See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/326286065

The solubility of silver in magmatic fluids: Implications for silver transfer to

the magmatic-hydrothermal ore-forming environment

Article  in  Geochimica et Cosmochimica Acta · July 2018

DOI: 10.1016/j.gca.2018.06.041

CITATIONS READS

0 290

2 authors, including:

Yiwei Yin
University of Toronto
1 PUBLICATION   0 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

The solubility of silver in magmatic fluids: Implications for Ag enrichment in hydrothermal ore deposits View project

The effect of pressure and temperature on solubility of Au, Cu and Ag in magmatic hydrothermal fluids View project

All content following this page was uploaded by Yiwei Yin on 15 August 2018.

The user has requested enhancement of the downloaded file.

 Available online at www.sciencedirect.com

ScienceDirect
Geochimica et Cosmochimica Acta 238 (2018) 235–251
www.elsevier.com/locate/gca

The solubility of silver in magmatic fluids: Implications for

silver transfer to the magmatic-hydrothermal ore-forming
environment
Yiwei Yin, Zoltán Zajacz ⇑
Department of Earth Sciences, University of Toronto, 22 Russell St., Toronto, ON M5S 3B1, Canada

Received 10 October 2017; accepted in revised form 30 June 2018; Available online 9 July 2018

Abstract

Silver is a common and economically important constituent of many magmatic-hydrothermal ore deposits, yet little is
known about its mobility during magma degassing. We performed experiments to determine the effect of various chemical
components (NaCl, KCl, LiCl, HCl, CaCl2, H2S) on the solubility and speciation of Ag in high-temperature, low-density flu-
ids (
0.38–0.54 g/cm3). The experiments were conducted at T = 900 °C, P = 2000 bar and oxygen fugacity (fO2) of 0.5 log
units below Ni-NiO buffer (NNO-0.5) in rapid-quench Molybdenum-Hafnium Carbide externally-heated pressure vessel
assemblies. The fluid phase was sampled at run conditions by the entrapment of synthetic fluid inclusions (SFI) in in situ frac-
tured quartz chips. As capsule material, Au97Ag2Cu1 alloy was used, which imposed an Ag activity of 0.005. The apparent Ag
solubility, defined as the equilibrium concentration of Ag in the fluid phase at an Ag activity of 0.005, exponentially increases
as a function of total chloride concentration in the NaCl-H2O and NaCl-HCl-H2O systems. In the mixed NaCl-HCl system, at
a fixed total Cl concentration of 1 mol/kg (1 m) H2O and varying NaCl/HCl ratios, the apparent solubility of Ag reaches a
maximum (432 ± 123 lg/g) at equal NaCl and HCl concentration (0.5 m each) and then decreases towards both end-members
(1 m for NaCl or HCl) following a parabolic function. Apparent silver solubilities predicted using the HKF model and
thermodynamic properties for traditional Ag-chloride and bisulfide complexes greatly underestimate the measured values.
Model calculations suggest that instead of charged AgCl 2 , a neutral NaAgCl2 species is the dominant dissolved Ag species
in S-free, chloride-bearing fluids with the additional presence of NaAgHSCl in S-bearing fluids. Comparison of the solubility
data in high-temperature fluids to measured Ag solubilities in silicate melts suggests that efficient Ag partitioning into
magmatic fluids will only take place when the composition of the silicate melt is felsic enough (rhyodacitic to rhyolitic),
similarly to the behavior of Cu but in contrast to that of Au.
Ó 2018 Elsevier Ltd. All rights reserved.

1. INTRODUCTION 2005; William-Jones and Heinrich, 2005; Wilkinson, 2013;

Silver is one of the major precious metals occurring in
magmatic-hydrothermal ore deposits such as porphyry
and epithermal-type mineralizations (e.g. Simmons et al.,
⇑ Corresponding author.
E-mail addresses: yiwei.yin@mail.utoronto.ca (Y. Yin), zajacz@
es.utoronto.ca (Z. Zajacz).
Zajacz et al., 2013). During the ascent and solidification
of magma in the Earth’s crust, crystallization and decom-
pression lead to the exsolution of a low-density fluid phase,
which contains water, various sulfur, carbon and chlorine
species and metals (Heinrich et al., 1999; Pokrovski et al.,
2005; Sillitoe, 2010; Wilkinson, 2013; Richards, 2011;
Hedenquist and Lowenstern, 1994). Many economically
important metals, such as Au, Cu and Mo are known to

https://doi.org/10.1016/j.gca.2018.06.041
0016-7037/Ó 2018 Elsevier Ltd. All rights reserved.
236 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
preferentially partition into such magmatic fluids, which in
turn precipitate ore minerals in the vicinity of the active
magma reservoirs due to cooling, vapor-liquid separation
and reaction with the country rocks. Studies on natural
samples have demonstrated that in many systems Ag is
transferred by fluids of probably magmatic origin to the
shallow level ore-forming environment (e.g. King et al.,
2014; Cicek and Oyman, 2016; Ke et al., 2017; Sabeva
et al., 2017). Yet, no experimental data exists that would
allow to assess the mobility of Ag in magmatic fluids and
predict the timing and efficiency of silver extraction from
magmas. Therefore, the investigation of silver solubility
and speciation in magmatic hydrothermal fluids will lead
us to better understanding of the formation of ore deposits
with Ag enrichment.
Silver hydrosulfide and Ag chloride complexes are
known to be the dominant Ag species in hydrothermal solu-
tions at relatively low temperature (<500 °C) conditions.
The stabilities of these are controlled by pH and the con-
centration of various chloride and sulfur species in the
hydrothermal fluids (Akinfiev and Zotov, 2001). Numerous
experimental studies have investigated Ag solubility in such
‘‘low- temperature” hydrothermal solutions (e.g. Seward,
1976; Webster, 1986; Gammons and Barnes, 1989;
Gammons and Williams-Jones, 1995a,b; Seward et al.,
1996; Gammons and Yu, 1997; Migdisov et al., 1999;
Stefansson and Seward, 2003; Simon et al., 2008; Simon
et al., 2009; Liu et al., 2012; Migdisov and Williams-
Jones, 2013; Pokrovski et al., 2013; Akinfiev and Zotov,
2016).
In chloride-bearing fluids, the di-chlorosiliver (I) com-
plex, AgCl 2 , was proposed to be the predominant species
at above 270 °C (Seward, 1976; Gammons and Williams-
Jones, 1995a,b). Later studies using in-situ X-ray absorp-
tion spectroscopy and first-principles molecular dynamics
calculations proposed that AgCl 2 was the dominant Ag
species in the hydrothermal fluids up to T = 450 °C and
P = 750 bar (Liu et al., 2012; Pokrovski et al., 2013).
Migdisov et al. (1999) conducted experiments to determine
the solubility of chorargyrite (AgCl) in water vapor at tem-
peratures (T) of 300–360 °C and pressures (P) up to 180
bar. Migdisov and Williams-Jones (2013) extended the P-
T range up to 240 bar and 440 °C. Based on their experi-
mental data from this P-T range, they derived thermody-
namic properties for various Ag species and model
calculated Ag solubilities up to T = 800 °C, P = 900 bar
to predict solubility of Ag in aqueous fluids. In addition
to traditional Ag complexes, they mentioned the possibility
of the existence of HAgCl2 in such high-T fluids (Migdisov
and Williams-Jones, 2013).
In S-bearing systems, Seward (1976) first inferred Ag
(HS) 2 as the dominant species in neutral hydrothermal
solutions at 300 °C, whereas Webster (1986) suggested the
existence of Ag-hydrosulfide species at ambient tempera-
ture in reducing alkaline solutions. The dominance of the
Ag(HS) 2 species has later been shown by further experi-
ments up to T = 300–400 °C P = 500 bar (Gammons and
Barnes, 1989; Stefansson and Seward, 2003).
Despite the abundance of data at relatively low P-T
hydrothermal conditions, only one study addressed the
solubility of Ag at P-T conditions relevant for the degassing
of upper crustal magma reservoirs. Simon et al. (2009)
performed experiments to investigate the partitioning
behavior of Ag in vapor-brine-rhyolite melt assemblage at
T = 800 °C and P = 100 and 1400 bar and suggested that
magma degassing in the upper crust is responsible for the
formation of the silver tonnage of many porphyry-type
and perhaps epithermal ore deposits. However, this study
was restricted to a system with sub-critical and S-free fluids
and did not systematically address the effect of fluid
compositional vectors.
In this study, we present systematic experimental data
on the solubility of Ag in chloride- and S-bearing aqueous
fluids at T = 900 °C and P = 2000 bar. The fluids were sam-
pled at the experimental P-T conditions using the synthetic
fluid inclusion (SFI) technique. The experiments were con-
ducted along compositional vectors that allowed us to best
constrain the speciation of Ag in the fluids, and thus the rel-
ative stability of various Ag complexes. The apparent solu-
bility data was compared to those predicted based on the
thermodynamic properties of traditional Ag-complexes,
and new Ag-complexes are proposed to resolve the mis-
match between the observed and predicted Ag solubilities.
The Gibbs-free energies of formation for these complexes
have been constrained allowing the extrapolation of the
experimental data to any fluid composition at the studied
P-T conditions. These data have been combined with previ-
ously published Ag solubility data for silicate melts to
derive model fluid/melt partition coefficients for Ag and
assess the efficiency of Ag extraction during magma degas-
sing in the upper crust.
2. METHODS
2.1. Experimental methods
We used the synthetic fluid inclusion technique (Sterner
and Bodnar, 1984) to sample the fluid phase at run condi-
tions as high P-T fluids are not quenchable. The experimen-
tal method is similar to that applied by Zajacz et al. (2010)
and Zajacz et al. (2011). The experiments were conducted at
run conditions of 2000 ± 20 bar and 900 ± 10 °C in rapid-
quench, externally-heated molybdenum-hafnium carbide
(MHC) pressure vessel assemblies at the University of Tor-
onto. The capsules containing the experimental phase
assemblage were made of Au97Ag2Cu1 alloy tubing (in mass
proportions), which imposed a constant Ag activity of
0.005 calculated using FactSage (Factsage.com). The
vapor-like low-density (
0.38–0.54 g/cm3) supercritical flu-
ids were trapped as SFI in cylindrical quartz chips. The
quartz was fractured in situ during the experiment after
18 h equilibration of the fluid phase with the capsule alloy.
For this purpose, the vessel-furnace assembly was rotated
to drop the capsule to the water cooled end and then back
to the hot end of the vessel. The thermal shock generated a
dense fracture network in the quartz, which was subse-
quently allowed to heal for 24 h allowing this way the for-
mation of SFI. An oxygen fugacity (fO2) value 0.5 log units
below that of the Ni-NiO buffer (NNO-0.5) was imposed by
admixing small concentrations of H2 gas into the Ar
Table 1
The composition of the fluid phase in the experiments and the measured Ag concentrations in the run product SFI. For chloride components, the concentrations in the starting solutions are shown,
whereas the amounts of various S species were calculated for the experimental P, T conditions using HCh.

Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251

Exp. Chloride components S (wt%) log fO2 cH2S(aq) cSO2(aq) cHS(aq) Measured Ag concentration Number of
no. (mol/kg H2O) (bars) (mol/kg H2O) (mol/kg H2O) (mol/kg H2O) (lg/g) ± 1r error measured SFI
#15-1 NNO-0.5 <1.05 7
#14-1 0.5 m NaCl NNO-0.5 11.7 ± 1.7 7
#13-1 1 m NaCl NNO-0.5 29 ± 2 5
#14-2 2 m NaCl NNO-0.5 73 ± 18 7
#13-2 4 m NaCl NNO-0.5 185 ± 21 5
#14-3 0.75 m NaCl, 0.25 m HCl NNO-0.5 295 ± 59 16
#16-4 0.5 m NaCl, 0.5 m HCl NNO-0.5 432 ± 123 17
#15-2 0.25 m NaCl, 0.75 m HCl NNO-0.5 325 ± 54 9
#17-1 0.9 m NaCl, 0.1 m HCl NNO-0.5 118 ± 13 8
#15-4 1 m HCl NNO-0.5 89 ± 26 8
#19-1 0.125 m HCl, 0.125 m NaCl NNO-0.5 42 ± 14 8
#17-4 0.25 m HCl, 0.25 m NaCl NNO-0.5 123 ± 32 11
#16-1 7.84 NNO-0.5 2.65 2.41  102 2.13  105 5.7 ± 1.9 10
#21-2 0.17 m CaCl2 7.43 NNO-0.5 2.54 2.31  102 2.21  105 8.1 ± 2.7 8
#20-1 0.4 m LiCl 7.82 NNO-0.5 2.71 2.42  102 2.12  105 40 ± 9.1 15
#17-3 0.4 m KCl 7.84 NNO-0.5 2.68 2.41  102 1.77  105 102 ± 25 10
#17-2 0.4 m NaCl 7.82 NNO-0.5 2.73 1.73  102 5.1  103 74 ± 18 21
#19-2 0.4 m NaCl 4.34 NNO-0.5 1.46 9.6  103 3.1  103 52 ± 12 11
#19-3 0.4 m NaCl 2.08 NNO-0.5 0.68 4.6  103 1.6  103 26 ± 4.4 7
#19-4 0.4 m NaCl 1.06 NNO-0.5 0.34 2.4  103 8.6  104 19 ± 2.3 14
#21-1 0.33 m NaCl, 0.07 m HCl 7.76 NNO-0.5 2.68 2.40  102 1.63  103 87 ± 15 13
   5
(a) The molality of SO2
4 (aq), HSO4 (aq) and NaSO4 (aq), NaHSO4(aq), HSO3 are all predicted to be below 10 for all experiments and therefore are not reported in the table.

237
238 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251

pressure medium. The H2 gas in turn diffused through the

capsule walls and reacted with the water inside to impose
fO2 inside the capsule through the decomposition of water.
The equilibrium constant of water decomposition reaction
was calculated using thermochemical data from the
JANAF database (Chase et al., 1985) to obtain the desired
fH2 inside the capsule. The amount of H2 to be loaded in
the pressure medium to achieve this fH2 was calculated tak-
ing into account non-ideal mixing in the Ar-H2 gas mix
both at high P-T (using the algorithm of Churakov and
Gottschalk, 2003) and at ambient T upon loading the vessel
[using equation of states of Ar and H2 from the NIST Ther-
mochemical Properties of Fluids database based on the
data of Tegeler et al. (1999) and Leachman et al. (2009)].
The accuracy of the method was confirmed by Zajacz
et al. (2010) using CoPd alloy redox sensors within 0.3
log units of fO2. The same study showed that about 0.3–
0.4 log unit/day increase in fO2 is experienced due to diffu-
sive hydrogen loss through the vessel walls from the pres-
sure medium at 1000 °C. For the experiments of this
study at 900 °C, this loss is likely significantly slower.
The starting solutions consisted of alkali and alkali-
earth chlorides (NaCl, KCl, LiCl and CaCl2), H2O,
H2SO4 and HCl (Table 1). High purity salts (>99.9%) and
reagent grade acids were used for the preparation of the Fig. 1. The capsule design used in the experiments.
solutions. All these chemicals were added to an aqueous
starting solution with
300 lg/g Cs and Rb in the form The pressure was monitored by factory-calibrated pressure
of chlorides to serve as internal standards for the quantifi- transducers and is constrained with better than 20 bar accu-
cation of Laser Ablation Inductively Coupled Plasma Mass racy and precision.
Spectrometry (LA-ICP-MS) analysis of the SFI. The Cs At first, the vessel was flushed with 20 bar H2 gas at least
and Rb concentrations were recalculated for each experi- 8 times to remove all traces of air, then pressurized to 2.5 ±
ment taking into account the dilution by the later added 0.025 bar with pure H2 (99.999% purity). Subsequently, it
solutes. was pressurized to 1250 bar using Argon (99.999% purity).
Considering the physical aspects of the capsule configu- Upon heating to 900 °C, the pressure increased to 2000 ±
ration (e.g. density of the fluid, internal volume), an 20 bar.
approximately 4–6 mm long and 2.2 mm in diameter,
inclusion-free cylindrical quartz chip was placed into a 2.2. Analytical methods
Au97Ag2Cu1 capsule (3 mm OD, 2.7 mm ID) along with
about 5 ll aqueous solution and 3 mg silica gel. The cap- The fluid inclusions were analyzed by Laser Ablation
sules were welded using a PUK 3 Professional welder and Inductively Coupled Plasma Mass Spectrometry (LA-ICP-
checked for potential weight loss by weighing before and MS) at the Magmatic and Ore-Forming Processes Research
after welding. Capsules showing a weight change more than Laboratory, Department of Earth Sciences, University of
2% of the total loaded fluid mass were discarded. Subse- Toronto. A NWR-193 UC laser ablation system attached
quently the capsules were held at 130 °C for at least 0.5 h to an Agilent 7900 quadrupole mass spectrometer was used.
and then weighed again to confirm the integrity of the Each analysis block consisted of at most 16 SFI analyses
welds. Two or four capsules were placed into a 5 mm bracketed by 2–2 external standard analyses at the begin-
OD, 4.6 mm ID holder made of the same alloy. This outer ning and the end. The NIST 610 glass was used as an exter-
capsule was sealed at only one end and only crimped on the nal standard. A He carrier gas flow 1 l/min was used and
other as it was only used to hold the smaller capsules the instrument was tuned to ThO/Th  <0.3%, Mass
together. The outside surface of the capsules was impreg- 21/42
Ca  <0.3%, and 238U/232Th of 1.0–1.1 using the NIST
nated with fine (<2 lm) ZrSiO4 powder to prevent them 610 glass. Both 107Ag and 109Ag isotopes were detected with
from sticking together at high T. Fig. 1 shows the schematic a dwell time of 40 ms, whereas the dwell time for all other
of the capsule design. analytes were set at 10 ms. The quantification of the data
The experimental T was measured using K-type thermo- was conducted using the software SILLS (Guillong et al.,
couples attached to the external surface of the Inconel 2008). The known Cs concentrations were used as an inter-
sheath protecting the MHC vessel from oxidation. The nal standard to quantify the SFI compositions. The Rb/Cs
internal temperature in the vessel was cross calibrated ratio in the quantified fluid compositions was 1.02 ± 0.04
against this external thermocouple beforehand. The T gra- which is very close to the nominal value of 1.00. Also, the
dient over the longest capsule length (18 mm) was <10 °C resulting Na concentrations are in good agreement with
and the T was constrained with better than 5 °C accuracy. the nominal values, demonstrating the quality of the data.
 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251 239

The measured Ag concentrations are shown in Table 1,
whereas all measured element concentrations are shown
in Electronic annex EA-1.
Supplementary data associated with this article can be
found, in the online version, at https://doi.org/10.1016/j.
gca.2018.06.041.
3. RESULTS
3.1. Fluid inclusion petrography
The thermal shock applied during the experiment led to
the development of a dense fracture network, and thus to
the formation of a large number of SFI by the subsequent
healing of these fractures. The SFI are typically somewhat
elongated oval shaped, with their long and short axes being
in the range of 10–50 and 5–20 lm, respectively (Fig. 2).
The fractures were less completely healed in experiments
with HCl-rich fluids, yet numerous well-formed SFI were
found in the run products of these experiments as well.
Although, these inclusions were typically smaller in diame-
ter (<20 lm) than those from the other experiments.
The apparent solubility of Ag in pure water (exp. #15-1)
is below a detection limit of 1 lg/g, which is negligible com-
pared to the concentrations measured in Cl and S-bearing
fluids indicating that hydroxyl complexes of Ag are rela-
tively unstable. As alkali-chlorides are major components
of magmatic fluids, we systematically investigated the solu-
bility of Ag in NaCl-H2O fluids as a function of NaCl
concentration (cNaCl). The apparent solubility of silver
increased from 11.7 ± 1.7 lg/g to 185 ± 21 lg/g as cNaCl
increased from 0.5 to 4 mol/kg H2O. On a log cAg versus
log cNaCl diagram, the data show a linear distribution with
a slope of 1.33 ± 0.01 (Fig. 3). Next, we studied how Ag
solubility responds to HCl addition to the system. For this
purpose, we conducted experiments with NaCl-HCl-H2O

3.2. The apparent solubility of silver as a function of fluid

composition

The measured Ag concentrations in the SFI are shown

in Table 1 along with the composition of the fluid phase.
It is important to emphasize again that these are apparent
Ag solubilities at an Ag activity of 0.005 imposed by the
capsule alloy. This means, that assuming Henrian behavior,
the true Ag solubility would be 200 times higher than the
measured values. However, at those concentrations, dis-
solved Ag-species would become major constituents of the
fluid phase, and thus Ag solubility itself would affect the Fig. 3. The apparent Ag solubility in H2O-NaCl fluids as a
physical-chemical properties of the fluid making meaning- function of NaCl concentration. The errors bars show one times
ful data interpretation impossible. Whereas, at the applied the standard deviation of the SFI compositions from each
experiment (1 r error). The line is an error weighted linear fit to
reduced Ag activity, Ag remained a trace component for
the data, the fit equation is shown in the top left corner.
all studied fluid compositions.

a b

Vapor inclusions

20 μm 30 μm

Fig. 2. Plane polarized transmitted light microscope images of synthetic fluid inclusions in the run product quartz cylinders. The dark vapor
bubble and the transparent liquid phase forms as the trapped originally supercritical single-phase fluid enters the two-phase, vapor-liquid
immiscibility field upon quenching; (a) close-up image of SFI from experiment #14-1, in which the fluid contained 0.5 m NaCl; (b) SFI trail
from experiment #19-4, in which the fluid contained 0.4 m NaCl and 1.06 wt% S.
240 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251

fluids with stepwise varying HCl/NaCl ratio while main-

taining a constant total chloride concentration of 1 m.
The measured apparent Ag solubility showed a parabolic
distribution as a function of the NaCl/(NaCl + HCl)
ratio (Fig. 4). The maximum Ag concentration
(432 ± 123 lg/g) was observed at equal NaCl and HCl
concentration of 0.5 m, whereas at the 1 m HCl and 1 m
NaCl end members, 89 ± 26 lg/g and 29 ± 2 lg/g apparent
Ag solubilites were measured, respectively. Additionally, 3
experiments were performed at a fixed 1:1 NaCl/HCl
ratio with an increasing total chloride concentration of
0.25 m, 0.5 m and 1 m. The apparent solubilities of Ag
are 42 ± 14 lg/g, 123 ± 31 lg/g and 432 ± 123 lg/g in
these fluids, which is shown on a log–log plot as a function
of total chloride concentration define a linear fit with a
slope of 1.69 ± 0.09 (Fig. 5).
As sulfur is also an important constituent of magmatic
fluids, we also performed experiments in the H-O-S-
alkali/alkali-earth chloride system. At our experimental Fig. 5. The apparent Ag solubility in NaCl-HCl-H2O fluids as a
run conditions, more than 99% of the S is predicted to be function of total chloride concentration at a constant NaCl/HCl
present as H2S in the fluid phase based on thermodynamic ratio of 1. The errors bars show one times the standard deviation of
calculations discussed in detail in section 4.3 (Table 1). the SFI compositions from each experiment (1 r error). The line is
Therefore, from here on, we will refer to the S component an error weighted linear fit to the data, the fit equation is shown in
the top left corner.
of the fluid phase as H2S, despite that minor SO2 is also pre-
dicted to be present, and the additional presence of minor
concentrations of S 3 is also possible (Pokrovski and response to the addition of 0.4 m NaCl. In addition, we per-
Dubrovinsky, 2011; Pokrovski and Dubessy, 2015). In formed 4 experiments varying cH2S from 0.34 m to 2.73 m
H2O-H2S fluids at cH2S = 2.65 m (7.84 wt% S in the fluid), while maintaining a constant NaCl concentration of 0.4 m.
the apparent solubility of Ag is only 5.7 ± 1.9 lg/g, which is The apparent solubility of Ag increased from 19 ± 2.3 lg/g
much lower than the values observed in most chloride- to 74 ± 18 lg/g in this set of experiments. To be able to
bearing fluids. As the presence of alkali-chlorides in assess Ag solubility resulting from S-bearing complexes,
H2S-bearing fluids were shown to significantly increase we deducted the Ag solubility value determined for the S-
the solubility of Au by the formation of alkali-Au- free 0.4 m NaCl fluid from these values. The results are
hydrosulfide complexes (Zajacz et al., 2010), we tested shown in Fig. 6. A linear correlation between log cH2S
how the addition of NaCl affects the solubility of Ag in and log cAg can be observed with a slope of 1.01 ± 0.07.
H2S-bearing fluids. At cH2S = 2.7 m, the apparent solubil-
ity of Ag increased from 5.7 ± 1.9 lg/g to 74 ± 18 lg/g in

Fig. 6. The apparent Ag solubility in NaCl-H2S-H2O fluids as a

Fig. 4. The apparent Ag solubility in NaCl-HCl-H2O fluids as a
function of NaCl/(NaCl + HCl) at a constant NaCl + HCl = 1 m.
The errors bars show one time the standard deviation of the SFI
compositions from each experiment (1 r error). The line is an error
weighted second order polynomial fit to the data, the fit equation is
shown in the top left corner.
function of cH2S. The errors bars show one times the standard
deviation of the SFI compositions from each experiment (1 r
error). The line is an error weighted linear fit to the data, the fit
equation is shown in the top left corner. The one symbol showing
much lower Ag concentration at log cH2S = 0.43 is from the NaCl-
free experiment and is only shown to illustrate the effect of the
addition of 0.4 m NaCl on Ag solubility in H2S-rich fluids.
 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
Fig. 7. The graph shows the apparent Ag solubility in alkali
chloride-H2S-H2O system as a function of the effective ionic radii of
the cations at a fixed chlorine concentration of 0.4 m and cH2S of
2.7 m (7.8 wt% S content). The errors bars show one times the
standard deviation of the SFI compositions from each experiment
(1 r error).
On the same diagram, we also show the apparent Ag solu-
bility in the NaCl-free fluid at cH2S = 2.65 m to illustrate
the effect of NaCl addition on the stability of Ag-
hydrosulfide complexes. Even on this diagram, which is cor-
rected for the effect of Ag-chloride complexes on the mea-
sured total Ag concentrations, the increase in apparent
Ag solubility is about an order of magnitude in response
to the addition of 0.4 m NaCl. Thus, we decided to test if
other alkali or alkali-earth chlorides (i.e. KCl, LiCl and
CaCl2) have a similar effect on Ag solubility in H2S-
bearing fluids. These experiments were conducted at a fixed
cH2S of 2.68 m and Cl concentration of 0.4 m. The results
are plotted as a function of effective ionic radii of the
cations in Fig. 7. It is apparent, that the effect of alkali
metal chlorides on the solubility of Ag in H2S-bearing fluids
is increasing with their increasing ionic radii from Li to K,
whereas the presence of CaCl2 does not affect Ag solubility
at all. In addition, we also conducted an experiment to test
the effect of HCl on the solubility of Ag in H2S-bearing flu-
ids (exp. #21-1). In response to the partial replacement of
NaCl by HCl in the fluid at 0.4 m total Cl (0.33 m NaCl
– 0.07 m HCl) and cH2S = 2.68 m, the apparent solubility
of Ag increased from 74 ± 18 lg/g to 87 ± 15 lg/g.
4. DISCUSSION
4.1. Silver solubility in aqueous chloride-bearing fluids
The Cl/Ag atomic ratio in the dominant dissolved Ag
complexes can be inferred from the slope of the fitted line
on the log cNaCl versus log cAg plot (Fig. 3). Normally,
the slope would equal the Cl/Ag ratio, however, our exper-
imental system imposes a somewhat more complicated rela-
tionship. As AgCl2 was proposed to be the dominant Ag
complex at lower-T hydrothermal conditions by numerous
studies (Seward, 1976; Gammons and Williams-Jones,
1995a,b; Liu et al., 2012; Pokrovski et al., 2013), our
241
working hypothesis is that a Cl/Ag ratio of 2 is maintained
in the predominant complexes at magmatic T as well.
However, at magmatic temperatures, charged complexes
are unlikely to be predominant and are most likely replaced
by neutral species (Barnes, 1997) due to the low density and
low dielectric constant of the solvent (Pitzer, 1983). Neutral
Ag-chloride complexes can be envisaged either as AgCl
complex, ion pairs between AgCl 2 complex and alkali
metal cations forming (Na/K)AgCl2 species, or as HAgCl2
species. As the slope of the fit in Fig. 3 is larger than 1
(1.33), it seems unlikely that the dominant complex is AgCl.
Therefore, the most likely Ag complex in NaCl-H2O fluids
is NaAgCl2, which would form according to the following
mass action expression:
AgðsÞ þ 2NaClðaqÞ þ H 2 OðaqÞ
¼ NaAgCl2 ðaqÞ þ NaOH ðaqÞ þ 0:5H 2 ðgÞ ð1Þ
The NaOH produced in Eq. (1) would react with the
quartz present in the capsule forming some sort of
Na-silicate species, which we represent as Na2SiO3 in the
following reaction:
SiO2 ðsÞ þ 2NaOH ðaqÞ ¼ Na2 SiO3 ðaqÞ þ H 2 OðaqÞ ð2Þ
Combining Eqs. (1) and (2) yields the following mass
action expression:
AgðsÞ þ 2NaClðaqÞ þ 0:5SiO2 ðsÞ þ 0:5H 2 OðaqÞ
¼ NaAgCl2 ðaqÞ þ 0:5Na2 SiO3 ðaqÞ þ 0:5H 2 ðgÞ ð3Þ
The equilibrium constant of Eq. (3) can be expressed as
follows:
aNaAgCl2  aNa2 SiO0:5
3 fH 2
0:5
K3 ¼ ð4Þ
aAg  aNaCl  aH 2 O  aSiO0:5
2 0:5
2
By rearranging Eq. (4), one can obtain:
K 3  aAg  aNaCl2  aH 2 O0:5  aSiO0:5
aNaAgCl2  aNa2 SiO0:5
3 ¼
2
fH 0:5
2
ð5Þ
One must note that the quantity of the NaAgCl2 and
Na2SiO3 produced in the reaction are tied together by the
reaction stoichiometry. Therefore, assuming that the activ-
ity coefficients are close to 1, which is reasonable for neutral
species in aqueous solutions, Eq. (5) can be rewritten as:
K 3  aAg  aNaCl2  aH 2 O0:5  aSiO0:5
s  aNaAgCl2 1:5 ¼ 2
fH 20:5
ð6Þ
where s is a constant. By rearranging Eq. (6), we get:
!2=3
1 K 3  aAg  aNaCl2  aH 2 O0:5  aSiO0:5
aNaAgCl2 ¼ 2
s fH 0:5
2
ð7Þ
In the presence of quartz and the capsule alloy, both
SiO2 and Ag activities are fixed, and fH2O/fH2 varies very
little due to the nearly constant fH2 imposed by the pressure
medium and the relatively low dissolved solute concentra-
tions. Therefore, if NaAgCl2 is the dominant dissolved
242 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
Ag species in chloride-bearing fluids, the solubility of Ag is
expected to be proportional to aNaCl4/3. This is consistent
with the data shown in Fig. 3. As the activity coefficients for
neutral species can be expected to remain nearly constant, a
similar relationship is expected with the dissolved NaCl
concentration. The exponent of 1.33 (=4/3) would translate
to a slope of 1.33 on the log cNaCl vs. log cAg diagram
(Fig. 3), which is an exact match to the observed value.
As AgCl23 was proposed to be an abundant species in
hydrothermal fluids at T = 200–300 °C (Liu et al., 2012;
Pokrovski et al., 2013), we also considered the potential
presence of neutral Na2AgCl3 species. The formation of this
complex could be described by the following mass action
expression:
AgðsÞ þ 3NaClðaqÞ þ 0:5SiO2 ðsÞ þ 0:5H 2 OðaqÞ
¼ Na2 AgCl3 ðaqÞ þ 0:5Na2 SiO3 ðaqÞ þ 0:5H 2 ðgÞ ð8Þ
The following rearranged equilibrium constant expres-
sion can be derived for this reaction:
!2=3
K 8  aAg  aNaCl3  aH 2 O0:5  aSiO0:5
fNa2 AgCl3 ¼ 2
fH 20:5
ð9Þ
Thus, using the same argument as for Eq. (7), if Na2-
AgCl3 was the dominant dissolved Ag species, the slope
of the fitted line in Fig. 3 would be 2. As this is inconsistent
with the observed value, it is likely that Na2AgCl3 species is
minor or non-existent at our experimental conditions. This
is consistent with the observations of Liu et al. (2012) and
Pokrovski et al. (2013) suggesting that the AgCl2
3 species
starts to dissociate into AgCl  nificant increase in apparent Ag solubility in response to the
2 and Cl with T increasing
above 300 °C.
The experiments conducted with NaCl-HCl-H2O fluids
further reinforce our proposition of NaAgCl2 being the
dominant Ag species in chloride-bearing fluids at our exper-
imental conditions. The maximum apparent Ag solubility
at NaCl/(NaCl + HCl) ratio of 0.5 at a fixed total Cl con-
centration can only be explained by the following reaction:
AgðsÞ þ NaClðaqÞ þ HClðaqÞ ¼ NaAgCl2 ðaqÞ þ 0:5H 2 ðgÞ
ð10Þ
Rearranging the equilibrium constant expression for Eq.
(10) yields:
 
cAg
aNaAgCl2 ¼  K 10  aNaCl  aHCl ð11Þ
fH 2
0:5
Thus, provided that NaAgCl2 is the major dissolved Ag
species, the measured Ag solubility should be proportional
to aNaCl * aHCl. Because cNaCl + cHCl, and thus assum-
ing constant activity coefficients, aNaCl + aHCl was held
constant, aNaCl * aHCl is a parabolic function with a max-
imum at aNaCl = aHCl, consistent with the fit to the exper-
imental data in Fig. 4. This observation is a strong
confirmation of the stability of the NaAgCl2 species, as this
particular distribution of the solubility data would be very
hard to explain by assuming any other species. This propo-
sition is in accord with the prediction of Seward (1976) who
tentatively suggested NaAgCl2 may become a predominant
complex at temperatures above the range covered in his
study (100–350 °C).
Furthermore, when considering the concentration series
experiments conducted at a fixed NaCl/HCl of 1, one can
derive the following relationship:
 
cAg
aNaAgCl2 ¼  K 10  x2 ð12Þ
fH 0:5
2
where x = aNaCl = aHCl. This should yield a slope of 2 for
the fitted line in Fig. 5, which is reasonably close to the
observed value (1.69 ± 0.09). Thus, this set of experiments
also supports NaAgCl2 as being the dominant Ag species
in chloride-bearing, S-free magmatic fluids.
Zajacz et al. (2010) and Zajacz et al. (2011) suggested
association of AuCl 
2 species and CuCl2 species with alkali
ions at P = 1500 bar and T = 1000 °C. Thus, our data show
that Ag behaves very similarly to Au and Cu in chloride-
bearing magmatic fluids.
However, this species does not explain the non-zero sol-
ubility in the pure HCl aqueous solution. The most likely
neutral species that could explain this is HAgCl2. A similar
species was also suggested for Au and Cu by Frank et al.
(2002), Zajacz et al. (2010) and Zajacz et al. (2011). This
species would form according to the following mass action
expression:
AgðsÞ þ 2HClðaqÞ ¼ HAgCl2 ðaqÞ þ 0:5H 2 ðgÞ ð13Þ
4.2. Silver solubility in aqueous sulfur-bearing fluids
The most interesting aspect of the data is the rather sig-
addition of even low concentrations of alkali chlorides into
the H2S-rich fluids. In the absence of alkali-chlorides, the
apparent Ag solubility was 5.7 ± 1.9 lg/g at a S concentra-
tion as high as 7.84 wt% in the fluid. This can be considered
low relative to those measured in chloride-bearing, S-free
fluids. However, the simultaneous presence of 0.4 m NaCl
and 7.82 wt% S yielded an apparent Ag solubility of 74 ±
18 lg/g (exp #17-2), which is comparable to that measured
in S-free fluids with as much as 2 m NaCl. Indeed, the pre-
dicted Ag solubility in a S-free fluid with 0.4 m NaCl is only
8.5 lg/g thus the large increase in Ag solubility in response
to NaCl addition to the H2S-H2O fluid cannot simply be
caused by the additional presence of Ag chloride com-
plexes, but rather indicate the formation of new stable
Ag-hydrosulfide complexes which incorporate either Na
or Cl or both in addition to S. The observation that the
apparent solubility of Ag as a function of cH2S showed a
linear correlation with a slope of 1 on a logarithmic plot
(Fig. 6) suggests a Ag/S molar ratio of 1 in the dominant
stable complex. The simplest dissolution reaction that could
account for this slope is the following:
AgðsÞ þ H 2 S ðaqÞ ¼ AgHS ðaqÞ þ 0:5H 2 ðgÞ ð14Þ
Previous experimental studies on Ag solubility in S-
bearing aqueous fluids at ambient or hydrothermal temper-
ature (25–400 °C) and pressure (1–500 bar), proposed
AgHS and Ag(HS) 2 as the dominant Ag species in acidic
and alkaline solutions, respectively (Melent’yev, 1970;
 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
Seward, 1976; Webster, 1986; Gammons and Barnes, 1989;
Stefansson and Seward, 2003). However, Eq. (14) cannot
explain the significant impact of NaCl on Ag solubility in
S-bearing fluids. One possible alternative species would be
NaAg(HS)2, which is analogous to the NaAgCl2 species
we propose for the H2O-NaCl fluids, and can be envisaged
as an ion pair between Na+ and Ag(HS) 2 . The formation of
such a complex can be described with the following mass
action expression:
AgðsÞ þ 2H 2 S ðaqÞ þ NaClðaqÞ
¼ NaAgðHS Þ2 ðaqÞ þ HClðaqÞ þ 0:5H 2 ðgÞ ð15Þ
This reaction would, however, yield a slope of 2 between
cH2S and the apparent Ag solubility on a log-log diagram,
which is inconsistent with the slope of 1.01 ± 0.07 observed
in Fig. 6. Also, if NaAg(HS)2 was the dominant S-bearing
Ag complex, the addition of HCl to the starting fluid should
significantly reduce Ag solubility as the concentration of
HCl on the right side of Eq. (15) would be increased by sev-
eral orders of magnitude. Thus, the observation that the
apparent Ag solubility from experiments #17-2 (0.4 m
NaCl, 7.82 wt% S – 74 ± 18 lg/g Ag) and #21-1 (0.33 m
NaCl, 0.07 m HCl, 7.76 wt% S – 87 ± 15 lg/g Ag) are iden-
tical within 1 r error also indicates that NaAg(HS)2 is not
the dominant species, though a potential reduction of the
concentration of Ag-S complexes could be partially masked
by the increase of the concentration of chloride complexes
due to the increased HCl/NaCl ratio. An alternative Ag dis-
solution reaction involving both H2S and NaCl is the
following:
AgðsÞ þ H 2 S ðaqÞ þ NaClðaqÞ ¼ NaAgHSClðaqÞ þ 0:5H 2 ðgÞ
ð16Þ
In this reaction, the S/Ag atomic ratio is 1, which should
yield a slope of 1 in Fig. 6, and therefore this species is more
consistent with the observed data. Also, Eq. (16) does not
have HCl on either the reactant or product side, thus it is
consistent with the observation that HCl did not have a sig-
nificant effect on the stability of the dominant S-bearing Ag
complex. Indeed, similar complex (NaCuHSCl) was sug-
gested to be one of the dominant S-bearing Cu-species in
magmatic fluids (Zajacz et al., 2011). The observation that
the positive effect of alkali chloride addition to H2S-H2O
fluids on Ag solubility increases with the increasing radius
of the alkali metal ion (Fig. 7) further supports the assump-
tion of alkali-AgHSCl being the dominant S-bearing Ag
complex. This complex can be envisaged as an ion pair
between an alkali metal cation and a AgHSCl anion.
The latter would be a soft base which should make stronger
complexes with softer acids (cations) within the framework
of the Hard-Soft Acid-Base (HSAB) theory (Pearson, 1969;
Parr and Pearson, 1983). As alkali metal cations become
increasingly softer acids with increasing ionic radius, the
observed parallel increase in Ag solubility further supports
the proposition of their direct involvement in the stable Ag-
S complexes. Calcium ion would be a harder acid than any
of the alkali metal ions because of its higher charge (2+) at
a comparable ionic radius, thus the observation that CaCl2
addition to H2S-H2O fluids does not have any significant
243
effect on Ag solubility further reinforces our proposition
of alkali-AgHSCl species being the dominant Ag-S complex
in magmatic fluids.
4.3. Thermodynamic model calculations of Ag solubility and
speciation
As the above discussion did not quantitatively take into
account any potential variation of the activity coefficients
of various solute and solvent species, the effect of potential
variabilities in free energies of solvation, and complex inter-
actions between various solute species, we also conducted
thermodynamic model calculations. We used the HCh soft-
ware package of Shvarov (2008) to model silver solubility at
our experimental conditions. This is a Gibbs free energy
minimization algorithm that uses the revised HKF equation
of state (Helgeson et al., 1981; Tanger and Helgeson, 1988)
to calculate the free energy of aqueous solute species
(Shvarov,1999, Shvarov, 2008). The thermodynamic prop-
erties of most major species in the system were taken from
the SUPCRT 97 database (Sverjensky et al., 1997). For
aqueous HCl, we used HKF parameters from Tagirov
et al. (1997), because these were optimized for relatively
low density solutions and Akinfiev and Zotov (2001) also
used these properties for HCl while deriving thermody-
namic constants for Ag species. For aqueous H2S and
SO2, the data of Akinfiev and Diamond (2003) were used.
The fH2 applied in the experiments were imposed for the
model calculation treating H2 as perfectly mobile compo-
nent (Korzhinskii, 1965), this way defining the fO2 for the
system in the presence of water. The species that were taken
into account by default for all calculations include: H2O,
H+, OH, NaCl, NaOH, HCl, SiO2, Si2O4, HSiO 
3 , HS ,
2   +  +
SO4 , HSO4 , Cl , Na , AgHS, Ag(HS)2 , Ag , AgCl,
AgCl 2 , H2, O2, H2S and SO2. We constrained the Ag activ-
ity to be 0.005 for the model calculations as this is the value
that was imposed by the capsule alloy in our experiments.
At first, we modeled the apparent Ag solubility at our
experimental conditions for all starting fluid compositions
using this set of species and including only Ag complexes
known from lower-T hydrothermal conditions. The ther-
modynamic properties of these ‘‘traditional” Ag species
were taken from Akinfiev and Zotov (2001), because this
database was optimized based on the largest set of experi-
mental values, and was found to predict experimental
results at lower T the best (Pokrovski et al., 2013). The
results are shown for three sets of experiments separately
in Figs. 8–10. It is apparent that the Ag concentrations were
significantly under-predicted relative to the experimental
data for all fluid compositions. For NaCl-H2O fluids, the
mismatch is about 1.5 orders of magnitude (Fig. 8), which
is further increased to about 2.5 orders of magnitude when
HCl is included in the system (Fig. 9). For S-bearing fluids,
the mismatch between the experimental and predicted val-
ues is 0.8–1.6 orders of magnitude, less at higher S concen-
trations. This suggests that traditional Ag complexes
account only for a small fraction of the experimentally-
determined apparent Ag solubilities at magmatic tempera-
tures. Thus, we included NaAgCl2, HAgCl2, NaAg(HS)2
and NaAgHSCl species in the simulation. The species
244 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
Fig. 8. The results of the model calculations with the HCh software
package of the experiments with NaCl-H2O fluids. (a) Comparison
of the model calculated apparent Ag solubilities to the experimen-
tal data. Blue open hexagons show the experimental Ag solubility
data, the error bars represent 1 relative standard deviation of the
fluid inclusion compositions, whereas the pink open triangles and
green open diamonds represent the modeled Ag concentrations
without and with the new Ag species, respectively. The purple dash
line represents the modeled apparent Ag solubility including the
new Ag species as a continuous function of cNaCl. (b) Speciation
diagram based on the HCh model calculation results for the fluids
shown on (a). The results shown are from calculations that
included the newly proposed neutral Ag complexes (NaAgCl2,
HAgCl2) in addition to the previously described Ag+, AgCl, AgCl 2
complexes from Akinfiev and Zotov (2001) and matched the
experimental data. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this
article.)
NaAgCl2 and NaAgHSCl were inferred to be a dominant
species from the semi-quantitative analysis of the experi-
mental data as discussed above, whereas HAgCl2 and
NaAg(HS)2 were included to test if the model calculations
Fig. 9. The results of the model calculations with the HCh software
package for the experiments with NaCl-HCl-H2O fluids. (a)
Comparison of the model calculated apparent Ag solubilities to
the experimental data. Blue open hexagons show experimental Ag
solubility data with 1 r error bars, whereas the pink open triangles
represent the modeled Ag concentrations without the new Ag
species. The purple dash line shows the modeled apparent Ag
solubility from the calculations that included the new Ag species as
a continuous function of the NaCl/(NaCl + HCl) ratio. (b)
Speciation diagram based on the HCh model calculation results
for the fluids shown on (a). The results shown are from the
calculations that included the newly proposed neutral Ag com-
plexes (NaAgCl2, HAgCl2) and matched the experimental data.
(For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.)
verify our proposition of them being minor species in the
experimental fluids. We also introduced an aqueous sodium
metasilicate (Na2SiO3) species as this is required for the
simulation of the dissolution reaction shown in Eq. (3).
Such species is likely very stable as Na2O and thus NaOH
is known to be highly reactive with SiO2 at magmatic tem-
peratures. The Na/Si ratio and thus the exact identity of the
Na-silicate species does not influence the results of the
model calculations.
 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
Fig. 10. The results of the model calculations with the HCh
software package for the experiments with NaCl-HCl-H2O fluids.
(a) Comparison of the model calculated apparent Ag solubilities to
the experimental data. Blue open hexagons show experimental Ag
solubility data with 1r error bars, whereas the pink open triangles
and green open diamonds represent the modeled Ag concentrations
without and with the new Ag species, respectively. The purple dash
line represents the modeled apparent Ag solubility including the
new Ag species. (b) Speciation diagram based on the HCh model
calculation results for the fluids shown on (a). The results shown
are from the calculations that included the newly proposed neutral
Ag complexes (NaAgCl2, HAgCl2) and matched the experimental
data. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)
The Gibbs free energies of these new species were opti-
mized to get the best match between the experimentally-
determined and model-calculated Ag concentrations. For
this purpose, the Excel macro OptimA of Shvarov (2015)
was used, which works in conjunction with the HCh code.
This program optimizes the free energy of specified com-
plexes to obtain the best least squares fit to the experimental
solubility data (Shvarov, 2015). The Gibbs free energy of
245
new Ag chloride complexes was determined by simultane-
ously optimizing their free energies to obtain the best match
to all experimental data from chloride-bearing, S-free flu-
ids. The free energy of the aqueous Na2SiO3 species was
optimized at the same time. Then, we fixed the obtained
free energy values of the new Ag chloride complexes and
Fig. 11. The results of the model calculations with the HCh
software package for the experiments with NaCl-H2S-H2O fluids.
(a) Comparison of the model calculated apparent Ag solubilities to
the experimental data. Blue open hexagons show experimental Ag
solubility with 1r error bars, whereas the pink open triangles and
green open diamonds represent the modeled Ag concentrations
without and with the new Ag species, respectively. The purple dash
line represents the modeled apparent Ag solubility including the
new Ag species as a continuous function of cH2S. (b) Speciation
diagram based on the HCh model calculation results for the fluids
shown on (a). The results shown are from the calculations that
included the newly proposed neutral Ag complexes (NaAgCl2,
HAgCl2, NaAgHSCl, NaAg(HS)2) and previously characterized
Ag+, AgCl, AgCl 
2 , AgHS, Ag(HS) complexes from Akinfiev and
Zotov (2001) and matched the experimental data. (For interpre-
tation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
246 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
Table 2
The 10 based logarithm of the equilibrium constants of the key reactions at P = 2000 bar and T = 900 °C describing the formation of the
proposed new aqueous Ag species.
Reactions
Ag(s) + 2NaCl(aq) + H2O(aq) = NaAgCl2(aq)+ NaOH(aq) + 0.5H2(g) (1)
Ag(s) + NaCl(aq) + HCl(aq) = NaAgCl2(aq) + 0.5H2(g) (10)
Ag(s) + 2HCl(aq) = HAgCl2(aq) + 0.5H2(g) (13)
Ag(s) + H2S(aq) +NaCl(aq) = NaAgHSCl(aq) + 0.5H2(g) (16)
a
Errors were estimated by iteratively changing the molar Gibbs free energy of formation for the specific aqueous Ag species until the
modeled Ag concentrations became inconsistent with more than half of the experimental data within 2r error in Figs. 8a–11a.
optimized the free energies of the new Ag-S species to yield
the best match between the experimental and predicted Ag
concentrations for all S-bearing experiments. The opti-
mized thermodynamic properties for the new Ag-
complexes were used alongside previously published data
for all other Ag-species to construct speciation diagrams
(Figs. 8b–11b).
It is apparent in Figs. 8–11 that the introduction of new
Ag species in the model calculations yielded very good
match between the experimental and predicted apparent
Ag solubilities for all studied fluid compositions. The abso-
lute Ag concentrations, the functional form and the slope of
the trends are all well reproduced. As apparent on the spe-
ciation diagrams, NaAgCl2 is the dominant dissolved Ag
species for most chloride-bearing, S-free fluids except for
those with HCl/(HCl + NaCl) ratios larger than 0.92
(Figs. 8b–10b). The relative abundance of the neutral AgCl
complex remains below 0.5% for all studied fluid composi-
tions. The most stable charged Ag species is AgCl 2 , but it
accounts for only a few % of the total dissolved Ag concen-
tration. The equilibrium constants for the reactions with
new Ag species were calculated based on the optimized free
energies of the new Ag species, and are reported in Table 2.
For the S-bearing fluids, the model also verified the
dominance of the anticipated NaAgHSCl complex, with
NaAg(HS)2 being only a minor species. However, one must
note here that the predicted relative proportion of these two
complexes is strongly dependent on the slope that the log
cH2S vs. log cAg values define (1.01 ± 0.07; Fig. 6). At a
slope of 1 or lower, NaAg(HS)2 complexes would be pre-
dicted to be basically non-existent, whereas a slope of 1.1
would yield a significant but still minor concentration of
NaAg(HS)2, as the dominant presence of this species would
require a slope close to 2. It is also worth mentioning that in
the fluid with 0.4 m NaCl (1.34 wt% Cl) and 1.06 wt% S, the
NaAgCl2 complex accounts for almost half of the total dis-
solved Ag concentration.
4.4. Geological implications
The solubility data obtained in this study can be com-
bined with previously published Ag solubility data for
fluid-saturated silicate melts obtained at similar P, T and
fO2 to obtain model fluid/melt partition coefficients for
Ag (DfAg=m ). Thus, we conducted a model calculation to sim-
ulate the efficiency of Ag extraction by exsolving fluids dur-
ing the differentiation of a typical upper crustal magma
reservoir for arc setting. The model scenario was the
log K Errora
10.60 ±0.06
4.09 ±0.07
5.37 ±0.20
5.33 ±0.15
following: A dacitic silicate melt formed by differentiation
of a primitive mantle melt in the lower crust is intruded into
the upper crust at P = 2000 bar (7 km depth) and T =
900 °C (Table 3). Subsequently, this intrusion cools and
crystallizes until 50 wt% crystal fraction is reached. By this
time, the residual melt becomes rhyolitic in composition. At
the time of emplacement, the melt is fluid saturated, as it
would commonly be expected for evolved arc magmas at
upper crustal pressures. The crystallization of the melt
induces further fluid exsolution because most crystallizing
minerals are anhydrous, during which some of the Ag con-
tent of the original silicate melt is transferred into the fluid
phase. We assumed that 90% of the water mass expelled
from the melt due to its decreasing mass fraction in the
magma was transferred into the fluid phase, whereas 10%
ended up in hydrous minerals such as amphibole and
biotite.
As Ag solubility in the fluid is strongly dependent on the
concentration of available ligands, the model had to predict
the concentration of S and Cl in the fluid phase during the
crystallization and degassing process. For S, we used a DSf =m
value of 462 based on the experimental data of Zajacz et al.
(2013) determined for a dacite melt composition at similar
conditions, most importantly at fO2 below the sulfide to
sulfate transition. As DfS =m increases <20% relative moving
from dacite to rhyolite melt composition (Zajacz et al.,
2013), we kept DfS =m value constant during the crystalliza-
tion of the magma. The same could not be done for Cl,
because DfCl=m increases significantly with melt composition
evolving from dacite to rhyolite. Based on previous experi-
mental studies, the value of DfCl=m is approximately 5 for
dacite melt compositions at similar P, T (Botchanikov
et al., 2004; T = 850 °C and P = 2000 bar), whereas it is
Table 3
Parameters used for the magma degassing model calculation.
Melt composition Water saturated dacite
T 900 °C
P 2000 bar
fO2 NNO-0.3
DS (f/m) 462
DCl (f/m) Scaled between 5 and 20
Degree of crystallization From 0 to 50%
CAg (melt, 0) 150 ng/g
CCl (melt, 0) 1500 lg/g
CS (melt, 0) 150 lg/g
 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251 247

about 20 for rhyolite melt compositions (Kravchuk and also a function of the Cl concentration in the fluid and melt
Keppler, 1994; T = 800 °C and P = 2000 bar). These values phases. However, the fluids in this simulation never reached
only hold as long as the total chloride concentration in the higher Cl concentrations than this. The crystallization and
fluid phase remains relatively low (<10 wt%), as DfCl=m is degassing of the magma were modeled in MATLAB using

Fig. 12. The results of the model calculations simulating the crystallization-driven degassing of a dacite magma emplaced into the upper crust
at P = 200 MPa and T = 900 °C. The blue lines represent open system degassing assuming that the fluid phase immediately leaves the magma
after exsolving, whereas the dashed red lines represent closed system degassing with the fluid phase staying in the magma. (a) the variation of
the Cl concentration in the silicate melt; (b) the variation of Cl concentration in the exsolving fluid phase in NaCl equivalent concentrations;
(c) the variation of the S concentration in the melt; (d) the variation of the S concentration in the fluid phase; (e) the variation of the fluid/melt
partition coefficients of Ag; (f) the evolution of the Ag concentration in the silicate melt. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
248 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
small discrete steps with 0.1 wt% newly formed crystal frac-
tion in each step. The value of DfCl=m was recalculated for
each step, using a linear scaling between the values of 5
and 20 as the crystal fraction increased from 0 to 50%.
We conducted the simulation for both open and closed sys-
tem degassing scenarios. The compositions of the fluid and
melt phases were recalculated for each step of the simula-
tion accordingly. In the possession of these, DfAg=m could also
be calculated for each crystallization step. To obtain appar-
ent Ag solubilities for the silicate melt, we used the results
of Zajacz et al. (2013). This study has shown that while tem-
perature has a significant effect on Ag solubility in silicate
melts, the effect of melt composition is relatively small.
For rhyolite melts, an apparent Ag solubility of 1 lg/g
was obtained at T = 900 °C and P = 2000 bar and fO2 =
NNO-0.8 log units and Ag activity identical to that used
in this study. This scaled to the fO2 of this study is 1.33
assuming 1+ oxidation state for dissolved Ag. For dacite
melts, no experimental data is available at 900 °C, but at
1000 °C, the Ag solubility was about 1.5 times higher in
the dacite than in the rhyolite melt (Zajacz et al., 2013).
Thus, we assumed that this relationship holds, and scaled
the apparent Ag solubility in the melt between 2 and 1.33
lg/g linearly while going from 0 to 50% crystal content.
The apparent solubility of Ag in the fluid phase was calcu-
lated based on the results of this study. We assumed an
HCl/total chloride ratio of 0.1 in the fluid phase for the
entire crystallization range. This is realistic for arc magmas
with residual melts typically evolving to metaluminous or
slightly peraluminous compositions based on experimen-
tally determined alkali chloride/HCl exchange equilibrium
between silicate melts and magmatic volatiles (Williams
et al., 1997; Zajacz et al., 2012a,b). The DfAg=m values were
obtained as the ratio of the apparent Ag solubilities in the
fluid and melt phases calculated for the same Ag activity.
The starting concentrations of the elements of interest in
the initial dacite melt were the following: CAg(melt, 0) =
150 ng/g, CCl(melt, 0) = 1500 lg/g and CS(melt,0) = 150
lg/g. These values are typical for dacitic arc magmas based
on data from silicate melt inclusions in minerals (Wallace,
2005; Grondahl and Zajacz, 2017).
The results are shown in Fig. 12. In Fig. 12a–d, it is
apparent that while the Cl concentration is increasing in
both the melt and the fluid phase with progressing crystal-
lization, the concentration of S rapidly drops to nearly zero
during early stages of crystallization because of the much
higher fluid/melt partition coefficient of S relative to that
of Cl. In response, the value of DfAg=m is initially decreasing
slightly with the decreasing S concentration, but soon starts
to increase due to the increasing Cl concentration in the
fluid phase, and rises to 100 by the time the magma
reaches 50% crystal content (Fig. 12e). Accordingly, the
concentration of Ag in the silicate melt initially remains
almost constant and subsequently drops with increasing
rate with progressing crystallization (Fig. 12f). By the time
50% crystal fraction is reached, the Ag concentration in the
melts drops to 1/3 of its original value, and thus 5/6 of
the original Ag budget of the magma is extracted by the
exsolving fluid phase.
Though natural magmas may show significant variabil-
ity relative to the model parameters used here, as a general
conclusion, it is safe to state that Ag extraction by exsolving
fluids will only be efficient from felsic magmas. This is
mainly because mafic and intermediate magmas will always
exsolve Cl-poor fluids (e.g. Zajacz et al., 2012a), and S by
itself is insufficient to support high enough Ag solubilities
in the fluid to yield sufficiently high DfAg=m for effective Ag
extraction. Many porphyry ore systems are associated with
magmas where S will be in higher oxidation states than in
our experiments and form species such as SO2, SO2 4 or
S3 (Binder and Keppler, 2011; Pokrovski and
Dubrovinsky, 2011; Jacquemet et al., 2014). Sulfate species
are less likely to complex with Ag than sulfide species based
on the HSAB theory, similarly to that experimentally
shown for Au and Cu (Zajacz et al., 2010; Zajacz et al.,
2011; Guo et al., 2018). Therefore, in oxidized fluids, it is
likely that chloride complexes would dominate and our
conclusions about Ag extraction from magmas would hold.
It is yet to be explored if Ag complexation with S 3 species is
as significant as that has been shown for gold (Pokrovski
et al., 2015).
The significance of understanding of the behavior of Ag
during magma degassing goes beyond simply allowing us to
assess which magmas may be fertile to form associated
Ag-rich porphyry or epithermal ore deposits. One of the
highly-debated subjects when assessing the ore-fertility of
arc magmas is the role of sulfide saturation during magma
evolution (e.g. Jenner et al., 2010; Grondahl and Zajacz,
2017; Zhang and Audetat, 2017). Silver is of particular
value when one tries to decipher if a magma was subject
to previous sulfide saturation or not, and what type of sul-
fide phase may have fractionated (i.e. pyrrhotite or Cu-rich
Fe sulfide liquid). While Au and Cu are sufficiently compat-
ible in both pyrrhotite and sulfide liquid to be depleted in
the residual silicate melt by the fractionation of either
phase, Ag is only moderately compatible in pyrrhotite, thus
it will be effectively depleted in the silicate melt only by
sulfide liquid fractionation (Zajacz et al., 2013; Li and
Audetat, 2015) possible for Ag as well using the data
presented in this study along with those p, 2015; Brenan
et al., 2016). However, when interpreting the variation of
chalcophile element concentrations during magma differen-
tiation, one must simultaneously asses the effect of magma
degassing in addition to potential sulfide saturation. This is
now possible for Ag as well using the data presented in this
study along with those previously reported for Au and Cu
(e.g. Williams et al., 1995; Simon et al., 2006; Botcharnikov
et al., 2010; Zajacz et al., 2012b).
5. CONCLUSIONS
The experimental results on Ag solubility interpreted
with the help of thermodynamic calculations and subse-
quently implemented into a magma degassing model lead
us to the following major conclusions:
1. Silver complexes show pronounced association with
alkali metals in high temperature, low-density magmatic
fluids – as previously shown for Au and Cu (Zajacz
 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
et al., 2010; Zajacz et al., 2011; Mei et al., 2014). The sol-
ubility of Ag is greatly increased by the presence of these
complexes compared to that predicted using the thermo-
dynamic properties of traditional Ag complexes known
to be present at lower temperatures.
2. In chloride-bearing magmatic fluids, NaAgCl2 is the
dominant Ag species with HAgCl2 becoming predomi-
nant only at very high HCl/(alkali chloride + HCl)
ratios of >
0.9, which are unlikely to occur in natural
systems at confining pressures characteristic of upper
crustal magma intrusions.
3. The addition of H2S in wt% level concentrations signif-
icantly increases the solubility of Ag in the presence of
alkali chlorides. In H2S-rich magmatic fluids,
NaAgHSCl is predicted to be the dominant Ag-S
species.
4. Predicted fluid/melt partition coefficients of Ag incorpo-
rated into a magma degassing model suggest that Ag
extraction will only be efficient from magmas degassing
in the upper crust when the composition of the silicate
melt phase is rhyodacitic to rhyolitic. However, at this
point, much of the Ag budget of the original magma
may be extracted by the exsolving volatile phase over a
relatively narrow crystallization interval. Thus magmatic
fluids may serve as an effective source of Ag for
hydrothermal ore deposit formation.
ACKNOWLEDGEMENTS
We are very grateful to Gleb Pokrovski for sharing his
experiences with using the HCh software and his updated ther-
modynamic database. We would also like to thank Alexandra
Tsay for her help in the experimental and analytical laborato-
ries. In addition, we would like to thank Artas Migdisov and
three anonymous reviewers for their constructive comments,
and Gleb Pokrovski for the editorial handling of this study.
Zoltan Zajacz acknowledges the financial support of the
National Sciences and Engineering Research Council of Canada
in the form of a Discovery Grant. Most facilities used for this
research were constructed with the financial support of a
Canada Foundation for Innovation – Leaders Opportunity
Fund grant and an Ontario Research Fund – Small Infrastruc-
ture grant to Zoltan Zajacz.
REFERENCES
Akinfiev N. N. and Zotov A. V. (2001) Thermodynamic descrip-
tion of chloride, hydrosulfide, and hydrooxo complexes of Ag
(I), Cu(I), Au(I) at temperature 25–600 °C and pressures of 1–
2000 bar. Geochem. Int. 39, 990–1006.
Akinfiev N. N. and Diamond L. W. (2003) Thermodynamic
description of aqueous nonelectrolytes at infinite dilution over a
wide range of state parameters. Geochim. Cosmochim. Acta 67,
613–627.
Akinfiev N. N. and Zotov A. V. (2016) Solubility of chlorargyrite
(AgCl(cr./l.)) in water: new experimental data and a predictive
model valid for a wide range of temperatures (273–873 K) and
water densities (0.01-1 g/cm3). Geochim. Cosmochim. Acta 178,
178–194.
Barnes H. L. (1997) Geochemistry of Hydrothermal Ore Deposits,
third ed. John Wiley & Sons, USA, p. 795.
249
Binder B. and Keppler H. (2011) The oxidation state of sulfur in
magmatic fluids. Earth Planet. Sci. Lett. 301, 190–198.
Botchanikov R. E., Behrens H., Holtz F., Koepke J. and Sato H.
(2004) Sulfur and chlorine solublity in Mt. Unzen rhyodacitic
melt at 850 °C and 200 MPa. Chem. Geol. 213, 207–225.
Botcharnikov R. E., Linnen R. L. and Holtz F. (2010) Solubility of
Au in Cl-and S-bearing hydrous silicate melts. Geochim.
Cosmochim. Acta 74, 2396–2411.
Brenan J., Bennett N. and Zajacz Z. (2016) Experimental results on
fractionation of the highly siderophile elements (HSE) at
variable pressures and temperatures during planetary and
magmatic differentiation. Rev. Mineral. Geochem. 81, 1–87.
Chase M. W., Davies C. A., Downey J. R., Frurip D. J.,
McDonaldR A. and Syverud A. N. (1985) Janaf thermochem-
ical tables – 3rd edition. 1 Al–Co. J. Phys. Chem. Ref. Data 14,
1–926.
Cicek M. and Oyman T. (2016) Origin and evolution of hydrother-
mal fluids in epithermal Pb-Zn-Cu +/- Au +/- Ag deposits at
Koru and Tesbihdere mining districts, Canakkale, Biga Penin-
sula, NW Turkey. Ore Geol. Rev. 78, 176–195.
Churakov S. V. and Gottschalk M. (2003) Perturbation theory
based equation of state for polar molecular fluids: II. Fluid
mixtures. Geochim. Cosmochim. Acta 67, 2397–2414.
Frank M. R., Candela A., Piccoli P. M. and Glascock M. D. (2002)
Gold solubility, speciation, and partitioning as a fuction of HCl
in the brine-silicate melt-metallic gold system at 300 °C and 100
MPa. Geochim. Cosmochim. Acta 66, 3719–3732.
Gammons C. H. and Barnes H. L. (1989) The solubility of Ag2S in
near-neutral aqueous sulfide solutions at 25 to 300 °C. Geochim.
Cosmochim. Acta 53, 279–290.
Gammons C. H. and Williams-Jones A. E. (1995a) Hydrothermal
geochemical of electrum: thermodynamic constraints. Econ.
Geol. 90, 420–432.
Gammons C. H. and William-Jones A. E. (1995b) The solubility of
Au-Ag alloy + AgCl in HCl/NaCl solutions at 300 °C: new
data on the stability of Au (I) chloride complexes in hydrother-
mal fluids. Geochim. Coschim. Acta 59, 3454–3468.
Gammons C. H. and Yu Y. (1997) The stability of aqueous silver
bromide and iodide complexes at 25–300 °C: experiments,
theory and geologic applications. Chem. Geol. 137, 155–173.
Grondahl C. M. and Zajacz Z. (2017) Magmatic controls on the
genesis of porphyry Cu-Mo-Au deposits: the Bingham Canyon
example. Earth Planet. Sci. Lett. 480, 53–65. https://doi.org/
10.1016/j.epsl.2017.09.036.
Guillong M., Latkoczy C., Seo J. H., Günther D. and Heinrich C.
A. (2008) Determination of sulfur in fluid inclusions by laser
ablation ICP-MS. J. Anal. At. Spectrom. 23, 1581–1589.
Guo H., Audétat A. and Dolejš D. (2018) Solubility of gold in
oxidized, sulfur-bearing fluids at 500–850 °C and 200–230 MPa:
A synthetic fluid inclusion study. Geochim. Cosmochim. Ac. 222,
655–670.
Hedenquist J. W. and Lowenstern J. B. (1994) The role of magmas
in the formation of hydrothermal ore-deposits. Nature 370,
519–527.
Heinrich C. A., Gunther D., Audetat A., Ulrich T. and
Frischknecht R. (1999) Metal fractionation between magmatic
brine and vapor, determined by microanalysis of fluid inclu-
sions. Geology 27, 755–758.
Helgeson H. C., Kirham D. H. and Flowers G. C. (1981)
Theoretical prediction of the thermodynamic behavior of
aqueous electrolytes at high pressures and temperatures: IV.
Calculation of activity coefficients, osmotic coefficients, and
apparent molal and standard and relative partial molal prop-
erties to 600 °C and 5KB. Am. J. Sci. 281, 1249–1516.
Jacquemet N., Guillaume D., Zwick A. and Pokrovski G. S. (2014)
In situ Raman spectroscopy identification of the S-3(-) ion in
250 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
S-rich hydrothermal fluids from synthetic fluid inclusions. Am.
Mineral. 99(5–6), 1109–1118.
Jenner F. E., O‘Neil H. S. C., Arculus R. J. and Mavrogenes J. A.
(2010) The magnetite crisis in the evolution of arc-related
magmas and the initial concentration of Au, Ag and Cu. J.
Petrol. 51, 2445–2464.
Ke L. L., Zhang H. Y., Liu J. J., Zhai D. G., Guo D. H., Yang J.
K., Tan Q. A., Xu Y. W., Zhang M. and Wang S. G. (2017)
Fluid Inclusion, H-O, S, Pb and noble gas isotope studies of the
Aerhada Pb-Zn-Ag deposit, Inner Mongolia, NE China. Ore
Geol. Rev. 88, 304–316.
King J., Williams-Jones A. E., van Hinsberg V. and Williams-Jones
G. (2014) High-sulfidation epithermal pyrite-hosted Au (Ag-
Cu) ore formation by condensed magmatic vapors on Sangihe
Island, Indonesia. Econ. Geol. 109, 1705–1733.
Korzhinskii D. S. (1965) The theory of systems with perfectly
mobile components and processes of mineral formation. Am. J.
Sci. 263, 193–205.
Kravchuk I. F. and Keppler H. (1994) Distribution of chloride
between aqueous fluids and felsic melts at 2 kbar and 800 °C.
Eur. J. Mineral. 6, 913–923.
Leachman J. W., Jacobsen R. T. and Lemmon E. W. (2009)
Fundamental equations of state for parahydrogen, normal
hydrogen, and orthohydrogen. J. Phys. Chem. Ref. Data.
https://doi.org/10.1063/1.3160306.
Li Y. and Audetat A. (2015) Effects of temperature, silicate melt
composition, and oxygen fugacity on the partitioning of V, Mn
Co, Ni, Cu, Zn, As, Mo, Ag, Sn, Sb, W, Au, Pb, and Bi between
sulfide phases and silicate melt. Geochim. Cosmochim. Acta 162,
25–45.
Liu X., Lu X., Wang R. and Zhou H. (2012) Silver speciation in
chloride-containing hydrothermal solutions from first principles
molecular dynamics simulations. Chem. Geol. 295–295, 103–112.
Mei Y., Liu W., Sherman D. M. and Brugger J. (2014) Metal
complexation and ion hydration in low density hydrothermal
fluids: ab initio molecular dynamics simulation of Cu(I) and Au
(I) in chloride solutions (25–1000 °C, 1–5000 bar). Geochim.
Cosmochim. Acta 131, 196–212.
Melent’yev A. C. (1970) Solubility of some ore-forming sulphides
under hydrothermal conditions. Geochem. Int. 7, 416–460.
Migdisov A. A., Willams-Jones A. E. and Suleimenov O. M. (1999)
Solubility of chlorargyrite (AgCl) in water vapor at elevated
temperatures and pressures. Geochim. Cosmochim. Acta 63,
3817–3827.
Migdisov A. A. and Williams-Jones A. E. (2013) A predictive
model for metal transport of silver chloride by aqueous vapor
in ore-forming magmatic-hydrothermal systems. Geochim.
Coschim. Acta 104, 123–135.
Parr R. G. and Pearson R. G. (1983) Absolute hardness-compar-
ison parameter to absolute electronegativity. J. Am. Chem. Soc.
105, 7512–7516.
Pearson R. G. (1969) Hard and soft acids and bases HSAB: 1.
Fundamental principles. J. Chem. Educ. 45, 581–587.
Pitzer K. S. (1983) Dielectric constant of water at very high
temperature and pressure. Proc. Natl. Acad. Sci. 80, 4575–4576.
Pokrovski G. S., Roux J. and Harrichoury J. (2005) Fluid density
control on vapor-liquid partitioning of metals in hydrothermal
systems. Geology 33, 657–660.
Pokrovski G. S. and Dubrovinsky L. S. (2011) The S-3 ion is stable
in geological fluids at elevated temperatures and pressures.
Science 331(6020), 1052–1054.
Pokrovski G. S., Roux J., Ferlat G., Jonchiere R., Seitsonen A. P.,
Vuilleumier R. and Hazemann J. (2013) Siver in geological
fluids from in situ X-ray absorption spectroscopy and first
principles molecular dynamics. Geochim. Cosmochim. Acta 106,
501–523.
Pokrovski G. S. and Dubessy J. (2015) Stability and abundance of
the trisulfur radical ion S3- in hydrothermal fluids. Earth Planet.
Sci. Lett. 411, 298–309.
Pokrovski G. S. et al. (2015) Sulfur radical species form gold
deposits on Earth. PNAS 112, 13484–13489.
Richards J. P. (2011) Magmatic to hydrothermal metal fluxes in
convergent and collided margins. Ore Geol. Rev. 40, 1–26.
Sabeva R., Mladenova V. and Mogessie A. (2017) Ore petrology,
hydrothermal alteration, fluid inclusions, and sulfur stable
isotopes of the Milin Kamak intermediate sulfidation epither-
mal Au-Ag deposit in Western Srednogorie, Bulgaria. Ore Geol.
Rev. 88, 400–415.
Seward T. M. (1976) The stability of chloride complexes of silver in
hydrothermal solutions up to 350 °C. Geochim. Cosmochim.
Acta 40, 1329–1341.
Seward T. M., Henderson C. M. B., Charnock J. M. and Dobson
B. R. (1996) An X-ray absorption (EXAFS) spectroscopic
study of aquated Ag+ in hydrothermal solution to 350 °C.
Geochim. Cosmochim. Acta 60, 2273–2282.
Shvarov Y. (1999) Algorithmization of the numeric equilibrium
modeling of dynamic geochemical processes. Geokhimiya 6,
646–652.
Shvarov Y. (2008) HCh: New potentialities for the thermodynamic
simulation of geochemical systems offered by windows.
Geochem. Int. 46, 834–839.
Shvarov Y. (2015) A suite of programs, OptimA, OptimB, OptimC,
and OptimS compatible with the Unitherm database, for
deriving the thermodymic properties of aqueous species from
solubility, potentiometry and spectroscopy measurements.
Appl. Geochem. 55, 17–27.
Sillitoe R. H. (2010) Porphyry copper system. Econ. Geol. 105, 3–
41.
Simmons S. F., White N. C. and John D. A. (2005) Geological
characteristics of epithemal precious and base metal deposits.
Econ. Geol. 100th Anniversary, 485–522.
Simon A. C., Pettke T., Candela P. A., Piccoli P. M. and Heinrich
C. A. (2006) Copper partitioning in a melt-vapor-brine-
magnetite-pyrrhotite assemblage. Geochim. Cosmochim. Acta
70, 5583–5600.
Simon A. C., Candela P. A., Piccoli P. M., Mengason M. and
Englander L. (2008) The effect of crystal-melt partitioning on
the budgets of Cu, Au, and Ag. Am. Mineral. 93, 1437–1448.
Simon A. C., Pettke T., Candela P. A. and Piccoli P. M. (2009) The
partitioning behavior of silver in a vapor-brine-rhyolite melt
assemblage. Geochim. Cosmochim. Acta 72, 1638–1659.
Stefansson A. and Seward T. M. (2003) Experimental determina-
tion of the stability and stoichiometry of sulphide complexes of
silver (I) in hydrothermal solutions to 400 °C. Geochim.
Cosmochim. Acta 67, 1395–1413.
Sterner S. M. and Bodnar R. J. (1984) Synthetic fluid inclusions in
natural quartz I. Compositional types synthesized and applica-
tions to experimental geochemistry. Geochem. Cosmochim. Acta
48, 2659–2668.
Sverjensky D. A., Shock E. L. and Helgeson H. C. (1997)
Prediction of the thermodynamic properties of aqueous metal
complexes to 1000 °C and 5kb. Geochim. Cosmochim. Acta 61,
1359–1412.
Tagirov B. R., Zotov A. V. and Akinfiev N. N. (1997) Experi-
mental study of dissociation of HCl from 350 to 500°C and
from 500 to 2500 bars: thermodynamic properties of HClo(aq).
Geochim. Cosmochim. Acta 61, 4267–4280.
Tanger J. C. and Helgeson H. C. (1988) Calculation of the
thermodynamic and transport properties of aqueous species at
high pressures and temperatures: revised equations of state for
the standard partial molal properties of ions and electrolytes.
Am. J. Sci. 288, 19–98.
 Y. Yin, Z. Zajacz / Geochimica et Cosmochimica Acta 238 (2018) 235–251
Tegeler C., Span R. and Wagner W. (1999) A new equation of state
for argon covering the fluid region for termperatures from the
melting line to 700K at pressures up to 1000 MPa. J. Phys.
Chem. Ref. Data 28, 779–850.
Wallace P. J. (2005) Volatiles in subduction zone magmas:
concentrations and fluxes based on melt inclusion and volcanic
gas data. J. Volcanol. Geoth. Res. 140, 217–240.
Webster J. G. (1986) The solubility of gold and silver in the system
Au-Ag-S-O2-H2O at 25 °C and 1atm. Geochim. Cosmochim.
Acta 50, 1837–1845.
Wilkinson J. J. (2013) Triggers for the formation of porphyry ore
deposits in magmatic arcs. Nat. Geosci. 6, 917–925.
William-Jones A. and Heinrich C. A. (2005) 100th anniversary
special paper: vapor transport of metals and the formation of
magmatic-hydrothermal ore deposits. Econ. Geol. 100, 1287–
1312.
Williams T. J., Candela P. A. and Piccoli P. M. (1995) The
Partitioning of copper between silicate melts and 2-phase
aqueous fluids – an experimental investigation at 1 kbar, 800 °C
and 0.5 kbar, 850 °C. Contrib. Mineral. Petrol. 121, 388–399.
Williams T. J., Candela P. A. and Piccoli P. M. (1997) Hydrogen-
alkali exchange between silicate melts and two-phase aqueous
mixtures: an experimental investigation. Contrib. Mineral.
Petrol. 128, 114–126.
Zajacz Z., Seo J. H., Candela P. A., Piccoli P. M., Heinrich C. A.
and Guillong M. (2010) Alkali metals control the release of gold
from volatile-rich magmas. Earth Planet. Sci. Lett. 297, 50–56.
View publication stats
251
Zajacz Z., Seo J. H., Candela P. A., Piccoli P. M. and Tossell J.
A. (2011) The solubility of copper in high-temperature
magmatic vapors: a quest for the significance of various
chloride and sulfide complexes. Geochim. Cosmochim. Acta 75,
2811–2827.
Zajacz Z., Candela P. A., Piccoli P. M. and Sanchez-Valle C.
(2012a) The partitioning of sulfur and chlorine between
andesite melts and magmatic volatiles and the exchange
coefficients of major cations. Geochim. Cosmochim. Acta 89,
81–101.
Zajacz Z., Candela P. A., Piccoli P. M., Sanchez-Valle C. and
Wälle M. (2012b) Gold and copper in volatile saturated mafic
to intermediate magmas: solubilities, partitioning and implica-
tions for ore deposit formation. Geochim. Cosmochim. Acta 91,
140–159.
Zajacz Z., Candela P. A., Piccoli P. A., Sanchez-Valle C. and Wälle
M. (2013) Solubility and partitioning behavior of Au, Cu, Ag
and reduced S in magmas. Geochim. Cosmochim. Acta 112, 288–
304.
Zhang D. and Audetat A. (2017) What caused the formation of the
giant Bingham canyon porphyry Cu-Mo-Au Deposit? Insights
from melt inclusions and magmatic sulfides. Econ. Geol. 112(2),
221–244.
Associate editor: Gleb S. Pokrovski