Hydro Term Al

Geochemistry of hydrothermal gold deposits:
A review
Yongfeng Zhu, ,
Fang An,
Juanjuan Tan
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http://dx.doi.org/10.1016/j.gsf.2011.05.006
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Open Access funded by China University of Geosciences (Beijing)
Under a Creative Commons license
Abstract
Mineral assemblages formed during hydrothermal alteration reflect the geochemical composition
of ore-forming fluids. Gold is mainly transported in solution as AuCl and AuS complexes. The
change of physicochemical conditions such as temperature, pressure, oxygen fugacity, and sulfur
fugacity are effective mechanisms for gold precipitation. Gold tends to be concentrated in the
vapor phase of fluids at high temperatures and pressures. AuAs and AuSb associations are
common in gold deposit. Native antimony and/or arsenic 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 solution 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.
Keywords
Geochemistry;
Hydrothermal fluid;
Alteration;
Gold deposits
1. Introduction
Ore deposits are the product of crustal evolution in specific areas and at particular stages. Hence,
a full understanding of the local geological setting is a prerequisite in studying the genesis of ore
deposits (Hedenquist and Lowenstern, 1994, Simmons and Brown, 2006, Zhu et al., 2007b, Hou
et al., 2008 and Baker et al., 2010). Studies of the geochemistry of ore deposits are based on the
structure and formation of ores. Models for ore genesis and 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 hydrothermal fluids and wall-rocks,
some elements are concentrated in specific locations to form hydrothermal ore deposits.
Hydrothermal ore systems can be found in various geological settings 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, hydrothermal 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 worlds natural gold endowment comes from hydrothermal ore
deposits (Frimmel, 2008). The characteristic Au concentrations in natural ore-forming
hydrothermal 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 indicate 1001000 times higher Au concentrations (Ulrich et al., 1999,
Pudack et al., 2009 and Seo et al., 2009), potentially implying much faster and more effective
metal enrichment.
The emplacement of magma causes and controls the circulation of hydrothermal fluids, which
can transport ore-forming elements to deposits of economic interest. Given ample time and
proper mechanisms, magma degassing can release enough ore-forming elements to form
economic deposits. As an example, consider the island arc hydrothermal system of White Island,
New 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 every year (Hedenquist et al., 1994). Another
representative case is the Ladolam gold deposit in Papua New Guinea with 1300 t Au (Simmons
and Brown, 2006), which is located in the center of an extinct volcano on Lihir Island that
formed 400,000 years ago. The oxidizing fluid in this area is mainly composed of magmatic
water, with 20,000 ppm Cl, 30,000 ppm SO4, and rare H2S (6 104 mol/kg). Au-bearing
magmatic fluids are usually neutral or slightly alkaline. Gold deposits related to magmatic fluids
at 150250 C are generally accompanied by wall-rock alteration, with a mineral assemblage of
quartz + K-feldspar + pyrite illite anhydrite calcite, as is the case for Ladolam.
2. Hydrothermal alteration
The processes of hydrothermal alteration are related to the interaction of wall-rocks with
hydrothermal fluids, which transport heat and chemical constituents in a series of evolving
physicochemical conditions. Factors that affect such alteration mainly include temperature
gradients between fluids and wall-rocks and wall-rock compositional variations. The
physicochemical gradient is generally large (see Fig. 1), but the reaction time of metasomatic
processes is limited, i.e., final equilibrium among different phases is hardly reached.
Figure 1.
Schematic diagram showing the alteration spaces in porphyry CuAu system at high
temperature and epithermal AuAsSb system at low temperature. The phase boundaries
are schematically constrained.
Modified from Seedorff et al., 2004.
Figure options
The salinity and temperature of ore-forming fluids have wide ranges. Salinities of some ore-
forming fluids are lower than sea water, whereas those in fluids forming porphyry deposits can
reach 80 wt.% NaCl (Heinrich, 2007). The salinity and temperature of most hydrothermal fluid
decrease during the late-stages of ore formation, suggesting either the attenuation of heat and
fluid source or the addition of meteoric water (Zhu et al., 2001, Tombros et al., 2007, Mao et al.,
2008 and Zhang et al., 2010). The geochemistry of the fluid can be interpreted by mineral
assemblages formed during fluid alteration. Reactions between specific minerals in wall-rocks
and fluid can be rather complex and variable for different types of deposits. The low to moderate
degrees of pervasive isochemical alteration that characterize almost any rock evolving in the
presence of fluid can be largely explained by hydrolysis or H+ metasomatism. This process can
be depicted in terms of chemical equilibria, or reactions, although it must be remembered that
these are likely to be simplifications of actual alteration processes. Hydrothermal alteration
includes hydration, hydrolysis, redox reaction and sulfidation, etc. For example:
3KAlSi3O8 K-feldspar + 2H+ = KAl3Si3O10(OH)2 muscovite + SiO2 + 2K+

2KAl3Si3O10(OH)2 muscovite + 2H+ + 3H2O = 3Al2Si2O5(OH)4 kaolinite + 2K+
3CaMg(CO3)2 dolomite + 4SiO2 + 6H+ + 4H2O = Mg3Si4O10(OH)2 talc + 6H2CO3 + 3Ca2+
FeCO3 siderite + 2H2S + 0.5O2 = FeS2 pyrite + CO2 + 2H2O
Hydrothermal alteration provides a significant guide to mineral exploration, as many deposits are
characterized by wide alteration haloes and zonations, such as those observed in porphyry
systems (Fig. 1) and chloritesericite alterations in the basement of volcanogenic massive sulfide
deposits. These deposits are characterized by well-developed metal zonation patterns defined by
a typical sequence from Fe to FeCu to CuPbZn to PbZnBaAu in an upward and lateral
sense. At a first approximation this sequence reflects the variable solubilities of these metals at
progressively lower temperatures and could be seen as a paragenetic sequence. The development
of this zonation reflects the evolution of fluids and the growth mechanism of the massive sulfide
mound with time. Although the presence of alteration does not necessarily guarantee the
occurrence of an ore-body, many deposits have been discovered on the basis of alteration
assemblage studies. Fig. 2 shows an example of gold-bearing veins in altered felsic tuff from the
Hatu gold deposit (west Junggar, Xinjiang); all gold-bearing veins are accompanied by strong
alteration in the wall-rocks characterized by quartz, sericite, calcite and chlorite, which coexist
with abundant pyrite and arsenopyrite.
Figure 2.
Photographs of gold-bearing veins in felsic tuff from the deep part of the Hatu gold
deposit (Xinjiang): (a) two albitequartz veins in felsic tuff. The tuff was cut also by
micro-veins consisting of quartzpyritearsnopyrite. Pyrite and arsnopyrite disseminated
in tuff; (b) gold-bearing quartzactinolitepyritecalcite micro-vein in felsic tuff,
crossed-polarized light; (c) gold-bearing quartzactinolitecalcite micro-vein in felsic
tuff, plane polarized light; (d) gold-rich quartzactinolitearsnopyrite micro-vein in felsic
tuff, reflected light.
Figure options
3. The geochemical behavior of gold in hydrothermal

systems
The occurrence of gold mainly depends on temperature, pressure, pH values, Cl concentration,
and fugacity of H2S in a hydrothermal system. Gold mostly occurs as AuCl2 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 H2SHS
SO24 equilibrium point; then, with the decline of oxygen fugacity, the AuS complex breaks
down, leading to gold precipitation (Cooke and Simmons, 2000 and Robb, 2005):
2Au(HS)2 + H2O 2Au + 4HS + 2H+ + 0.5O2

2Au(HS)2 + 8H2O 2Au + 4SO42 + 4H+ + 8H2
FeCO3 + Au(HS)2 = FeS2 pyrite + CO2 + H2O + 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
into the H2S domain, HAu redox would be accompanied by the transformation of HS to H2S,
leading to gold precipitation. When the sulfide is oxidized into sulfate, Au would precipitate via
following reaction:
2Au(HS)2 + H2O + 7.5O2 2Au + 4SO42 + 6H+
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,
depressurization (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 AuSb element association develop in an alkaline

environment (e.g., talc-carbonate or limestone 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 native gold assemblages which frequently occur in black shale hosted gold deposits.
On the other hand, Sb(OH)3 can be reduced to native Sb when the S concentration is lower,
forming native antimony and native gold. The change of sulfur fugacity and f(O2) in fluid can
commonly lead to the separation of Sb and Au. Native antimony, discovered in the Baogutu gold
deposit (west Junggar, Xinjiang), precipitated slightly later than native gold (An and Zhu, 2010).
The mineral assemblage of arsenopyritepyrrhotitetennantiteullmanitenative antimony
stibnite developed at 280240 C, log f(S2) of 12 to 14 and log f(O2) < 38. A gradual
decrease of temperature and sulfur fugacity is principal mechanism triggering precipitation of
native gold and antimony (Fig. 3).
Figure 3.
Evolution curve of the hydrothermal fluid in the Baogutu gold deposit. I, II, and III
represent three ore-forming stages.
Figure options
The AsAu correlation has drawn great attention. Experimental work shows that the solubility of
gold increases with the concentration of As in alkaline fluid (God and Zemann, 2000). The major
gold-bearing minerals are As-bearing pyrite and arsenopyrite in Carlin-type gold deposits.
Because gold- and As-bearing minerals (pyrite and arsenopyrite) correlate positively, As is
considered to play an important role in the concentration of Au in hydrothermal systems. When
the S content is extremely low, native As would form, such as the case in the Baogutu gold
deposit, where native As is the predominant gold carrier (Fig. 4). The mineral assemblage
formed in this deposit is native Asnative gold/electrumstibnite at 230270 C, log f(O2) is 42
to 56.5 with log f(S2) of 13.3 to 16.6 (An and Zhu, 2009).
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.
Figure options
Anionic species, or ligands, of chloride (Cl) and sulfide (specifically HS) are essential in gold-
bearing aqueous solution. 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 species for the movement of
gold in low-sulphidation environments. By contrast, Au is mostly transported as chlorides in
fluids at high temperature. HCl is an important constituent in volcanic exhalation. If Au is
partitioned into a volcanic exhalative phase, its major component would possibly be a AuCl
complex. James and Hager (1978) calculated the pressure of Au in AuCl2 system to be
7.9 104 bar at 300 C and pCl2pCl2 = 1 bar. In contrast, at the same temperature and
pCl2pCl2 = 0.1 bar, the pressure of Au decreases to 1.1 106 bar; when the temperature is raised
to 360 C (pCl2pCl2 = 1 bar), the partial pressure of Au will be 1 104 bar. Studies of the Au
solubility in AuH2OHCl system have suggested that the dominant transport form of Au is
AuClm(H2O)n via the following reactions where m stands for the number of Cl, n is the number
of hydrated ions of gold in vapor ( Archibald et al., 2001):
Au + mHCl + nH2O = AuClm(H2O)n + 0.5mH2
The solubility of Au drops with a temperature increase within the range of 300360 C under the
same condition of f(H2O) and f(HCl).
Zajacz et al. (2010) show that gold hydrosulfide complexes supersede gold chloride complexes,
and more importantly, that the stability of gold hydrosulfide complexes is greatly increased by
the presence of minute concentrations of KCl or NaCl (0.10.5 mol/kg H2O). The amplifying
effect of alkali chlorides on the solubility of gold in H2S-bearing volatiles may explain the
preferential association of many giant hydrothermal gold deposits with alkaline mafic to
intermediate igneous rocks, which exsolve volatiles that simultaneously contain both H2S and
alkali chlorides in significant concentrations. The prominent solubility maximum can be
explained by the following dissolution reaction (Pokrovski et al., 2009 and Zajacz et al., 2010):
Au + HCl + NaCl = NaAuCl2 + 0.5H2

Au + 2Cl + H+ + 0.25O2 = AuCl2 + 0.5H2O
Au + 4Cl + 3H+ + 0.75O2 = AuCl4 + 1.5H2O
The solubility of Au as a function of NaCl/(NaCl + HCl) supports the suggested stoichiometry of

the Au alkali chloride complex in low density magmatic fluids (Zajacz et al., 2010). Simple
chloride complexes (such as AuCl2) support modest gold solubilities in magmatic fluids at
subsolidus conditions around 400 C and 50180 MPa (Pokrovski et al., 2009 and Williams-
Jones et al., 2009).
A model has been provided for the formation of high-sulphidation epithermal systems that
reflects the complexities related to possible variations of gold speciation in this environment
(Arribas et al., 1995). The first involves degassing of hot, acid magmatic vapors that are
responsible for intense leaching of the host rock to form the porous vuggy quartz zone in
fumarolic conduits and the advanced argillic alteration halo around them. The vapor phase could
also mix with meteoric waters to form an acidic sulfate fluid that has a low Au solubility, but is
also implicated in the alteration process. The secondary porosity and permeability created during
this alteration is considered to be a necessary preparatory stage for the influx of later metal-
bearing fluids. A hot, acidic, and saline ore fluid, carrying gold as a AuCl2 complex, could be
derived directly from the subjacent magma and move directly up into the alteration zone. Ore
precipitation would then occur as a result of mixing and dilution of this fluid by cooler meteoric
waters.
Gold mostly concentrates in high-sulphidation systems at 300 C at low pH (<2) and high log
f(O2)(28). For example, the concentration of Au in the vapor phase is 0.06 ppb at pH = 2 and
log f(O2) = 28 (Archibald et al., 2001). Under the condition of the same oxygen fugacity but at
pH = 1, the Au concentration is 0.6 ppb. The Au concentration reaches 3.5 ppb when log f(O2)
increases to 25. Assuming the outgassing of HCl in an active volcano at a rate of 700 t/day, and
a Au concentration of 4.0 ppb (pH = 1, log f(O2) = 25), this hydrothermal system could form a
deposit with gold reserve of 50 tons in about 5 Ma.
4. Transportation of Au through vapor in porphyry system

Boiling, a prevalent phenomenon in hydrothermal systems, can produce vapor and liquid capable
of carrying ore-forming elements. Many ore-forming elements have been found in vapor-
precipitated fumarolic deposits in active volcanoes. Direct proof of vapor-transportation comes
from the Grasberg CuAu deposits in Indonesia, where the vapor-rich inclusion contain 10 ppm
Au, whereas the coexisting fluid inclusions contain less than 0.3 ppm Au (Ulrich et al., 1999).
The concentration of Cu in condensed vapors separating from basaltic magma reaches the order
of magnitude of ppm, whereas the concentration of Cu in volcanic rocks is in the order of ppb
(Quisefit et al., 1989, Bernard et al., 1990 and Taran et al., 2000). This implies that Cu prefers to
participate into vapor separating from the melt. Magnetite, stibnite and wolframite frequently
precipitate at or in the vicinity of the volcanic conduits, in contrast to chalcopyrite, sphalerite and
pyrite that precipitate at relatively lower temperature. Galena, lead sulfate and native arsenic
form when the temperature is even lower.
High concentrations of Cu and other ore-forming elements have been found in fluid inclusions
from many deposits (Audetat et al., 1998, Baker et al., 2004 and Williams-Jones and Heinrich,
2008). Investigations on coexisting single brine and vapor inclusions have demonstrated that
partitioning has taken place between saline fluid and vapor for specific elements, with K, Mn,
Fe, Rb and Cs more likely to enter the liquid, in contrast to B, Cu, As, Sb, Au and Li, which tend
to go into the vapor phase. For instance, spatially related sericitic alteration in early stage
stockworks of CuMo porphyry systems was caused by relatively low saline (4 wt.% NaCleq)
and medium density (0.6 g/cm3) fluid (Rusk et al., 2004). This fluid contains as much Cu as
1 wt.% prior to the saturation of chalcopyrite and pyrite. Both single-phase fluid inclusions and
two-phase inclusions are rich in Cu before saturation (0.2 < Cu/Na < 1, Redmond et al.,
2004 and Landtwing et al., 2005) in high-grade porphyry CuAuMo deposits.
Gold concentrations decrease from 36 ppm to 5 ppm in vapor (and from 50 ppm to 28 ppm in
brine) with a pressure drop from 1450 bar to 1100 bar in a brine + synthetic granite + magnetite
system (800 C, 11001450 bar, NNO buffer, Simon et al., 2005). The partition coefficients of
Au in vapor and brine are similar at conditions close to crucial pressure. Au strongly partitions
into brines at low pressure.
Low saline hydrothermal fluid is capable of carrying a great amount of Au at ppm-levels in

vapor inclusions in porphyry according to Ulrich et al. (1999). The process of cooling and
precipitation of pyrite and CuFe sulfide would rapidly consume reducing sulfur, triggering Au
to precipitate with CuFe sulfide (Heinrich, 2005). Consequently, this mechanism limits the
ability of low saline fluid to transport Au into the epithermal environment. Vapors released from
active volcanoes or shallow subvolcanic intrusions are usually rich in SO2, H2S and HCl. As
such, they can produce acidic fluids during cooling that react with wall-rocks to form advanced
argillic alteration haloes (kaolinite, pyrophyllite and alunite) and induce intensive leaching the
wall-rock of epithermal Au Cu deposit (Landis and Rye, 2005). This magmatic vapor can
transport metal and precipitate it from the vapor phase directly. Advanced argillic alteration takes
place prior to the deposition of ore-forming metals involved in late-stage aqueous liquid or
mediumlow saline fluid in most high-sulphidation epithermal systems.
5. Controls of sulfide on gold occurrences

The crystallization or dissolution of silicate minerals has an insignificant effect on the form of
Au in granitic magma, because most such gold is generally hosted in sulfides. Au behaves as an
incompatible element, and tends to concentrate in residual melts in which sulfur dissociates.
Experiments have demonstrated that Au is hosted in sulfide minerals with the following
decreasing order of Au concentration: bornite > chalcopyrite > pyrrhotite > pyrite (Cygan and
Candela, 1995, Jugo et al., 1999 and Simon et al., 2000). An experiment on a pyrrhotite ISS
(intermediate solid solution) granitic melt Au system (850 C, 100 MPa) has shown that most
Au separated from the melt would enter into the ISS rather than pyrrhotite (Jugo et al., 1999).
Experiments at 700 C and 140 MPa have demonstrated that pyrite can hold 6 ppm Au in a Au-
saturated chloride solution (Cygan and Candela, 1995), in contrast to chalcopyrite (3000 ppm
Au), pyrrhotite (9 ppm Au), and magnetite (3 ppm Au; Simon et al., 2000). Magnetite
contains 3 ppm Au, whereas quartz contains only 0.5 ppm Au in a Au-saturated, sulfur-poor
water vapor brine silicate melt system (800 C, 140 MPa, NNO buffer, Simon et al., 2003).
Gold is primarily hosted in chalcopyrite, arsenopyrite, pyrrhotite and pyrite in most hydrothermal
gold deposits, and its concentration in sulfide varies to a great extent (Morey et al.,
2008 and Large et al., 2009). Au content can be varied (0.071.96 ppm) within even single
grains. Yang et al. (2006) demonstrated that Au concentrations in pyrite within granite can range
from <0.02 to 21 ppm. The Au concentration is much less varied in pyrrhotite (<0.020.34 ppm)
than in pyrite. In fine-grained veins, Au concentration in chalcopyrite ranges from below
detection limit to 5.33 ppm, but Au in pyrite that has replaced chalcopyrite can reach 21 ppm.
Gold generally occurs as micro-inclusions in over-saturated conditions (Reich et al., 2005). Au

and As are intimately related in arsenian pyrite with a linear relationship: cAu = 0.02
cAs + 4 105 (cAu and cAs represent the mole percentage of Au and As concentration,
respectively). The solid solution gold (Au+) enters arsenopyrite by replacing Fe2+ ( Tarnocai
et al., 1997 and Cabri et al., 2000). X-ray adsorption near edge structure, extended X-ray
adsorption fine structure, and secondary ion mass spectroscopy analyses on As-bearing pyrite
show that solid solution gold has two coordination species: Au0 and Au+. The Au+ can occur in
more than one form, including Au+ in vacancies in an unknown AuAsS complex and a
distorted Fe2+ octahedral place (Simon et al., 1999). If the mechanism that Au(HS) and Au(HS)2
is absorbed on the growing surface of As-rich pyrite is feasible (Widler and Seward, 2002), the
entrance of Au into As-bearing pyrite depends on its vacancies or surface defects. Thus, the
maximum solubility of Au is the function of As content of surface and available vacancies or
structure defects. The quasi-steady arsenian pyrite in Carlin-type and epithermal deposits has
abundant Au contents, because those pyrites are formed at low-temperatures (<250 C), in which
disequilibrium conditions and surface defects are pervasively developed.
Gold is generally transported as Au(HS) in under-saturated, sulfur-bearing fluids. As-bearing

pyrite crystallizes from Au under-saturated solutions in Carlin-type deposits according to the
following reactions (Reich et al., 2003):
Fe(S, As)2 + 2Au(HS) = Fe(S, As)2Au2S + H2S

Fe2+ + 2HAsS2 + 2Au(HS) + 2H2 = Fe(S, As) Au2S + 3H2S + 2H+
The above reactions are mainly controlled by the activity of H2S. The decrease of H2S caused by
boiling and/or alteration can enhance the crystallization and the entry of solid solution Au+. The
composition of As-bearing pyrite in Carlin-type and epithermal deposits has shown that the state
of gold is variable in the ore-forming fluid. Hydrothermal fluids forming epithermal deposits are
Au-saturated to a great extent, whereas those of Carlin-type are Au-undersaturated. The quasi-
steady As-bearing pyrite extracts Au+ from hydrothermal fluid by absorption. The capability of
As-bearing pyrite to absorb gold from under-saturated fluid is the key to forming large-scale
Carlin-type deposits.
6. Gold precipitation
Exceptionally extensive natural processes are required to concentrate gold from crustal
background levels into gold deposits. For example, four thousand tonnes of gold have been
mined from the 300 km by 200 km Abitibi greenstone belt of Canada (Kerrich, 1999). An
estimated 1000 km3 of aqueous fluids with a starting temperature of 500 C must have leached
this huge block, transported gold as an aqueous species, and become channeled along faults
where gold precipitated with quartz in vein deposits over the temperature interval of 400300 C
(Kerrich, 1999).
Gold mineralization in most shear zones is post-peak metamorphism and involves a multi-stage
alteration event accompanied by gold mineralization through continuous fluid flow over a long
period of time. The f(O2) decrease was the dominant cause of gold precipitation from the fluid
containing Au(HS)2 in shear zone. Precipitation of thin films of graphite in most shear zones is
interpreted to have been the result of heterogeneous reaction between CO2 and CH4.
Simultaneous entrapment of aqueous and carbonic inclusions in auriferous laminated quartz
veins in different gold deposits (e.g., Zhu et al., 2001 and Pal and Mishra, 2002) was due to
unmixing of an initial H2OCO2 fluid at lower temperature. Accordingly, gold precipitation was
primarily due to a decrease in S in the aqueous part, a consequence of phase separation related to
cyclic decompression events.
Gold precipitation in shear zones can happen in different ways. For example, studies at Sunrise
Dam gold deposit of western Australia have defined distinct relationships between the
orientation and style of orebodies and their host structures (McLellan et al., 2007 and Baker
et al., 2010). The orebodies formed in response to multiple episodes of deformation (from D1 to
D4). Many structures were created during D1 and D2 shortening (the early episodes of
deformation), whereas the bulk of the gold was deposited during D3 and D4 (the episodes of
extensional deformation following the shortening episodes). The bulk of the high-grade
mineralization was formed during D4 that produced both steep and flat veins and breccias.
The modeled location of the solvus and estimated pT conditions for the early CO2H2O fluids
suggest that a pressure drop alone would not cause the fluids to enter the two-phase field. It
seems more likely that a pressure decrease combined with a drop in temperature below 300 C
would have been an important factor. Exhumation may have been one such factor in changing
the structural regime and pT conditions. Similar fluid evolution and gold precipitation
mechanism have been described in the Tianger region of Chinas Tianshan Mountains ( Zhu
et al., 2007b). Three stages have been identified in the Tianger gold deposits. Stage I occurs at a
depth of 10 km under conditions of the amphibolite facies. Stage II, as constrained by
metamorphic facies, is represented by zoisite amphibolites in mylonitized granite and the
reaction of albite + 4 anorthite + 2H2O = pargasite + 2 zoisite + 2 quartz. Stage III,
corresponding to major gold precipitation, represents brittle deformation following the ductile
shear processes.
The giant Muruntau gold deposit in Uzbekistan, located in the southwest Tianshan mountains
and hosted in Early Paleozoic black carbonaceous shales, is controlled by huge shear zones
(Drew et al., 1996, Graupner et al., 2000 and Bierlein and Wilde, 2010). A late-stage mineral
assemblage consisting of quartznative goldamesitesericitecalcitedolomitepyriteapatite
appears to be related to the high to medium temperature alteration of wall-rocks. The ReOs age
of gold-bearing arsenopyrite (290 Ma) overlaps regional magmatism in the Muruntau (Morelli
et al., 2007). The analyses of noble gas, carbon isotopes, and halogen elements in fluids included
in the hydrothermal minerals related to gold mineralization have illustrated that the dominant He
comes from the continental crust, whereas the noble gases mostly originated from the
atmosphere (Graupner et al., 2006). Studies on Os initial values and the He isotopes of fluid
inclusions in gold-bearing arsenopyrite show that the values of non-radiogenic Os and 3He/4He
ratios are higher than that of the crustal reservoir (Morelli et al., 2007). This suggests that
mantle-derived sources contributed to the ore-forming fluid. Gold exceeding 6000 t gathered in
the Muruntau deposit. This requires a prolonged fluid evolution involving elements such as Os,
He, Au of various origin and sources to evolve into ore-forming fluid during a complex crust
mantle interaction. Shear zones that controlled gold deposits are principal features in the central
Asia metallogenic region (e.g., Yang et al., 2007, Zhu et al., 2007a, Zhu et al.,
2007b and Graupner et al., 2010) and, thus, remain the major targets for gold exploration (e.g.,
Xiao et al., 2010 and Zhu, 2011).
7. Conclusions
The local enrichment of gold within the deposits is controlled by mineral precipitation from an
aqueous fluid. The change of physicochemical conditions such as temperature, pressure, oxygen
fugacity, and sulfur fugacity are effective mechanisms for gold precipitation. Gold tends to be
concentrated in the vapor phase of fluids at high temperatures and pressures. The AuAs and
AuSb associations are common in gold deposit. Hydrothermal fluids forming epithermal gold
deposits are Au-saturated in most cases, whereas deposits of Carlin-type are Au-undersaturated.
Quasi-steady As-bearing pyrite extracts solid solution Au from hydrothermal fluids through
absorption. Research continues on the geochemistry of gold deposits for the purpose of tracing
the origin of ore-forming fluids, the source of gold, and the transportation of gold and other
related ore-forming elements including Si, S, F, Cl, As and Ag. With the application of new
techniques, present and future high demands for gold, it is clear that new geochemical data and
prospecting approaches will greatly facilitate gold explorations.
Acknowledgements
Our thanks are due to the National Natural Science Foundation of China (Nos. 41072041,
40821002) for financial support. Prof. Gregory Davis (University of Southern California) and
anonymous reviewers who offered insightful and detailed comments on the earlier manuscript
have helped us to complete this paper and, are, therefore gratefully acknowledged.
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Fasa Hidrotermal
Hidrothermal adalah larutan sisa magma yang bersifat "aqueous" sebagai hasil differensiasi magma.
Hidrothermal ini kaya akan logam-logam yang relatif ringan, dan merupakan sumber terbesar (90%) dari
proses pembentukan endapan. Berdasarkan cara pembentukan endapan, dikenal dua macam endapan
hidrothermal, yaitu :
Cavity filing, mengisi lubang-lubang (opening-opening) yang sudah ada di dalam batuan.
Metasomatisme, mengganti unsur-unsur yang telah ada dalam batuan dengan unsur-unsur baru dari
larutan hidrothermal.
Berdasarkan cara pembentukan endapan, dikenal beberapa jenis endapan hidrothermal, antara lain
Ephithermal (T 00C-2000C), Mesothermal (T 1500C-3500C), dan Hipothermal (T 3000C-5000C). Setiap
tipe endapan hidrothermal diatas selalu membawa mineral-mineral yang tertentu (spesifik), berikut
altersi yang ditimbulkan barbagai macam batuan dinding. Tetapi minera-mineral seperti pirit (FeS2),
kuarsa (SiO2), kalkopirit (CuFeS2), florida-florida hampir selalu terdapat dalam ke tiga tipe endapan
hidrothermal.
Paragenesis endapan hipothermal dan mineral gangue adalah : emas (Au), magnetit (Fe3O4), hematit
(Fe2O3), kalkopirit (CuFeS2), arsenopirit (FeAsS), pirrotit (FeS), galena (PbS), pentlandit (NiS), wolframit :
Fe (Mn)WO4, Scheelit (CaWO4), kasiterit (SnO2), Mo-sulfida (MoS2), Ni-Co sulfida, nikkelit (NiAs),
spalerit (ZnS), dengan mineral-mineral gangue antara lain : topaz, feldspar-feldspar, kuarsa, tourmalin,
silikat-silikat, karbonat-karbonat
Sedangkan paragenesis endapan mesothermal dan mineral gangue adalah : stanite (Sn, Cu)
sulfida, sulfida-sulfida : spalerit, enargit (Cu3AsS4), Cu sulfida, Sb sulfida, stibnit (Sb2S3), tetrahedrit
(Cu,Fe)12Sb4S13, bornit (Cu2S), galena (PbS), dan kalkopirit (CuFeS2), dengan mineral-mineral
ganguenya : kabonat-karbonat, kuarsa, dan pirit.
Paragenesis endapan ephitermal dan mineral ganguenya adalah : native cooper (Cu), argentit
(AgS), golongan Ag-Pb kompleks sulfida, markasit (FeS2), pirit (FeS2), cinabar (HgS), realgar (AsS),
antimonit (Sb2S3), stannit (CuFeSn), dengan mineral-mineral ganguenya : kalsedon (SiO2), Mg karbonat-
karbonat, rhodokrosit (MnCO3), barit (BaSO4), zeolit (Al-silikat).

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Geochemistry of hydrothermal gold deposits:

Modified from Seedorff et al., 2004.

3KAlSi3O8 K-feldspar + 2H+ = KAl3Si3O10(OH)2 muscovite + SiO2 + 2K+

3. The geochemical behavior of gold in hydrothermal

2Au(HS)2 + H2O 2Au + 4HS + 2H+ + 0.5O2

2Au(HS)2 + H2O + 7.5O2 2Au + 4SO42 + 6H+

A large numbers of deposits with a AuSb element association develop in an alkaline

Au + mHCl + nH2O = AuClm(H2O)n + 0.5mH2

Au + HCl + NaCl = NaAuCl2 + 0.5H2

The solubility of Au as a function of NaCl/(NaCl + HCl) supports the suggested stoichiometry of

4. Transportation of Au through vapor in porphyry system

Low saline hydrothermal fluid is capable of carrying a great amount of Au at ppm-levels in

5. Controls of sulfide on gold occurrences

Gold generally occurs as micro-inclusions in over-saturated conditions (Reich et al., 2005). Au

Gold is generally transported as Au(HS) in under-saturated, sulfur-bearing fluids. As-bearing

Fe(S, As)2 + 2Au(HS) = Fe(S, As)2Au2S + H2S

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