13.

2 The Chemistry of Metal Transport and Deposition by Ore-Forming

Hydrothermal Fluids
TM Seward, Victoria University of Wellington, Wellington, New Zealand
AE Williams-Jones and AA Migdisov, McGill University, Montréal, QC, Canada
ã 2014 Elsevier Ltd. All rights reserved.

13.2.1 Introduction 29
13.2.1.1 Compositions of Ore-Forming Fluids 30
13.2.2 Hydrothermal Ore Solution Chemistry – The Main Dissolved Components 33
13.2.2.1 Water Solvent at Hydrothermal Conditions 33
13.2.2.2 NaCl – The Main Dissolved Electrolyte Component 35
13.2.2.3 Ion Hydration, Association, and Water Activity 35
13.2.2.4 Weak Acid/Base Equilibria in Hydrothermal Systems 36
13.2.3 Mineral Solubility in Water and Salt Solutions at High Temperature and Pressure 37
13.2.4 Ore Metal Transport and Deposition 40
13.2.4.1 Ore Fluids with Liquid-Like Densities 40
13.2.4.1.1 Ligands in hydrothermal ore solutions 40
13.2.4.1.2 Metal chloride complexing 41
13.2.4.1.3 Complexing with other halide ligands 42
13.2.4.1.4 Metal complexes with hydroxide and other oxygen electron donor ligands 43
13.2.4.1.5 Complexing with hydrosulfide/sulfide ligands 45
13.2.4.1.6 Thioanions 46
13.2.4.1.7 Complexing with other sulfur-containing ligands 47
13.2.4.1.8 Other complexing ligands 48
13.2.4.1.9 Ore fluids with gas-like density 48
13.2.5 Epilogue 50
Acknowledgments 50
References 50

13.2.1 Introduction example, the fluids venting through chimneys at spreading

Economically exploitable deposits of metallic minerals (ore
deposits) form in the Earth’s crust through a variety of geologic
processes. These involve extraction of metals at low
concentration and transport of these metals to sites of deposi-
tion where they accumulate in very much higher concentra-
tion. Hydrothermal fluids are by far the most important agents
of metal transport. They may be formational waters of meteoric
or seawater origin, metamorphic fluids produced during devo-
latilization of hydrous minerals, or magmatic fluids released
during decompression and/or crystallization of magmas. Their
physical state may be that of liquid, vapor, or a supercritical
fluid, and chemically, they have highly variable concentrations
of dissolved components, including charged and uncharged
species containing elements such as Na, K, Ca, Fe, Si, Cl, C,
H, O, and S and, of course, the ore metals. The challenge, if
we are to understand the processes involving the hydrothermal
extraction, transport, and deposition of metals, is to determine
the nature of these fluids, the properties that allow them to
dissolve metals, and the conditions under which dissolution
and deposition are optimized.
Active hydrothermal systems are an important source of
information on the composition of ore fluids either because
they are forming deposits analogous to those that are mined or
there is strong evidence linking them to such deposits. For
centers and subduction zones are currently forming deposits
with the characteristics of volcanogenic massive sulfide (VMS)
base metal deposits (Scott, 1997). There is strong evidence
that, in many cases, geothermal fluids of the type employed
in energy generation are responsible for the formation of low-
sulfidation epithermal precious metal deposits (Barnes and
Seward, 1997; Clark and Williams-Jones, 1990; Krupp and
Seward, 1987, 1990; Weissberg et al., 1979). The same is true
for oil-field brines, which are analogous to the basinal brines
interpreted to form Mississippi Valley-type (MVT) lead–zinc
deposits. Although they are not ore fluids, per se, volcanic
gases are representative of the fluids that at greater pressure
may form high-sulfidation epithermal precious metal and por-
phyry copper deposits. Indeed, the ore fluids forming these
deposits actually may be gases, albeit of greater density than
volcanic gases (Williams-Jones and Heinrich, 2005). The fluids
from these active hydrothermal systems have been sampled
extensively during the past 50 years and have provided
people with a wealth of data on the chemistry of ore-forming
fluids and, in some cases (e.g., VMS and low-sulfidation
epithermal deposits), the pressure–temperature conditions of
potential ore formation. The other important sources of infor-
mation on the composition of ore-forming fluids and the
conditions of ore formation are fluid inclusions. With the
recent development of tools capable of analyzing their element

Treatise on Geochemistry 2nd Edition http://dx.doi.org/10.1016/B978-0-08-095975-7.01102-5 29

30 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
concentrations down to ppm levels, fluid inclusions are now
starting to provide chemical data comparable in quality to
those available from active hydrothermal systems. They are
also the principal source of data on the pressure–temperature
conditions of ore formation.
13.2.1.1 Compositions of Ore-Forming Fluids
Hydrothermal fluids venting on the seafloor were first discov-
ered in 1977 (Weiss, et al., 1977). Since then, large numbers of
studies, mainly along mid-ocean ridges, have documented the
chemistry of these fluids (Table 1) and shown that those at
T
350  C are forming massive sulfide base metal (and gold)
deposits similar to VMS deposits mined in terrestrial settings
(Scott, 1997; Tivey, 2005). Studies of mid-ocean ridge systems
have established that the composition of the fluids (for the
most part, hydrothermal liquids) is largely the result of inter-
action of seawater with basalt; there are also minor additions of
magmatic fluids (Shanks, 2001; Yang and Scott, 1996, 2006).
During this interaction, there is a sharp decrease in ex situ pH
(from 7.8 to between 3 and 4) due to removal of magnesium
to form secondary silicate minerals (Seyfried, 1987). Chlorine
is conserved, and consequently, the chlorinity of the hydro-
thermal fluids is generally very similar to that of seawater, that
is,  0.5 m (German and Von Damm, 2003). Sodium, which is
the overwhelmingly dominant cation in the hydrothermal
fluids, is also largely conserved, in most cases, retaining its
seawater concentration of  0.45 m; some Na may be lost to
albitization. Among the major elements, only Mg and S are lost
from the seawater, Mg almost completely so. The sulfur con-
tent drops from nearly 30 mm in seawater to <10 mm in the
vent fluid. However, the major change is in its oxidation state.
Whereas in seawater, sulfur occurs as sulfate, in the vent fluid it
is present dominantly as H2S (Shanks, 2001). The carbon
content, mainly in the form of CO2, is typically two to five
times its seawater content of  2.3 mm. The other major ele-
ments, that is, K and Ca, are also added (Ca through the
breakdown of the anorthite component in plagioclase), typi-
cally reaching concentrations two to three times their seawater
concentration of  0.01 m. Silicon, which is a minor constitu-
ent of seawater, becomes a major element with a concentration
of  0.02 m. Iron, which is present in seawater at very low
concentrations (<1 nm), may also become a major element
in the hydrothermal fluid; in some cases, its concentration may
exceed 0.1 m. The concentrations of the main ore elements
(Cu, Zn, and Pb) are highly variable, generally ranging from
a few tens to a few thousand ppb, but are thousands to tens of
thousands of times higher than in seawater; gold concentra-
tions have not been measured (Table 1).
Although most of the information on the composition of
seafloor hydrothermal fluids comes from systems at mid-ocean
ridges, data on the compositions of hydrothermal fluids in arcs
and back-arc basins are being increasingly reported (Table 1).
The back-arc fluids are very similar in composition to those of
mid-ocean ridges and are also mainly products of seawater–
basalt interaction (Reeves et al., 2011). However, in the arc and
near-arc environment, where the magmas are much more si-
licic, their compositions differ considerably from those of hy-
drothermal fluids at mid-ocean ridges. The main differences
are significantly lower pH (2–3 vs. 3–4), very much higher CO2
(0.25 m) and F contents (0.4 mm), and higher concentrations
of K (up to 0.1 m). These differences are attributed to the
addition of a large magmatic component to the hydrothermal
fluid, possibly as much as 25% (Reeves et al., 2011).
The only ligands likely to be present in concentrations
sufficient to form the complexes necessary for metal transport
are Cl, CO2 species, reduced sulfur species, and F (in arc
environments) (Table 1). Ammonium ions are generally not
detected, except in sediment-covered settings (German and
Von Damm, 2003), and in these settings, it seems likely that
they are incorporated at relatively shallow depths of several
hundred meters (Lizarralde et al., 2010) and thus are not likely
to play a significant role in metal extraction, which is thought
to mainly take place at greater depth (Lowell et al., 1995;
Tivey, 2005).
Geothermal well fluids have been extensively sampled and
analyzed for over 50 years. Until recently, this sampling had
been restricted to the wellhead, and because the fluid generally
boils (a requirement for conventional geothermal energy pro-
duction) and precipitates minerals before reaching the surface,
the composition of the fluid differs considerably from that of
the reservoir fluid. Geothermal fluids display a broad range of
compositions, reflecting the diverse geology of terrestrial set-
tings (Table 1). For example, the chlorinity of the high-
temperature fluids (>250  C) in the Taupo volcanic zone, a
young rifted arc dominated by andesites and rhyolites, ranges
between 0.02 and 0.05 m, an order of magnitude lower than that
of seawater (Ellis, 1979a,b; Ellis and Mahon, 1977). At the other
extreme, the high-temperature fluids (>250  C) in the Salton Sea
geothermal system, which is located in a closed evaporitic,
sedimentary basin (Imperial Valley), commonly have a chlorin-
ity between 3 and 4 m; immediately to the south, in the same
basin, geothermal fluids at Cerro Prieto have a chlorinity of 0.2
to 0.5 m (Mercado and Hurtado, 1992; Williams and McKibben,
1989). In both the Taupo volcanic zone and the Imperial Valley,
the fluid is predominantly meteoric water with a small contri-
bution of magmatic water. Geothermal systems may also be
dominated by seawater, as is the case for the Reykjanes field in
Iceland where the chlorinity is very similar to that of seawater
(Arnórsson, 1978). The other major components of geothermal
fluids, for example, Na, K, Ca, and CO2, also vary considerably in
concentration; the seawater-dominated, basalt-hosted Reykjanes
fluids are compositionally very similar to seafloor vent fluids
(Table 1). Until relatively recently, it has not been possible to
directly measure the metal concentrations of preboiled geo-
thermal fluids; however, such data are now starting to become
available through the development of ‘downhole’ devices that
can sample the reservoir fluids directly (e.g., Simmons and
Brown, 2006). For example, in the case of the geothermal fields
of the Taupo volcanic zone, these data show that the reservoir
fluid contains up to 23 ppb Au, 2400 ppb Ag, and 4850 ppb As;
the H2S content ranges up to 0.007 m (Ellis, 1979a,b; Seward,
1989). Lower concentrations of these metals were measured
in the Reykjanes reservoir fluid using the same method, that
is, up to 6 ppb Au, 34 ppb Ag, and <1 ppb As; concentrations
for Cu, Zn, and Pb were 16, 26, and <1 ppb, respectively
(Hardardottir et al., 2009). By comparison, concentrations of
Cu, Zn, and Pb reported for the very high-salinity Salton Sea
geothermal fluid, although sampled at the wellhead, are up to 7,
518, and 107 ppm, respectively; the H2S concentration is
Table 1 Selected analyses of the composition of fluids in active hydrothermal systems

Seafloor vent fluids Geothermal fluids Oil-field brines

Seawater Spreading Back-arc basin Arc Rotokawa Salton Sea Cerro Prieto Reykjanes Ladolam gold Mississippi
center deposit

Temp ( C) 2 350 282 268 320 330 337 296 275 107
pH (25  C) 7.8 3.400 4.1 2.6 6.03 5.1 8 – 8.01 5.650
Na (mm) 469.003 436.334 540.637 449.600 12.139 2382.609 419.980 393.000 1154.697 76.257
K (mm) 9.804 23.021 24.023 86.290 2.046 453.846 77.064 38.000 125.641 17.686
Ca (mm) 10.204 16.010 82.270 15.009 0.012 712.500 10.059 47.000 0.227 774.343
Mg (mm) 52.768 – 0.000 0.000 0.000 2.042 0.002 0.390 0.004
Mn (mm) – 0.960 0.348 3.117 – 27.273 0.010 52 000.000 – 1.163
Fe (mm) – 1.664 0.109 2.404 – 30.536 0.004 0.430 – 6.198
Si (mm) 0.200 18.010 15.007 16.008 23.409 9.800 48.169 10.000 19.238 0.712
Ba (mm) 0.140 8.000 17.000 91.001 – 2576.642 – 71.000 – 1056.004
Cu (ppm) – 2.224 0.127 2.288 – 6.800 0.005 16.586 4.450 0.020
Zn (ppm) – 6.931 0.654 7.520 – 507.000 0.006 24.987 0.185 222.000
Pb (ppm) – 63.818 0.829 1450.400 – 102.000 0.005 0.001 0.023 53.200
Mo (ppm) – – – – – – – 0.015 0.043
Sn (ppm) – – – – – – – 0.001 0.840
Cd (ppm) – 0.180 – – – 2.300 – 0.135 – 0.830
Ag (ppb) – 0.037 – – 1100.000 1400.000 4.000 34.626 6.000
Au (ppb) – – – – 7.800 – 4.000 6.106 16.000
As (ppm) – – – – 5.400 – 2.000 0.112 17.000
Sb (ppm) – – – – 1.200 – 0.400 0.025 0.004
Cl (mm) 551.626 497.669 730.500 583.889 14.620 4500.000 526.019 524.000 613.923 5614.690
Br (mm) 0.808 0.855 1.030 1.000 – 1.388 – 0.780 0.451 13.029
F (mm) 0.064 – 0.023 0.116 0.300 – – – – 0.042
B (mm) 0.426 0.548 0.240 1.620 9.000 24.636 2.220 0.709 12.213 8.049
SO4 (mm) 22.366 0.400 1.880 0.420 0.041 0.552 – – 410.375 0.187
H2S (mm) 0.000 7.303 1.800 6.803 7.310 0.294 22.617 0.900 –
HCO3 (mm) 2.931 7.266 7.649 40.854 1.072 35.909 1.072 – 48.261
References Seawater EPR 21 N Vienna Woods PACMANUS Rotokawa Salton Sea Cerro Prieto Reykjanes Ladolam gold Oil-field brines
(Hannington (Hannington (Hannington basin (Weissberg (Williams (Weissberg (Hardardottir deposit (Kharaka et al.,
et al., 2005) et al., 2005) et al., 2005) (Hannington et al., 1979; and et al., 1979; et al., 2009) (Simmons 1987)
et al., 2005) Krupp and McKibben, Clark and and Brown,
Seward, 1989) Williams- 2007)
1990; Jones, 1990)
Simmons
and Brown,
2007)
Table 2 Compositions of selected fluid inclusions from a variety of ore deposit types

Deposit type Sn granite Sn granite Porphyry Cu Porphyry Cu Porphyry Cu Porphyry Cu Zn skarn REE granite MVT MVT MVT

Fluid type Brine Vapor Brine Brine Brine Vapor Brine Brine Brine Brine Brine
Salinity 35.20 4.00 31.20 33.10 49.90 9.50 72.50 19.30 23.70 19.70
Temp ( C) 453 650 720 471 395 372 595 112 114 110
Na (ppm) 74 000 14 000 75 000 67 900 80 000 30 000 95 461 222 600 60 000 74 000 67 000
K (ppm) 57 000 3300 61 300 58 300 99 000 16 000 41 530 92 600 <1040 1400 7200
Ca (ppm) – – – – – – – – 23 000 – 14 000
Mg (ppm) – – – – – – – – 2110 – 1400
Mn (ppm) 22 000 1600 n.a. 14 200 23 000 1500 – 17 900 <32.7 – –
Fe (ppm) 73 000 4100 54 700 74 700 130 000 29 000 – 43 700 – –
Cu (ppm) 2300 4600 2200 2300 5500 30 000 – 230 50 6 –
Zn (ppm) 3600 680 n.a. 3400 9900 6500 5930 2500 n.d. 13 –
Pb (ppm) 3400 190 780 800 2400 620 4350 470 240 – 180
Mo (ppm) – – n.a. <120 90 n.a. – 81 – – –
Sn (ppm) 390 – n.a. <350 n.a. n.a. – 63 – – –
W (ppm) 56 – 57 <67 <80 <50 – 30 – – –
Ag (ppm) 290 5 7 <67 n.a. <70 50 3 – – –
As (ppm) 120 34 8 <400 50 n.a. 248 25 – – –
Sb (ppm) 110 31 – – – – 365 – – –
Ce (ppm) 2 – 6 15 210 <2 – 300 – – –
Bi (ppm) 10 3 n.a. n.a. – – – 5 – – –
Cl (ppm) – – – – – – – – 117 000 140 000 120 000
References Mole granite Mole granite Santa Rita Santa Rita Bajo de la Bajo de la El Mochito Capitan REE Ozark MVT Pb– North Tri-State MVT
(Audétat (Audétat porphyry Cu porphyry Cu Alumbrera Alumbrera Zn–Ag granite Zn deposits Arkansas Pb–Zn
et al., et al., 2000) deposit deposit porphyry Cu–Au porphyry skarn (Banks (Wilkinson MVT Pb–Zn deposits
2000) (Audétat (Audétat deposit (Ulrich Cu–Au deposit (Samson et al., et al., 2009) deposits (Stoffell
et al., 2008) et al., 2008) et al., 2002) (Ulrich et al., et al., 1994) (Stoffell et al., 2004)
2002) 2008) et al., 2004)
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
0.0005 m (Williams and McKibben, 1989). The giant
Ladolam gold deposit (a low-sulfidation epithermal deposit) is
an actively forming ore deposit on Lihir Island, Papua New
Guinea, which contains 1300 t of gold. The fluids forming
this deposit contain up to 16 ppb Au and 4450 ppb Cu; the
chloride content is 0.6 m, the CO2 content 0.2 m, and the H2S
content 0.0006 m (Simmons and Brown, 2006).
The ligands that could be important for metal transport in
geothermal fluids vary considerably with the environment in
which the geothermal system is located. In systems like the
Salton Sea, Cerro Prieto, Reykjanes, and Lihir Island, chloride is
clearly an important complexing ligand for some metals such as
Pb. However, in systems like those of the Taupo volcanic zone,
the chloride concentrations are typically low (e.g., 0.02–0.06 m),
although some of these systems have quite elevated reduced
sulfur concentrations, such as at Ohaaki (0.002 m) and Roto-
kawa (0.007 m) (Krupp and Seward, 1987, 1990; Seward, 1989).
Other species reported to be present in active geothermal systems
that might be important for metal transport are ammonia and
sulfate, the latter reaching 0.02 m at Salton Sea and >0.3 m at
Lihir Island (Simmons and Brown, 2006; Williams and Mckib-
ben, 1989). Ammonia (i.e., NH3 þ NH4þ) occurs ubiquitously in
geothermal fluids at concentrations up to and/or >0.002 m (see
Ellis, 1979a,b) and forms as an expected consequence of the
redox equilibria involving N2 and H2 (Seward, 1974a,b).
Oil-field brines, as noted earlier, have long been considered
to be modern analogues of the fluids interpreted to form MVT
lead–zinc deposits (Hall and Friedman, 1963). Although the
origin of these basinal brines is still a matter of conjecture, for
example, connate or evaporated seawater, variably modified by
mixing with meteoric water and diagenetic reaction (Wilson
and Long, 1993), they are able to transport significant concen-
trations of metals at relatively low temperature (85–150  C).
Their chlorinity ranges from about 2 to nearly 6 m, and Naþ is
the dominant cation (up to 3.5 m), followed by Ca2þ (up to
2 m; Table 1). The sulfate content ranges up to 0.004 m and that
of NH4þ to 0.01 m, but H2S and inorganic carbon concentra-
tions are very low, <1  107 and <5  104 m, respectively
(Carpenter et al., 1974; Kharaka et al., 1987). In addition, oil-
field brines contain significant proportions of dissolved organic
species, such as acetate (Table 1). The principal ore metals are
Zn and Pb, which can reach concentrations of up to 350 ppm
and 100 ppm, respectively (Carpenter et al., 1974; Kharaka
et al., 1987). Copper concentrations are typically <200 ppb.
On the other hand, gold concentrations as high as 18 ppb
have been reported (Saunders and Swann, 1990).
Volcanic gases are the surface representatives of magmatic
hydrothermal fluids, and although they are considerably less
dense than the vapors that are believed to be ore fluids in some
settings, they do provide information about the compositions
of these fluids. In addition to water vapor, volcanic gases can
contain >30 mol% CO2, >20 mol% SO2, >5 mol% H2S,
>2mol% HCl, and >0.2 mol% HF; the average contents of
these gases for 19 representative volcanoes are 10.6, 5.2, 1.1,
0.8, and 0.1 mol%, respectively (Halmer, 2002). Metal con-
tents of volcanic gases range up to 6 ppm Cu, 12 ppm Pb,
11 ppm Zn, 7 ppm Sn, 250 ppb Ag, and 24 ppb Au (e.g.,
Symonds et al., 1987; Wahrenberger et al., 2002; Williams-
Jones et al., 2002), and the total metal content of discharging
volcanic gases from a single volcano may constitute an
33
appreciable metallic flux on the order of thousands of tonnes
per annum to the atmosphere (Calabrese et al., 2011).
Fluid inclusions provide the most direct source of data on
the compositions of ore fluids in extinct hydrothermal systems,
and analyses of individual fluid inclusions (e.g., using LA-
ICPMS) are the most reliable sources for these data (Table 2).
With a few exceptions, studies reporting compositions of indi-
vidual inclusions have focused on magmatic hydrothermal ore
deposits, and data are available for both the single-phase fluids
that exsolved from the magma and the later brine and vapor
that were the products of phase separation (Klemm et al., 2007;
Samson et al., 2008). These data show that supercritical mag-
matic fluid inclusions typically contain 0.1–0.8 m Cl, 0.1–
0.6 m Na, up to 0.3 m K, up to 0.1 m Fe, on average
3500 ppm Cu, 200 ppm Zn, 40 ppm Pb, and 10 ppm Mo.
Gold concentrations are typically at high ppb levels. The com-
positions of magmatic vapor inclusions are similar, except that
Cu concentrations can be very much higher, over 1 wt%, and
gold concentrations up to 10 ppm have been reported (Ulrich
et al., 1999). Magmatic brine inclusions have much higher
concentrations of salts, commonly >6 m Cl, >3 m Na,
>1.5 m K, >1.5 m Fe, and on average 1500 ppm Cu,
3500 ppm Zn, 2000 ppm Pb, and 80 ppm Mo, and up to
3000 ppb Au. Some compositional data have been reported by
Stoffell et al. (2004) for fluid inclusions from MVT deposits.
These show that the fluids contain an average of 3.4 m Cl, 2.6 m
Na, 0.2 m K, 0.6 m Ca, 212 ppm Zn, and 94 ppm Pb.
13.2.2 Hydrothermal Ore Solution Chemistry –
The Main Dissolved Components
13.2.2.1 Water Solvent at Hydrothermal Conditions
The review of the chemistry of ore-forming fluids has shown
clearly that they are multicomponent aqueous electrolyte solu-
tions containing both simple ionic and more complex molec-
ular species. In this section, the properties of water solvent that
enable it to be an effective agent for the transport of ore metals
and associated elements are considered.
At ambient temperature and pressure, water is the archetype
protic solvent that exhibits various unusual properties that may
be attributed to the large dipole moment of water and the
associated hydrogen bonding among neighboring molecules.
Dissolved ionic and molecular species are ‘hydrated’ and inter-
act with water solvent (Figure 1). As temperature and pressure
increase at conditions defined by the two-phase curve (i.e.,
liquid–vapor equilibrium), liquid water expands as the posi-
tional and orientational constraints alter and the extent of
hydrogen bonding diminishes. The increasing molar volume
(decreasing density) of water liquid as one proceeds to the
critical point is thus accompanied by concomitant decreases
in its dielectric permittivity and other properties, such as vis-
cosity. The decrease in the dielectric constant from 80.10 to
7.22 for liquid water as temperature increases from 20 to
373  C (at the equilibrium vapor pressure) (Fernandez et al.,
1997; Uematsu and Franck, 1980) gives some premonition of
the changing nature of water dipole–ion interaction, which
results in enhanced ion pairing/association and metal complex
formation. Increasing pressure acts in an opposing way, caus-
ing an increase in the static permittivity (Fernandez et al.,
34 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
49.9 ⬚
Å percritical water comprising small domains of water molecules
2.952
48.5 ⬚
-
+ Petterssen (2011).
Figure 1 Structure of water in the vicinity of a metal cation. Water
molecules immediately adjacent to the ion are arranged so that their
negatively charged oxygen atoms are directed inward to form an inner
hydration shell; these molecules are surrounded by an outer shell of
water molecules that are similarly directed but with less consistency and
locally share hydrogen bonds with the bulk water solvent. The
development of hydration shells facilitates dissolution by separating
cations from anions.
1997), thus encouraging the stability of some ionic species
under supercritical conditions. The self-ionization of liquid
water as manifested by the ion product constant, Kw, changes
as a function of temperature and pressure as the energetics of
deprotonation of water molecules changes in response to re-
lated changes in the hydrogen bonding array. Steam is domi-
nated by the presence of water clusters that increasingly
interact with each other via hydrogen bonding as the density
of the vapor phase increases to liquid-like densities as the
critical point is approached. As expected, therefore, the viscos-
ity of steam increases with increasing temperature at liquid–
vapor equilibrium.
The molecular structure and nature of the hydrogen bond-
ing of liquid water and supercritical water at liquid-like densi-
ties continues to be an important and ongoing research area of
fundamental importance to hydrothermal geochemistry and
ore solution chemistry. It has been generally considered that
liquid water exhibits a short-range tetrahedral ordering with
respect to the nearest neighbor water molecules, apparently
inheriting some remnant configurational aspects from ice.
Above about 150  C, the ‘evidence’ from X-ray diffraction
and neutron diffraction isotopic dilution (NDIS) (Gorbaty
and Kalinichev, 1995; Soper, 2000) for the nearest neighbor
ordering diminishes, suggesting that water might be con-
sidered as a hydrogen-bonded continuum. But recent X-ray
Raman scattering data (Wernet et al., 2005) and NDIS mea-
surements and simulations (Bernabei et al., 2008) of supercrit-
ical water indicate that such a view is too simplistic. The X-ray
Raman spectra are consistent with a structural model for su-
in various tetrahedral configurations in a gas-phase-like mo-
lecular continuum. Extensive hydrogen bonding persists with
increasing temperature and pressure, as demonstrated by com-
putational/theoretical and spectroscopic (Raman and NMR)
studies (e.g., Chialvo and Cummings, 1994; Hoffmann and
Conradi, 1997; Kalinichev et al., 1999; Walrafen et al., 1996).
For example, the NMR data of Hoffmann and Conradi (1997)
indicate that at 400  C and 400 bar, 29% of the hydrogen
bonding still exists, compared to ambient conditions. Never-
theless, the detailed interpretation of such results on a molec-
ular level is awaited. The current perspective on the structure
of liquid water from X-ray scattering, spectroscopic and dif-
fraction data, as well as molecular dynamics (MD) and ab
initio approaches, is elegantly summarized by Nilsson and
Self-ionization is an important property of water and aque-
ous solutions, which involves the loss of a proton from the
water molecule, leaving behind a hydroxide ion (OH). Spon-
taneous reaction of the hydrogen nucleus with another water
molecule produces the hydronium ion, H3Oþ. The value of
pKw (i.e.,  log Kw of the equilibrium ion product constant)
depends on temperature, pressure, and, in the case of an aque-
ous solution, ionic strength. It decreases with increasing tem-
perature to a minimum at between 250 and 350  C
(depending on pressure), above which it increases. For exam-
ple, the pKw at 250  C and saturated water vapor pressure
(swvp) is 11, whereas it is 14 at 25  C and swvp. The equilib-
rium pH therefore drops from 7 at 25  C to 5.5 at 250  C at
swvp. Increasing pressure decreases the pKw (due to the higher
stability of ionized species) and shifts the temperature mini-
mum to higher temperature (Marshall and Franck, 1981).
Addition of salts to the water may either increase or decrease
the ion product, depending on the nature and concentration of
the salt present in the solution (Kron et al., 1995). For example,
measurements of the ion product constant of water in solu-
tions of NaCl, KCl, KNO3, and NaNO3 at 25  C and at swvp
demonstrate that addition of these electrolytes progressively
decreases Kw of water to a minimum value at an ionic strength
characteristic for the particular electrolyte; further addition of
these electrolytes increases the ion product, potentially to
values well above 14 (Figure 2). Although the pKw minima
for the salts in question are at concentrations <1 m, those for
other salts may occur at significantly higher concentrations
(Kron et al., 1995). As most interactions of water with rock
(i.e., with silicate minerals) occur through pH-dependent re-
actions and concentrations of many aqueous species also de-
pend on pH, pKw is one of the major parameters controlling
speciation in hydrothermal solutions. For example, the species
AlOH2þ forms via the reaction Al3þ þ OH ⇆ AlOH2þ, and its
stability therefore depends on the concentration of the hy-
droxyl ion and, in turn, the solvent self-ionization.
As discussed earlier, the ability of water to stabilize ionized
(charged) species is controlled by the development of
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
14.6
14.4
14.2
pKw
14.0
13.8
13.6
0 1 2 3 4 5 6 7
NaCl (mol kg-1)
Figure 2 The effect of salinity on the ionization constant of water (pKw)
at 25  C; the experimental points are shown by the open circles and
calculated values by the solid line. Modified from Kron I, Marshall SL,
May PM, Hefter G, and Konigsberger E (1995) The ionic product of water
in highly concentrated aqueous electrolyte solutions. Monatshefte für
Chemie 126: 819–837. With permission from Springer.
hydrogen-bonded networks of water molecules. The expansion
associated with increasing temperature distorts these networks
and leads to a decrease in the relative permittivity and associ-
ated destabilization of ionized species. In the extreme, water
can expand to a fluid with gas-like density or separate a vapor,
and in this state, there is complete destruction of the network.
Water molecules cease to be part of a continuum but instead
form isolated clusters with small numbers of molecules
(Kalinichev and Churakov, 1999). Consequently, the ability
of gas-like aqueous fluids to stabilize ionized species is lower
(see the succeeding text), and metal solubility in these fluids is
predominantly, but not exclusively, molecular (i.e., dissolved
species have no charge). Nevertheless, these species commonly
disobey the rules for simple gaseous mixtures. In particular,
hydration still occurs and neutrally charged species may be
incorporated into water clusters. Moreover, there is evidence
that the clusters can even support charged species (e.g.,
Likholyot et al., 2005, 2007).
13.2.2.2 NaCl – The Main Dissolved Electrolyte Component
Hydrothermal ore fluids are multicomponent electrolyte solu-
tions in which NaCl is generally the dominant salt component.
Of course, natural hydrothermal systems are more complex
with numerous interrelated heterogeneous equilibria deter-
mining the hydrolytic (pH) and redox state of the fluids that
undergo phase separation as they migrate and ascend buoy-
antly though the Earth’s crust. Sodium chloride is the classic
strong electrolyte whose aqueous solutions are considered to
be extensively ionized into hydrated Naþ and Cl ions at
ambient temperature and pressure, although concentrated so-
lutions (saturation ¼ 6.013 m at 20  C) may exhibit some as-
sociation. However, with increasing temperature and at lower
35
pressures (e.g., P  500 bar), sodium chloride solutions be-
come progressively more associated (to form simple NaCl0
ion pairs), as was elegantly demonstrated by the earlier con-
ductance study of Quist and Marshall (1968). For example, a
1.0 m NaCl solution at 300  C and at the equilibrium vapor
pressure is about 50% associated. They also showed that in-
creasing pressure up to 4000 bar has the opposite effect and
causes the disproportionation of associated species, thus favor-
ing the formation of the simple hydrated ions, Naþ and Cl,
whose partial molar volumes are electrostrictively enhanced
relative to the associated moieties.
A number of recent MD and ab initio/MD studies have also
shed light on the molecular nature of sodium chloride solu-
tions at elevated temperatures and pressures (e.g., Dong et al.,
2008; Driesner et al., 1998; Guardia et al., 2006a,b; Sherman
and Collings, 2002; Yui et al., 2010). Driesner et al. (1998)
showed that for a 1 m NaCl solution at 380  C and solution
density of 0.55 g cm3, the simple hydrated ions (i.e., Naþ and
Cl) comprise only about 13% of the species in solution, with
the remainder of the solute consisting of associated species such
as NaCl0, Na2Clþ, NaCl2, and Na2Cl2 but with the dominant
associated species being the simple NaCl0 ion pair. Some
short-lived, larger associated species, such as Na3Cl4, were
also observed in the simulations but have lifetimes of 2 ps.
In summary then, the main electrolyte salt component of
hydrothermal fluids in the Earth’s crust is, with few exceptions,
NaCl. The bulk electrolyte salt association chemistry at high
temperatures and pressures plays a fundamental role in the
complexing and transport/deposition chemistry of many tran-
sition metals in hydrothermal ore-forming systems. Thus, in a
cooling hydrothermal solution ascending buoyantly through
the Earth’s crust at lower pressures (e.g., P  500 bar), more
chloride ligands become available for metal complexing as
associated sodium chloride solute species disproportionate
with decreasing temperature. Conversely, a hydrothermal ore
solution decompressing isothermally will lead to instability of
some metal complexes as chloride ligands are consumed by
association of the bulk electrolyte.
13.2.2.3 Ion Hydration, Association, and Water Activity
Of particular interest, as well, is the changing nature of ion
hydration in hydrothermal fluids as a function of temperature
and pressure. Insight into ion–solvent interaction at elevated
temperatures and pressures comprising ion hydration coordi-
nation numbers, ion–water bond lengths, and solvated water
residence times has come relatively recently from spectro-
scopic, neutron, and X-ray diffraction and computational stud-
ies, many of which are summarized and discussed by Seward
and Driesner (2004). More recently, computational studies
(ab initio, MD, and ab initio/MD) have added significantly
to our knowledge of ion hydration under hydrothermal con-
ditions, especially with respect to NaCl solutions (e.g.,
Bondarenko et al., 2006; Chialvo et al., 2009; Dong et al.,
2008; Fedotova, 2008; Guardia et al., 2006a,b; Nahtigal and
Svishchev, 2009). Driesner et al. (1998) studied (using MD)
Naþ ion hydration for both cases of infinite dilution and 1.0 m
from 30 to 590 K and at several densities. They showed that
there is a contraction (i.e., 2.26 to 2.23 Å) of first-shell waters
around Naþ, which is also accompanied by a decrease in the
36 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
number of coordinated water molecules with increasing tem-
perature. Moreover, the residence times of first-shell waters
around Naþ and Cl (in a 1.0 m solution) at 298 K are found
to be 22.5 and 12.0 ps, respectively, but decrease by about an
order of magnitude to 2.2 and 2.4 ps with increasing temper-
ature to 650 K (Guardia et al., 2006b).
In addition, a number of systematic X-ray absorption spec-
troscopic studies (i.e., EXAFS (extended X-ray absorption fine
structure)) of Agþ and Sr2þ hydration up to 350  C and at
equilibrium saturated vapor pressures (Seward et al., 1996,
1999) have also demonstrated a contraction of the cation–
oxygen (water) distances with increasing temperature as well
as a decrease in the number of the first-shell water molecules. In
the case of Agþ, for example, the Agþ–oxygen (water) distance
undergoes an appreciable contraction of 0.1 Å as temperature
increases from 25 to 350  C, with an accompanying decrease in
the number of first-shell waters from 4 to 3. However, data for
Cd2þ hydration up to 300  C and at equilibrium vapor pres-
sures indicate a decrease in the Cd2þ–oxygen (water) distance
with increasing temperature but with no change in the number
of first-shell waters (Seward et al., 2013). In the case of the
trivalent cation, In3þ, the hydration environment remains
unchanged (six first-shell waters bound to the In3þ at a distance
of 2.14 Å) over the same temperature range (i.e., 25 to 300  C)
at saturated vapor pressures (Seward et al., 2000).
The nature of ion hydration (i.e., ion–solvent interaction) is
complex and varies with the changing dielectric properties of
water solvent, which depend fundamentally on the nature
and extent of hydrogen bonding, which is a function of temper-
ature and pressure. However, NaCl is the most concentrated
salt component in hydrothermal fluids in the Earth’s crust, and
its hydration behavior is therefore of importance in determining
the water activity in hydrothermal ore solutions. Changes in
the hydration of Naþ and Cl ions as well as the formation
of associated species, such as NaCl0 (weakly hydrated), can
fundamentally affect water activity and hence the solubility of
minerals. Thus, a hydrothermal ore solution migrating through
the Earth’s crust will experience a range of physical and chemical
phenomena as it cools and decompresses (e.g., Heinrich
et al., 2004), which include element partitioning, mineral
precipitation, and changing metal complex stabilities, which
may, in some cases, be temporarily enhanced as a result of the
myriad of changes occurring in a complex multicomponent
system. As shown, for example, by the solubility of a simple
gangue mineral such as quartz in sodium chloride and other
electrolyte salt solutions (Newton and Manning, 2000, 2010;
Shmulovich et al., 2006), the dissolved silica concentration var-
ies not only with temperature and pressure but also with the salt
concentration and hence the extent and molecular nature of
association (ion pairing) and ion–solvent interaction with con-
sequent effects on water solvent activity. The changing value of
pK1 of silicic acid as a function of temperature and pressure as
well as bulk salt hydrolysis may also be of importance.
13.2.2.4 Weak Acid/Base Equilibria in Hydrothermal
Systems
In addition to the main electrolyte salt, NaCl, there are other
important solute components in hydrothermal ore solutions
in the Earth’s crust such as CO2, H2S, and NH3, which
are involved in various, weak acid hydrolytic equilibria and
play a role in metal transport by fluids in the Earth’s crust. CO2
may occur in high concentrations greater than 20 mol%
in H2O þ CO2 þ NaCl fluids associated with metamorphic
reactions; however, in the majority of hydrothermal ore fluids
in the upper crust, the CO2 (as H2CO3 þ HCO3 þCO32)
would be in the range from 0.01 to 1.0 m. CO2 being a volatile
component means that carbonate equilibria and pH are sensi-
tive to phase separation and boiling in hydrothermal systems.
In active geothermal/hydrothermal systems, it is well known
that CO2 partitioning into the vapor (steam) phase during
boiling leads to an increase in the residual liquid-phase pH
by as much as two pH units (e.g., from, say, 6 to 8). This affects
the stability of metal carbonate complexes as well as the stabil-
ity of any other pH-dependent metal complex equilibria, such
as hydroxide and/or hydrosulfide complexes.
Of particular importance is H2S and its first deprotonation
equilibrium in aqueous media,
H2 S ¼ Hþ þ HS
the equilibrium constant, K1, for which has been accurately
determined up to 360  C at the equilibrium vapor pressure
(Suleimenov and Seward, 1997) as well as at 500 bar and up
to 500  C (Stefansson and Seward, 2004). Note that the equi-
librium constant, K2, for the second ionization of H2S,
HS ¼ Hþ þ S2
is small (i.e., pK2 > 17.1 at 24  C and >12.5 at 200 to 270  C;
Giggenbach, 1971a), and hence, the sulfide ion, S2, is present
at negligible concentrations in natural hydrothermal solutions.
However, the hydrosulfide ligand, HS, plays a fundamental
role in the transport and deposition chemistry of some
elements, such as gold in hydrothermal ore solutions, and
the availability of reduced sulfur is crucial for the precipitation
of sulfide ore minerals. During boiling and/or phase separa-
tion, H2S and volatile components, such as CO2, NH3, and H2,
partition into the vapor (steam) or less dense, volatile-rich
phase, which affects the stability of various metal complexes
with respect to ligand availability (e.g., H2S loss) and increas-
ing redox potential of the residual liquid (H2 loss) or more
dense supercritical fluid.
The volatile species NH3 and N2 and H2 are involved in
heterogeneous redox equilibria and ammonium ion stability
through the reactions
N2ðgÞ þ H2ðgÞ ¼ NH3ðgÞ
and
NH3ðaqÞ þ Hþ ¼ NH4 þ
The stability of simple amino complexes (involving the NH3
ligand) of transition metals under hydrothermal conditions is
still poorly known. The ammonium ion also participates in
wall rock alteration reactions in hydrothermal systems, giving
rise to the formation of ammonium-containing silicate min-
erals such as buddingtonite and tobelite.
Thus, it is against this background of changing water prop-
erties (e.g., hydrogen bonding) with associated changes in ion–
solvent interaction and ion pairing/association and changes in
water activity in the presence of ligand-supplying weak acid/
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids 37

base systems that metal complex equilibria, metal transport

mechanisms, and ore mineral precipitation chemistry at ele- 20 MPa
vated temperatures and pressures relevant to hydrothermal
ore-depositing systems must be considered. 30 High-salinity
liquid

wt% NaCl

Immiscibility
20
13.2.3 Mineral Solubility in Water and Salt 10
Solutions at High Temperature and Pressure 3.2
0

Quartz solubility (mmol kg-1)

10
The main interests of geochemists investigating hydrothermal
Single-phase fluid Low-salinity
processes, including those of ore formation, are the mecha-
(a) vapor
nisms that control the transport of elements in aqueous solu-
tions and the saturation of the solutions with minerals
50
containing them. At any given set of physicochemical condi- 50 MPa
tions, the concentration of an element in an aqueous solution High-salinity
is limited by the solubility of the least soluble mineral contain- liquid
40
ing this element. For example, in the system Na–Ca–F–H2O,

Immiscibility
the concentration of fluorine is determined by the solubility of
fluorite (CaF2). Consequently, the mineral villiaumite (NaF), wt% NaCl 10
30
which is much more soluble than fluorite, will not form unless

Retrograde
solubility
the buffering capacity of fluorite is exhausted, that is, the con- 3.2
centration of Ca is so low that the solubility product for the ions 20
0
comprising fluorite is less than that for villiaumite. In this
section, a brief review is provided of the data available on the
solubility of the major gangue (non-ore) minerals commonly 10
encountered in hydrothermal ore deposits. Single-phase fluid Low-salinity
vapor
Hydrothermal gangue minerals can be subdivided into two (b)
groups, namely, those that display prograde solubility, that is, 0
their solubility increases with increasing temperature, and 0 100 200 300 400 500
those that display retrograde solubility, that is, decrease in Temperature (⬚C)
solubility with increasing temperature. Most chloride, oxide, Figure 3 Isobaric quartz solubility as a function of temperature in pure
sulfide, and silicate minerals exhibit prograde solubility, H2O, H2O þ 3.2 wt% NaCl, and H2O þ 10 wt% NaCl fluids, (a) at 20 MPa
whereas sulfates, carbonates, and phosphates commonly (bottom) and (b) at 50 MPa; the shaded areas represent regions of
show retrograde solubility. These minerals can be further clas- retrograde solubility. Modified from Steele-MacInnis M, Han L,
sified according to whether their dissolution is congruent or Lowell RP, Rimstidt JD, and Bodnar RJ (2012) The role of fluid phase
incongruent. In the case of the former, all products of the immiscibility in quartz dissolution and precipitation in sub-seafloor
dissolution reaction are transferred stoichiometrically to the hydrothermal systems. Earth and Planetary Science Letters
solution. By contrast, incongruent dissolution involves forma- 321/322: 139–151.
tion of both aqueous species and new solids. Simple com-
pounds such as chlorides and oxides generally display
The solubility of quartz in pure water is controlled by a
congruent dissolution, whereas complex silicates and sulfides
number of hydrated ‘SiO2’ species of which silicic acid,
typically undergo incongruent dissolution.
H4SiO40 (Si(OH)40), and its corresponding anions, H3SiO4
Quartz is without question the gangue mineral most com-
and H2SiO42, are the most important, although H2SiO42 is a
monly encountered in ore-forming hydrothermal systems and
negligible species in hydrothermal fluids in the Earth’s crust.
has been the subject of large numbers of studies by both
Neutrally charged species predominate at pH< 9, and therefore,
experimentalists and theoreticians. In pure water, the solubility
the solubility of quartz is independent of pH, except at condi-
of quartz increases systematically with temperature up to
tions of extreme alkalinity. At these conditions, the formation of
370  C, but at higher temperature, its solubility is retrograde;
ionized species of silicic acid causes quartz solubility to increase
quartz solubility increases with pressure at all temperatures.
with increasing pH and, in salt solutions, this may be further
The presence of alkali salts, such as NaCl and KCl, reduces the
enhanced by the formation of ion pairs such as NaH3SiO40
solubility of quartz (salting out) at low temperature but in-
(Seward, 1974a,b). Aqueous silica is also known to form poly-
creases it at temperatures above 250  C (Figure 3). However,
mers (Chan, 1989; Iler, 1979), as illustrated by the following
an understanding at a molecular level of how the presence of
stepwise reactions (e.g., Newton and Manning, 2010):
an electrolyte salt, such as NaCl, affects quartz solubility over a
wide range of temperature and pressure, as illustrated by the SiO2 þ 4H2 O ¼ SiðOHÞ4ðaqÞ
experiments of Newton and Manning (2000), eludes us at quartz
silica monomer
present. It will necessarily involve a complex interplay of sol-
and
vent interaction with both ionic and molecular species as well
as the effect of temperature and pressure on ion pairing/asso- 2SiðOH4 ÞðaqÞ ¼ Si2 OðOHÞ6ðaqÞ þ H2 O
ciation, salt hydrolysis, and the ionization of silicic acid. silica monomer silica dimer
38 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
An understanding of the nature and kinetics of silica poly-
merization as a function of temperature, pressure, pH, and salt
concentration (ionic strength) is of considerable importance in
the exploitation of active geothermal systems for energy use
(Gunnarsson and Arnorsson, 2005; Rothbaum and Rhode,
1979), particularly in managing the reservoir environment
when hot, ‘flashed,’ fluids (oversaturated with respect to amor-
phous silica) are reinjected. However, the chemistry of silica
polymerization, especially in the presence of aluminum and
salts (e.g., NaCl and KCl), under more extreme hydrothermal
conditions is still poorly known.
Another very common gangue mineral is calcite. Studies
of its solubility in hydrothermal fluids date back to the
publication of Ellis (1963) and have continued to the present
(e.g., Duan and Li, 2008a). In all cases and for most crustal
conditions, these studies have shown that calcite exhibits ret-
rograde solubility, that is, its solubility decreases in pure water
with increasing temperature. However, its solubility increases
with increasing pressure. Calcite solubility also increases with
increasing NaCl concentration up to a molality of  1–1.5
(Figure 4); however, it decreases at higher NaCl concentration
(Duan and Li, 2008; Newton and Manning, 2002). Neverthe-
less, at deep crustal conditions (i.e., at very high temperature
and pressure), the solubility of calcite is prograde, even at
relatively high salinity (Newton and Manning, 2002). The
aqueous species controlling the solubility of calcite are the
aquated ion and the ion pairs, Ca2þ, CaHCO3þ, and CaCO30
(the list also includes CaClþ and CaCl20 in chloride-containing
solutions), and the carbonic acid species, CO2(aq), HCO3,
and CO32. The hydrolytic species, CaOHþ, may also form,
but its contribution to calcite solubility is likely to be
insignificant in CO2-saturated solutions.
The other important carbonate mineral in ore-forming hy-
drothermal systems, particularly in systems forming MVT de-
posits, is dolomite. The behavior of this mineral at elevated
temperature, however, has attracted considerably less attention
from experimentalists than has calcite. A number of studies
were conducted on the solubility of dolomite at ambient tem-
perature during the 1950s and 1960s (e.g., Garrels et al., 1960)
but reported values for its solubility product differed by up to
three orders of magnitude. The probable reason for this has
since been revealed by experimental studies of the kinetics of
dolomite dissolution (Arvidson and Mackenzie, 1999;
6.0
300 ⬚C, 500 bar
5.0
Ca (mmol kg-1)
4.0 te
ydri
Anh
3.0
2.0
Calcite
1.0
Fluorite
0.0
0 0.2 0.4 0.6 0.8
NaCl (mol kg-1)
Figure 4 The solubility of anhydrite, calcite, and fluorite as a function of
NaCl molality at 300  C and 500 bar; calculated using thermodynamic
data from Holland and Powell (1998) and Shock et al. (1997).
Sherman and Barak, 2000). These studies showed that the
CaCO3 and MgCO3 components of dolomite dissolve at con-
siderably different rates. Consequently, evaluations of the
solubility of dolomite in aqueous solutions are now based on
calorimetric determinations of its enthalpy, entropy, and heat
capacity (e.g., Hemingway and Robie, 1994; Navrotsky and
Capobianco, 1987).
Sulfate minerals, such as anhydrite (CaSO4) and its hy-
drated form, gypsum (CaSO4 2H2O), and, to a lesser extent,
barite (BaSO4), are also important in some types of hydrother-
mal ore deposits, notably porphyry copper and molybdenum
deposits (anhydrite) and VMS deposits (anhydrite and barite).
The solubility of gypsum, which is significantly lower than that
of calcite, increases to a maximum of 0.015 m at 40  C in
pure water and then decreases with further increases in tem-
perature (Booth and Bidwell, 1950). At 97  C, gypsum dehy-
drates to anhydrite, generally via formation of an intermediate
hemihydrate phase, CaSO4  0.5H2O; anhydrite displays ret-
rograde solubility. As is the case for calcite, the solubility of
gypsum and anhydrite increases with increasing pressure. Sim-
ilarly, their solubility increases with addition of NaCl up to a
concentration of  1–2 m (Figure 4) and decreases at higher
NaCl concentration (Blount and Dickson, 1973; Raju and
Atkinson, 1990). Anhydrite also displays pronounced pro-
grade solubility in saline fluids at high temperature and pres-
sure. The main aqueous species controlling the solubility of
gypsum and anhydrite are Ca2þ, CaSO40, CaHSO4þ, CaClþ,
CaCl20, HSO4, and SO42.
The behavior of barite (BaSO4) is similar to that of gypsum,
except that it is considerably less soluble. The solubility of
barite in pure water increases with temperature to a maximum
of 0.000 02 m at  150  C and, thereafter, decreases with in-
creasing temperature. With the addition of NaCl and/or KCl,
this maximum shifts to higher temperature. Pressure has a
similar effect, increasing the solubility of barite by a factor of
3 from 100 to 1000 bar (Blount, 1977). The speciation con-
trolling barite solubility is effectively the same as that for
gypsum and anhydrite, except that Ca is replaced by Ba.
Fluorite (CaF2) is by far the most commonly occurring
fluorine-containing mineral and is an important gangue min-
eral in MVT deposits, as well as in rare earth element (REE)
deposits, where it shows a clear spatial association with the
REE mineralization (Williams-Jones et al., 2000). In pure
water, fluorite is relatively insoluble, with a maximum solubil-
ity of 0.000 2 m, which is reached at a temperature of 100  C at
swvp (Strübel, 1965). Thus, like gypsum, its solubility is pro-
grade at low temperature and retrograde at higher temperature;
however, its maximum solubility is only about 10% of that of
gypsum. With the addition of alkali chlorides, fluorite solubil-
ity increases (Figure 4), and in a 2 m NaCl solution, its solu-
bility is prograde at all temperatures. The solubility of fluorite,
like that of the carbonate and sulfate minerals, also increases
with pressure (Tropper and Manning, 2007). Species control-
ling the solubility of fluorite comprise Ca2þ, CaClþ, CaCl20,
HF, and F.
1 From the preceding paragraphs, it is apparent that the
effects of temperature, pressure, and salinity on the solubility
of calcite, gypsum, anhydrite, and fluorite are quite similar,
although the absolute solubility of these minerals varies con-
siderably at comparable conditions. All these minerals display
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids 39

retrograde solubility in dilute aqueous solutions, albeit over
quite different temperature intervals. They also all revert to
prograde solubility with the addition of alkali chlorides, and
they all increase in solubility within increasing pressure. The
main reason for their similar behavior is that these minerals
only differ in the nature of the ligand that binds with Ca2þ (i.e.,
CO32, SO42, or F). These are all hard ligands having high
charge/radius ratios and are strong electron acceptors, and
therefore, their bonding with Ca2þ is dominantly ionic. More-
over, as the relative order of hardness for these ligands is F >
CO32 > SO42, then Ca2þ should form its strongest bonds
with these ligands in the same order, and consequently, at a
given set of conditions, anhydrite should have the highest
solubility followed, in turn, by calcite and fluorite. This is
what is observed (Figure 4).
Pyrite (FeS2) is the most important sulfide gangue mineral
and occurs in virtually all major hydrothermal base and pre-
cious metal mineral deposits, except those subjected to high-
grade metamorphism, in which pyrrhotite has commonly
replaced pyrite. Furthermore, pyrite is the principal sulfide
mineral in most of these deposits, and its concentration is
generally much greater than that of the sulfide minerals con-
taining the ore metals of interest. Numerous studies have
investigated the dissolution of pyrite and its deposition from
aqueous solutions (Ohmoto et al., 1994; Schoonen and
Barnes, 1991a,b). These studies have shown that the solubility
of pyrite is prograde and depends strongly on pH.
Formally, the dissolution of sulfide minerals can be de-
scribed by reactions of the type
sulfur, thiosulfate, or polysulfides, the rate of conversion of
these intermediate phases to pyrite is extremely fast and may
occur within minutes, whereas with only hydrogen sulfide
or bisulfide present, the conversion rate is much slower
(Schoonen and Barnes, 1991a).
One of the important roles of pyrite in hydrothermal sys-
tems is to buffer parameters such as fO2 (or f H2 ) and pH
through reactions with minerals like pyrrhotite, magnetite,
and hematite. For example, the assemblage pyrite–pyrrhotite
constrains oxygen fugacity under acidic conditions through the
reaction
ð1  xÞFeS2 þ ð1  xÞH2 O ¼ Fe1x S þ ð1  xÞH2 S
þ 0:5ð1  xÞO2
and the assemblage pyrite–pyrrhotite–magnetite buffers both
f O2 and pH, in both cases for a given total concentration of
aqueous sulfur (Figure 5).
The solubility of most silicate minerals increases with tem-
perature in aqueous solutions, that is, it is prograde, and de-
pends strongly on pH. In most cases, these minerals dissolve
incongruently, and the nature of the phase formed depends
strongly on the composition of the solution, including its pH.
For example, at relatively low pH and/or low activity of Kþ, the
dissolution of K-feldspar may involve formation of kaolinite
(or another aluminosilicate phase) through the reaction
2KAlSi3 O8 þ H2 O þ 2Hþ ¼ Al2 Si2 O5 ðOHÞ4
þ 4SiO2ðaqÞ þ 2Kþ

MeS ¼ Me2þ þ S2

but as hydrothermal solutions invariably contain insignificant

-10
concentrations of S2 (Ellis and Giggenbach, 1971; Migdisov
250 ⬚C, 1 m NaCl,
et al., 2002), the dissolution of these minerals is more conve- pH 4.5
niently described by reactions involving H2S and HS, the
dominant sulfide species in solution, at acidic and near-neutral
-4
to alkaline conditions, respectively. As mentioned earlier, pK2 -8
for H2S is
17 at 25  C. However, the sulfur in most sulfide
Hematite

minerals is in the 2 state, whereas in pyrite, the sulfur occurs

in both the zerovalent and 2 state as the S0.S2 ion (i.e., as the
simple S22 polysulfide ion). The solubility of pyrite is there- -6
log aH2 aq

fore most appropriately described by a reaction involving the Pyrite

-3
polysulfane, H2S2, but as the stability of polysulfanes and -8
-6
especially their nondissociated forms is poorly known at ele- -4
vated temperature, the dissolution of pyrite is normally -4 Magnetite
described by redox reactions involving H2S and HS, that is,

FeS2 þ 2Hþ þ H2 O ¼ Fe2þ þ 2H2 S þ 0:5O2

-2 -2
or -3
-4
FeS2 þ H2 O ¼ Fe2þ þ 2HS  þ 0:5O2 -2
Pyrrhotite
The dissolution of pyrite is incongruent and, depending on 0
the system, may proceed via complex reactions involving for- -6 -4 -2 0
log aH2S aq
mation of elemental sulfur or iron oxides (e.g., Caldeira et al.,
2010; Rimstidt, 2003). The process of pyrite precipitation is Figure 5 Solubility contours (logm SFe) for pyrite, pyrrhotite,
also complex and, below 300  C (and perhaps at higher magnetite, and hematite as a function of log aH2 S aq and log aH2 aq in a 1 m
temperature), proceeds via intermediate steps involving forma- SCl aqueous solution at pH 4.5, a temperature of 250  C, and vapor-
tion of precursor iron monosulfide, mackinawite (FeS), and saturated water pressure; calculated using thermodynamic data from
the thiospinel, greigite (Fe3S4). In the presence of elemental Holland and Powell (1998) and Shock et al. (1997).
40 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
6 100 ⬚C, swp
5
4 Muscovite
aH+
aK+
3 K-feldspar
log 2 Ammonia (ammine)
1 Oxyanions
0 Kaolinite
-1
-2
-4 -3 -2 -1 0 1
log aSiO2
Figure 6 Stability relationships among muscovite, kaolinite, and


K-feldspar as a function of log aSiO2 aq and log aKþ =aHþ at 100  C and
vapor-saturated water pressure; calculated using thermodynamic data
from Holland and Powell (1998) and Shock et al. (1997).
By contrast, at higher pH and/or higher activity of Kþ, the disso-
lution reaction leads to the formation of muscovite (or illite):
3KAlSi3 O8 þ 2Hþ ¼ KAl3 Si3 O10 ðOHÞ2 þ 6SiO2ðaqÞ þ 2Kþ
Both reactions also depend on the activity of aqueous silica
(Figure 6).
Because of their importance as rock-forming minerals,
many of these silicates play an important role in buffering
fluid composition, and analysis of hydrothermal equilibria
involving them may help in evaluating compositional param-
eters such as pH. As hydrothermal fluids commonly saturate
with respect to quartz, aqueous silica activity is typically buff-
ered, and reactions involving K-feldspar, muscovite, and an
aluminosilicate mineral can be rewritten as follows:
3K-feldspar þ 2Hþ ¼ Muscovite þ 6Quartz þ 2Kþ
2Muscovite þ 3H2 O þ 2Hþ ¼ 3Kaolinite þ 2Kþ
Thus, the coexistence of K-feldspar with muscovite in the
presence of quartz or muscovite with kaolinite buffers the Kþ/
Hþ activity ratio and, if albite is also present, the Kþ activity can
be deduced from fluid inclusion salinity and the Kþ/Naþ ratio
corresponding to equilibrium between K-feldspar and albite,
thereby permitting evaluation of pH (see also the discussion in
Chapter 13.1). At given concentrations of Kþ or Naþ, hydro-
lysis of alkali feldspar to muscovite and paragonite, or the latter
minerals to an aluminosilicate mineral, buffers pH to a fixed
value that depends only on temperature and pressure (e.g.,
Hemley et al., 1992).
13.2.4 Ore Metal Transport and Deposition
13.2.4.1 Ore Fluids with Liquid-Like Densities
13.2.4.1.1 Ligands in hydrothermal ore solutions
Ore-forming hydrothermal fluids migrate through the Earth’s
crust transporting metals as complex ions and molecules.
Focused deposition of metals to form an ore deposit occurs
in response to physicochemical changes in the local environ-
ment. In essence then, ore deposition as a manifestation of the
stability/instability or disproportionation of metal complexes
at a given temperature and pressure (or T–P range) may be
considered. A detailed knowledge of the stability and
Table 3 Ligands occurring in hydrothermal ore solutions
Hydroxide OH
Halide ions F, Cl, Br, I
Sulfur species HS, Sn, SnS2, SO32, S2O32, SO42
NH3
CO32, PO43, AsO33, SbO33, MoO42,
WO42, SiO44
Thioanions AsS33, SbS33, MoS42, WS42
Carboxylates CH3COO (acetate), C2H5COO (propionate),
CH2(COO)22 (malonate), (COO)22 (oxalate)
Miscellaneous HTe, Te22, CN, SCN
ligands of possible
interest
stoichiometry of metal complexes with available ligands as a
function of temperature, pressure, pH, and redox potential
comprises the fundamental basis for understanding the pro-
cesses of hydrothermal ore formation.
What ligands are present in hydrothermal ore solutions?
The three most important are Cl, HS, and OH, although
various other electron donors are also present (Table 3) and
may be important in the complexing and transport of some
metals and under certain conditions. In natural systems, ligand
availability is important. For example, chloride is always pre-
sent at much higher concentrations than, say, iodide, and
hence, in a 1.0 m chloride ore fluid at 500  C and 500 bar,
chloride would be the more important complexing ligand for
gold transport even though the gold(I) iodide complex, AuI2,
is more stable than AuCl2.
Ligand availability and stability may be affected by various
homogeneous reactions occurring within the hydrothermal
ore solution itself. The activity of free chloride ion in an aque-
ous NaCl solution is much diminished with increasing tem-
perature due to ion pairing as discussed earlier. A 1.0 m NaCl
solution at 400  C and 300 bar will be >99% associated,
which will determine the number of coordinated chlorides in
metal complexes. In addition, phase separation and boiling
may dramatically decrease the activity of compounds such as
H2S, H2Te, H2Se, NH3, and CO2 in the residual liquid (or
denser supercritical) phase, effectively removing the corre-
sponding weak acid/base ligands. Changes in the redox envi-
ronment that accompany boiling and/or mixing with
oxygenated fluids in the upper parts of geothermal/hydrother-
mal systems also lead to ligand destruction by oxidation as in
the case of H2S/HS, which reacts to sulfate and other inter-
mediate oxidation state species of sulfur. Mineral deposition
(e.g., sulfide precipitation) also causes H2S/HS loss, especially
in the ore-depositing environment where a cascade of interre-
lated chemical events leads to the almost complete deposition
of various metals from the ore fluid. In addition, some ligands
are not thermally stable. Acetate (CH3COO) is well known to
decarboxylate at elevated temperatures (Bell and Palmer,
1994), and thiosulfate (S2O32) disproportionates at elevated
temperatures Giggenbach, 1974b).
Finally, it is noted that complex stabilities differ signifi-
cantly because of the differing metal–ligand bonds. The differ-
ing complex stabilities can be predicted using hard/soft Lewis
acid/base theory (Ahrland, 1968; Pearson, 1963) as discussed
by Seward and Barnes (1997) with reference to hydrothermal
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids 41

metal complexing. Thus, a soft electron donor such as HS
would be predicted to form very stable complexes with Auþ (a
soft electron acceptor), whereas the fluoride (hard Lewis base/
electron donor) complexes of Auþ are much less stable and the
first isolatable Au(I) fluoride complex has only recently been
synthesized (Laitar et al., 2005), although fluoride complexes
with higher oxidation states of gold are well documented
(Mohr, 2004). This approach is simplistic compared to the
modern quantum chemical assessment of metal complex ge-
ometries and metal–ligand bond energies of complexes of
geochemical interest (e.g., Boily and Seward, 2005; Sherman,
2010) but facilitates an overview of the important metal
transport mechanisms in the multicomponent electrolyte
solutions, which comprise the diversity of hydrothermal ore
solutions.
13.2.4.1.2 Metal chloride complexing
Sodium chloride is the ubiquitous salt in hydrothermal ore
solutions, and hence, the stability of chloride complexes of
many elements at high temperatures and pressures plays a
fundamental role in the transport of these elements by migrat-
ing ore fluids throughout the Earth’s crust and their subsequent
precipitation as ore minerals in an ore-depositing environment
at a given temperature and pressure. It has long been known
that chloride may form a stepwise series of complexes with
many metal cations at ambient temperature as defined by
Mnþ þ mCl ¼ MClm nm
but, until relatively recently, few studies extended to higher
temperatures. Most earlier studies have been discussed/sum-
marized by Seward (1981) and Seward and Barnes (1997).
Sverjensky et al. (1997) tried to overcome the paucity of reli-
able, experimentally based thermodynamic data for metal
complex equilibria at extreme conditions with computational
predictions extending to 1000  C and 5000 bar. Studies of
chloridosilver(I) and chloridolead(II) stepwise complex for-
mation up to 350  C and 300  C, respectively (Seward, 1976,
1984), demonstrated that the higher coordination number
species, such as AgCl43 and PbCl42, are not observed at
elevated temperatures (e.g., 350  C) and equilibrium saturated
vapor pressures, mainly because of the low chloride ion activity
due to NaCl association. Several recent studies (Figure 7) reaf-
firm earlier observations concerning stepwise complex forma-
tion as well as demonstrating the coordination geometry
changes that may occur at elevated temperatures, as discussed
in some detail by Seward (1981) and Seward et al. (1996). In
the case of complexing of tin(II) with chloride (Müller and
Seward, 2001; Figure 7), the distribution of species changes
and the SnCl42 species is not observed in the more concen-
trated chloride solutions up to 3.0 m at 300  C at the equilib-
rium saturated vapor pressure.
Coordination geometry changes attending stepwise com-
plex formation and changes in temperature and pressure
have long been known (Seward, 1981), especially in the case
of cobalt(II) and nickel(II) species in aqueous solution (e.g.,
Lüdemann and Franck, 1967). Recently, the stepwise formation

100 100
25 ⬚C 300 ⬚C
0 0 3
80 80

60 60
% Sn

% Sn

1 2
2 3 4
40 40
1
20 20

0 0
-3 -2 -1 0 1 -3 -2 -1 0 1
log Cltotal / mol kg-1 log Cltotal / mol kg-1

100 100
35 ⬚C 4 350 ⬚C
80 0 80

60 1 60
% Co
% Co

40 40
2-o 2-t
20 20
1
4
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Cltotal / mol kg-1 Cltotal / mol kg-1

Figure 7 Stepwise formation of chloridotin(II) and chloridocobalt(II) complexes at ambient and elevated temperatures at saturated vapor pressure; the
curves are labeled according to the number of chloride ligands bound to each metal cation (i.e., Sn2þ or Co2þ). In the case of the cobalt(II) chloride
complexes, 2-o refers to octahedrally coordinated CoCl2(H2O)4 and 2-t refers to tetrahedrally coordinated CoCl2(H2O)2. Modified from Müller B and
Seward TM (2001) Spectrophotometric determination of the stability of tin(II) chloride complexes in aqueous solution up to 300 C. Geochimica et
Cosmochimica Acta 65: 4187–4199; Liu W, Borg SJ, Testemale D, Etschmann B, Hazemann J-L, and Brugger J (2011) Speciation and thermodynamic
properties for cobalt chloride complexes in hydrothermal fluids at 35–440 C and 600 bar: An in-situ XAS study. Geochimica et Cosmochimica Acta 75:
1227–1248.
42 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids

of cobalt(II) complexes and their octahedral/tetrahedral con-
figurational changes have been revisited by Liu et al. (2011)
(Figure 7), who demonstrated the predominance of tetrahe-
drally coordinated moieties, including CoCl42, in expanded
high-temperature water. Of particular interest as well is the
nature of complex geometry and the manner in which the
solvent molecules interact with metal complex ions/molecules
to affect metal–ligand bonds and complex stability. In the case
of stepwise complex formation between Cd2þ and Cl, for
example, solvent molecules (i.e., H2O) contribute fundamen-
tally to the stability of the complex (Seward et al., 2013). As
shown in Figure 8, the Cd–O (water) and Cd–Cl distances
obtained from EXAFS measurements are 2.30 and 2.50 Å,
respectively, for the octahedral CdCl(H2O)5þ complex, but
these values differ from the quantum chemically calculated
values with only five first-shell water molecules bound to the
Cd2þ. However, with stepwise addition of solvated waters to the
second shell, one observes that the calculated Cd–O distance
asymptotically approaches the value measured by X-ray absorp-
tion spectroscopy when n
4. However, at least eight second-
shell waters are necessary to reproduce the measured Cd–Cl
distance. These concepts are of considerable importance in
understanding the partitioning of metal complex ions and mol-
ecules to a steam-phase or low-density supercritical fluid in
hydrothermal systems. Metal complexes in such lower-density
fluids are also hydrated moieties, which comprise molecular
aggregates or clusters, as discussed in the succeeding text.
In recent years, further advances in our understanding of
metal chloride complexing at hydrothermal conditions have
come from solubility measurements, UV/Vis and X-ray absorp-
tion spectroscopy, and ab initio and ab initio/MD calculations.
These include studies of the chloride complexes of Ti4þ
(Ryzhenko et al., 2006), Mn2þ (Suleimenov and Seward,
2000), Fe2þ and Fe3þ (Liu et al., 2007; Stefansson et al.,
2008; Testemale et al., 2009), Co2þ (Liu et al., 2011; Migdisov
et al., 2011a,b), Ni2þ (Tian et al., 2012), Cuþ and Cu2þ
(Etschmann et al., 2010; Fulton et al., 2000; Liu et al., 2002,
2008; Sherman, 2007; Xiao et al., 1998), Zn2þ (Anderson et al.,
2000; Harris et al., 2003; Trevani et al., 2009), Cd2þ (Bazarkina
et al., 2010; Palmer et al., 2000; Seward and Driesner, 2004;
Seward et al., 2013), In3þ (Seward et al., 2000), Sn2þ and Sn4þ
(Kovalenko and Ryzhenko, 1997; Müller and Seward, 2001;
Sherman et al., 2000a,b; Uchida et al., 2002), Sb3þ (Oelkers
et al., 1998; Pokrovski et al., 2006), Pd2þ (Boily and Seward,
2005; Seward and Driesner, 2004), Auþ and Au3þ (Gammons
et al., 1997; Stefansson and Seward, 2003a,b,c; Usher et al.,
2009), Tlþ (Bebié et al., 1998), rare earth(III) elements except
Pm3þ (Gammons et al., 2002; Mayanovic et al., 2002, 2007,
2009; Migdisov and Williams-Jones, 2002, 2006; Migdisov
et al., 2008, 2009; Stepanchikova and Kolonin, 2005), Y3þ
(Ragnarsdottir et al., 1998), and U4þ (Kovalenko et al.,
2011). All these studies provide thermodynamic data and/or
molecular insight into complex energetics, geometries, and
metal–ligand bond lengths, the aim being to understand fun-
damental aspects of metal transport, metal (complex) parti-
tioning during fluid phase separation, and ore mineral
precipitation in ore-forming hydrothermal systems.
13.2.4.1.3 Complexing with other halide ligands
With the exception of Gammons and Yu (1997) and Liu et al.’s
(2012) studies of bromide and iodide complexes of silver and
zinc at elevated temperatures, there have been few studies of

Stepwise hydration of CdCl(H2O)5+

2.65 Cd–Cl
[CdCl(H2O)5(H2O)n]+
2.60
2.55
EXAFS bulk, Cd–Cl, 298 K
2.50

Cd–Cl (Å)
Cd–O (Å)

2.45
[CdCl(H2O)5(H2O)1]+ [CdCl(H2O)5(H2O)2]+ [CdCl(H2O)5(H2O)3]+
2.40
2.35
Cd–O
2.30 EXAFS bulk, Cd–O, 298 K
MP2/aug-cc-pVDZ(PP), this study
2.25 MP2/aug-cc-pVTZ(PP), this study
HF/MSI*, Butterworth92
2.20
0 1 2 3 4 5 6
n, Solvation number
[CdCl(H2O)5(H2O)4]+ [CdCl(H2O)5(H2O)5]+ [CdCl(H2O)5(H2O)6]+

MP2 optimized geometries

Figure 8 EXAFS and ab initio data for cadmium(II) chloride and oxygen (water) distances for the octahedral monochloridocadmium(II) complex, CdCl
(H2O)5þ; the EXAFS-determined Cd–O (water) and Cd–Cl distances are given by the horizontal dashed lines. The quantum chemically calculated
distances for the optimized geometries resulting from the addition of each second-shell water are also shown. Reproduced from Seward TM, Lemke KH,
Henderson CMB, and Charnock JM (2013) An X-ray absorption spectroscopic and ab initio computational study of the Cd(II) aquated ion and
chlorocadmium(II) complexing in hydrothermal solutions. Chemical Geology (in review).
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
metal bromide and iodide complexes under hydrothermal
conditions from which thermodynamic data have been
obtained. In near-magmatic to epithermal hydrothermal
fluids, bromide and iodide complexes are not considered to
play a significant role in ore transport. Nevertheless, bromide
and iodide complexes may play a role in the volatile metal
complex chemistry in magmatic/volcanic gas systems and tran-
sition metal transport chemistry. Various sulfide/halide subli-
mate minerals containing bromide and iodide occur in
fumarolic deposits of active volcanoes, such as at Vulcano in
Italy (Demartin et al., 2010). Bromide and iodide complexes
may play a role in metal transport in sedimentary basinal brines,
but this has been little studied. Bromide interaction with some
metal cations has been studied at hydrothermal conditions
using X-ray absorption spectroscopy (Ni2þ: Hoffmann et al.,
1999; Wallen et al., 1998; Zn2þ: Anderson et al., 2000; Liu
et al., 2012; Simonet et al., 2002). These latter studies emphasize
the tendency toward tetrahedrally coordinated species, such as
ZnBr2(aq) (i.e., ZnBr2(H2O)20) and ZnBr42, with increasing
temperature, as shown also by the high-temperature (up to
500  C) Raman data of Mibe et al. (2009).
However, fluoride plays an important role in the transport
of some metals/elements such as titanium, tin, rare earths,
zirconium, and uranium in hydrothermal ore solutions. In
the case of titanium, for example, the solubility of rutile in
high-temperature hydrothermal fluids is much enhanced by
the presence of fluoride (Rapp et al., 2010) due to the complex-
ing of Ti4þ by F (Ryzhenko et al., 2006) and the formation of
mixed hydroxofluoro -complexes, such as TiF(OH)30,
TiF2(OH)20, and TiF(OH)4. Kovalenko et al. (1992) and
Kovalenko and Ryzhenko (1997) have demonstrated the im-
portance of tin(II) fluoride complexes, such as SnF(OH)2 and
SnFCl0, in hydrothermal fluoride solutions at 500  C and
1 kbar, but more experimentally based thermodynamic data
are required in order to adequately understand the hydrother-
mal transport and deposition chemistry of tin by fluids in the
Earth’s crust. Recent experimental studies (Migdisov et al.,
2011a,b; Prisyagina et al., 2008; Ryzhenko et al., 2008) have
also demonstrated that the zirconium(IV) hydroxofluoride
complexes are important in determining the transport (i.e.,
the mobility) of zirconium (and the solubility of zircon and
baddeleyite) in hydrothermal fluids in the Earth’s crust. The
fluoride complexes of the rare earth(III) elements (except
Pm3þ) have been studied using solubility and spectrophoto-
metric methods by Migdisov and Williams-Jones (2007) and
Migdisov et al. (2009) up to 300  C at the equilibrium vapor
pressure. Previous theoretical predictions had overestimated
the stability at elevated temperatures of species such as NdF2þ
and hence its importance in hydrothermal fluids relative to the
chloride complexes, NdCl2þ and NdCl2þ. The values of the
equilibrium constants for the formation of the monofluorido-
and monochlorido-complexes of the rare earth(III) elements
are summarized in Figure 9. More data are required to under-
stand REE transport and deposition chemistry by hydrother-
mal fluids at T > 350  C. Kovalenko et al. (2012) have
measured the solubility of uraninite (UO2) in HF solutions at
500  C and 1000 bar and identified the hydroxofluoride spe-
cies, U(OH)3F0 and U(OH)2F20, thus emphasizing the proba-
ble importance of fluoride complexing of U4þ in hydrothermal
transport, but more experimental studies are required before
43
an adequate understanding of the hydrothermal transport and
deposition chemistry of uranium is available. The uranyl ion,
UO22þ, also plays a role in hydrothermal uranium transport in
environments of intermediate redox potential.
13.2.4.1.4 Metal complexes with hydroxide and other
oxygen electron donor ligands
Many metal ions hydrolyze in high-temperature aqueous solu-
tions in the pH range encompassed by natural hydrothermal
fluids in the Earth’s crust, and hence, the hydroxide complexes
can play an important role in the chemistry of hydrothermal
ore transport. A detailed overview of metal ion hydrolysis
speciation is given by Baes and Mesmer (1976), and
Wesolowski et al. (2004) provide an erudite summary of
metal ion hydrolysis and metal oxide solubility measurements
at elevated temperatures. It is well known that the solubility of
metal oxides in aqueous media over wide ranges of tempera-
ture and pressure is pH-dependent (Wesolowski et al., 2004),
and as in the case of rutile solubility at 300  C, for example, the
minimum solubility in the near-neutral region and the overall
shape of the solubility curve is due to the hydrolysis of Ti4þ
with the formation of various Ti(OH)n4n species (Knauss
et al., 2001) according to the reaction
TiO2 ðrutileÞ þ ð4  nÞHþ þ ðn  2ÞH2 O ¼ TiðOHÞ4 4n
The elevated solubility of rutile in supercritical water (up to
1000  C and 2.3 GPa) in the presence of albite (Audétat and
Keppler, 2005; Hayden and Manning, 2011; Manning et al.,
2008) indicates that dissolved Ti(IV) forms some sorts of ad-
ducts with dissolved aluminum silicate species in solution.
Iron occurs ubiquitously in hydrothermal ore deposits as
sulfide, oxide, silicate, and carbonate minerals. The hydrother-
mal ore transport chemistry of Fe(II) and Fe(III) is dominated
by chloride complexing (see the preceding text) and by hydro-
lysis equilibria, which have been extensively studied up to
300  C (Wesolowski et al., 2004). Recently, the formation
of Fe(OH)2þ has been studied spectrophotometrically by
Stefansson et al. (2008) up to 300  C, and their thermody-
namic data are in good agreement with the few earlier reported
data. Unfortunately, there are essentially no experimentally
derived thermodynamic data for iron complexing and hydro-
lysis at higher temperatures from 350  C to supercritical
conditions, which limits our ability to model the transport
and precipitation chemistry of iron in many ore-depositing
environments in the Earth’s crust.
Significant gallium enrichments occur in the metal-
enriched surface precipitates of some active geothermal sys-
tems (Krupp and Seward, 1987), but the aqueous chemistry
of gallium (predominantly as Ga3þ) has been little studied at
elevated temperatures and pressures, and the transport chem-
istry by hydrothermal fluids in the Earth’s crust is poorly
known. Bénézeth et al. (1997) measured the solubility of
a-GaOOH from 150 to 250  C and estimated the equilibrium
formation constants for Ga(OH)n3n from 25 to 300  C.
The hydrolysis Nd3þ has been studied by solubility and
potentiometric methods up to 290  C by Wood et al. (2000),
but otherwise, there are few experimentally based data available
on REE hydroxide complexes under hydrothermal conditions.
44 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids

9
250 ⬚C

8
200 ⬚C
250 ⬚C
150 ⬚C

Log b F1
7
200 ⬚C
6

5 150 ⬚C

4
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

3.5
250 ⬚C
3

2.5 200 ⬚C
Log b Cl1

1.5
150 ⬚C
1

0.5
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Figure 9 The equilibrium cumulative formation constants for the monofluorido- and monochlorido-complexes of the rare earth elements in
aqueous solution up to 250  C and at the saturated vapor pressure. Modified from Migdisov AA, Williams-Jones AE, and Wagner T (2009)
An experimental study of the solubility and speciation of rare earth(III) elements in fluoride and chloride bearing aqueous solutions at temperatures
up to 300 C. Geochimica et Cosmochimica Acta 73: 7087–7109.

Hydrothermal molybdate chemistry has been studied by
Ulrich and Mavrogenes (2008) who measured the solubility
of Mo and MoO3 in water and KCl solutions from 500 to
800  C and to 3000 bar and suggested (with the aid of
XANES spectra) that solubility was due to the simple molybdic
acid species as well as to chloromolybdate species (e.g.,
MoOmCln2) (see also the thioanion discussion in the succeeding
text). Minubayeva and Seward (2010) used ultraviolet spectros-
copy to obtain the first thermodynamic data for molybdic acid
ionization up to 300  C at the equilibrium saturated vapor
pressure, that is,
H2 MoO4 ¼ HMoO4 þ Hþ and
HMoO4 ¼ MoO4 2 þ Hþ
and Yan et al. (2011) have confirmed the MoO4 stoichiometry
(using EXAFS) in hydrothermal solutions up to 600  C.
In addition, Borg et al. (2012) have confirmed molybdate
stoichiometry and geometry up to 385 C and 600 bar using
X-ray absorption spectroscopy and also identified chloromo-
lybdate species in concentrated HCl solutions. There are few
studies of hydrothermal tungstate chemistry, and the earlier
potentiometric study by Wesolowski et al. (1984) still com-
prises the benchmark work on aqueous tungstate chemistry
(i.e., tungstic acid ionization and polynuclear tungstate forma-
tion) up to 300  C. Recently, Minubayeva and Seward (2013)
have also studied (spectrophotometrically) the deprotonation
of simple monomeric H4WO4 up to 300  C and reported
similar results to those of Wesolowski et al. (1984).
Arsenic and antimony are fellow travelers in hydrothermal
ore fluids and are often involved in ore mineral deposition,
and hence, an understanding of their hydrothermal chemistry
will provide additional insight into ore formation. The equilib-
rium constants for arsenous and antimonous acid ionization
have been determined up to 300  C at saturated vapor pressures
by Zakaznova-Herzog et al. (2006) and Zakaznova-Herzog and
Seward (2006). Their data permit the modeling of arsenic(III)
and antimony(III) transport and deposition in hydrothermal/
geothermal fluids having low, reduced sulfur activity. The
dilemma, of course, is that hydrothermal ore fluids contain
reduced sulfur and thioarsenite, and thioantimonite species
(i.e., H3(As,Sb)S3(As,Sb)(HS)3) will also contribute to the
total dissolved As(III) and Sb(III) in the fluids. The thermody-
namic data for these species are sparse and in poor agreement, as
discussed briefly in the succeeding text:
H3 AsO3ðaqÞ ¼ H2 AsO3 þ Hþ and
H3 SbO3ðaqÞ ¼ H2 SbO3 þ Hþ
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids 45

Carbonate and bicarbonate are ubiquitous ligands in natu-

ral hydrothermal fluids and form stable complexes with many 100
metals (i.e., with hard/intermediate Lewis acids or class A
acceptors), such as Pb2þ, UO22þ, and REE ions, but there are AuOH0
80
essentially no systematic studies of metal carbonate complexes
up to elevated temperature and pressure and from which ther-
60
modynamic data are available. Such complexes will be pH-

% Au
sensitive, and their stabilities will decrease dramatically during
boiling or with the precipitation of carbonate minerals. 40
Au(OH)2-
Various carboxylic acid and other organic species occur in Au(HS)2-
sedimentary basin brines, the most important of which is AuCl2-
20
acetate (Shock and Koretsky, 1993), and a number of metal AuHS0
acetate complexes have been studied at elevated temperatures 0
up to 300  C. These include potentiometric and spectroscopic
measurements of the acetate complexes of Fe2þ (Giordano and (a)
Drummond, 1991; Palmer and Drummond, 1988), Co2þ
(Bridger et al., 1981), Cuþ (Liu et al., 2001), Zn2þ and Pb2þ 100
(Yang et al., 1989), Cd2þ (Bénézeth and Palmer, 2000), Csþ
and Sr2þ (Ragnarsdottir et al., 2001), and Nd3þ, Eu3þ and Y3þ 80
AuOH0
(Tagirov et al., 2007a,b; Wood et al., 2000; Zotov et al., AuCl2-
2002). Other literature data on metal–organic complexing
60
relevant to ore-depositing systems are discussed by Seward

% Au
and Barnes (1997). Au(OH)2-
40
Au(HS)2-
13.2.4.1.5 Complexing with hydrosulfide/sulfide ligands 20
The hydrosulfide ligand, HS, plays a fundamentally impor- AuHS0
tant role in the transport and deposition chemistry of some 0
elements in hydrothermal ore solutions. Auþ is the archtype (b)
soft Lewis acid (class B) electron acceptor and, as such, forms
very stable complexes with HS. The stoichiometry and stabil- 100 AuCl2-
ity of the AuHS0 and Au(HS)2 species were first reported by AuHS0
Seward (1973), and there have been numerous studies of the 80
interaction of Auþ with reduced sulfur ligands since then (e.g.,
Baranova and Zotov, 1998; Benning and Seward, 1996; Dadze 60 Au(HS)2-
% Au

et al., 2000; Gibert et al., 1998; Loucks and Mavrogenes, 1999;

Pokrovski et al., 2009; Renders and Seward, 1989a; Shenberger
and Barnes, 1989; Stefansson and Seward, 2004; Tagirov et al.,
2005, 2006). The study of Stefansson and Seward (2004) pro-
vides thermodynamic data for the formation of the hydrosulfido-
gold(I) complexes, AuHS0 and Au(HS)2, up to 500  C and
500 bar, which, together with the data for hydroxide and
chloride complexes (Stefansson and Seward, 2003a,b), enable
the modeling of gold transport and deposition chemistry in
hydrothermal ore fluids over a wide range of temperature and
pressure (Figure 10). As shown in Figure 11, the solubility of
gold in aqueous sulfide solution at elevated temperature is very
sensitive to changes in pH and redox potential. In addition,
any process that causes a loss of reduced sulfur (i.e.,
H2S þ HS) will lead to complex instability and, hence, the
precipitation of gold. Boiling a hydrothermal fluid can be
catastrophic for the stability of the gold(I) hydrosulfide com-
plexes. Partitioning of volatiles into the vapor phase in epither-
mal environments leads to a loss of H2S (i.e., loss of the HS
ligand), H2 (i.e., a redox change), and CO2 (i.e., an increase in
pH). A change in the redox potential of the residual liquid
phase during boiling and /or mixing with oxygenated meteoric
waters encountered in the upper parts of geothermal/epither-
mal systems removes sulfide sulfur (Seward, 1989). The pre-
cipitation of pyrite and other sulfide minerals also extracts
40
20
0
(c) 0 2 4 6 8
pH
Figure 10 The distribution of gold complexes in solutions of different
composition at 400  C and 500 bar. (a) H2S þ HS ¼ 0.001 m,
Cl ¼ 0.001 m; (b) H2S þ HS ¼ 0.001 m, Cl ¼ 0.5 m;
(c) H2S þ HS ¼ 0.5 m, Cl ¼ 0.5 m. Modified from Stefansson A and
Seward TM (2004) Gold(I) complexing in aqueous sulfide solutions to
500 C at 500 bar. Geochimica et Cosmochimica Acta 68: 4121–4143.
reduced sulfur from the ore fluid. In supercritical, magmatic
hydrothermal fluids, the condensation of an iron-rich brine
during phase separation allows the less dense, volatile-rich
(H2S-containing) phase to then cool, contract, and ascend
buoyantly in the Earth’s crust without losing most of its dis-
solved sulfide to pyrite precipitation, as discussed by Heinrich
et al. (2004).
46 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids

-29 or H2S/HS) concentration, as discussed, for example, by

- Stefansson and Seward (2003a,b,c). The stoichiometry and sta-
AuCl2 AuHS0

b
pp
HSO4- bility of zinc(II) hydrosulfide/sulfide complexes have been stud-

10
1 pp SO42- ied by Tagirov et al. (2007a,b) and Tagirov and Seward (2010)
b
-33 up to 250  C. At 300  C and the equilibrium vapor pressure, the
10 ppb Au(HS)2-
two hydrosulfide species, Zn(HS)20 and Zn(HS)3, predominate
1 pp
b in the near-neutral 0.10 m sulfide solutions, but for concentra-
AuHS0
log f O2

tions of Cl >0.1 m, the transport of zinc will be dominated by

10
-37

pp
ZnCln2n complexes (Ruaya and Seward, 1986). The stability of

b
1 ppb

pp
100 ppb
the monohydrosulfido-complex of cobalt(II) has recently been

10

pb
1p
reported by Migdisov et al. (2011a,b), who suggested that the
-41 HS - CoHSþ may play some role in cobalt transport in sulfide-con-
H2S Au(HS)2- taining fluids at T < 200  C. The relevance of the related mono-
hydrosulfide complexes of iron and nickel to ore transport under
hydrothermal conditions is not known. Mercury(II) forms stable
-45
hydrosulfide/sulfide complexes under hydrothermal conditions
2 4 6 8 10
(see Barnes and Seward, 1997, and references therein), and other
(a) pH studies pertaining to ambient/low-temperature conditions using
-2 solubility, ab initio, and EXAFS methods (Bell et al., 2007;
250 ⬚C Au(HS)2- Lennie et al., 2003; Paquette and Helz, 1997; Tossell, 2001a)
emphasize the stability of the mercury(II) hydrosulfide/sulfide
-4
log mAu/ mol kg-1

complexes, but more detailed studies under hydrothermal con-

-6
-8
AuOH0
-10
0 2 4 6
(b) pH
Figure 11 (a) The solubility of gold (contour lines in ppb) and
speciation at 250  C and 500 bar as a function of pH and log fO2 in a
solution containing 1.0 m NaCl and SS ¼ 0.01 m. The dashed lines define
regions of predominance of the various sulfur species; the regions of
highest gold solubility are colored yellow (10–100 ppb) and red
(>100 ppb). Thermodynamic data for the gold(I) hydrosulfide
complexes are from Stefansson and Seward (2004). Modified from
Williams-Jones AE, Bowell RJ, and Migdisov AA (2009) Gold in solution.
Elements 5: 281–287. With permission from the Mineralogical
Association of Canada. (b) The solubility (molal) of gold at 250  C and
500 bar and showing the species contributing to the solubility curve as a
function of pH. Reproduced from Stefansson A and Seward TM (2004)
Gold(I) complexing in aqueous sulphide solutions to 500 C at 500 bar.
Geochimica et Cosmochimica Acta 68: 4121–4143.
In addition to gold, the other group IB (group 11) elements,
Cu and Ag, also form stable hydrosulfide complexes. Thermody-
namic and local structural data for CuHS0 and Cu(HS)2 have
been studied under hydrothermal conditions by Mountain
and Seward (1999, 2003) and Etschmann et al. (2010), and
Stefansson and Seward (2003a,b,c) have studied the stability of
AgHS0 and Ag(HS)2 up to 400  C and at 500 bar. At alkaline
conditions, the Cu2S(HS)22 and Ag2S(HS)22 stoichiometries
have been identified, but these are not considered to play a
significant role in ore transport. Whether the dominant ore
transport mechanism is chloride or hydrosulfide complexing
depends upon the temperature, pressure, pH, and ligand (Cl
ditions are required.
13.2.4.1.6 Thioanions
Of particular interest as well are the various thio-substituted
AuHS0
oxyanions of As, Sb, Mo, and W, which have been little studied
at elevated temperatures and pressures. There have been a
number of recent spectroscopic (X-ray absorption and ultravi-
olet) studies of aqueous thioarsenite species (Beak et al., 2008;
Bostick et al., 2005; Zakaznova-Herzog and Seward, 2012, and
8 10 12 references therein) that confirm the simple thioarsenous acid
stoichiometry (i.e., H3AsS3 or As(HS)3), but the system is also
complicated by the formation of intermediate oxythio-species
(i.e., AsOS23 and AsO2S3) and their protonated equivalents,
all of whose stabilities are pH-dependent. Thioantimonite and
thioantimonate species have also been reported at elevated
temperatures to 350  C (Krupp, 1988; Sherman et al., 2000a,b),
but there is a desperate need for further systematic, corrob-
orative studies to confirm stoichiometries and provide high-
quality equilibrium thermodynamic data, especially for
thioantimonite and oxythioantimonite (SbO3mSm3) in hy-
drothermal solutions. As noted earlier, the thermodynamics of
molybdic and tungstic acid ionization up to 300  C (i.e.,
H2(Mo,W)O4) are known, but this is not the case for the
sulfur-substituted analogues. Thiomolybdate and thiotung-
state, ((Mo,W)O4mSm2, where m ¼ 1–4), are well known at
ambient temperature (e.g., Erickson and Helz, 2000) and may
be extensively polymerized (e.g., Mo4S156, Mo4S132, and
Mo2S72) (Saxena et al., 1968), depending on the moly-
bdenum and/or tungsten activity. Zhang et al. (2012) have
measured the solubility of MoS2 (molybdenite) from 600 to
800  C at 200 MPa and suggested that an ion-paired dithiomo-
lybdate species, NaHMo2S2, may account for the observed sol-
ubilities. All of these various thioanions will be potentially
important transporting moieties for elements such as As, Sb,
Mo, and W in sulfide-containing hydrothermal fluids in the
Earth’s crust, but there is a dearth of data at elevated tempera-
tures and pressures. In addition, these thioanions may them-
selves act as complexing ligands as in the case of the Cu(I)
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
thioarsenite complex, CuAsS(SH)(OH) (Clarke and Helz,
2000; Tossell, 2001a,b), but there are no data pertaining to
the stability of such species under hydrothermal conditions.
The transport of gold in ore solutions as a gold(I) thioarsenite
complex has long been hypothesized, but there are no available
data pertaining to the stability and stoichiometry of such spe-
cies at high temperatures and pressures.
It should be noted as well that As(V) and Sb(V) thio-species
have been identified in surface hot springs of active geothermal
systems (Planer-Friedrich and Scheinost, 2011; Planer-Friedrich
et al., 2010). This raises the possibility of thioarsenate and
thioantimonate species facilitating the mobilization of As and
Sb in the upper parts of geothermal/hydrothermal systems in
which the redox potential of the liquid phase has become
elevated due to boiling and mixing with circulating, steam-
heated, oxygenated meteoric waters.
13.2.4.1.7 Complexing with other sulfur-containing
ligands
The possible role of intermediate oxidation state sulfur species,
such as polysulfides (SnS2 and Sn), thiosulfate (S2O32), and
sulfite (SO32), in the hydrothermal transport of gold has been
discussed by Seward (1982), and this topic has recently been
revisited by Pokrovski et al. (2009). The divalent polysulfide
ions (SnS2) disproportionate to Sn, thiosulfate, and monosul-
fide (H2S/HS) at T > 150  C, as noted by Giggenbach (1974a,
b). The SnS2 ligands form complexes with Auþ up to moderate
temperatures of  150  C (Berndt et al., 1994; Kakovski and
Tyurin, 1962), and such species may play a role in gold precip-
itation and local remobilization in the upper parts of geo-
thermal systems where fluids of intermediate redox potential
occur. Polysulfide complexes of other elements, for example,
mercury, are known (e.g., Jay et al., 2000; Paquette and Helz,
1997), but there are no studies at hydrothermal conditions from
which thermodynamic data have been obtained.
However, in terms of hydrothermal complexing of gold and
other ‘soft’ metal cations, the S3 ion might be of more impor-
tance. S3 has long been known to occur in ethanol (a low
dielectric protic solvent having some similarities to high-
temperature water with respect to metal complex equilibria)
and salt melts at high temperatures to 600  C (Giggenbach,
1968, 1971c). This blue polysulfide ion, now considered to be
the S3 species (Seel et al., 1977), was also shown to be
stabilized in high-temperature water by Giggenbach (1971b),
suggesting that it could play a role in metal complex formation
in some hydrothermal ore solutions of intermediate redox po-
tential and at temperatures in excess of 300  C, as has also been
noted recently by Pokrovski and Dubrovinsky (2011). Tossell
(2012) has also studied the properties of the S3 anion using
quantum mechanical methods and demonstrated that S3 may
form complexes with Cuþ (e.g., Cu(S3)2 and Cu(S3)(H2O)0)
having similar stability to the Cu(I) hydrosulfide moieties.
The intermediate oxidation state oxyanions of sulfur, thio-
sulfate (S2O32), sulfite (SO32), polythionates (SnO62), and,
of course, sulfate (SO42), are known to occur in active geo-
thermal systems, especially in surface hot springs/pools as well
as some well discharges and hot crater lake environments
(Kaasalainen and Stefansson, 2011; Takano et al., 1994;
Webster, 1987; Wilson, 1941; Xu et al., 2000). The sulfur oxya-
nions and divalent polysulfides (i.e., SnS2) undoubtedly play a
47
role in metal transport/remobilization in the supergene
environment, and a number of thiosulfate and sulfite minerals
have been identified in oxidized supergene zones of ore deposits
(e.g., sidpietersite, Pb4(S2O3)O2(OH)2, and scotlandite,
PbSO3). Hannebachite, CaSO3 H2O, occurs in late-stage,
lower-temperature vesicle fillings of the Eifel volcanics
(Hentschel et al., 1985). In the case of gold(I), for example,
the thiosulfate and sulfite complexes are very stable at 25  C
with the equilibrium formation constant, log b2 ¼ 26–29.4 (Au
(S2O3)23) and log b2 ¼ 30.1 (Au(SO3)23) (Peshchevitsky
et al., 1970; Pouradier and Gadet, 1969), and the local, near-
linear, structure of the thiosulfate moiety has been studied using
EXAFS and ab initio DFT methods (Bryce et al., 2003).
In addition, the mixed ligand ammine/thiosulfate and sulfite/
thiosulfate gold(I) species have also been studied at 25  C
(Perera and Senanayake, 2004; Perera et al., 2005). However,
the importance of these complexes in hydrothermal ore trans-
port is strongly dependent on the stability of the ligands
themselves, at elevated temperatures and pressures. The poly-
thionates, thiosulfate, and the divalent polysulfides all disp-
roportionate at elevated temperatures (i.e., at T  250  C), and
the kinetics of these disproportionations are also sensitive to pH
as noted by various workers (Foerster et al., 1923; Giggenbach,
1974a,b; Mizoguchi et al., 1976; Pryor, 1960). Nevertheless,
these intermediate oxidation state, anionic sulfur species may
play some role in the mobilization of some metals such as
gold in the upper, cooler parts of ore-depositing geothermal
systems.
In higher temperature, supercritical hydrothermal systems,
the sulfur redox chemistry is often considered in terms of the
reaction
H2 SðgÞ þ 2H2 OðgÞ ¼ SO2ðgÞ þ 3H2ðgÞ
In magmatic and volcanic gases, both H2S and SO2 occur,
but the thermodynamics of the reaction favors SO2 at high
temperatures. However, the stability of solvated SO2, that is,
sulfite as SO32 and HSO3, at T > 300  C, is poorly known,
although sulfite (SO32 and HSO3) has been shown to dispro-
portionate to elemental sulfur and sulfate at temperatures from
150 to 200  C, sometimes with the formation of transient thio-
sulfate (Foerster et al., 1923; Mizoguchi et al., 1976), depending
on pH. Elemental sulfur hydrolyzes to H2S/HS and HSO4/
SO42 in high-temperature water (Ellis and Giggenbach, 1971).
The reactivity of magmatic sulfur dioxide in the presence of
supercritical water with decreasing temperature is given by
4SO2 þ 4H2 O ¼ H2 S þ 3HSO4 þ 3Hþ
and this reaction together with the dissociation of HCl0 ion
pairs generates acidity which is then ‘titrated’ by reaction with
silicate minerals (see Giggenbach, 1992).
Sulfate complexes (ion pairs) of the divalent first-row tran-
sition element cations, Fe2þ (Rudolph et al., 1997), Ni2þ
(Madekufamba and Tremaine, 2011), Cu2þ (Mendez de Leo
et al., 2005), and Zn2þ (Rudolph et al., 1999), have been
studied under hydrothermal conditions, but none of these
simple ion pairs (i.e., MSO40) are considered to play a signif-
icant role in ore metal transport in saline hydrothermal fluids
of reduced to intermediate redox potential in the Earth’s crust.
48 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
Migdisov and Williams-Jones (2008) have studied the forma-
tion of Nd(III), Sm(III), and Er(III) sulfate complexes up to
250  C (i.e., (REE)(SO4)þ and (REE)(SO4)2) and concluded
that these stable complexes would be the principal REE species
in natural hydrothermal solutions in the absence of elevated
concentrations of other complexing ligands, such as fluoride
and chloride.
13.2.4.1.8 Other complexing ligands
Metal ammine complexes are known at ambient temperature
for many elements, but the stability and stoichiometry of metal
ammino-complexes in hydrothermal solutions are essentially
unstudied, with the exception of the Cu(II) ammine com-
plexes, Cu(NH3)n2þ (1  n  4), in Trevani et al. (2001), who
investigated (visible spectroscopy) their formation up to
150  C. Amminosilver(I) and amminogold(I) complexes are
known at ambient temperature (Perera and Senanayake, 2004;
Skibsted and Bjerrum, 1974), but there are no studies of the
stability and stoichiometry of these potentially important, ore-
transporting species under hydrothermal conditions.
13.2.4.1.9 Ore fluids with gas-like density
Hydrothermal fluids, such as those of magmatic hydrothermal
systems, are commonly supercritical and may vary in density
from low (gas-like) to high (liquid-like), depending on the
level of emplacement of the hydrothermal system. On cooling,
these fluids generally separate into vapor and liquid by con-
densation or boiling, although the gas-like fluid may contract
to a liquid and the liquid-like fluid may expand to a vapor
(Heinrich, 2005). This separation of formerly supercritical hy-
drothermal fluids into vapor and liquid leads to partitioning of
the components of the original fluid between these two phases.
Volatile components, such as acidic gases (e.g., CO2, H2S, and
HCl), partition preferentially into the vapor, whereas compo-
nents with low volatility, such as NaCl and KCl, partition
preferentially into the liquid. This does not mean, however,
that low-volatility components are absent from the vapor. On
the contrary, salts like NaCl (e.g., Armellini and Tester, 1993;
Bischoff et al., 1986) and NH4Cl (Palmer and Simonson,
1993) dissolve in appreciable concentrations in water vapor
(depending on density), although in much lower concentra-
tions than in liquid water. Nonetheless, there are important
differences in the nature of the species dissolved in aqueous
vapor and liquid.
As discussed earlier, ionic species, including simple and
complex ions, are important in aqueous liquids and com-
monly predominate. By contrast, aqueous vapor is dominated
by molecular, uncharged species. For example, the nature of
the predominant reduced sulfur species in aqueous liquids
depends on pH and can be either H2S(aq) or HS, whereas in
the vapor, the predominant form is molecular H2S. The frac-
tionation of solution components between aqueous liquids
and vapor therefore varies, even at constant temperature and
pressure, and depends strongly on the properties of the aque-
ous liquid, namely, the degree of ionization of the dissolved
components. As a result, the fractionation cannot be described
by a simple partition coefficient. However, it can be predicted
by using Henry’s law to determine the distribution of the
molecular species between gas and liquid, and ionization con-
stants to determine the proportion of the component of inter-
est that is in molecular form in the liquid (e.g., H2S0 relative to
H2S(aq) þ HS). Henry’s law relates the partial pressure of
the gas species over the liquid to its concentration in the
liquid phase and, via the Henry’s law constant, enables the
distribution of the molecular species to be calculated from its
thermodynamic properties. Salting-out effects may give rise
to induced phase separation (e.g., Duan and Li, 2008;
Suleimenov and Krupp, 1994), and this calculation requires
that the liquid should be at the same temperature as the gas.
During the past three decades, a large body of experimental
data has been gathered on the solubility of acid gases in aque-
ous solutions, and these have been used to develop models
that describe the behavior of some of these gases in the two-
phase region (e.g., CO2, CH4, and H2S) (Dubessy et al., 2005;
Majer et al., 2008). Because of nonideal behavior, accurate
prediction of the partitioning of gas species between vapor
and liquid necessitates that these models also employ equa-
tions of state for the gas phase (e.g., Stryjek and Vera, 1986)
and activity models for the liquid solutions (e.g., Helgeson
et al., 1981), in addition to the Henry’s law and ionization
constants referred to earlier.
Deviations from ideal behavior in aqueous vapor are due
largely to the ability of water molecules to form van der Waals
and hydrogen bonds, which, as shown experimentally by Liu
and Cruzan (1996), leads to the formation of weakly bound
gas-phase clusters, even in pure water vapor. In addition,
solutes in water vapor or supercritical, low-density steam do
not exist as ‘anhydrous’ molecular moieties but rather as hy-
drated clusters. For example, calculations by Lemke and
Seward (2008a) showed that even at the conditions of the
Earth’s atmosphere, mixtures of H2O, CO2, and N2O contain
ppm levels (molar) of hydrated CO2(H2O)n, N2O(H2O)n, and
H2O(H2O)n clusters (n  4). Such relatively modest cluster
formation is also typical of mixtures of water vapor with highly
volatile compounds. For example, no significant contribution
of hydrated species to arsenic solubility was detected in the
system As(OH)3–H2O (Pokrovski et al., 2002) and to boron
solubility in the system B(OH)3–H2O (Kukuljan et al., 1999),
although the well-known solubility of both arsenic and boron
in steam suggests the formation of hydrate clusters.
In contrast to volatile compounds, water clusters contribute
significantly to the solubility of weakly volatile species in water
vapor. For example, the solubility of NaCl in water vapor has
been shown experimentally to be many orders of magnitude
higher than that calculated assuming the absence of hydrated
NaCl gas species (e.g., Armellini and Tester, 1993; Bischoff
et al., 1986; Suleimenov et al., 2006). Suleimenov et al.
(2006) showed that the solubility of NaCl in supercritical
‘steam’ at 450  C and up 350 bar is due primarily to an assem-
blage of the three even-numbered clusters, NaCl(H2O)n, where
n ¼ 4, 6, and 8. Thus, NaCl dissolves in water vapor predomi-
nantly as NaCl(H2O)n clusters, and the contribution of unhy-
drated NaCl gas species to the NaCl solubility is insignificant.
Based on these experimental data, a set of models describing
the formation of these clusters and their stability has been
proposed (Pitzer and Pabalan, 1986; Suleimenov et al.,
2006). Similar behavior has been demonstrated for KCl
(Hovey et al., 1990) and for a set of chlorides and oxides of
economically important metals, that is, Cu, Ag, Au, Sn, and Mo
(Figure 12; Archibald et al., 2001, 2002; Migdisov and
Williams-Jones, 2005; Migdisov et al., 1999; Rempel et al.,
2006; Zezin et al., 2011).
 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids 49

AgCl–HCl–H2O 100
100 ppb
12.0 r = 0.2 g cm-3
360 ⬚C 75

Au in Vapor (ppm)
10.0
X AgCl (10-9)

50
8.0 AgCl + H2O =
50 ppb AgCl:(H2O)
6.0
25
Ideal solubility
4.0 0
330 ⬚C 400 450 500 550 600 650 700
2.0
10 ppb (a) T (⬚C)
0.0
6.0
0 50 100 150 200
pH2O (bar) 5.0

Figure 12 Experimentally determined concentration of AgCl in vapor as
a function of pH2O. Ideal solubility refers to the vapor pressure of AgCl
over the corresponding solid. Modified from Migdisov AA, Williams-
Jones AE, and Wagner T (2009) An experimental study of the solubility
and speciation of rare earth(III) elements in fluoride and chloride bearing
aqueous solutions at temperatures up to 300 C. Geochimica et
Cosmochimica Acta 73: 7087–7109.
These findings have important implications for theories of
ore formation. It is known, for example, that the hydrothermal
systems responsible for the formation of porphyry deposits are
dominated by vapor, rather than liquid (Henley and McNabb,
1978). There is also compelling evidence that the alteration
associated with the formation of high-sulfidation epithermal
Au–Ag deposits is caused by extremely acidic fluids that prob-
ably can only be produced by the condensation of acidic
magmatic vapors. Consequently, it is attractive to postulate,
as some researchers have, that the ore-forming fluid for these
deposits was a supercritical, low-density fluid that evolved by
condensation and/or contraction to a fluid of liquid-like den-
sity (Williams-Jones and Heinrich, 2005). Calculations of the
solubility of Cu and Au in vapor as CuCl(H2O)n and AuCl
(H2O)n clusters at 360  C and pressures up to 200 bar reach
levels of 102.8 and 106.5 m, respectively (Archibald et al.,
2001, 2002). Such concentrations are high enough to form a
hypothetical 50 million tonne porphyry copper deposit with a
grade of 0.5% Cu in 20 500–56 000 years (depending on
composition of the fluid) or a 36 tonne Au deposit in
167 000–238 000 years. However, the experimentally deter-
mined concentrations are considerably lower than those mea-
sured in vapor inclusions, albeit at much higher temperature
and pressure (Ulrich et al., 1999). This apparent disagreement
has recently been resolved as a result of the discovery that
the solubility of metals in chloride-bearing aqueous fluids in-
creases exponentially with the density of the fluid, due to the
formation of increasingly larger clusters of water molecules
around the metal, and that the free energy of cluster formation
varies linearly with reciprocal temperature (Migdisov and
Williams-Jones, 2013). Using these observations, Migdisov
and Williams-Jones (2013) have extrapolated the solubility
data for silver and gold and shown that they reach the ppm
levels measured in vapor inclusions at the near-magmatic con-
ditions of their entrapment (Figure 13).
Cadmium exhibits volatility in high-temperature systems
and occurs in volcanic gases (e.g., Symonds et al., 1987;
Au in Vapor (ppm)
4.0 Au + HCl + H2O =
AuCl:(H2O) + 0.5H2
3.0
r = 0.2 g cm-3
2.0 HCl = 0.1 vol%
Ni/NiO buffer
1.0
0.0
400 500 600 700 800
(b) T (⬚C)
Figure 13 The predicted concentration of (a) Ag and (b) Au in aqueous
fluid of density 0.2 g cm3 as a function of temperature. The fluid in
(a) was saturated with AgCl and in (b) with elemental gold; the fO2 of the
latter system, which contained 0.1 vol% HCl, was buffered by the Ni/NiO
buffer. Modified from Migdisov AA and Williams-Jones AE (2013)
A predictive model for metal transport of silver chloride by aqueous vapor
in ore-forming magmatic-hydrothermal systems. Geochimica et
Cosmochimica Acta 104: 123–135.
Wahrenberger et al., 2002) and in high-temperature fumarole
sublimates (e.g., Chaplygin et al., 2005); however, the molecular
basis for its gas-phase transport and volatility is poorly
known. Recent FT-ICR/MS (Fourier transform ion cyclotron res-
onance mass spectrometry) measurements combined with ab
initio quantum chemical calculations have identified an exten-
sive array of gas-phase cadmium(II) chloride–water clusters
(Lemke and Seward, 2013), such as (CdCl)þ(H2O)n (n ¼ 1–4).
Various dimers, trimers (with respect to cadmium), and higher-
order polynuclear species, such as (Cd4Cl7)þ(H2O) as well as
larger, doubly charged clusters, were also identified mass
spectrometrically.
As noted earlier in the case of volatile Cd chloride–water
clusters, the dominance of molecular solubility in low-density
fluids does not exclude the formation of clusters containing
ionized species in the vapor phase, especially in the super-
critical region. Indeed, proton–water clusters have been
detected over boiling water and in supercritical steam using
infrared spectroscopy (Carlon, 1979), nuclear magnetic reso-
nance (Matubayasi et al., 1997), and high-pressure mass spec-
trometry (Likholyot et al., 2007). Clusters containing ionized
halide ions (Cl, Br, and I) have also been detected experi-
mentally at temperatures from 45 to þ175  C (Likholyot
et al., 2005). Recent studies based on ab initio calculations
50 The Chemistry of Metal Transport and Deposition by Ore-Forming Hydrothermal Fluids
have reported standard thermodynamic properties for such
clusters and predicted them for more complex aggregates,
such as H3Oþ(H2O)m(H2S)n, NH4þ(H2O)m(H2S)n, and H3Sþ
(H2O)m(H2S)n, where m  6 and n  4 (Lemke and Seward,
2008b).
Although there is compelling evidence for the transport of
metals in water vapor, it seems probable that deposition of
these metals occurs after condensation and/or contraction
of the vapor to liquid. Evidence for this is provided by the
blanket-like distribution of gold in high-sulfidation epithermal
deposits, interpreted to represent a level where the temperature
of the host rocks is below the dew point of the fluid
(Chouinard et al., 2005b). In many cases, the mechanisms of
deposition are likely to be the same as those discussed earlier
for the liquid. However, as the concentrations of the metals
may be relatively low, it is likely that they may be insufficient to
saturate the ore fluid of interest, particularly in relatively low-
pressure environments such as those of some high-sulfidation
epithermal systems. In these systems, the metals may therefore
concentrate, not by precipitation of an ore mineral of the
metal, but rather by adsorption onto the surface of a gangue
mineral like pyrite or other sulfide minerals (Chouinard et al.,
2005a), as demonstrated by Renders and Seward (1989),
Cardile et al. (1993), and Widler and Seward (2002).
Finally, the intriguing but as yet unstudied role of super-
critical CO2 in the transport of some elements in high-
temperature–high-pressure environments in the Earth’s lower
crust should be mentioned. Numerous authors have reported
the occurrence of fluid inclusions containing pure CO2 and
CO2 þ CH4 þ N2 fluids that have been trapped in minerals
formed at granulite and amphibolite facies metamorphic con-
ditions (e.g., Andersen et al., 1997; Cuney et al., 2007;
Munyanyiwa et al., 1993; Touret, 1971). The question arises
as to the role, if any, of supercritical CO2 solvent in element
transport at high temperatures and pressures in the deep crust.
It is well known that molecular (uncharged) metal complexes
and metal chelates have appreciable solubility in supercritical
CO2 (e.g., Ashraf-Khorassani et al., 1997; Haruki et al., 2011).
What might be the solubility of transition metal carbonyl
complexes such as Fe(CO)5 or Ni(CO)4 or even simple ion
pairs (e.g., HCl0 and/or NaCl0) in supercritical CO2 at deep
crustal temperatures and pressures (e.g., 700 to 850  C and up
to 15 kbar)? Other molecular components such as TiCl4 and
SiCl4 are highly ‘soluble’ in supercritical CO2, and in fact,
the phase equilibria in the binary systems TiCl4–CO2 and
SiCl4–CO2 (Suleimenov et al., 2003; Tolley and Tester, 1989)
indicate extensive miscibility between the two end-member
components. For example, in the binary SiCl4–CO2 system at
T > 150  C and P > 125 bar, both components mix/interact
to give a homogeneous fluid phase throughout the entire
composition range.
13.2.5 Epilogue
Despite the extensive archive of information on ore deposits,
which includes knowledge of tectonic settings and regional
permeabilities, mineralogy, trace element and isotope geo-
chemistry, fluid inclusion compositions, temperatures, and
pressures, our understanding of the chemistry of metal
transport and ore mineral deposition (i.e., ore formation) is
still fraught with inadequacy because of the lack of data per-
taining to metal complex stoichiometry and stabilities at ele-
vated temperatures and pressures. At temperatures up to about
300  C and at moderate pressures not far removed from satu-
rated vapor pressures, we have some considerable knowledge
of complex equilibria for a few metals such as Fe, Cu, Pb, Zn,
Ag, and Au. For most other metals, the data may pertain to
complexing with only one ligand or derive from a single ex-
perimental study at restricted conditions, such as at one ele-
vated temperature and pressure. As summarized in the
discussions earlier, information has also been acquired at a
molecular level from spectroscopic (X-ray absorption, Raman,
and UV–Vis) and quantum chemical computations. While this
information is fundamental and necessary, high-quality ther-
modynamic data with which to model metal transport and
deposition over the range of fluid compositions, temperature,
and pressure occurring in hydrothermal environments
throughout the Earth’s crust are also required. At present,
gold is the only metal for which reliable thermodynamic
data exist over a wide range of temperature and pressure to
supercritical conditions(i.e., up to 600  C and 1800 bar) for
a number of important complexes (i.e., with HS, Cl, and
OH). Thus, Heinrich et al. (2004) were able to model gold
transport and deposition associated with phase separation
and subsequent magmatic vapor contraction from the mag-
matic porphyry to the epithermal environment by combining
the relevant thermodynamic data for the gold(I) complexes
with phase equilibria in the system NaCl–H2O and fluid
inclusion data.
A priority must therefore be to acquire high-quality thermo-
dynamic and molecular data on metal complex equilibria per-
tinent to ore transport and deposition processes over wide
ranges of temperature and pressure. As would be expected, the
ion pairing of metal complexes with the bulk electrolyte salt
cations, such as Naþ and Kþ, at near-magmatic supercritical
conditions will also be of interest, but such species have been
little studied. These species (e.g., NaAu(HS)20 or NaHMoO2S20)
may play an important role in enhancing metal solubilities and
partitioning into a magmatic volatile-rich phase as noted, for
example, by Zajacz et al. (2010) and Zhang et al. (2012). This
will be a challenging endeavor at high temperatures >350  C
and at pressures up to 5000 bar. The lack of such data comprises
the major barrier to the further understanding of the formation
of hydrothermal ore deposits as well as to the molecular intri-
cacies of the chemistry involved.
Acknowledgments
We thank our colleagues, Chris Heinrich and Steve Scott, for
their helpful suggestions on an earlier version of this chapter.
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