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Geochemistry of hydrothermal gold deposits: A review

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DOI: 10.1016/j.gsf.2011.05.006

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 GEOSCIENCE FRONTIERS 2(3) (2011) 367e374

available at www.sciencedirect.com

China University of Geosciences (Beijing)

GEOSCIENCE FRONTIERS
journal homepage: www.elsevier.com/locate/gsf

REVIEW

Geochemistry of hydrothermal gold deposits: A review

Yongfeng Zhu*, Fang An, Juanjuan Tan

Key Laboratory of Orogenic Belts and Crustal Evolution of Ministry of Education, School of Earth and Space Sciences,
Peking University, Beijing 100871, China

Received 13 October 2010; accepted 9 April 2011

Available online 25 May 2011

KEYWORDS Abstract Mineral assemblages formed during hydrothermal alteration reflect the geochemical compo-
Geochemistry; sition of ore-forming fluids. Gold is mainly transported in solution as AueCl and AueS complexes. The
Hydrothermal fluid; change of physicochemical conditions such as temperature, pressure, oxygen fugacity, and sulfur fugacity
Alteration; are effective mechanisms for gold precipitation. Gold tends to be concentrated in the vapor phase of fluids
Gold deposits at high temperatures and pressures. AueAs and AueSb associations are common in gold deposit. Native
antimony and/or arsenic e native gold assemblages may precipitate from hydrothermal fluids with low
sulfur fugacity. Hydrothermal fluids forming epithermal gold deposits are Au-saturated in most cases,
whereas fluids of Carlin-type are Au-undersaturated. Quasi-steady As-bearing pyrite extracts solid solu-
tion Au from hydrothermal fluids through absorption. The capability of As-bearing pyrite to absorb Au
from under-saturated fluid is the key to the formation of large-scale Carlin-type deposits. With increasing
new data, studies on the geochemistry of gold deposits can be used to trace the origin of ore-forming
fluids, the source of gold, and the transporting form of Au and other ore-forming elements, such as Si,
S, F, Cl, As and Ag.
ª 2011, China University of Geosciences (Beijing) and Peking University. Production and hosting by
Elsevier B.V. All rights reserved.

1. Introduction

Ore deposits are the product of crustal evolution in specific areas

* Corresponding author.
and at particular stages. Hence, a full understanding of the local
E-mail address: [email protected] (Y. Zhu).
geological setting is a prerequisite in studying the genesis of ore
1674-9871 ª 2011, China University of Geosciences (Beijing) and Peking
University. Production and hosting by Elsevier B.V. All rights reserved.
deposits (Hedenquist and Lowenstern, 1994; Simmons and
Brown, 2006; Zhu et al., 2007b; Hou et al., 2008; Baker et al.,
Peer-review under responsibility of China University of Geosciences 2010). Studies of the geochemistry of ore deposits are based on
(Beijing). the structure and formation of ores. Models for ore genesis and
doi:10.1016/j.gsf.2011.05.006 exploration rely on the analysis of the various elements, their ore-
forming conditions (p, T, f(O2), f(S2), etc.), and their processes of
concentration. During the reaction between ore-bearing hydro-
thermal fluids and wall-rocks, some elements are concentrated in
Production and hosting by Elsevier
specific locations to form hydrothermal ore deposits. Hydro-
thermal ore systems can be found in various geological settings
368 Y. Zhu et al. / Geoscience Frontiers 2(3) (2011) 367e374

and are hosted in different types of wall-rocks. They are usually

controlled by faults or shear structures, occurring as veins and
stockworks, or by strata in the case of stratiform ores. Although
ore-forming fluids derived from magma are common, hydro-
thermal systems without distinct affinities to magmatic activity
can also result in the formation of large hydrothermal ore deposits
(e.g., Au, Ag, Pd, Zn, Sb, Hg, etc.).
A significant portion of the world’s natural gold endowment
comes from hydrothermal ore deposits (Frimmel, 2008). The
characteristic Au concentrations in natural ore-forming hydro-
thermal fluids and the time scale of deposit formation are a focus
of scientific debate. Simmons and Brown (2006) suggested that
typical Au concentrations were at most 15 ng/g in the ore-forming
fluids of the giant Ladolam Au deposit, based on direct analysis of
active geothermal fluids. By contrast, microanalyses of fluid
inclusions in several magmatic- hydrothermal ore deposits indi-
cate 100e1000 times higher Au concentrations (Ulrich et al.,
1999; Pudack et al., 2009; Seo et al., 2009), potentially implying
much faster and more effective metal enrichment.
The emplacement of magma causes and controls the circula-
tion of hydrothermal fluids, which can transport ore-forming
elements to deposits of economic interest. Given ample time and Figure 1 Schematic diagram showing the alteration spaces in
proper mechanisms, magma degassing can release enough ore- porphyry CueAu system at high temperature and epithermal
forming elements to form economic deposits. As an example, AueAseSb system at low temperature. The phase boundaries are
consider the island arc hydrothermal system of White Island, New schematically constrained. Modified from Seedorff et al., 2004.
Zealand. It has been active for over 10,000 years and generates
about 130,000 t SO2, 440,000 t CO2, 1.1 Mt Cu and >350 kg Au
minerals in wall-rocks and fluid can be rather complex and vari-
every year (Hedenquist et al., 1994). Another representative case
able for different types of deposits. The low to moderate degrees
is the Ladolam gold deposit in Papua New Guinea with 1300 t Au
of pervasive isochemical alteration that characterize almost any
(Simmons and Brown, 2006), which is located in the center of an
rock evolving in the presence of fluid can be largely explained by
extinct volcano on Lihir Island that formed 400,000 years ago.
hydrolysis or Hþ metasomatism. This process can be depicted in
The oxidizing fluid in this area is mainly composed of magmatic
terms of chemical equilibria, or reactions, although it must be
water, with 20,000 ppm Cl, 30,000 ppm SO4, and rare H2S
remembered that these are likely to be simplifications of actual
(w6
104 mol/kg). Au-bearing magmatic fluids are usually
alteration processes. Hydrothermal alteration includes hydration,
neutral or slightly alkaline. Gold deposits related to magmatic
hydrolysis, redox reaction and sulfidation, etc. For example:
fluids at 150e250  C are generally accompanied by wall-rock
alteration, with a mineral assemblage of quartz þ K-feld- 3KAlSi3 O8 Kfeldspar þ 2Hþ Z KAl3 Si3 O10 ðOHÞ2 muscovite
spar þ pyrite  illite  anhydrite  calcite, as is the case for
Ladolam. þ SiO2 þ 2Kþ

2KAl3 Si3 O10 ðOHÞ2 muscovite þ 2Hþ þ 3H2 O

2. Hydrothermal alteration Z 3Al2 Si2 O5 ðOHÞ4 kaolinite þ 2Kþ

The processes of hydrothermal alteration are related to the inter- 3CaMgðCO3 Þ2 dolomite þ 4SiO2 þ 6Hþ þ 4H2 O
action of wall-rocks with hydrothermal fluids, which transport Z Mg3 Si4 O10 ðOHÞ2 talc þ 6H2 CO3 þ 3Ca2þ
heat and chemical constituents in a series of evolving physico- FeCO3 siderite þ 2H2 S þ 0:5O2 Z FeS2 pyrite þ CO2 þ 2H2 O
chemical conditions. Factors that affect such alteration mainly
include temperature gradients between fluids and wall-rocks and Hydrothermal alteration provides a significant guide to mineral
wall-rock compositional variations. The physicochemical gradient exploration, as many deposits are characterized by wide alteration
is generally large (see Fig. 1), but the reaction time of meta- haloes and zonations, such as those observed in porphyry systems
somatic processes is limited, i.e., final equilibrium among (Fig. 1) and chloriteesericite alterations in the basement of vol-
different phases is hardly reached. canogenic massive sulfide deposits. These deposits are charac-
The salinity and temperature of ore-forming fluids have wide terized by well-developed metal zonation patterns defined by
ranges. Salinities of some ore-forming fluids are lower than sea a typical sequence from Fe to FeeCu to CuePbeZn to
water, whereas those in fluids forming porphyry deposits can PbeZneBaeAu in an upward and lateral sense. At a first
reach 80 wt.% NaCl (Heinrich, 2007). The salinity and tempera- approximation this sequence reflects the variable solubilities of
ture of most hydrothermal fluid decrease during the late-stages of these metals at progressively lower temperatures and could be
ore formation, suggesting either the attenuation of heat and fluid seen as a paragenetic sequence. The development of this zonation
source or the addition of meteoric water (Zhu et al., 2001; Tom- reflects the evolution of fluids and the growth mechanism of the
bros et al., 2007; Mao et al., 2008; Zhang et al., 2010). The massive sulfide mound with time. Although the presence of
geochemistry of the fluid can be interpreted by mineral assem- alteration does not necessarily guarantee the occurrence of an ore-
blages formed during fluid alteration. Reactions between specific body, many deposits have been discovered on the basis of
 Y. Zhu et al. / Geoscience Frontiers 2(3) (2011) 367e374 369

transformation of HS to H2S, leading to gold precipitation. When

the sulfide is oxidized into sulfate, Au would precipitate via
following reaction:

2AuðHSÞ
2 þ H2 O þ 7:5O2 / 2Au þ 4SO4
2
þ 6Hþ

Loucks and Mavrogenes (1999) have exploited a natural

crystal growth phenomenon in which gold was dissolved as
AuHS(H2S)3. The experimental results show that the solubility of
AuHS(H2S)3 is extremely sensitive to changes in temperature and
pressure. Cooling from 400 to 340  C results in precipitation of
90% of the dissolved gold as metallic Au. Furthermore, depres-
surization (which occurs as hot fluids ascend up faults) decreases
gold solubility by 90%. This explains the narrow temperature
range over which most gold deposits form (Kerrich, 1999).
A large numbers of deposits with a AueSb element association
develop in an alkaline environment (e.g., talc-carbonate or lime-
stone wall-rock). Acidic or oxidizing fluids are able to transport
Sb(OH)3. Sb2S3 can form when the S concentration is high,
leading to the formation of stibnite e native gold assemblages
Figure 2 Photographs of gold-bearing veins in felsic tuff from the
which frequently occur in black shale hosted gold deposits. On the
deep part of the Hatu gold deposit (Xinjiang): (a) two albiteequartz
other hand, Sb(OH)3 can be reduced to native Sb when the S
veins in felsic tuff. The tuff was cut also by micro-veins consisting of
concentration is lower, forming native antimony and native gold.
quartzepyriteearsnopyrite. Pyrite and arsnopyrite disseminated in
The change of sulfur fugacity and f(O2) in fluid can commonly
tuff; (b) gold-bearing quartzeactinoliteepyriteecalcite micro-
lead to the separation of Sb and Au. Native antimony, discovered
vein in felsic tuff, crossed-polarized light; (c) gold-bearing
in the Baogutu gold deposit (west Junggar, Xinjiang), precipitated
quartzeactinoliteecalcite micro-vein in felsic tuff, plane polarized
slightly later than native gold (An and Zhu, 2010). The mineral
light; (d) gold-rich quartzeactinoliteearsnopyrite micro-vein in felsic
assemblage of arsenopyriteepyrrhotiteetennantiteeullmanitee
tuff, reflected light.
native antimonyestibnite developed at 280e240  C, log f(S2) of
alteration assemblage studies. Fig. 2 shows an example of gold- 12 to 14 and log f(O2) < 38. A gradual decrease of
bearing veins in altered felsic tuff from the Hatu gold deposit temperature and sulfur fugacity is principal mechanism triggering
(west Junggar, Xinjiang); all gold-bearing veins are accompanied precipitation of native gold and antimony (Fig. 3).
by strong alteration in the wall-rocks characterized by quartz, The AseAu correlation has drawn great attention. Experi-
sericite, calcite and chlorite, which coexist with abundant pyrite mental work shows that the solubility of gold increases with the
and arsenopyrite. concentration of As in alkaline fluid (God and Zemann, 2000).
The major gold-bearing minerals are As-bearing pyrite and arse-
3. The geochemical behavior of gold in nopyrite in Carlin-type gold deposits. Because gold- and As-
bearing minerals (pyrite and arsenopyrite) correlate positively, As
hydrothermal systems is considered to play an important role in the concentration of Au

The occurrence of gold mainly depends on temperature, pressure,

pH values, Cl concentration, and fugacity of H2S in a hydro-
thermal system. Gold mostly occurs as AuCl 2 in a system with
temperature higher than 400  C (Gammons and Williams-Jones,
1997), and with decreasing temperature being the primary
mechanism causing gold deposition. Au(HS) 2 is the dominant
phase at lower temperature, and the maximum solubility exists in
the vicinity of the H2SeHSeSO2 4 equilibrium point; then, with
the decline of oxygen fugacity, the AueS complex breaks down,
leading to gold precipitation (Cooke and Simmons, 2000; Robb,
2005):

2AuðHSÞ
2 þ H2 O / 2Au þ 4HS

þ 2Hþ þ 0:5O2

2AuðHSÞ
2 þ 8H2 O / 2Au þ 4SO4
2
þ 4Hþ þ 8H2

FeCO3 þ AuðHSÞ
2 Z FeS2 pyrite þ CO2 þ H2 O þ Au

The solubility of gold will change with oxygen fugacity and

hydrogen fugacity at given PT and consistent water activity and
sulfur fugacity (Candela and Piccoli, 2005). If the pH value drops Figure 3 Evolution curve of the hydrothermal fluid in the Baogutu
into the H2S domain, HeAu redox would be accompanied by the gold deposit. I, II, and III represent three ore-forming stages.
370 Y. Zhu et al. / Geoscience Frontiers 2(3) (2011) 367e374

in hydrothermal systems. When the S content is extremely low, with alkaline mafic to intermediate igneous rocks, which exsolve
native As would form, such as the case in the Baogutu gold volatiles that simultaneously contain both H2S and alkali chlorides
deposit, where native As is the predominant gold carrier (Fig. 4). in significant concentrations. The prominent solubility maximum
The mineral assemblage formed in this deposit is native can be explained by the following dissolution reaction (Pokrovski
Asenative gold/electrumestibnite at 230e270  C, log f(O2) is et al., 2009; Zajacz et al., 2010):
42 to 56.5 with log f(S2) of 13.3 to 16.6 (An and Zhu,
2009). Au þ HCl þ NaCl Z NaAuCl2 þ 0:5H2
Anionic species, or ligands, of chloride (Cl) and sulfide
(specifically HS) are essential in gold-bearing aqueous solution. Au þ 2Cl þ Hþ þ 0:25O2 Z AuCl
2 þ 0:5H2 O
In reduced, near-neutral pH, Au is likely to be transported as the
Au(HS) 2 complex, and this is also likely to be the preferred ionic Au þ 4Cl þ 3Hþ þ 0:75O2 Z AuCl
4 þ 1:5H2 O
species for the movement of gold in low-sulphidation environ-
ments. By contrast, Au is mostly transported as chlorides in fluids The solubility of Au as a function of NaCl/(NaCl þ HCl)
at high temperature. HCl is an important constituent in volcanic supports the suggested stoichiometry of the Au alkali chloride
exhalation. If Au is partitioned into a volcanic exhalative phase, its complex in low density magmatic fluids (Zajacz et al., 2010).
major component would possibly be a AueCl complex. James and Simple chloride complexes (such as AuCl 2 ) support modest gold
Hager (1978) calculated the pressure of Au in AueCl2 system to solubilities in magmatic fluids at subsolidus conditions around
be 7.9
104 bar at 300  C and pCl2 Z 1 bar. In contrast, at the 400  C and 50e180 MPa (Pokrovski et al., 2009; Williams-Jones
same temperature and pCl2 Z 0.1 bar, the pressure of Au decreases et al., 2009).
to 1.1
106 bar; when the temperature is raised to 360  C A model has been provided for the formation of high-sulphi-
(pCl2 Z 1 bar), the partial pressure of Au will be 1
104 bar. dation epithermal systems that reflects the complexities related to
Studies of the Au solubility in AueH2OeHCl system have sug- possible variations of gold speciation in this environment (Arribas
gested that the dominant transport form of Au is AuClm$(H2O)n et al., 1995). The first involves degassing of hot, acid magmatic
via the following reactions where m stands for the number of Cl, vapors that are responsible for intense leaching of the host rock to
n is the number of hydrated ions of gold in vapor (Archibald et al., form the porous vuggy quartz zone in fumarolic conduits and the
2001): advanced argillic alteration halo around them. The vapor phase
could also mix with meteoric waters to form an acidic sulfate fluid
Au þ mHCl þ nH2 O Z AuClm $ðH2 OÞn þ 0:5mH2 that has a low Au solubility, but is also implicated in the alteration
process. The secondary porosity and permeability created during
The solubility of Au drops with a temperature increase within this alteration is considered to be a necessary preparatory stage for
the range of 300e360  C under the same condition of f(H2O) and the influx of later metal-bearing fluids. A hot, acidic, and saline
f(HCl). ore fluid, carrying gold as a AuCl 2 complex, could be derived
Zajacz et al. (2010) show that gold hydrosulfide complexes directly from the subjacent magma and move directly up into the
supersede gold chloride complexes, and more importantly, that the alteration zone. Ore precipitation would then occur as a result of
stability of gold hydrosulfide complexes is greatly increased by mixing and dilution of this fluid by cooler meteoric waters.
the presence of minute concentrations of KCl or NaCl Gold mostly concentrates in high-sulphidation systems at
(0.1e0.5 mol/kg H2O). The amplifying effect of alkali chlorides 300  C at low pH (<2) and high log f(O2)(e28). For example, the
on the solubility of gold in H2S-bearing volatiles may explain the concentration of Au in the vapor phase is 0.06 ppb at pH Z 2 and
preferential association of many giant hydrothermal gold deposits log f(O2) Z 28 (Archibald et al., 2001). Under the condition of

Figure 4 (a) Native arsenic (As) in quartz cementing tuff breccias in the Baogutu gold deposit; (b) Microphotograph showing gold-bearing
native arsenic grains in comb quartz with growth zone. The dark gray zone contains relatively high abundance of micrograins of native arsenic and
actinolite relatively to the light gray zone. Crossed-polarized light.
 Y. Zhu et al. / Geoscience Frontiers 2(3) (2011) 367e374 371

the same oxygen fugacity but at pH Z 1, the Au concentration is wall-rocks to form advanced argillic alteration haloes (kaolinite,
0.6 ppb. The Au concentration reaches 3.5 ppb when log f(O2) pyrophyllite and alunite) and induce intensive leaching the wall-
increases to 25. Assuming the outgassing of HCl in an active rock of epithermal Au  Cu deposit (Landis and Rye, 2005). This
volcano at a rate of 700 t/day, and a Au concentration of 4.0 ppb magmatic vapor can transport metal and precipitate it from the
(pH Z 1, log f(O2) Z 25), this hydrothermal system could form vapor phase directly. Advanced argillic alteration takes place prior
a deposit with gold reserve of 50 tons in about 5 Ma. to the deposition of ore-forming metals involved in late-stage
aqueous liquid or mediumelow saline fluid in most high-sulphi-
dation epithermal systems.
4. Transportation of Au through vapor in porphyry
system
5. Controls of sulfide on gold occurrences
Boiling, a prevalent phenomenon in hydrothermal systems, can
produce vapor and liquid capable of carrying ore-forming The crystallization or dissolution of silicate minerals has an
elements. Many ore-forming elements have been found in vapor- insignificant effect on the form of Au in granitic magma, because
precipitated fumarolic deposits in active volcanoes. Direct proof most such gold is generally hosted in sulfides. Au behaves as an
of vapor-transportation comes from the Grasberg CueAu deposits incompatible element, and tends to concentrate in residual melts
in Indonesia, where the vapor-rich inclusion contain 10 ppm Au, in which sulfur dissociates. Experiments have demonstrated that
whereas the coexisting fluid inclusions contain less than 0.3 ppm Au is hosted in sulfide minerals with the following decreasing
Au (Ulrich et al., 1999). The concentration of Cu in condensed order of Au concentration: bornite > chalcopyrite > pyrrhotite >
vapors separating from basaltic magma reaches the order of pyrite (Cygan and Candela, 1995; Jugo et al., 1999; Simon et al.,
magnitude of ppm, whereas the concentration of Cu in volcanic 2000). An experiment on a pyrrhotite e ISS (intermediate solid
rocks is in the order of ppb (Quisefit et al., 1989; Bernard et al., solution) e granitic melt e Au system (850  C, 100 MPa) has
1990; Taran et al., 2000). This implies that Cu prefers to partici- shown that most Au separated from the melt would enter into the
pate into vapor separating from the melt. Magnetite, stibnite and ISS rather than pyrrhotite (Jugo et al., 1999). Experiments at
wolframite frequently precipitate at or in the vicinity of the 700  C and 140 MPa have demonstrated that pyrite can hold
volcanic conduits, in contrast to chalcopyrite, sphalerite and pyrite 6 ppm Au in a Au-saturated chloride solution (Cygan and
that precipitate at relatively lower temperature. Galena, lead Candela, 1995), in contrast to chalcopyrite (3000 ppm Au),
sulfate and native arsenic form when the temperature is even pyrrhotite (w9 ppm Au), and magnetite (w3 ppm Au; Simon
lower. et al., 2000). Magnetite contains 3 ppm Au, whereas quartz
High concentrations of Cu and other ore-forming elements contains only 0.5 ppm Au in a Au-saturated, sulfur-poor water
have been found in fluid inclusions from many deposits (Audetat vapor e brine e silicate melt system (800  C, 140 MPa, NNO
et al., 1998; Baker et al., 2004; Williams-Jones and Heinrich, buffer, Simon et al., 2003). Gold is primarily hosted in chalco-
2008). Investigations on coexisting single brine and vapor inclu- pyrite, arsenopyrite, pyrrhotite and pyrite in most hydrothermal
sions have demonstrated that partitioning has taken place between gold deposits, and its concentration in sulfide varies to a great
saline fluid and vapor for specific elements, with K, Mn, Fe, Rb extent (Morey et al., 2008; Large et al., 2009). Au content can be
and Cs more likely to enter the liquid, in contrast to B, Cu, As, Sb, varied (0.07e1.96 ppm) within even single grains. Yang et al.
Au and Li, which tend to go into the vapor phase. For instance, (2006) demonstrated that Au concentrations in pyrite within
spatially related sericitic alteration in early stage stockworks of granite can range from <0.02 to 21 ppm. The Au concentration is
CueMo porphyry systems was caused by relatively low saline much less varied in pyrrhotite (<0.02e0.34 ppm) than in pyrite.
(w4 wt.% NaCleq) and medium density (w0.6 g/cm3) fluid (Rusk In fine-grained veins, Au concentration in chalcopyrite ranges
et al., 2004). This fluid contains as much Cu as 1 wt.% prior to the from below detection limit to 5.33 ppm, but Au in pyrite that has
saturation of chalcopyrite and pyrite. Both single-phase fluid replaced chalcopyrite can reach 21 ppm.
inclusions and two-phase inclusions are rich in Cu before satu- Gold generally occurs as micro-inclusions in over-saturated
ration (0.2 < Cu/Na < w1, Redmond et al., 2004; Landtwing conditions (Reich et al., 2005). Au and As are intimately related in
et al., 2005) in high-grade porphyry CueAueMo deposits. arsenian pyrite with a linear relationship: cAu Z 0.02
Gold concentrations decrease from 36 ppm to 5 ppm in vapor cAs þ 4
105 (cAu and cAs represent the mole percentage of Au
(and from 50 ppm to 28 ppm in brine) with a pressure drop from and As concentration, respectively). The solid solution gold (Auþ)
1450 bar to 1100 bar in a brine þ synthetic granite þ magnetite enters arsenopyrite by replacing Fe2þ (Tarnocai et al., 1997; Cabri
system (800  C, 1100e1450 bar, NNO buffer, Simon et al., 2005). et al., 2000). X-ray adsorption near edge structure, extended X-ray
The partition coefficients of Au in vapor and brine are similar at adsorption fine structure, and secondary ion mass spectroscopy
conditions close to crucial pressure. Au strongly partitions into analyses on As-bearing pyrite show that solid solution gold has
brines at low pressure. two coordination species: Au0 and Auþ. The Auþ can occur in
Low saline hydrothermal fluid is capable of carrying a great more than one form, including Auþ in vacancies in an unknown
amount of Au at ppm-levels in vapor inclusions in porphyry AueAseS complex and a distorted Fe2þ octahedral place (Simon
according to Ulrich et al. (1999). The process of cooling and et al., 1999). If the mechanism that Au(HS) and Au(HS)2 is
precipitation of pyrite and CueFe sulfide would rapidly consume absorbed on the growing surface of As-rich pyrite is feasible
reducing sulfur, triggering Au to precipitate with CueFe sulfide (Widler and Seward, 2002), the entrance of Au into As-bearing
(Heinrich, 2005). Consequently, this mechanism limits the ability pyrite depends on its vacancies or surface defects. Thus, the
of low saline fluid to transport Au into the epithermal environ- maximum solubility of Au is the function of As content of surface
ment. Vapors released from active volcanoes or shallow sub- and available vacancies or structure defects. The quasi-steady
volcanic intrusions are usually rich in SO2, H2S and HCl. As such, arsenian pyrite in Carlin-type and epithermal deposits has abun-
they can produce acidic fluids during cooling that react with dant Au contents, because those pyrites are formed at
372 Y. Zhu et al. / Geoscience Frontiers 2(3) (2011) 367e374

low-temperatures (<250  C), in which disequilibrium conditions deformation following the shortening episodes). The bulk of the
and surface defects are pervasively developed. high-grade mineralization was formed during D4 that produced
Gold is generally transported as Au(HS) in under-saturated, both steep and flat veins and breccias.
sulfur-bearing fluids. As-bearing pyrite crystallizes from Au The modeled location of the solvus and estimated peT
under-saturated solutions in Carlin-type deposits according to the conditions for the early CO2eH2O fluids suggest that a pressure
following reactions (Reich et al., 2003): drop alone would not cause the fluids to enter the two-phase field.
It seems more likely that a pressure decrease combined with
FeðS; AsÞ2 þ 2AuðHSÞ Z FeðS; AsÞ2 $Au2 S þ H2 S a drop in temperature below w300  C would have been an
important factor. Exhumation may have been one such factor in
Fe2þ þ 2HAsS2 þ 2AuðHSÞ þ 2H2 Z FeðS; AsÞ$Au2 S changing the structural regime and peT conditions. Similar fluid
evolution and gold precipitation mechanism have been described
þ 3H2 S þ 2Hþ in the Tianger region of China’s Tianshan Mountains (Zhu et al.,
2007b). Three stages have been identified in the Tianger gold
The above reactions are mainly controlled by the activity of
deposits. Stage I occurs at a depth of 10 km under conditions of
H2S. The decrease of H2S caused by boiling and/or alteration
the amphibolite facies. Stage II, as constrained by metamorphic
can enhance the crystallization and the entry of solid solution
facies, is represented by zoisite amphibolites in mylonitized
Auþ. The composition of As-bearing pyrite in Carlin-type and
granite and the reaction of albite þ 4 anorthite þ
epithermal deposits has shown that the state of gold is variable
2H2O Z pargasite þ 2 zoisite þ 2 quartz. Stage III, corresponding
in the ore-forming fluid. Hydrothermal fluids forming epithermal
to major gold precipitation, represents brittle deformation
deposits are Au-saturated to a great extent, whereas those of
following the ductile shear processes.
Carlin-type are Au-undersaturated. The quasi-steady As-bearing
The giant Muruntau gold deposit in Uzbekistan, located in the
pyrite extracts Auþ from hydrothermal fluid by absorption. The
southwest Tianshan mountains and hosted in Early Paleozoic
capability of As-bearing pyrite to absorb gold from under-
black carbonaceous shales, is controlled by huge shear zones (Drew
saturated fluid is the key to forming large-scale Carlin-type
et al., 1996; Graupner et al., 2000; Bierlein and Wilde, 2010).
deposits.
A late-stage mineral assemblage consisting of quartzenative
goldeamesiteesericiteecalciteedolomiteepyriteeapatite appears
6. Gold precipitation to be related to the high to medium temperature alteration of wall-
rocks. The ReeOs age of gold-bearing arsenopyrite (w290 Ma)
Exceptionally extensive natural processes are required to overlaps regional magmatism in the Muruntau (Morelli et al., 2007).
concentrate gold from crustal background levels into gold The analyses of noble gas, carbon isotopes, and halogen elements in
deposits. For example, four thousand tonnes of gold have been fluids included in the hydrothermal minerals related to gold miner-
mined from the 300 km by 200 km Abitibi greenstone belt of alization have illustrated that the dominant He comes from the
Canada (Kerrich, 1999). An estimated 1000 km3 of aqueous fluids continental crust, whereas the noble gases mostly originated from the
with a starting temperature of 500  C must have leached this huge atmosphere (Graupner et al., 2006). Studies on Os initial values and
block, transported gold as an aqueous species, and become the He isotopes of fluid inclusions in gold-bearing arsenopyrite show
channeled along faults where gold precipitated with quartz in vein that the values of non-radiogenic Os and 3He/4He ratios are higher
deposits over the temperature interval of 400e300  C (Kerrich, than that of the crustal reservoir (Morelli et al., 2007). This suggests
1999). that mantle-derived sources contributed to the ore-forming fluid.
Gold mineralization in most shear zones is post-peak meta- Gold exceeding 6000 t gathered in the Muruntau deposit. This
morphism and involves a multi-stage alteration event accom- requires a prolonged fluid evolution involving elements such as Os,
panied by gold mineralization through continuous fluid flow He, Au of various origin and sources to evolve into ore-forming fluid
over a long period of time. The f(O2) decrease was the dominant during a complex crustemantle interaction. Shear zones that
cause of gold precipitation from the fluid containing Au(HS) 2 in controlled gold deposits are principal features in the central Asia
shear zone. Precipitation of thin films of graphite in most shear metallogenic region (e.g., Yang et al., 2007; Zhu et al., 2007a,b;
zones is interpreted to have been the result of heterogeneous Graupner et al., 2010) and, thus, remain the major targets for gold
reaction between CO2 and CH4. Simultaneous entrapment of exploration (e.g., Xiao et al., 2010; Zhu, 2011).
aqueous and carbonic inclusions in auriferous laminated quartz
veins in different gold deposits (e.g., Zhu et al., 2001; Pal and
Mishra, 2002) was due to unmixing of an initial H2OeCO2 fluid 7. Conclusions
at lower temperature. Accordingly, gold precipitation was
primarily due to a decrease in S in the aqueous part, a conse- The local enrichment of gold within the deposits is controlled by
quence of phase separation related to cyclic decompression mineral precipitation from an aqueous fluid. The change of
events. physicochemical conditions such as temperature, pressure, oxygen
Gold precipitation in shear zones can happen in different ways. fugacity, and sulfur fugacity are effective mechanisms for gold
For example, studies at Sunrise Dam gold deposit of western precipitation. Gold tends to be concentrated in the vapor phase of
Australia have defined distinct relationships between the orienta- fluids at high temperatures and pressures. The AueAs and AueSb
tion and style of orebodies and their host structures (McLellan associations are common in gold deposit. Hydrothermal fluids
et al., 2007; Baker et al., 2010). The orebodies formed in response forming epithermal gold deposits are Au-saturated in most cases,
to multiple episodes of deformation (from D1 to D4). Many whereas deposits of Carlin-type are Au-undersaturated. Quasi-
structures were created during D1 and D2 shortening (the early steady As-bearing pyrite extracts solid solution Au from hydro-
episodes of deformation), whereas the bulk of the gold was thermal fluids through absorption. Research continues on the
deposited during D3 and D4 (the episodes of extensional geochemistry of gold deposits for the purpose of tracing the origin
 Y. Zhu et al. / Geoscience Frontiers 2(3) (2011) 367e374 373

of ore-forming fluids, the source of gold, and the transportation of Drew, L.J., Berger, B.R., Kurbanov, N.K., 1996. Geology and structural
gold and other related ore-forming elements including Si, S, F, Cl, evolution of the Muruntau gold deposit, Kyzylkun desert, Uzbekistan.
As and Ag. With the application of new techniques, present and Ore Geology Reviews 11, 175e196.
future high demands for gold, it is clear that new geochemical Frimmel, H.E., 2008. Earth’s continental crustal gold endowment. Earth
and Planetary Science Letters 267, 45e55.
data and prospecting approaches will greatly facilitate gold
Gammons, C.H., Williams-Jones, A.E., 1997. Chemical mobility of gold in
explorations. the porphyry-epithermal environment. Economic Geology 92, 45e59.
God, R., Zemann, J., 2000. Native arsenic-realgar mineralization in
marbles from Saualpe, Carinthia, Austria. Mineralogy and Petrology
70, 37e53.
Acknowledgements Graupner, T., Goetze, J., Kempe, U., 2000. CL for characterizing quartz
and trapped fluid inclusions in mesothermal quartz veins: Muruntau
Our thanks are due to the National Natural Science Foundation of Au ore deposit, Uzbekistan. Mineralogical Magazine 64,
China (Nos. 41072041, 40821002) for financial support. Prof. 1007e1016.
Gregory Davis (University of Southern California) and anony- Graupner, T., Niedermann, S., Kempe, U., 2006. Origin of ore fluids in the
mous reviewers who offered insightful and detailed comments on Muruntau gold system: constraints from noble gas, carbon isotope and
halogen data. Geochimica et Cosmochimica Acta 70, 5356e5370.
the earlier manuscript have helped us to complete this paper and,
Graupner, T., Niedermann, S., Rhede, D., Kempe, U., Seltmann, R.,
are, therefore gratefully acknowledged.
Williams, C.T., Klemd, R., 2010. Multiple sources for mineralizing
fluids in the Charmitan gold (-tungstan) mineralization (Uzbekistan).
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