the ore
at the base are overlapping CTTC rocks and marbles that
contain pockets of breccias with twisted fragments of carbonate. They are stratiform, have thicknesses of 2 to 22 m, widths
between 80 and 200 m, and lengths of at least 600 m. The lens
with Fe (Cu, Zn) gradually changes in composition in the direction of the stratigraphic top into an Fe-Cu-Zn-type ore.
The other lens of Fe (Cu, Zn)-type ore, located laterally and
at the greatest depth, are covered by chlorite-rich rock with
porphyroblasts of biotite followed by CTRh and BR rocks
overlain by metaturbidites and metarhythmites that are intercalated with metachert.
Zone 3 is above and next to the fault, in the same structural
position as the AREX mineralized zone. The largest mineralized body of this zone, at nearly 50 m in width, 2 to 8 m in
thickness, and at least 200 m in length, consists of Fe-Cu-Zntype ore with a matrix of chlorite, biotite, and talc. Zone 4 was
intercepted by only one drill hole (FPAR-72, Fig. 8) in which
a Zn-Pb-Fe-type ore was described as overlapping CTTC
rocks and carbonate breccias and covered by two horizons of
fluoritic chert separated by a tremolitic zone.
There is not enough information to define the geometry
and the dimensions of the Babau and Massaranduba mineralized zones, but the alteration and mineralization features
are similar to those of the AREX and AMBREX areas.
Geochemistry of Ores and Related Rocks
Geochemistry of the major elements
Elements related to hydrothermal rocks: The volcanic rocks
have SiO2 varying between 60 and 82% and CaO + MgO less
than 6%, increasing toward the mineralized bodies (Fig. 9).
For instance, SiO2 decreases and CaO + MgO increases in
the following order: volcanic rocks CTRh BR, TAR, and
TRR rocks CTTC rocks marbles. This variation in composition reflects two independent but simultaneous processes:
(1) silicification and sericitization of the volcanic and volcaniclastic rocks caused by the initial hydrothermal alteration,
which increasingly affects the rocks as they get closer to the
mineralized bodies and/or the hydrothermal conduits (vents);
and (2) the increasing abundance of hydrothermal carbonates
approaching the mineralized bodies and/or vents, which
mixed and reacted with clays and volcanic ash-size pyroclastic
rock fragments, derived from ash and volcanic tuffs.
791
792
BIONDI ET AL.
+ Carbonate
Talc rock
Marble
100
CTTC
100
Eu
Tremolite rock
Eu
1
CTTC rocks
50
100
100
Eu
Massive-silicic
marble and
carbonate chert
Biotite rock
100
Eu
+ Clay and
CaO + MgO (%)
40
30
10
Fluoritictremolititerich rock
F - Chert
100
Biotite-rich rock
1
Fluoritic talc-rich rock
20
ash size
epiclastic
sediments
Eu
CTTC rock
Eu
Fluoritic
carbonate
chert
Cb Turbidite
Fluoritic meta-turbidites and meta

-ritmites
100
Carbonate
turbidites
and chert
Eu
Hanging wall tuff

00
10
20
30
Regional volcanic
40
50
SiO 2 (%)
60
70
80
Fluoritic tremolite-rich rock
Footwall volcanic
Hanging wall volcanic
Biotite-rich rock
Carbonatic turbidite, rhythmite and chert
CTTC rocks
Fluoritic carbonate chert
Massive and silicic marble

and carbonatic chert
100
Eu
-
Footwall volcanics
100
Eu
-
FIG. 9. (A). Relationship of the average contents of SiO2 vs. CaO + MgO for rocks of Aripuan (crosses indicate 2).
(B-J). Normalized REE diagrams of the Aripuan deposit rocks. Contents of REEs normalized with the composition of
Nakamura (1974) chondrite. Each rock type is related to its REE distribution pattern. Cb = carbonate, F = fluoritic.
Distribution of the ore elements: Table 1 presents the average

grades and the standard deviations of the SiO2, MgO, CaO,
Ctotal, Na2O, K2O, Zn, Pb, Cu, Ag, Au, REE, Eu, Sr, Al2O3
and As, for the regional rocks and mineralized rocks related to
the deposit. These were calculated for all lithology types shown
in Appendix 1. The average grades of the rock types presented
in Table 1 were plotted in Figure 10. The data in this figure
were grouped according to lithologies and their relationship
with ore zones: host rock, outside the mineralized zone, and
the mineralized zone. The average SiO2 content of the footwall (Fig. 10A, lithology No. 4 = 75.62%) and of the hanging
wall rocks (No. 5 = 75.40%) are slightly higher than that of the
caldera (No. 2 = 70.70%). Moreover, the SiO2 concentration
decreases toward the mineralized body and then increases and
exceeds that of CaO + MgO in the mineralized rocks (Fig.
10A, B). The variation in the amount of total carbon indicates
that, in the marbles and in the CTTC rocks, the CaO and the
MgO are mainly contained in carbonate, and the carbonate
contents of the TRR-, TAR-, and BR-rich rocks are low.
Figure 10B and C show that the trends of Zn, Pb, Cu, Ag,
and Au have a good correlation on a decameter scale, but not
0361-0128/98/000/000-00 $6.00
as good on the scale of the sample (meters). This correlation

is better for the trends corresponding to Zn, Pb, Ag, and Au
than for Cu. In general, in the ore zones Zn (430%) presents
the higher concentration, followed by Pb (420%), and then
by Cu (0.11.0%). The amounts of Cu exceed those of Zn and
Pb only in the horizons within chlorite rocks, in which the
contents of Ag (50670 g/t) are close to 100 times greater
than those of Au (0.051.0 g/t). The correlation coefficients
R2 between Zn and Pb vary between 0.38 and 0.68 in the
AMBREX area and between 0.80 and 0.91 in the AREX area.
For Zn and Cu, they vary from 0.001 to 0.09 in the AMBREX
area and from 0.002 to 0.19 in the AREX area.
The only lithologies in which the content of Cu is greater
than that of Zn and Pb are the volcanic rocks of the footwall
(Fig. 10B, lithology 4), in which the concentrations of these
elements are lower than 100 ppm. The facies that generally
are mineralized are the CTTC rocks, the TRR-, the TAR-,
secondarily the carbonate breccias and, more rarely, the BRrocks. Among the facies that comprise the mineralized bodies, the marbles are not mineralized, and their contents of Zn,
Pb, and Cu are generally less than 100 ppm. Feldspar is
792
793
TABLE 1. Average Concentrations of Elements and Substances from Lithology Related to the Aripuan Deposit
Lithology
no.1
10
11
12
Number of
samples
10
76.76
4.71
11.58
70.7
3.15
14.03
73.01
1.27
13.48
75.62
1.52
12.48
75.4
6.57
11.71
65.49
9.48
11.76
53.61
10.9
14.50
1.46
0.9
0.04
17.77
7.13
1.77
53.91
2.75
2.83
39.76
4.4
0.85
41.55
6.83
7.63
0.44
0.28
0.83
0.64
2.39
1.19
4.58
1.01
0.04
0.02
29
32
3
2
3
1
<LLD
<LLD
<LLD
0.3
1
0.4
0.51
0.2
1.53
2.21
3.61
2.09
5.58
2.36
0.07
0.07
10
5
2
1
2
1
<LLD
<LLD
<LLD
<LLD
20
51.7
0.39
0.14
1.35
0.3
3.88
0.95
4.14
1.14
0.02
0
19
11
9
5
4
3
<LLD
<LLD
2
4.8
1
0.7
2.59
0.99
0.01
0.01
0.08
0.02
3.6
0.83
0.02
0.01
12
11
2
1
31
46
<LLD
<LLD
<LLD
<LLD
1
0.1
1.5
1.2
0.25
0.13
2.29
2.14
4.2
1.49
0.07
0.04
46
55
33
58
12
27
0.2
0.2
<LLD
<LLD
61
169.3
12.0
18.5
0.3
2.3
10.2
19.2
0.7
16.4
22.07
7.25
23.28
13.4
0.02
0.01
<LLD
<LLD
12.88
0.81
31
15
22
37
5
10
0.3
<LLD
4
<LLD
29
38.3
231
197
1.0
1.5
1.0
52.0
13.02
4.81
28.97
7.51
0.04
0.02
<LLD
<LLD
7.46
2.62
51328
79899
19163
37893
720
1512
46.9
79.7
44
45.1
49
40.6
1031
317
4.2
6.8
1.0
56.0
17.51
1.47
1.59
0.39
0.03
0.01
0.48
0.5
0.05
0.04
33607
8219
4505
4498
43
31
9.5
7.3
17
9.5
18
28.3
(5110)
15.3
21.8
1.2
46.2
6.49
3.15
10.14
2.27
1.32
0.75
1.82
1.05
0.86
0.4
296
438
102
109
27
28
1.6
0.1
6
4.8
14
17
881
299
14.5
23.9
1.5
108.3
19.64
2.31
11.6
0.51
0.12
0.11
0.34
0.62
0.43
0.29
1431
1863
235
205
4
1
0.9
0.7
3
3.4
11
20.7
(3170)
15.4
26.4
0.99
98.7
1.57
1.12
5.01
4.77
1.54
1.69
3.69
2.12
1.14
0.95
260
313
478
643
43
44
1.9
0.3
14
1
83
136.9
722
564
16.4
26.5
1.2
35.4
17.69
7.24
7.9
<LLD
0.07
1.48
2.87
<LLD
0.95
1.34
40017
94
109
66
43
1
0.6
0.6
2
29.5
78
140.9
5660
3121
6.6
10.1
1.2
9.1
% SiO2
s.d.
% Al2O3
s.d.
% MgO
s.d.
% CaO
s.d.
% Na2O
s.d.
% K2O
s.d.
% Total C
s.d.
ppm Zn
s.d.
ppm Pb
s.d.
ppm Cu
s.d.
ppm Ag
s.d.
ppm Au
s.d.
ppm As
s.d.
ppm F
s.d.
ppm REE
s.d.
ppm Eu
ppm Sr
21.9
36.1
1.4
128.5
4.3
6.2
1.2
8.8
1.6
2.9
0.4
1.4
Notes: LLD = lower limit of detection, s.d. = standard deviation, (XXXX) = only one sample analyzed
1 Lithology numbers: 1 = regional red metarhyodacite and metadacite, 2 = gray caldera metarhyolites, 3 = caldera granites, 4 = footwall least altered gray
rhyolitic ignimbrite, 5 = hanging-wall gray silicified metamorphosed rhyolite and dacite, 6 = metaturbidites, meta-rhythmites and metacherts, 7 = carbonate metachert, metaturbidite, and metarhythmites, 8 = massive marble, silicic marble, and carbonate chert, 9 = CTTC rock, 10 = tremolite-rich rock, 11 =
fluoritic talc-rich rock, 12 = Fluoritic biotite-rich rock
almost absent in marbles, CTTC, TRR-, TAR-, and BR-rocks,

thus explaining the low concentration of Na2O + K2O (Fig.
11A) and Al2O3 (Fig. 10D) in these rocks.
The contents of fluorine (Fig. 10B) vary similarly to those
of silica and independently from the Ctotal and MgO + CaO
contents, thus suggesting that the precipitation of fluorite and
silica were controlled by a similar process, which did not
control carbonate precipitation. The marbles have the lowest
average fluorine values and the concentration of this element
increases with Zn, Pb, Cu, Ag, and Au contents, but they do
not proportionally, suggesting that these constituents may have
precipitated during a single event but by different processes.
Figure 10C shows that the amounts of Ag, Au, and As increase toward the mineralized bodies. The contents of Zn,
Pb, Cu, Ag, and Au are greater in the lithologies with higher
CaO + MgO and lower Na2O + K2O values, but these parameters vary independently of the total contents of C, CaO +
MgO, and Na2O + K2O, which indicate that the crystallization
of the ore minerals occurred associated with carbonate precipitation and feldspar destruction.
0361-0128/98/000/000-00 $6.00
Immobile substances associated with mineralization

High field strength elements (HFSEs): Elements such as Al,
Ti, and HFSEs (e.g. Zr, Nb, and Y) are generally immobile
during metamorphism and hydrothermal alteration, which
allow them to be used to identify the chemical compositions
of original rocks (Gresens, 1967; Finlow-Bates and Stumpfl,
1981; Grant, 1986; MacLean and Barrett, 1993; Winchester
and Floyd, 1997).
The diagrams of MacLean and Barrett (1993) allow rocks to
be identified from volcanic episodes in which there were distinct magmatic differentiation (Fig. 12A), or alteration trends
in each chemically distinct rock unit (Fig. 12B-D). In Figure
12A, the volcanic rocks of the footwall and of the hanging wall
are grouped according to the slope of their trend lines, which
is consistent with their distinct stratigraphic positions and
with the fact that they may correspond to two different volcanic episodes. The CTRh and CTTC rocks, which host the
mineralized bodies, and the recrystallized rocks (TRR, TAR,
BR, and CR) are well correlated (R2 = 0.94) and indicate a
793
794
BIONDI ET AL.
0 20
60
100 140
LITHOTYPE - NUMBER Outside mineralized

zone
Regional volcanics
1
1
1
10 10 10 10 10
Outside mineralized
zone
-1
10
1
10
-2
10
10
Outside mineralized
zone
Caldera granites
Footwall volcanics
Carbonatic metaturbidites and meta6

rhythmites
Fluoritic carbonate
7
meta-cherts, metaturbidites and rhythmites
Hosting
rocks
Hosting
rocks
CTTC rock
10
10
10
10
Fluoritic talc-rich rock 11
11
11
11
Fluoritic biotite-rich
rock
12
12
12
Mineralized zone
% SiO2
% MgO + %CaO
10 x ( % Na 2O + %K2O)
10 x %total C
10
10
Hosting
rocks
Marbles
Fluoritic tremolititerich rock
10
Outside mineralized zone
Hosting
rocks
Caldera volcanics
Hanging wall volcanics 5
-1
10
12
Mineralized zone
Mineralized zone
Mineralized zone
Zn (ppm)
Pb (ppm)
Cu ( ppm)
F (ppm)
Ag (ppm)
Au (ppb)
As (ppm)
REE average (ppm)

Eu average (ppm)
Sr average (ppm)
Al2 O3 average (%)
FIG. 10. Variation in the contents of: (A). SiO2, MgO, CaO, total C, Na2O, K2O. (B). Zn, Pb, Cu, F. (C). Ag, Au, As. (D).
REE, Eu, Sr, and Al2O3 of the regional, mineralized, and hostess rocks related to the Aripuan deposit.
line of independent evolution, suggesting either that they

have a magmatic affinity that is different from those of the
volcanic rocks, or that they were generated by independent
processes.
The relationships between incompatible and compatible
elements (i.e., Zr vs. TiO2), and compatible and compatible
elements (i.e., Al2O3 vs. TiO2) produce trends that separate
chemically distinct rock units and are useful for identifying
homogeneous rock units that may be on the interior or that
cross the hydrothermal alteration zones (MacLean and Barrett, 1993). In Figure 12B, C, and D, the alteration lines of
the metarhyolites, metadacites, and metatuffs of the hanging
wall and of the footwall are different from those of the marbles (Fig. 12C), the CTTC rocks, and the TRR-, TAR-, BR-,
and CR-rocks (Fig. 12B-D), which indicate that they were
altered by distinct processes.
Rare earth elements (REEs): Normalization to chondritic
values (Fig. 9B-J) is the most appropriate for discussing the
0361-0128/98/000/000-00 $6.00
REE contents of the volcanic rocks and for showing that the
rocks of the footwall and of the hanging wall (Figs. 9I and J)
have similar REE distribution patterns. In these profiles, the
light rare earth elements (LREEs) were enriched relative to
the heavy ones (HREEs). There is a small variation of HREEs,
and concentrations are 20 to 30 times greater than those of
the chondrites. There are also prominent negative anomalies
of Eu, probably due to plagioclase removal.
From turbidites and rhythmites to marble, as the proportions of carbonate and/or clastic increases, there is a gradual
decrease in REE content, from 10 to 100 times greater than
chondrites in turbidites and rhythmites, until 1 to 10 times
greater in marbles. Additionally, there is a gradual change of
the Eu anomaly from turbidites and rhythmites (and volcanic
rocks), with strong negative Eu anomaly (Fig. 9H-J), to the
marbles, with strong positive Eu anomaly (Fig. 9B).
Therefore, volcanic rocks of the footwall exhibit a negative
Eu anomaly but, above the footwall, the Eu anomaly became
794
parallel, both in the mineralized zone and among the host

rocks, suggesting that Eu substitutes for Ca in carbonate cells.
All rocks exhibit a positive Ce anomaly based on seawater
REE normalization (Fig. 11A-D), suggesting that the total contents of REEs in the carbonate rocks reflect a seawater source.
100
+ Clastic
Sample/Seawater
1000
10
10
Geochemistry of fluorine
Microcrystalline fluorite associated with microcrystalline
quartz and carbonate occurs disseminated in the TRR, BR,
and TAR rocks, metacherts and epiclastic metasediments.
The highest fluorine contents, on the order of 2,000 to 8,000
ppm (Figs. 10B, 13), occur in BR, TAR, and TRR rocks, and,
above all, in metacherts, which contain locally up to 10% fluorite (Fig. 5M). With the exception of marbles, fluorine content seems to increase with carbonate (Ctotal) content (Fig.
13), suggesting a relationship between the crystallization of
fluorine and carbonate.
Isotopic Geochemistry of the Carbonate Rocks
1
0.1
Carbonate meta-turbidite and meta-rhythmite

Fluoritic meta-turbidites and meta-rhythmites
0.01
1000
Sample/Seawater
B
100
0.1
Composition of the carbonates

Table 2 presents the chemical compositions and the 13C
and 18O values of the carbonates divided on the basis of mineral composition and rock texture. The carbonates are predominantly ferroan and ankeritic dolomite, with 42 to 55 mol
% of siderite and magnesite (Fig. 14). Some of the silicic marbles, carbonate cherts, massive epiclastic rocks with carbonate
blebs, and mineralized rocks have calcite with less than 12%
siderite + magnesite. All of the facies of the carbonate rocks
have dolomite and calcite, with the exception of some translucent and massive marbles, which are dolomitic or ankeritic,
and the carbonate blebs, which are composed only of calcite.
Fluoritic biotite-rich rock

Chlorite-rich rock
0.01
Sample/Seawater
1000
100
10
1
0.1
100
10
+ Carbonate

0.01
1000
Sample/Seawater
795
1
0.1
Massive marble
CTTC rocks
0.01
La
Ce Nd Sm Eu Gd Dy Er
Yb
FIG. 11. Normalized REE diagrams of the Aripuan deposit rocks. Contents of REEs were normalized by the average composition of seawater, as
per Elderfield and Greaves (1982). Note that carbonate-rich rocks have
REE similar to seawater and that all rocks have Ce positive anomalies.
more positive reflecting more carbonate content in the rocks,

although the Eu concentrations, next to 1 ppm, are constants in
all rocks, and only the footwall volcanic and TAR have low concentrations of Eu. The same behavior is shown in Figure 10D,
in which the trends of REE and Al2O3 contents are almost
parallel, for rocks outside and inside the deposit, which corroborates the direct relationship between the REE and rock clastic contents. The trends of Eu and Sr contents are also almost
0361-0128/98/000/000-00 $6.00
13CPDB and 18OSMOW values of the carbonates

The 18OSMOW values, between 8 and 13, and the 13CPDB
values, between +1 and 7 (Fig. 15A), of the rocks and
ores (Table 2) overlap the published domains of the VHMS
deposits (Huston, 1999) and magmatic carbonates (Ohmoto,
1986, 1996). These compositions are restricted to the part of
the VHMS field outside of the field of the hydrothermal carbonates of the Besshi-type deposits (Peter and Scott, 1999),
and are distinct from the field of the Cambrian marine carbonates (Vezier and Hoefs, 1976). The field occupied by the
Aripuan carbonates (Fig. 15B) is superimposed among the
fields for Thalanga (Hermann and Hill, 2001), Rosebery and
Hercules (Khin Zaw and Large, 1990), Horne (MacLean and
Hoy, 1991), Buchans (Kowalick et al., 1981), and Mount Morgan (Golding et al., 1993), whereas the carbonates of West
Bergslagen (Groot and Sheppard, 1988), Mount Chalmers
(Huston, 1999), Afterthought (Eastoe and Nelson, 1988),
Franklin Marble and Sterling Hill (Peck et al., 2009) have isotopic compositions close to those of Aripuan. All the above
cited deposits have been interpreted as related to submarine
environments.
Relationships among the facies of the carbonate rocks
and their 13C and 18O values
Various facies of carbonate rock were identified and their
13C and 18O values are presented in Table 2. The CTRh are
clastic-chemical rocks with values of 13CPDB less than 4.6,
795
796
BIONDI ET AL.
25
0.6
Nb (ppm)
R = 0.56
2
R = 0.036
5
0
90
15
10
0.5
4
0.9
TiO2 (%)
20
0.4
64
0.
0.3
0.2
50
100
150
200
250
300
350
100
0.6
8
0.9
0.4
0.
58
0.3
.8 7
=0
TiO2 (%)
R
0.5
2
0.9
10
400
R=
300
15
200
Zr (ppm)
Zr (ppm)
Al2O3 (%)
0.
0.1
20
0.2
0.1
100
200
300
400
10
15
20
Al2O3 (%)
Zr (ppm)
Footwall gray meta-ignimbrites and meta-tuffs
CTTC rock
Hanging-wall gray meta-rhyolite, meta-dacite and meta-tuffs
Meta-turbidites and meta-rhythmites
Fluoritic meta-turbidites and meta-rhythmites
Marbles
Chlorite-rich rock
FIG. 12. Mass ratio diagrams of immobile elements of rocks of the Aripuan deposit. (A). Zr vs. Nb. (B). Zr vs. TiO2. (C).
Zr vs. Al2O3. (D). Al2O3 vs. TiO2. The regression lines and the corresponding correlation coefficients were fitted for the
metaignimbrites and metatuffs located below the mineralized bodies (dotted), for the volcanic rocks that host the mineralized bodies (dashed) and for the marbles, CTTC rocks and recrystallized rocks (continuous line). Arrows indicate direction
of trend evolution with mass loss during alteration.
which places their carbonates in high-temperature domain

(cf. Fig. 16A with 15A). In contrast, banded and massive marbles facies have similar ferroan dolomite compositions and
isotopic values between 2 and zero (Fig. 16A). The veinlets
and twisted fragments of carbonate breccias are also composed of ferroan dolomite and their 18OSMOW and 13CPDB
values coincide with the values of the marble, rocks with
which it is always associated (Fig. 16A), which suggests that
marble and breccias formed simultaneously, in low-temperature conditions (Fig. 15A). Therefore, if the 18OSMOW and
13CPDB values of the carbonate breccias (Fig. 16B) overlap
those from the marbles (Fig. 16A, F), and the lowest 13CPDB
values of the breccias (Fig. 16B) are equal to the highest values of the carbonate turbidites (Fig. 16A) and cherts (Fig.
16D), than these values, and the stratigraphy sequence observed in Figure 8, suggests that the marbles, carbonate breccias, chert, and carbonate turbidites were formed sequentially, in this order, in similar environments, while the
0361-0128/98/000/000-00 $6.00
temperature of the hydrothermal fluid increased and the 13C

values of these rocks changed from 5 to zero (Fig. 15A).
TRR and CR rocks also have the 13CPDB values between 7
and 5, in the domain of magmatic carbonate, but these rocks
are metamorphic, recrystallized 200 Ma later (Fig. 2), and do
not belong to volcanosedimentary sequence.
Herrmann and Hill (2001) analyzed rhombohedral carbonates from Thalanga that had 13CPDB and 18OSMOW values
that differ from those of Aripuan (Fig. 16B), but the carbonate spheroids of Aripuan are similar to those of Thalanga, in
that they were described as spheroids and were considered to
be of hydrothermal origin, formed by the same process that
generated the rhombohedral carbonate crystals (Herrmann
and Hill, 2001). Only two spheroids were analyzed, and they
have 18OSMOW and 13CPDB values that are different from
those of the Thalanga deposit (Fig. 16C). The CTTC rocks
are the most common carbonate rocks of the Aripuan deposit and similar rocks form lenses that are associated with
796
the mineralized body west of Thalanga (Herrmann and Hill,

2001). They are composed of mixtures of ferroan dolomite
(Fig. 14), chlorite, tremolite, talc and, less commonly, biotite.
The greatest accumulations of mineralization and the
largest horizons of massive mineralization occur in rocks with
talc, chlorite, ankerite, and ferroan ankerite (Fig. 14). The
carbonates of the Zn-Pb-Fe and those of the Fe-Cu-Zn and
Fe (Cu, Zn) mineralization types define two fields (Fig. 16E)
that overlap those of all of the other rocks (Fig. 16F), except
for the quartz-feldspar massive epiclastic metasedimentary
rocks with carbonate blebs. The fields of the 18OSMOW and
13CPDB values from the Thalanga ore carbonates do not coincide with those of the Aripuan mineralized rocks (Fig. 16E).
Finally, values of 18O greater than 11 distinguish carbonate blebs of massive epiclastic rocks from other clastic-chemical facies (Fig. 16A).
Total C (moles)
10
10 -1
10 -2
-3
10
-4
10
10
-3
10 -1
10 -2
F (moles)
Meta-turbidites, meta-rhythmites and meta-chert
Fluoritic meta-chert,
meta-turbidite and meta-rhythmite
Isotopic Modeling
Massive and silicic marbles and carbonaceous chert

CTTC rock

FIG. 13. Diagram of moles of fluorine vs. moles of total C (= total carbonate in the rocks) of the fluorite-bearing rocks.
Carbonation
Aripuan carbonates are characterized by a larger variation
of 13C (6.5 to +1.0) when compared to 18O values
(8.411.5), which explains the elongated data distribution depicted in Figure 15A and B. The exception is a small
group of samples that have 18O values above 11.5 (Table
2, Fig. 17B). The larger variation of 13C values of Aripuan
carbonates is striking because carbon mineral-fluid isotope
Massive-milky marble
Transparent marble
Banded marble
Silicic marble
Milky-carbonate rhombohedron
Transparent rhombohedron
Argillic-carbonate chert
Carbonate flake
Milky-carbonate glomerule
Twisted silicic-carbonate fragment
Carbonate zone - Dexheimer et al. 2005
Ore zone - Dexheimer et al. 2005
Tremolite zone - Dexheimer et al. 2005
Calcite
CaCO 3
Calcite
Ankerite
(Ca, Mg)(CO 3) 2
Ferroan
ankerite
797
Dolomite
(Ca, Mg)(CO 3) 2
Ferroan
dolomite
Ankerite
Mg:Fe<1 Mg:Fe>4
Sideroplesite
Pistomesite
Breunnerite
FeCO 3+MnCO3
Siderite+Rhodochrosite
MgCO3
Magnesite
Ankerite
0361-0128/98/000/000-00 $6.00
FIG. 14. Composition of the carbonate rocks of

the Aripuan deposit. Also shown are the contents
analyzed by Dexheimer Leite et al. (2005).
Ferroan
dolomite
797
798
BIONDI ET AL.
TABLE 2. Carbon and Oxygen Isotope Data of Carbonates from the Aripuan Zn, Pb, Ag (Cu, Ag, Au) Deposit
Drill hole ID-depth (m)
18O
PDB
18O
SMOW
13C
PDB
(Ca,Mg,Fe,Mn)CO3
1. Clastic-chemical fcies
1.1. Carbonate-quartz-feldspar metaturbidites and meta-rhythmite
F-27-555.70
F-27-570.40
FPAR-09-144.60
F-55-549.15
FPAR-05-104.50
FPAR-11-156.60
21.11
21.07
21.12
21.06
20.82
20.43
9.15
9.19
9.14
9.2
9.45
9.85
4.57
4.38
5.51
5.78
5.66
5.58
(Ca50Mg12FeMn38)CO3
(Ca68Mg7FeMn25)CO3
1.2. Quartz-feldspar massive epiclastic metasedimentary rock with carbonate flakes

F-43-105.60
F-43-105.60
F-43-105.40
FPAR-68-82.70
FPAR-68-213.60 (A)
FPAR-68-213.60 (B)
FPAR-68-213.60 (C)
19.13
18.86
18.99
18.98
19.47
19.27
19.52
11.19
11.47
11.33
11.34
10.84
11.04
10.79
2.81
3.11
2.35
2.62
3.47
2.94
3.16
(Ca88Mg5FeMn7)CO3
2. Chemical facies
2.1. Banded marble
FPAR-14-231.90 (A)
FPAR-14-231.90 (B)
FPAR-49-76.65 (A)
F-50-625.25 (A)
F-50-625.25 (B)
F-24-466.90 (A)
FAREX-35-184.45 (A)
FPAR-09-242.85 (A)
FPAR-09-359.70 (A)
20.61
20.56
20.2
20.63
20.63
18.78
20.34
20.19
20.17
9.66
9.71
10.09
9.64
9.64
11.55
9.94
10.1
10.12
1.09
2.37
1.36
1.35
-0.96
1.18
1.83
1.38
1.4
9.72
10.09
10.21
8.44
9.89
9.96
10.11
-0.09
4.66
2.08
4.55
-0.89
3.19
3.31
(Ca55Mg39FeMn6)CO3
(Ca54Mg41FeMn5)CO3
(Ca55Mg40FeMn5)CO3
(Ca54Mg42FeMn4)CO3
(Ca53Mg30FeMn17)CO3
(Ca51Mg34FeMn15)CO3
(Ca50Mg40FeMn10)CO3
2.2. Massive marble and massive carbonate chert

F-21-375.70
FAREX-35-184.45 (B)
FPAR-49-76.65 (B)
FPAR-11-172.70
F-21-371.30
FPAR-06-282.50 (A)
FPAR-06-282.50 (B)
20.55
20.2
20.08
21.8
20.39
20.32
20.18
(Ca51Mg37FeMn12)CO3
(Ca54Mg39FeMn7)CO3
(Ca91Mg1FeMn8)CO3
(Ca56Mg32FeMn12)CO3
(Ca55Mg35FeMn10)CO3
3. Breccia facies
3.1. Breccia with twisted carbonate fragments
F-21-366.50
FPAR-68-213.60
FPAR-09-242.85 (B)
FPAR-09-242.85 (D)
FPAR-09-242.85 (E)
FPAR-09-248.40
FPAR-09-359.70 (B)
FPAR-09-359.70 (C)
FPAR-09-362.80 (A)
FPAR-09-362.80 (B)
FPAR-09-362.80 (C)
FPAR-09-362.80 (D)
FPAR-09-362.80 (E)
FPAR-11-327.40
FPAR-20-31.00
FPAR-06-349.50
20.41
20.05
20.17
20.22
20.24
20.06
20.21
19.99
19.89
19.68
20.07
19.61
20.09
19.86
20.19
20.05
9.87
10.24
10.12
10.06
10.04
10.23
10.08
10.3
10.41
10.62
10.22
10.69
10.2
10.44
10.1
10.24
1.06
-0.96
1.5
1.25
1.92
-0.11
1.47
1.86
2.21
1.06
1.41
1.43
2.35
1.73
1.92
-0.96
9.91
10.18
9.93
1.24
-0.82
-0.62
3.2. Mosaic breccia with carbonate-chlorite-tremolite

FPAR-04-389.70
FPAR-06-350.40
FPAR-70-335.50
0361-0128/98/000/000-00 $6.00
20.37
20.11
20.35
798
(Ca48Mg37FeMn15)CO3
(Ca52Mg36FeMn12)CO3
(Ca46Mg40FeMn14)CO3
(Ca49Mg41FeMn10)CO3
(Ca52Mg41FeMn7)CO3
(Ca52Mg38FeMn10)CO3
TABLE 2. (Cont.)
Drill hole ID-depth (m)
18O
PDB
18O
SMOW
13C
PDB
(Ca,Mg,Fe,Mn)CO3
9.25
9.42
9.19
8.95
9.26
10.55
10.97
4.06
3.35
5.11
4.39
4.83
3.78
2.76
(Ca53Mg34FeMn13)CO3
3.3. Breccia with rhombohedral carbonate-chlorite (tremolite)

F-50-625.25 (C)
F-50-625.25 (D)
FPAR-17-224.40 (A)
FPAR-17-224.40 (B)
FPAR-17-224.40 (C)
F-24-466.90 (B)
F-24-466.90 (C)
21.01
20.85
21.07
21.3
21
19.75
19.34
(Ca57Mg31FeMn12)CO3
(Ca51Mg34FeMn15)CO3
(Ca22Mg58FeMn20)CO3
(Ca3Mg69FeMn28)CO3
4. Breccia-like facies
4.1. Mixed carbonate-tremolite- talc-chlorite (biotite) rock (CTTC rock)
F-24-402.50
F-27-542.60
FAREX-35-184.45 (C)
FPAR-09-274.25
F-24-466.90 (D)
20.35
20.36
20.41
20.18
19.25
9.93
9.92
9.87
10.11
11.06
2.13
2.01
3.85
1.61
2.76
(Ca50Mg34FeMn16)CO3
4.2. Cauliflower-like clumps carbonate spheroids with chlorite (tremolite + talc) sphalerite + pyrite) matrix
FPAR-06-261.65
FPAR-06-261.60
20.88
20.75
9.38
9.52
3.27
1.95
5. Talc-tremolite (carbonate, fluorite) facies

F-27-512.55
F-27-535.95
21.08
20.57
9.18
9.7
6.5
5.09
6. Quartz-fluorite rock with tremolite-talc-carbonate nodules

FPAR-14-300.40
FPAR-70-297.55
F-54 - 277.70
FPAR-06 - 432.25
20.18
21.01
21.47
20.74
10.11
9.25
8.78
9.53
5.21
4.98
5.03
5.05
(Ca89Mg6FeMn5)CO3
7. Biotite breccia with quartz, feldspar, and carbonate

F-55-528.70
FPAR-06-182.50 (A)
FPAR-06-182.50 (B)
20.86
20.84
20.41
9.41
9.43
9.87
5.6
5.64
5.42
8. Ore facies
8.1. Carbonate-fragment breccia with massive sphalerite (+ pyrite + chalcopyrite)
FAREX-13-86.70
FPAR-09-419.00
17.59
18.16
12.78
12.19
1.02
1.43
8.2. Breccia with twisted carbonate fragments and massive sphalerite (galena, chalcopyrite) (+ pyrite + chalcopyrite)
FPAR-09-242.85 (C)
FPAR-11-301.40
FPAR-11-334.80
FPAR-09-362.80 (E)
20.36
20.06
19.82
19.68
9.92
10.23
10.48
10.62
3.69
1.58
1.91
1.06
(Ca48Mg33FeMn19)CO3
8.3. Mixed chlorite-tremolite-talc-carbonate rock (CTTC) with sphalerite + galena

F-49 424.90
FAREX-13-75.50
FPAR-06-282.50 (A)
FPAR-06-282.50 (B)
FPAR-14-250.80
FAREX-35-185.20
19.92
19.92
20.32
20.18
20.08
20.4
10.38
10.37
9.96
10.11
10.21
9.88
2.64
2.71
3.19
3.31
3.87
4.11
8.4. Mixed chlorite-tremolite-talc-carbonate rock with pyrrhotite + chalcopyrite (+ magnetite)

FPAR-09-236.70
FPAR-09-331.05
F-49-381.90
FPAR-06-348.10
20.2
20.38
20.86
20.49
10.09
9.9
9.41
9.79
2.28
3.57
5.14
2.77
10.33
8.59
5.95
6.39
8.5. Biotitite with tremolite + carbonate and magnetite

FPAR-06-160.90
F-27-519.50
0361-0128/98/000/000-00 $6.00
19.96
21.65
799
(Ca56Mg32FeMn12)CO3
(Ca55Mg35FeMn10)CO3
799
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BIONDI ET AL.
Besshi
mafic
volcanogenic
hydrothermal
carbonate
Cambrian
marine
carbonate
0
-1
THALANGA
Buchans
C PDB ()
13
13
C PDB ()
-2
-4
Mt Chalmers
-5
-6
-6
Magmatic
carbonate
Bergslagen
South
Hercules
-3
-5
-7
Franklin
marble
-1
VHMS
Acid
volcanogenic
hydrothermal
carbonate
-4
Mt Morgan
-2
-3
Sterling
Hill
-7
Afterthought
ARIPUAN
-8
-8
0
10
15
20
25
18
10
15
20
25
18
OSMOW ()
O SMOW ()
Aripuan (Brazil) - Dexheimer et al. (2005)
Aripuan (Brazil) - This work
FIG. 15. (A). 12CPDB and 18OSMOW values of the carbonates of Aripuan compared with the domains of carbonates of the
VHMS- and Besshi-type deposits, magmatic carbonates, and Cambrian marine carbonates. (B). 13CPDB vs. 18OSMOW domains of the carbonates of Aripuan and Thalanga compared to those of VMS deposits that contain abundant carbonate.
fractionation is much less dependent on temperature than

that of oxygen (ONeil et al., 1969). In contrast, carbon isotopic fractionation between calcite and CO3 is nearly constant
at 1.5 with temperature between 25 and 100C (Mook et
al., 1974), whereas the carbon isotope fractionation between
calcite and CO2 varies between +3.8 and 2.9 for temperatures ranging from 100 to 300C, respectively (Chacko et al.
1991).
The carbon and oxygen isotope composition of Aripuan
contrasts with other carbonate-bearing hydrothermal systems
in which there is a much larger variation of oxygen isotopes
relative to carbon (Pineau et al., 1973; Clayton and Steiner,
1975; Muehlenbachs and Clayton, 1976; Gregory and Taylor,
1981; Ito and Clayton, 1983; Zheng and Hoefs, 1993; Santos
and Clayton, 1995). The larger 18O variations have been related to fluid-rock interactions combined with the strong dependence of mineral-fluid oxygen isotope fractionation on
temperature.
The carbon and oxygen isotope compositions of hydrothermally formed carbonates are controlled mainly by fluid
composition and temperature. In most instances, fluids are
composed mostly of H2O and variable proportions of CO2,
meaning that oxygen is usually much more abundant than
carbon. The limited variation of the oxygen isotope composition of Aripuan carbonates suggests a narrow temperature
range in the environment of the hydrothermal system. This
narrow temperature range hardly explains the isotopic variation in carbon, because the calcite-HCO3 fractionation factor
is not very dependent on temperature. Thus, it is likely that
the 13C values of the Aripuan carbonates are related to the
0361-0128/98/000/000-00 $6.00
mixture of fluids with different carbon isotope composition,

as for example, a fluid of magmatic origin (13C 5) and
another of marine origin (13C 0).
To better understand the precipitation mechanisms of the
Aripuan carbonates, the isotopic composition of these carbonates may be modeled under different conditions.
1. The carbonates were precipitated at temperatures between 100 and 500C in isotopic equilibrium with an infinite
amount of a CO2-enriched aqueous solution (a high fluid/rock
ratio) derived from an acidic magma (18O = +6 and 13C
= 5.5; Fig. 18). This model predicts that the isotopic composition of the fluid phase depends on the CO2/H2O ratio as
well as on the temperature of the magma. Furthermore, the
assumption of an infinite amount of fluid implies a rock/fluid
ratio close to zero; that is, the isotopic composition of the precipitated carbonate depends only on the composition of the
fluid and the temperature.
2. The carbonates were formed from a carbon dioxide and
water fluid that was outgassed following a Rayleigh process.
In this kind of process, as pressure is released, an infinitesimal
amount of fluid escapes, affecting the isotopic composition of
the remaining fluid. Besides temperature, fluid composition
(CO2/H2O ratio) and the different degassing rate of CO2 and
H2O play a major role in the isotopic composition of the carbonate being precipitated. Figure 19 presents the results of
two scenarios. One (in solid line) models the composition of
calcite being precipitated from a fluid with a CO2:H2O ratio
of 2:3 in which the CO2 is released four times faster than the
H2O. It shows that, for temperatures below 177C, in which
800
1
Clastic-chemical and
chemical facies
0
Banded and massive
marble and chert
13CPDB ()
-1
Thalanga spheroids
-1
-2
-2
-2
-3
-3
-3
-4
-4
Epiclatic sediments
with carbonate flakes
Aripuan rhombohedral
carbonate and
spheroids
-5
Carbonate
turbidites
-6
-7
8
10
11
-6
A
12
13
Fluoritic tremolite-,
and biotite-rich rocks
-1
-2
-2
-3
-3
-4
-5
10
11
12
13
-7
-7
C
8
13
12
11
10
VENT A
Thalanga
ore
177 C
VENT B
o
130 C
-2
CTTC rock
(440-490 oC)
-3
-4
Carbonate
Fe-Cu-Zn-rich
facies with py+
po+cpy+mgt+sph
E
8
OSMOW ()
18
10
11
12
OSMOW ()
18
13
Fluoritic chert and

biotite rock
(350-450 oC)
-5
-6
-6
Aripuan
spheroids
-5
-1
Biotite-rich rock
Tremolite-rich
rock 490-530C
-4
Carbonate Zn-Pb-Ferich facies with py+

sph+gal (+cpy)
-5
-7
13
-4
Fluoritic chert
-6
B
12
11
10
Mineralized facies
-1
CTTC
Mixed
chlorite-tremolite
talc-carbonate
rock
-6
Breccia facies
-7
CTTC and breccialike facies
-1
-5
13CPDB ()
Thalanga rhombohedral
carbonates
Twisted fragment
0
and mosaic
breccias
-7
Tremolite
o
rock (490-530 C)
200 C
8
10
11
12
F
13
OSMOW ()
18
Fig. A - Clastic-chemical carbonate facies
Fig. C - CTTC and breccia-like facies
Carbonate meta-turbidite and rhythmite

Quartz-feldspar massive epiclastic sediment with
carbonate flake
CTTC - Mixed chlorite-talc-tremolite-(biotite)

carbonate rock
Cauliflower-like clumps carbonate spheroids
Fig. A - Chemical carbonate facies
Thalanga-Cauliflower-like clumps carbonate spheroids
Banded marble
Fig. D - Fluoritic tremolite-, and biotite-rich rocks
Massive marble and massive carbonate chert
Fluoritic meta-chert with tremolite + talc + carbonate

nodules
Fig. B - Volcanogenic carbonate breccia
Talc-fluorite tremolite-rich rock with carbonate
Carbonate breccia with twisted fragments
Fluoritic biotite-rich rock with tremolite,

carbonate (quartz, feldspar)
Breccia with rhombohedra carbonate

Mosaic carbonate - chlorite breccia
Fig. E - Mineralized facies
Thalanga - Rhombohedra carbonate-chlorite breccia
Carbonate Fe-Cu-Zn-rich facies with py+

po+cpy+mgt+sph
Carbonate Zn-Pb-Fe-rich facies with py+
sph+gal (+cpy)
FIG. 16. Diagrams of 13CPDB vs. 18OSMOW from carbonates of rocks in the Aripuan deposit. (A). Clastic-chemical and
chemical facies. (B). Carbonate breccias. (C). CTTC-pseudo fragmental carbonate rocks. (D). Fluoritic TRR, BR, and CTRh
rocks. (E). Carbonate ores. (F). This figure shows the deposition sequence of the hydrothermal carbonate rocks of Aripuan,
deduced on the basis of field observations. The carbonate facies precipitated sequentially from the top to the bottom of the
figure. The 13C and 18O isotope fields of the carbonate facies (A-E) were superimposed on the isotopic models of carbonation (Fig. 17A, B) and decarbonation (Fig. 21B). The star has the same meaning as in Figure 21. The temperatures were
calculated (Dexheimer et al., 2005) using the chlorite geothermometer (Cathelineau, 1988; Zang and Fyfe, 1995).
0361-0128/98/000/000-00 $6.00
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BIONDI ET AL.
3. The carbonates were precipitated in isotopic equilibrium with an infinite amount of HCO-enriched aqueous fluid
(a high fluid/rock ratio) with 18O equal to 0, that is, with
an isotopic composition of oxygen similar to that of seawater
(Fig. 17), as suggested by the concentrations of REE of the
originally chemical sedimentary rocks (marbles and CTTC
rocks; Figure 12D). In contrast, the carbon isotope composition of the aqueous fluid would be related to the mixture of
carbon derived from two main sources: (1) the first, related to
a higher temperature source, that would have 13C values
similar to magmatic fluids (5) and (2) another, related to
a low-temperature source, that would have 13C values close
to that of the sea (0). Similarly to condition (1), it is assumed an infinite amount of water thus implying a rock/fluid
ratio close to zero.
2
Marine
carbon
A
177 C
13
130 C
Line of mixing
CPD B ( )
-2
-4
-6
200 C
Magmatic
carbon
-8
10
14
12
16
OSMOW ()
18
FIG. 17. Diagram modeling the isotopic composition of carbonates precipitated in isotopic equilibrium with an infinite amount of HCO3-enriched
aqueous fluid (a high fluid/rock ratio), in which the oxygen isotope composition is controlled mostly by seawater (0), whereas the carbon isotope
composition is controlled by a mixture magmatic fluids (5) and seawater (0). In contrast to the model depicted here, the isotopic composition
of the precipitated carbonates depends both on temperature and on the
source of C.
the carbon isotope fractionation between calcite and CO2 is

positive (Chacko et al., 1991), the isotopic composition of the
carbonate being formed increases as the fluid outgasses. Similar results are observed for a fluid with a CO2:H2O ratio of
1:4, in dashed lines, except that the carbonate isotopic composition curves present a gentler slope.
Decarbonation
Carbonate devolatilization under metamorphic conditions
has been widely discussed in studies that address skarn formation (e.g., Valley, 1986; Oliveira and Santos, 2003; Timn et
al., 2007; Santos et al., 2009). During metamorphic processes
that release CO2 produced by carbonate and silicate reactions, the isotopic composition of the residual carbonate becomes progressively more negative because under these temperature conditions the heavy carbon and oxygen isotopes
fractionate to CO2 (Chacko et al., 1991). In spite of not having been a major process in Aripuan, carbonate devolatilization may have affected samples from Aripuan that contain
tremolite (CTTC rocks), because metamorphic reactions may
have also produced CO2 during carbonate consumption. In
order to better understand this process, we have modeled the
isotopic evolution of calcite with initial 13C of 2 and 18O
of +10.3 that reacts with silicate minerals to produce tremolite and CO2 (Fig. 20). The model assumes that the devolatilization of CO2 follows a Rayleigh law and that the carbonate (its
Increasing CO2/H2O
2:1
100C
-2
13
CPDB ()
1:1
1:2
1:5
100C
100C
100C
1:10
100C
-4
-6
250C
-8
-10
250C
250
250C
250C
500C
10
12
14
16
18
20
OSMOW ()
18
FIG. 18. Diagram modeling the 13C and 18O composition of carbonates precipitated at temperatures between 100 and
500C in isotopic equilibrium with an infinite amount of a CO2-enriched aqueous solution (a high fluid/rock ratio) derived
from an acidic magma (18O = 6 and 13C = 5.5). Because we assume an infinite amount of fluids, the isotopic composition of the precipitated carbonates depends only on temperature. The filled squares correspond to the isotopic compositions of the Aripuan samples in this figure and in Figures 19 and 20.
0361-0128/98/000/000-00 $6.00
802
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+2
CO2:H2O = 2:3 100 C
+2
100 C
CO2:H2O = 1:4
125 C
125 C
0.7:0.75
150 C
CPDB ()
150 C
-4
13
13C PDB ()
0.7:2.25
-2
-2
-6
177 C
O
CO2:H2
CO2:H2O = 1:4
0.7:0.25
-8
= 2:3
-8
0.9:0.5
0.8:0.5
177 C
100%
-6
-4
200 C 10%
200 C
10
12
-10
14
18
OSMOW ()
FIG. 19. Diagram showing the isotopic composition of carbonates that
were formed from a CO2 -H2O fluid that outgases following a Rayleigh
process. The two groups of curves represent different scenarios: one, in full,
models a fluid with a CO2:H2O ratio of 2:3 in which the CO2 is released 4
times faster than the H2O; and another, dashed, models a fluid with CO2:H2O
ratio of 1:4 that is outgassed under the same conditions. The numbers close
to the curves represent the temperature, while the numbers within the black
rectangles represent the amount of remaining fluid along each curve. Isotopic fractionation factors between calcite and CO2 were obtained from
Chacko et al. (1991) and for calcite and water from ONeil et al. (1969).
initial isotopic composition is represented by the star) is kept

in isotopic equilibrium with the associated silicate minerals,
which means that the total amount of carbon in the system is
restricted to the carbonate, while that of oxygen includes both
the carbonate and silicate minerals.
As shown in Figure 20, the isotopic composition of the
residual carbonate becomes progressively more negative because of the positive isotope fractionation factor between CO2
and calcite at temperatures above 270C. Curves A and B
correspond to two different proportions of carbonate to silicate minerals in the rock, ultimately reflecting the O/C ratio
of the reactants. The numbers next to the curves represent
the fraction of remaining oxygen and carbon of the reactants
carbonate plus silicates. For instance, the values of 0.8 and
0.1 indicate, respectively, that around 20% of the oxygen and
90% of the carbon were transformed into CO2. Because the
isotopic composition of oxygen is buffered by the presence of
silicates, it does not change as fast as that of carbon. Based on
the modeling, we argue that CO2 devolatilization related to
metamorphism was not a major process in Aripuan, even for
rocks like CTTC and TRR.
Discussion
Carbonate in hydrothermal systems and
seawater as a fluid source
Rocks from Aripuan are dominated by felsic volcanic and
plutonic rocks, and volcaniclastic sediments with low iron and
0361-0128/98/000/000-00 $6.00
0.8:0.10
-12
6
10
12
14
OSMOW ()
18
FIG. 20. Evolution of the isotopic composition of a rock composed of carbonate and silicate that is subjected to metamorphism at 500C. The curves
model a Rayleigh devolatilization of CO2 as tremolite is formed as a result of
a reaction between carbonates and silicates. The initial isotopic composition
of the carbonates is represented by the star (initial 13C = 2% and initial
18O = 10.3%). The composition of the residual carbonate evolved according
to curves A and B, which refers to rocks with O/C ratios of 2.5/1 and 5/1, respectively. The numbers next to the points on the curves indicate the proportion of oxygen and carbon remaining in the reactants carbonate and silicates. The open squares represent samples with tremolite.
very low calcium and magnesium contents. Carbonate rocks

have not been described in the area before, in spite of being
a major product of hydrothermal alteration. Ferroan dolomite
and ankerite calcite are present in almost all rocks, varying
from 98 to 5% in the following order: marble, CTTC, CTRh,
TRR, TAR rocks and fluoritic carbonate, and BR chert (Fig.
14). According to Mueller (2009), carbonates with compositions such as those shown in Figure 14 indicate that Aripuan
is similar to distal or medial deposits formed in volcanic
calderas, similar to the rock sequence dominated by felsic
rocks, in the Normetal caldera (Abitibi, Canada).
Published literature on volcanogenic massive sulfide deposits shows that volcanogenic deposits with large quantities
of hydrothermal carbonate are uncommon, even if this mineral is usually found in minor amounts in most deposits; for
example, Rosebery (Cambrian, Tasmania; Solomon and Walshe, 1979; Huston and Large, 1988; Khin Zaw and Large,
1990; Large, 1992; Orth and Hill, 1994); Mattabi (Archean,
Sturgeon Lake region, Superior Province, Canada; Franklin
et al.,1975); the Kuroku-type deposits (Afterthought-Ingot
region, Permian, East Shasta District, California, United
States; Eastoe and Nelson, 1988); the various VHMS deposits
of the Hokuroku district (Japan; Shikazono et al., 1998);
Lewis Pond (Silurian, New South Wales, Australia; Agnew et
al., 2005); Hellyer (Cambrian, Mount Read, Tasmania;
803
804
BIONDI ET AL.
Bradley, 1997, in Herrmann and Hill, 2001; Gemmel and

Large, 1992); Mount Morgan (Devonian, Queensland, Australia; Ulrich et al., 2003); Mount Chalmers (Large and Both,
1980); South Hercules (Cambrian, Australia; Large and Both,
1980; Kin Zaw and Large, 1992; Large, 1992); the Middle
Valley area, northern part of the Juan de Fuca ridge, where
there are active hydrothermal systems that may be analogous
to the ancient submarine hydrothermal systems in which
Aripuan carbonate was precipitated (Goodfellow et al., 1993;
Baker et al., 1994; Fruh-Green et al., 1994); Horne (Archean,
Quebec, Canada; MacLean and Hoy,1991) and Buchans (Ordovician-Silurian, Newfoundland, Canada; Kowalick et
al.,1981); the Bergslagen district (Paleoproterozoic, Sweden;
Vivallo, 1985; Allen et al., 1996), and Thalanga (Cambrian-Ordovician, North Queensland, Australia; Paulick et al., 2001;
Herrmann and Hill, 2001). All of these are volcanogenic deposits have carbonate, and their geology is comparable to
Aripuan. Besides Aripuan, major amounts of carbonate
rock and of carbonate-talc-tremolite-chlorite paragenesis
have been described in volcanogenic deposits only in Thalanga. The main similarity among these deposits is that the
carbonate was precipitated near hydrothermal vents when the
hydrothermal fluid mixed with seawater. In some other deposits in which carbonates are present (e.g. Rosebery,
Hellyer, and South Hercules), there is also a genetic relationship between the carbonates and the sulfide ore.
Field and petrographic studies indicate that the deposit of
Aripuan was formed in submarine back-arc volcanic caldera
located to the northeast of an ocean basin. Their characteristics are comparable to VHMS deposits formed on the ocean
floor, being locally composed of dacitic lavas and rhyolitic ignimbrites. The subcalderas, including the ore deposit, were
filled with cherts, turbidites, and rhythmites, subaqueous sediments with preserved sedimentary structures, such as upward-coarsening beds, laminated carbonate rocks, convolute
folds, flame structures delineated by fragments of sphalerite
and pyrite (Fig. 5), and banded marbles. The Aripuan mineralized rocks and mineralized bodies are hosted by these
rocks which, below the stringer zones, grade into quartzfeldspar metadacites, and then, into metadacites, that do not
have carbonates. The CTTC rocks, spheroids, and carbonate
rhombohedra from Aripuan are also similar to carbonate
lenses associated with the submarine mineralized body west
of Thalanga (Herrmann and Hill, 2001).
The Aripuan granite crops out about 5 km from the deposit and no drill hole within the Aripuan area intersected
granite. The granite has low concentration of iron, magnesium, and calcium and does not have any evidence of hydrothermal alteration. If carbonates were crystallized by metasomatism caused by an unknown granite body emplaced bellow
the deposit, carbonate alteration should be found also in
rocks located between granite and the deposit, including
stringer zone and volcanic rocks below it, but this does not
happens.
Immobile elements (Fig. 12A) indicate that the volcanic
rocks of the hanging wall and footwall of Aripuan are part of
different magmatic differentiation series. Moreover, the alteration trend of hydrothermal rocks (from the marbles to the
fluoritic metaturbidites) does not fit with trends of volcanic
rocks, indicating that volcanic and hydrothermal rocks are not
0361-0128/98/000/000-00 $6.00
genetically correlated and that volcanic rocks were not the

precursors of the hydrothermally altered rocks (in the sense
of MacLean and Barret, 1993).
The trend defined by hydrothermal rocks is composed of
two groups (Fig. 11B-D): (1) marbles, CTTC, TRR, TAR, BR,
and CR rocks that are placed between the origin and the middle of the trend and; (2) CTRh rocks that are placed between
the middle to the end of the trend. These figures show that
CTRh, BR, CR, CTTC, and TAR rocks and marble fit to a single alteration trend, with a correlation coefficient (R2) between 0.87 (Fig. 12B) and 0.98 (Fig. 12C). According to the
criteria of MacLean and Barrett (1993), metaturbidite and
metarhythmite could be altered (= precursors) to BR, CR,
CTTC, TAR rocks and marble, in this order, by hydrothermal
activity which due to the gain of mass.
The problems with this model are (1) as discussed above,
neither the Aripuan granite nor the footwall dacites and rhyolitic ignimbrites could have been the main magnesium, iron,
and calcium source for this alteration; and (2) for hydrothermal carbonate to replace silicates, the Al2O3 of the silicates
must be leached by hydrothermal fluids. Taking into account
the lack of evidence for both these processes, only seawater
remains as possible source for carbonate cations.
The distribution of data seen in Figure 12 may be explained
if the line that extends from the marbles up to the carbonate
metaturbidites was formed by hydrothermal carbonate deposited successively with decreasing quantities of carbonate
and increasing quantities of clay minerals with a high content
of immobile elements (Al, Ti, and Zr). In this case, the marbles would originally have been hydrothermal precipitates
devoid of, or with very little, clastic contribution. The CTTC
rocks would have been mixtures of carbonates and clays, and
the BR and CR rocks would originally have been lenses composed essentially of smectite. Similarly, the TAR rocks would
have been derived from clastic-chemical siliceous-dolomitic
sediments devoid of, or with, minor argillic contribution,
whereas the TRR rocks would have been derived from Si-CaFe-Mg-rich sediments (dolomitic marl). Contrary to the interpretation of a metasomatic alteration of a precursor (the
carbonate metaturbidites and metarhythmites), the model
proposed here suggests that the rocks of Aripuan are mixing
products of volcaniclastic and hydrothermal carbonate sediments generated in various episodes of clastic-chemical sedimentation. This interpretation explains the morphology of the
lithologic units and the sedimentary subaqueous structures described in the mineralized region and the entire deposit. Evidence that carbonate precipitated from seawater is also shown
by isotopic, fluid inclusions, and REE geochemical studies.
The most common mechanism of carbonate precipitation
in hydrothermal systems involves heating a solution at low
salinities and/or temperatures, accomplished by mixing a cold
with a hot solution; degassing and boil CO2 from a solution in
which HCO3 is dominant over H2CO3, and increasing the pH
(Rimstidt, 1997). Because CO2 plus H2O dissociate to H+ and
HCO3, removing CO2 from solution raises the solutions pH.
Raising the pH causes HCO3 to dissociate to H+ and CO2
3
and the increased activity of carbonate causes carbonate mineral precipitation. The 18OSMOW and the 13CPDB values of
the rocks and ores (Fig. 15) overlap the domains of the many
VHMS deposits. Isotopic modeling has shown that the 13C
804
values of the Aripuan carbonates may be related to a mixture

of magmatic (13C 5) and seawater fluids (13C 0).
The Eifuku volcano, located in the Marianas arc, in a place
called Champagne, emits bubbles of liquid CO2, with approximately 98% CO2 and 1% of H2S (Lupton et al., 2006). Sakai
et al. (1990) reported the existence of a similar volcano situated in the central part of the Okinawa trough. In this case the
exhaled fluid is made up of 86% CO2, 3% H2S, and 11% of
other gases, mainly CH4 + H2. In the Eifuku volcano the
CO2/H2O of the fluid is approximately 1:7, which is less than
the 1:2 ratio of the curve of our model that best fits the
Aripuan data (Fig. 18). Thus, the fluids vented from the
Aripuan volcano may not have been formed solely by fluids
exhaled from an acid magma. Lupton et al. (2006) and Sakai
et al. (1990) do not report which minerals precipitate near the
volcanoes they have studied. In both cases, the temperatures
are low, below 10C, and there is a layer of CO2 hydrates that
makes the sampling of sediments around the vents difficult.
In contrast to these studies, Khin Zaw and Large (1992) reported carbonate precipitates from CO2-rich fluids at South
Hercules (Tasmania). They reported carbonate precipitates
with amounts and features similar to those observed in
Aripuan, including carbonate blebs and spheroids, as well as
comparable 13C and 18O values. Khin Zaw and Large proposed a model of mixing of fluids similar to that presented in
Figure 17, and did not make any comment about the
CO2/H2O ratio of South Hercules mineralizing fluid. They
concluded that The presence of extensive carbonate alterationindicates the ore fluids resulted from mixing (of
magmatic fluid) with seawater in the porous volcaniclastic
subsea floor. Thus, based on the proposed carbonation models, it is clear that a simple precipitation of carbonates in isotopic equilibrium with CO2-enriched aqueous solution derived from magmatic fluids does not reproduce the observed
values in Aripuan.
Similarly, a model involving degassing of CO2-H2O fluids
may fit part of the data, but seems not to be the major process
that controls the isotopic composition of Aripuan carbonates. On the other hand, a model based on a mixture of fluids
fits the data much better, specifically for thermal gradients
between 177 and 200, and 130 and 200C. These thermal
gradients would be related to temperature differences within
the volcanic structure and imply that the carbonates were
formed within temperature intervals ranging from 30 to
70C. Thus, it is suggested that the Aripuan carbonates were
formed from a mixture of fluids with distinct isotopic ratios of
carbon, at temperatures between 130 and 200C (Fig. 17A,
B) and, as shown in the decarbonation modeling (Fig. 21), it
is likely that the tremolites of the CTTC, TRR, and TAR rocks
crystallized under the conditions of model B. Based on 34S
values of sulfides from Aripuan, Dexheimer Leite et al.
(2005) also concluded that the primary mineralizing fluids
were a mixture of evolved heated seawater and magmatic
fluid with sulfur from the leached of volcanic rocks.
The positive Ce anomaly observed in all rocks normalized
to average seawater (Fig. 11) may be related to loss of dissolved Ce due to sedimentation on the ocean floor, below the
redoxcline (Planavsky et al., 2010). The depletion of LREEs
observed in the majority of samples from the Aripuan mineralized region could be related to leaching of reducing fluids
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805
under high temperatures (MacLean, 1988; MacLean and

Hoy, 1991; Liaghat and MacLean, 1995), as observed for the
marbles (Fig. 9B), CTTC (Fig. 9C), TRR and TAR (Fig. 9D,
E), and BR rocks (Fig. 9F). Distributions patterns with
LREE enrichment and positive anomalies of Eu (Fig. 9E)
have been observed in vent fluids of the East Pacific Rise
(Michard et al., 1983, Michard and Albarde, 1986), the MidAtlantic Ridge (Campbell et al., 1988), and in rocks located in
hydrothermal discharges zones in which the temperature is
up to 350C. According to Barrett et al. (1991), the enrichment of LREEs could be related to primary precipitation of
silica and carbonate from a fluid undergoing temperature decrease and oxidation due to mixing with seawater. The distribution patterns of REEs and the relationships among the
trends of the contents of ore elements and Na2O + K2O indicate the same process.
As observed for chondrite normalized rocks (Fig. 9), the
positive Eu anomalies of carbonate rocks reinforce the presence of hydrothermal fluids in the crystallization process of
the carbonates (Elderfield and Greaves, 1982; Elderfield,
1988). Furthermore, the total contents of REEs in the carbonate rocks are equal to the average composition of seawater
(Figs. 9D, 11), suggest that the composition of the hydrothermal fluid was dominated by seawater, from which carbonate crystallized.
Fluorite in rocks of the Aripuan deposit
There are no reports in the literature of VHMS base metal
deposits of documented submarine exhalative hydrothermal
fluorite. Occurrences of fluorite are common among exhalative submarine deposits such as Rosebery (Khin Zaw et al.,
1999), Henty and Mount Julia (Callaghan, 2001), but they are
usually associated with magmatic and late metasomatic events
following volcanogenic mineralization.
In the Aripuan deposit, cherts with nodules of tremolitetalc and carbonate and up to 10% of microcrystalline fluorite
occur in BR rocks on the top of the hydrothermal rocks piles
(Figs. 7, 8), and disseminated in TRR, BR, and TAR rocks.
They have convoluted folds (Fig. 5C), which are typical structures of subaqueous environments.
Seawater heating experiments show that fluorine is a particularly reactive element and an important component in different minerals over a wide range of temperatures (Seyfried
and Ding, 1995). Reactions of this sort occur during seawater
recharge of subsea-floor hydrothermal systems, similar to that
interpreted for Aripuan. Seyfried and Ding (1995) have
shown that carbonate minerals precipitate from seawater
between 150 and 225C, under conditions where fluorine
removal occurs. It has also been long recognized that carbonate minerals can incorporate fluorine (Kitano and Okimura,
1973; Rude and Aller, 1989, 1991). Furthermore, dissolved Mg
and magnesite formation also contributes to fluorine removal
(Ohde and Kitano, 1980), although the exact mechanism of
exchange between F and CO2
3 still needs to be clarified
(Seyfried and Ding, 1995). Data from Seyfried and Ding (1995)
also shows that dissolved fluorine partition into solids at temperatures below 200C, even if the fluid contains as little fluorine as seawater. These conditions, in which the precipitation of carbonate and incorporation of fluorine occurs, are
similar to those estimated in Aripuan by carbon and oxygen
805
806
BIONDI ET AL.
Sea level
Redoxcline
Marble
1.76 - 1.75 Ga
Sea level
1.76 - 1.75 Ga
Smectitic-silty
mood
A
Dacites and rhyolitic
ignimbrites
Stringer
Sea level
Redoxcline
1.76 - 1.75 Ga
Sulfide and carbonate
crystallization and sedimentation
within ocean floor mud
Regional folding and

metamorphic foliation
Contact metamorphism
1.56
and metasomatism
Gossan Hill
1,69 - 1.63
1.69
1,63 Ga
1.76 - 1.75 Ga
Sea level
Ash fall
Redoxcline
Turbidite flows
and carbonate
sedimentation
Sea level
D
D
Redoxcline
u
Fa
lt z
- 1.53 Ga
e
on
1.76 - 1.75 Ga
Aripuan
granite (?)
FIG. 21. Interpretation of the sequence of events that generated the Aripuan deposit. (A). The beginning of the hydrothermal exhalation, within the silty-smectite mud layer that covers dacites and rhyolitic ignimbrites of the submerged floor
of a volcanic caldera, and simultaneous sedimentation of carbonate and ash-size pyroclastic rock fragments, forming a clastic-chemical sediment. (B). The first hydrothermal volcanogenic cycle, with the precipitation of massive and stringer mineralized bodies. (C). Explosive volcanism and emission of turbidite flows and clouds of ash and tephra, simultaneously to the
sedimentation of hydrothermal carbonate, forming laminated carbonate-silty turbidites and rhythmites. (D). Burial of the
mineralized bodies and the structures from the first cycle. (E). Second hydrothermal volcanogenic cycle and formation of
new mineralized zones that formed lenses of mineralized rocks among the clastic-chemical carbonate turbidites and rhythmites. (F). Regional metamorphism at the low green-schist facies, rocks recrystallization, and deformation of the rocks and
structures. (G). Intrusion of granites, contact-metamorphism, and metasomatism of the rocks and mineralized bodies. Clastic-chemical carbonate rocks were transformed at CTTC rocks.
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806
807
METAMORPHIC/METASOMATIC
SEQUENCE
VOLCANOGENIC SEQUENCE
Smectitic-silty mud
Hanging wall rhyolitic and dacitic meta-rhythmite and meta-turbidite
Fluoritic-silicic and argillic mud
Carbonate meta-rhythmite and meta-turbidite
Carbonate rhythmite and turbidite
Fluoritic biotite-rich rock and fluoritic meta-chert with tremolite + chlorite nodules
Carbonate veins and fragments with smectitic-silty mud matrix
CTTC rock - Mixed carbonate-talc-chlorite-tremolite rock
Explosive rhyolitic and dacitic breccia
Fluoritic tremolite-, talc-tremolite-, and talc-rich rock
Mineralized rock with py + sph + gal (cpy)

Mineralized rock with py + po + mgt + cpy (sph,gal)
Mineralized rock with py + cpy + mgt + po
Footwall meta-dacite and meta-rhyolite
Twisted fragment carbonate breccia inside marble
Aripuan granite
Stringer fractured dacite with sulfides

Massive chlorite veins with biotite porphyroblasts, pyrrhotite and chalcopyrite
Altered quartz - sericite - chlorite rock
Footwall dacite and rhyolitic ignimbrite
FIG. 21. (Cont.)
isotopes modeling (Fig. 17). Except for the marbles, Figure

13 shows that the fluorine content of hydrothermal rocks
from Aripuan is associated with carbonate precipitation,
similar to the model proposed by Seyfried and Ding (1995).
The marbles from Aripuan have the lowest average fluorine
content probably because of the high pH conditions, whereas
black smokers with elevated fluorine concentrations, as that
of Manus Basin (Craddock et. al., 2010), develop in low pH
environments.
The presence in the AMBREX area of four horizons of fluoritic chert in distinct stratigraphic positions (Fig. 8) suggests
that the deposit was formed by at least four distinct sedimentary exhalative episodes. The mixing of seawater and hydrothermal fluorine-bearing fluids explains the precipitation of
fluorite in that stratigraphic position. On the other hand, if
fluorine had been introduced by metasomatic process alone,
it is not clear what may have triggered the four episodes of
fluorite precipitation. Because of the positive correlation between fluorine and silica concentrations (Fig. 10B), the same
process may have controlled the precipitation of fluorite and
microcrystalline quartz. Fluorite metacherts have the lowest
13C values (Fig. 16D), and the hydrothermal carbonates of
the CTRh rocks (Fig. 16A) fall within the same isotopic domains of the carbonates of the fluoritic metacherts, BR, and
TRR rocks (Fig. 16D), thus suggesting that all these rocks
were originally hydrothermal clastic-chemical sediments.
In spite of the correlation between fluorite and carbonate,
there is no relationship between these minerals and the contents of Zn, Pb, Cu, Ag, and Au (Fig. 10B). This implies that
fluorine and these metals probably had different origins and
the precipitation of these elements may have been controlled
by other processes, distinct from that which caused the coprecipitation of Zn, Pb, Cu, Ag, and Au.
Genetic Model
Mixing of ash-size pyroclastic rock fragments, hydrothermal carbonate, and mud may explain the chemical and mineralogical variations of Aripuan rocks, including their REE
contents (Fig. 9). This scenario could have also caused the
positive Eu anomalies to vary according to the amount of
hydrothermal carbonate crystallized within the mud of the
sea floor.
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The positive correlations of Zn, Pb, Cu, Ag, and Au indicate

the coprecipitation of sphalerite, argentiferous galena, chalcopyrite, and gold during mineralization. In the Japanese
Kuroko-type deposits (Ohmoto, 1983, 1996), the coprecipitation of metals occurs in submarine environments in which the
temperature is less than 250C. This temperature decreases
rapidly due to the mixture of hydrothermal fluid with cold
seawater, similar to the isotopic modeling of 13C and 18O of
carbonate precipitation of Aripuan.
Similar to carbonates, sulfides also precipitated in the
ocean-floor mud mixed with carbonate in various proportions.
They formed mineralized sediments with different sulfide,
carbonate, and clay concentrations, as observed in mineralized CTTC. In the Aripuan deposit there is a metal zonation
(Fig. 8) in which Fe-Cu sulfides (+ magnetite) are formed at
the base, followed by Fe-Cu (Zn-Pb) sulfides (+magnetite),
and by Zn-Pb (Fe, Cu) sulfides at the top, similar to classic
zonation observed in VHMS deposits. Zinc-, Pb-, and Ag-bearing sulfides precipitated from hydrothermal fluids at temperature lower than 280C (Sato, 1973; Large, 1977; Hannington
et al., 1999). Because the Aripuan mineralized bodies are essentially composed of pyrite, sphalerite, and argentiferous
galena, it is likely that the deposition occurred at relatively
low temperatures (between 150 and 250C), which is consistent with the temperatures modeled in Figure 17A and B.
The high correlation coefficients observed among metal
contents in samples of the AREX area suggest that there was
a single mineralization episode in this area and that the original metals distribution was not significantly modified, not
even by late thermal-metamorphism and/or metasomatism.
The low correlations observed in the AMBREX area must be
the consequence of several episodes of mineralization (Fig.
8), such as the zone refining process in which the most recent hydrothermal episode partially remobilized the metals
deposited in the previous one. This could also explain the lack
of a correlation, on a meter scale, between Cu and other more
mobile metals as Zn and Pb. The preservation of the original
distributions of metals in the AREX area indicates that the
thermal metamorphism and metasomatism only caused the
recrystallization of minerals.
The majority of the modeled carbonates underwent metamorphism with tremolite and chlorite in a situation similar to
807
808
BIONDI ET AL.
that of Thalanga (Herrmann and Hill, 2001; Paulick et al.,

2001). According to Slaughter et al. (1975) and Winkler (1976),
this assemblage is produced in metamorphic conditions by
the reaction:
8 silica + 5 dolomite + H2O 1 tremolite + 3 calcite + 7 CO2,
which occurs at temperatures close to 450C. This is not consistent with the modeled crystallization of carbonate, but it is
consistent with the crystallization temperatures of chlorites of
CTTC rocks (between 380 and 530C) calculated by Dexheimer Leite et al. (2005) by means of chlorite geothermometry (Cathelineau, 1988; Zang and Fyfe, 1995). The isotopic
models of carbonation (Fig. 17) and decarbonation (Fig. 21)
allow for the consideration that the two processes occurred in
Aripuan. Carbonation occurred at temperatures between
130 and 200C during the VHMS hydrothermal activity that
precipitates carbonate along smectitic clay from the mud of
the sea floor. Decarbonation probably occurred during the regional metamorphism at temperatures close to 500C (Fig.
21B) and crystallized tremolite only in the hydrothermal
marls, where there was carbonate and smectite, transforming
them into chlorite-(talc)-tremolite-carbonate shales.
The quantities of tremolite, talc, and chlorite formed during
the regional metamorphism was controlled by the presence of
smectite (= silica) and carbonate in the original sediments,
and the carbonate must have kept the original volcanogenic
isotopic signature because: (1) metamorphic reequilibration
would have had to occur at temperatures close to 900C,
which is, as at Thalanga (Herrmann and Hill, 2001), unrealistic for the location of the deposit; (2) the preservation of primary structures of carbonate-rich rocks, such as the rhombohedra of carbonate, the spheroids, and the twisted carbonate
fragments, suggesting that the residual carbonate was not recrystallized. If this is correct, the original 18O and 13C values of the carbonates would have been preserved, thus being
consistent with precipitation from a hydrothermal fluid similar to seawater (18O 0) at temperatures between 130
and 200C, which agrees with the model proposed here; and
(c) as seen in Figure 16A and D, despite the coincidence among
the isotopic 18OSMOW and 13CPDB values of TRR, CR, and
CTRh, the CTRh rocks always have metamorphic foliation,
which is lacking in the TRR and CR rocks, indicating that the
regional and the contact metamorphism did not change the
18OSMOW and 13CPDB values of original carbonate.
The 13C and 18O fields of different carbonate facies are
assembled in Figure 16F, overlying the isotopic models of
carbonation (Fig. 17A, B) and decarbonation (Fig. 21B). With
the information contained in Figure 16F and knowledge of
the sequence of the deposition of the rocks of the deposit,
based on the facies deposition sequence (Figs. 7, 8), a series
of cartoons were designed aiming to summarize the interpretation of the sequence of events that generated the Aripuan
deposit (Fig. 22).
The submarine exhalative hydrothermal activity began at
1.76 to 1.75 Ga along a fracture on the floor of the main
Aripuan caldera below the redoxcline. The exhalation formed
carbonate precipitates at temperatures close to 180C (Figs.
16F, vent A, 17, 22A), together with ash-size pyroclastic rock
fragments and clays mixed to the sea-floor mud (Fig. 22A)
and also silicifying, sericitizing, and chloritizing dacites and
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rhyolitic ignimbrites (Fig. 22B). A vent system developed precipitating massive sulfides (py + cpy + mt sph) and carbonates over the center of hydrothermal calcareous bodies. Talus
breccias and brecciated rocks, composed of fragments of calcareous rocks with rhombohedra and carbonate spheroids,
were formed in the upper and lateral parts of the hydrothermal vents. During the waning stage of the exhalative cycle,
carbonate cherts were precipitated, which were locally covered by carbonate epiclastic sediments (Fig. 22B).
The volcanism of the caldera gained energy and increased
in temperature and evolved from exhalative to explosive (Fig.
22C), while the fractures still exhaled carbonic fluid. The
hydrothermal system was covered by turbidites and rhythmites interlayered with sedimented hydrothermal carbonate
and, after the end of the first exhalation cycle, by epiclastic
turbidites only (Fig. 22D). If fluorite was formed from vent
fluids, it precipitated together with the carbonate cherts at
the end of the exhalation cycle.
The volcanism was reactivated, initiating a second exhalative
cycle, which repeated the sequence of events of the first cycle
(Fig. 22E). In this second cycle, fluids from type A vents were
again emitted, which precipitated Fe (Cu, Zn), then fluids
from type B vents, which were less isolated from the seawater
(Figs. 16F, vent B, 17), precipitated less iron sulfides, with FeCu-Zn (py + cpy + po sph), followed by Zn-Pb-Fe sulfides
(sph + gal + py cpy po) and carbonate, while massive epiclastic sediments with blebs of carbonate also precipitated. At
least two other hydrothermal cycles occurred, generating
mineralized zones 3 and 4 (Fig. 8), until the extinction of the
hydrothermal system and the diagenesis of the sediments.
During the Quatro Cachoeiras orogeny (1.681.63 Ga), the
region was folded and metamorphosed at greenschist-facies
conditions (Fig. 22F) and later (1.561.53 Ga) it was thermally metamorphosed during the intrusion of Aripuan granite (Fig. 22G). In this last event, magmatic fluids related to
granite emplacement mineralized faults with massive pyrite
and with py + po + mgt sph cpy gal and formed massive chlorite veins with biotite, pyrrhotite, and chalcopyrite. If
fluorite is metasomatic it crystallized from fluids emitted by
Aripuan granite at this phase.
Conclusions
The Aripuan deposit is a 1.76 to 1.75 Ma Zn, Pb, and Ag
(Cu, Au) volcanic- and sediment-hosted massive sulfide
(VHMS) deposit located on the edge of a caldera. Carbonates
are important minerals in Aripuan and were formed by mixing CO2-rich vent fluids, at temperatures greater than 300C,
with cold seawater, resulting in a mixed solution with temperatures between 130 and 200C. Hydrothermal carbonate
precipitated below the redoxcline, at the same time that ashsize pyroclastic rock fragments from ash falls and fragments
from turbidites were deposited. Mixing, in various proportions, of these sediments and ocean-floor mud produced the
main rock facies described in Aripuan (CTTC, TTR, TAR,
BR, and CR rocks).
The mineralization is essentially composed of pyrite, pyrrhotite, sphalerite, and argentiferous galena, with minor chalcopyrite and magnetite. These minerals form lenses of massive
sulfides and zones of semimassive, as well as disseminated
sulfide concentrations with varied quantities of carbonate,
808
chlorite, tremolite, talc, and biotite. The ore deposit has four
mineralized zones located at discrete stratigraphically positions. Above the sulfide lenses, closing each exhalative cycle,
silica-carbonate sediments precipitated along with smectite,
followed by carbonate rhythmites and turbidites.
Rock compositions at present are directly related to original sediments. Diagenesis transformed the mixture of the
hydrothermal carbonate and silica into marbles, siliceous
marbles, and carbonate cherts; the clastic-chemical mixture
of carbonate and clay into marls and breccia-like carbonate
rocks with a smectitic clay matrix; the silica-(fluoritic?)-carbonate sediments into carbonate and (fluoritic?) chert; the
precipitates with sulfides and carbonate into argillic-carbonate sulfide ore and the mudstones into shales and argillites.
Between 1.69 and 1.63 Ga the entire region was metamorphosed at lower greenschist grade. The marbles were recrystallized, whereas the marls and carbonate breccia rocks with
a smectite-clay matrix were transformed into carbonate breccias with a quartz-chlorite-tremolite matrix. The carbonate
and chert became marble and metacherts. The lenses with
sulfide were recrystallized. The shales recrystallized into
quartz-feldspar-chlorite schists, and the rhythmites and turbidites recrystallized into metaturbidites and metarhythmites.
Between 1.56 and 1.53 Ga, intrusion of granites contact
metamorphosed and metasomatized the deposit and host
rocks, obliterating the regional metamorphic foliation. Siliceous
marbles were transformed into talc-tremolite- and talc-rich
rocks with small quantities of carbonate and biotite. The carbonate breccias with quartz-chlorite-carbonate matrices were
transformed into breccia-like (pseudofragmental) rocks with
carbonate, tremolite, talc, and chlorite (CTTC rocks). The
argillites were transformed into biotite rocks; the mineralization was recrystallized a second time, and the other rocks recrystallized without changing their mineral composition.
Metasomatic fluids filled the fractures with massive chlorite
with porphyroblasts of biotite, pyrrhotite and chalcopyrite
(+fluorite?).
Carbonates and quartz of the mineralized rocks are in disequilibrium with the recrystallized rocks with talc, tremolite,
carbonate, chlorite, and biotite, which crystallized between
350 and 530C. However, the preservation of the primary
hydrothermal textures in the carbonates and sulfides suggests
that recrystallization was restricted to the silica-carbonate rocks
and that the original isotopic signatures were maintained.
Field and experimental evidence points to the possibility of
fluorite chert to be a sedimentary hydrothermal rock, but
there is no direct evidence to confirm this hypothesis and
eliminate the genesis of fluorite by metasomatism related to
Aripuan granite.
Acknowledgments
The authors are grateful to Economic Geology reviewers.
We are particularly indebted to Robert Seal, Associate Editor
of Economic Geology, for discussions, advice, and multiple
careful revisions of the text.
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2013 Society of Economic Geologists, Inc.

Economic Geology, v. 108, pp. 781811

The Paleoproterozoic Aripuan Zn-Pb-Ag (Au, Cu) Volcanogenic Massive

de Geologia, Universidade Federal do Paran (UFPR), C.P. 19.001, 81531-980 Brazil

Istopos Estveis, Universidade de Braslia (UnB) 70910-900 Brazil

scale of the deposit including mineralogical, textural, isotopic,

Submitted: March 8, 2011

Rio Vermelho Granite

Rio do Sangue Suite

Z do Torno granite (U-Pb, 1755 5 Ma)

Canam Alkaline rocks

Roosevelt Group (U-Pb, 1762 6

Dexheimer Leite et al. (2005) mapped and sampled the

mineralizing fluids had compositions that could be modeled

seawater and magmatic fluid with sulfur from the leached of

Regional Geologic and Tectonic Settings

DEPOSIT RELATED ROCKS

Hanging wall meta-dacite

Quatro Cachoeiras Orogeny

Serra da Providncia Suite

Sunss Orogen - Candeias Orogeny

Sampling and Analytical Methods

FIG. 2. Distribution of 54 U-Pb SHRIMP radiometric ages from samples

During the Mesoproterozoic, the Rio Vermelho porphyritic

Green schist metamorphism

Gray-vesicular meta-rhyolites interbedded

Red meta-dacites and meta-rhyolites

The volcanic rocks of the Aripuan caldera have Zr/Y ratios

Chloritized and tremolitized meta-tuffs,

FPAR -10 ( 164,35)

F PAR -06 ( 261,65)

F PAR -14 (250,80)

FPAR -08 (765,60)

FPAR -11 (330,60)

chalcopyrite, and magnetite. These breccias occur in the

Twisted-fragment carbonate breccias (Fig. 5J) and breccias

in TRR and CTTC rocks, which are composed of carbonate

6F, H) mixed with carbonate and biotite. They are always

of fluorite-bearing chert in the AMBREX area, each one on

chlorite (530%), and talc + tremolite (210%; App. 2). They

Brecciated fault zone

Tremolitic sulfide ore with

Twisted carbonate breccia with tremolite

Chloritic (tremolite, biotite) sulfide

Pyrrhotite, pyrite, chalcopyrite,

Brecciated fault zone

Tremolitic sulfide ore with

Twisted carbonate breccia with tremolite

Chloritic (tremolite, biotite) sulfide

Pyrrhotite, pyrite, chalcopyrite,

tremolite are uncommon and the fluorine contents of 0.2 to

The main mineralized bodies are located in four zones in the

CaO + MgO (%)

Fluoritic talc-rich rock

Fluoritic meta-turbidites and meta

Hanging wall tuff

Fluoritic tremolite-rich rock

Fluoritic talc-rich rock

Hanging wall volcanic

Carbonatic turbidite, rhythmite and chert

Fluoritic carbonate chert

Massive and silicic marble