Sulfide Minerals in

Hydrothermal Deposits
Llus Fontbot1, Kalin Kouzmanov1, Massimo Chiaradia1,
Gleb S. Pokrovski2
1811-5209/17/0013-0097$2.50DOI: 10.2113/gselements.13.2.97

H
ydrothermal ore deposits are large geochemical anomalies of sulfur oxidation of sulfide minerals is a
and metals in the Earths crust that have formed at <1 to ~8 km depth. major environmental concern in
many mines and after the closure
Sulfide minerals in hydrothermal deposits are the primary economic of mine sites.
source of metals used by society, which occur as major, minor and trace
Ta ble 1 and Ta ble 2 summa-
elements. Sulfides also play a key role during magmatic crystallization in rize the key features of selected
concentrating metals that subsequently may (or may not) be supplied to sulfide minerals and their hydro-
hydrothermal fluids. Precipitation of sulfides that themselves may have little thermal ore deposits, and Figure
1 illustrates the variety of sulfide
economic value, like pyrite, may trigger the deposition of more valuable metals textures in them. The amount
(e.g. Au) by destabilizing the metal-bearing sulfur complexes. We review why, (vol%) of sulfide minerals in ores
where and how sulfide minerals in hydrothermal systems precipitate. from the different deposit types
is highly variable from <1%
Keywords : hydrothermal ore deposits, sulfide minerals, fluids, metal solubility, in low-grade ores (e.g. porphyry
precipitation deposits, Fig.1A) to several 10s %
in high-grade ores [e.g. massive
INTRODUCTION sulfide and carbonate-replacement deposits (Figs. 1D, 1E)].
Hydrothermal ore deposits are the major source of metals Crosscutting and other textural relationships of sulfide
that are needed for our modern society. Magmatic crystalli- minerals, such as open-space infill (Fig. 1B) or replace-
zation generates hot aqueous fluids that migrate in the crust ment of other minerals (e.g. Figs. 1C, 1F), help researchers
and that have the potential to form hydrothermal deposits. to recognize the sequence of sulfide precipitation stages
Metals can also be transported via heated basinal brines, and to trace the evolution of ore-forming fluids.
modified meteoric water and seawater, and by metamor-
This article briefly reviews why, where and how sulfide
phic fluids. Precipitation of sulfides from hydrothermal
minerals (hereafter sulfides) precipitate in hydrothermal
fluids at temperatures typically ranging between 500C
systems. These precipitation processes are key to under-
and 100C is the major process of base-metal concentra-
standing the formation of hydrothermal ore deposits
tion that allows the metals to be mined economically.
those fascinating and critically important concentration
Sulfide minerals in hydrothermal deposits are the primary
anomalies of sulfur and metals in the Earths crust.
source of the base metals Cu, Zn, Pb and a large number
of other, lower-concentration metals that include Ag, As,
Au, Bi, Cd, Co, Ga, Ge, In, Hg, Mo, Ni, Re, Sb, Se, Sn, Te, METAL ABUNDANCE IN SULFIDES
and Tl. These metals may form their own sulfides or occur FROMHYDROTHERMAL ORE DEPOSITS
as minor or trace elements in other sulfides and sulfosalts. Sulfides in hydrothermal ore deposits are of economic
Subsequent weathering leading to oxidation of pyrite, the interest not only because of their major components, but
most abundant sulfide in hydrothermal deposits, is the also because they are the main carriers for some minor and
main process that generates acidic supergene (secondary) trace metals. Their trace-element components have gained
fluids that leach copper and other metals from the original importance in recent times because some elements Ge,
sulfide-bearing hypogene (primary) ore bodies. These Ga, In, Sn and Bi are critical for the development of new
supergene-remobilized metals may eventually precipitate technologies, everything from cell phones to renewable
in enrichment zones and increase the value of the deposit, energy. Now, in situ element analyses of sulfide minerals,
particularly copper ore deposits of initially low hypogene using LAICPMS (laser ablation inductively coupled
grade. On the other hand, some minor and trace elements plasma mass spectrometry), provide accurate, rapid and
in sulfides (e.g. As, Cd, Tl and Hg) may decrease the value low-cost multi-element data from common minerals, such
of the ore concentrate because of their deleterious environ- as pyrite, sphalerite, chalcopyrite, galena and bornite (e.g.
mental effects. Acid rock drainage caused by weathering Cook et al. 2016).
Trace elements in sulfides occur in different chemical
states, being either incorporated into the crystal structure
of the major minerals or occurring as nanoparticles of other
1 Department of Earth Sciences sulfides or sulfosalts that themselves are either homoge-
University of Geneva neously or selectively distributed in the host mineral. For
rue des Marachers 13, CH-1205 Geneva, Switzerland example, sphalerite from various hydrothermal deposits
Corresponding author e-mail: lluis.fontbote@unige.ch
may contain from a few ppm up to 1,000 ppm Ge, Ga, Co
2 Gosciences Environnement Toulouse, GET and Se; up to 10,000 ppm Sn, In, Cu, Ag and Sb; and even
Universit de Toulouse III, CNRS-IRD-OMP
higher values for Mn, Cd and Fe (e.g. Cook et al. 2009).
14 Av. Edouard Belin, F-31400 Toulouse, France

E lements , V ol . 13, pp. 97103 97 A pr il 2017

 A B
D E
Characteristic ore textures in some of the main types
Figure 1
of hydrothermal sulfide deposits. (A) Sulfides in stock-
work quartz veins or disseminated in the wallrock. From the
Atlantida porphyry CuAu deposit (Chile). (B) Banded sulfides as
open-space filling with gangue minerals, indicating episodic precip-
itation. From the Laki epithermal polymetallic PbZn vein deposit
(Bulgaria). (C) Sulfides associated with quartz, carbonates, and
retrograde calc-silicate skarn minerals that replace prograde skarn
pyroxene. From the Madan distal PbZn skarn deposit (Bulgaria).
(D) Sulfide minerals in the form of fine grained layers and showing
syn-sedimentary features. From the Navan sedimenthosted ZnPb
Galena can incorporate up to 1,000 ppm Sn, Cu, Cd, Se
and Te and up to 10,000 ppm Bi, Sb and Ag (e.g. George et
al. 2016). In contrast, chalcopyrite commonly has orders
of magnitude lower concentrations of most trace elements,
typically less than several 10s ppm (Sn, Ga, Sb, Te, Bi) or
100s ppm (Zn, Mn, Se, In) (George et al. 2016). Pyrite is
the most common sulfide in hydrothermal ores and large
data sets exist for porphyry, epithermal, orogenic gold,
volcanic-hosted massive sulfide (VHMS) and sedimentary
rockhosted deposits (e.g. Large et al. 2014; Franchini et
al. 2015). The most abundant elements in pyrite are Co,
Ni, Cu, As and Zn, reaching >10,000 ppm levels, followed
by Se, Mo, Ag, Sb, Pb (up to 1,000 ppm) and most scarce
are Au, Bi, Sn (10s to 100s ppm).
THE ROLE OF MAGMATIC SULFIDES
AS TRAPS OR SOURCE OF METALS IN
MAGMATICHYDROTHERMAL SYSTEMS
The magmatic component of the mineralizing fluids in
many high- to moderate-temperature (>500C to ~150C)
hydrothermal deposits is sourced in volcanic arcs (e.g.
porphyry, skarn, epithermal, and SnW vein deposits.
These fluids have metal budgets derived (almost) entirely
from their parental magma (Cline and Bodnar 1991). A
cooling and/or decompressing magma will saturate with
respect to an aqueous phase once it reaches the limit of
water solubility in the silicate melt, resulting in exsolu-
tion of a metal- and volatile (e.g. S, Cl, F, CO2 )-bearing
aqueous fluid phase (F ig. 2). Other physico-chemical
conditions being equal (e.g. pressure, temperature, fluid
composition, fluidmelt partition coefficients), the poten-
tial of a magma to exsolve a more-or-less metal-rich fluid
primarily depends on the initial metal concentration in
E lements
C
F
deposit (Ireland). (E) Fine grained, layered sulfides commonly
associated with barite and anhydrite. The base metal sulfides usually
postdate the Fe-sulfides. From the Rammelsberg sediment-hosted
massive sulfide deposit (Germany). (F) Pyrite and chalcopyrite
replacing the host rocks (preserving their original textures) or
locally occurring as open-space filling in late veins. From the Punta
del Cobre iron oxidecoppergold (IOCG) deposit (Chile).
Abbreviations: bar (barite); bn (bornite); carb (carbonates); cp
(chalcopyrite); gn (galena); px (pyroxene); py (pyrite); sp (sphal-
erite); qtz (quartz).
the silicate melt (Fig.2): the richer in metals the magma
is, the richer in metals will be the fluid exsolved from it.
Chalcophile metals in magmatichydrothermal systems
(e.g. Cu, Au) have a very high affinity not only for fluids
(with aqueous fluid/silicate melt partition coefficients
of ~101 to 102 ) (see Pokrovski et al. 2013), but also for
sulfide melts (sulfide/silicate melt partition coefficients of
103 to 105). If sulfide melts form during the evolution of
a magmatic system, then these tiny sulfide droplets can
nearly control the entire budget of chalcophile metals in
an evolving magma reservoir. Consequently, the timing
of sulfide melt saturation with respect to aqueous fluid
in a magma exerts a critical control on the exsolution of
metal-rich versus metal-poor aqueous fluids (Candela and
Piccoli 2005):
If aqueous fluid saturation occurs before magmatic
sulfide saturation, the exsolved fluid will be metal-rich
because it will strip metals from a metal-rich magma
(Fig. 2A).
If aqueous fluid saturation occurs after magmatic sulfide
saturation (Fig. 2B), the fluid will be generated from
a melt already depleted in chalcophile metals, which
may be unfavourable for the generation of metal-rich
magmatichydrothermal systems.
The magmatic sulfides themselves can melt and be incorpo-
rated into subsequent magmatic pulses, thereby enriching
the pulses in metals that can be later exsolved with aqueous
fluids. Magmatic recycling of sulfide-rich cumulates in the
lower crust (Chiaradia 2014) or upper mantle has been
suggested for magmatic systems associated with porphyry
deposits in collisional to post-collisional settings (e.g.
98 A pr il 2017

A extensive literature now exists on the composition of
B metal crustal abundances. Second-order processes, such as
Effects of magmatic sulfide saturation on trapping or
Figure 2
providing metals in magmatichydrothermal systems.
(A) Aqueous fluid saturation occurs before sulfide saturation in the
magma. Metal content in residual melt increases because metals are
not significantly sequestered by the crystallizing silicate oxide
minerals (a1 a3) and metals are optimally transferred to the
magmatic fluid when saturation occurs. (B) Sulfide saturation
occurs before aqueous fluid saturation in the magma. Metal
concentrations initially increase until sulfide saturation occurs
(b1b2) then sharply decrease (b3). Transfer of metals to fluid is
not optimal because significant proportions of metals have been
sequestered by sulfides. (b4) Magmatic sulfides may be destabilized
by aqueous fluids exsolved from the same magma in which sulfide
saturation previously occurred. (b5) Magmatic sulfides may be
destabilized by aqueous fluids exsolved from an underplated mafic
magma. (b6) A sulfide-undersaturated mafic magma may recycle
the sulfides and release the metals contained therein once the mafic
magma becomes saturated in an aqueous fluid.
Richards 2009). Alternatively, subsequent oxidation of
magmatic sulfides can also supply metals to aqueous fluids
(Fig. 2).
SULFUR AND METAL CONTENT
OFHYDROTHERMAL FLUIDS
In contrast to bulk salinity (NaCl+KCl+CaCl2), which is
reliably determined by microthermometry of fluid inclu-
sions, the concentrations of metals and sulfur in hydro-
thermal fluids became measurable when in situ methods
such as LAICPMS and PIXE were developed in the late
1990s. These methods can accurately analyse individual
fluid inclusions trapped in minerals during growth or during
post-growth deformation, providing quantitative determi-
nations of the metal content to the ppm level (e.g. Heinrich
et al. 2003). In combination with near-infrared microscopy,
in situ methods have been extended to the analysis of fluid
inclusions in opaque sulfide minerals (Kouzmanov et al.
2010). Quantification of sulfur concentrations in individual
E lements
fluid inclusions is also possible (Guillong et al. 2008). An
ore-forming fluids from magmatichydrothermal systems,
including porphyry, skarn and epithermal polymetallic
deposits worldwide (see Kouzmanov and Pokrovski 2012).
Metal contents of pristine magmatic fluids show patterns
that are controlled by the metal abundances in the source
magmas and by elevated fluidmelt partition coefficients.
As a result, metal concentrations in pristine magmatic fluids
typically range between 10s and 1,000sppm, one to three
orders of magnitude higher than the corresponding average
separation of aqueous liquid and vapour phases, result in
additional enrichment, with the brine phase containing up
to several wt% Fe, Cu, Zn, Pb and Mn; thus these metals
become major fluid constituents, along with Na and K.
Concentrations of other metals of economic interest, such
as Mo, As, Sb and Ag, vary between 10s and 100s ppm.
Some of these metals, especially those transported as
sulfide complexes (e.g. Au), may also be enriched in the
vapour phase (Heinrich et al. 2003; Pokrovski et al. 2013).
The sulfur content of magmatichydrothermal ore-forming
fluids varies substantially, reaching wt% concentrations,
and so indicating that the major ingredients for sulfide
precipitation are available from the hydrothermal fluid
itself and do not require an external source.
For VHMS, iron oxidecoppergold (IOCG), sediment-
hosted, and orogenic gold deposits, data pertaining to
the mineralizing fluid compositions are still fragmentary.
Nevertheless, existing datasets on some sediment-hosted
deposits indicate that, despite the two orders of magni-
tude lower metal contents (10s to 100s ppm Zn and Pb)
in basinal brines compared to magma-derived fluids, the
reported measured concentrations are much higher than
those predicted in the past (e.g. Wilkinson et al. 2009).
These new findings sharply changed the understanding
of transport mechanisms, of metal deposition efficiency,
and of the time span of hydrothermal sulfide ore-forming
processes.
SULFUR SOURCES AND MAIN REACTIONS
Geological and isotope evidence indicates that sulfur in
hydrothermal sulfides can have four sources: (i) segregated
from a magma together with water; (ii) leached from sulfides
disseminated in rocks (since most magmatic, sedimen-
tary, and metamorphic rocks contain small quantities of
sulfides, mainly pyrite and pyrrhotite); (iii) derived from
sulfate minerals in evaporites; (iv) derived from seawater
sulfate and basinal brines.
Sulfide precipitation can be described by the following
schematic reaction (where aq = aqueous, Me = metal, s=
solid)
Me2+ (aq) + H2 S (aq) = MeS (s) + 2H + (aq) (1)
At least three of the four sulfur sources listed above contain
sulfur in oxidized form. But, as shown by reaction (1),
sulfur must be in its reduced state (S2) to allow precipita-
tion of sulfides. In addition to biogenic sulfate reduction
(Rickard et al. 2017 this issue), there are two other sulfate
reduction mechanisms that are key for the precipitation
of hydrothermal sulfides.
Magmatichydrothermal fluids, depending on their oxida-
tion state, contain different proportions of sulfur species,
including H2S, HS , SO2, SO42, HSO4, and S3. Hydrothermal
fluids originating from calc-alkaline magmas are enriched
in oxidized sulfur species, to a large extent made up of SO2.
In the following disproportionation reaction, which occurs
upon fluid cooling, S 4+ undergoes both oxidation and
99 A pr il 2017
reduction and provides the S2 necessary to form sulfides decreases with increasing pH (Fig. 3C) and increasing H2 S
and the S6+ necessary to form sulfates such as alunite and (Fig. 3D). By contrast, because gold is mainly transported
anhydrite; as sulfide complexes, the removal of H 2 S from the fluid
causes Au precipitation, typically through boiling in epith-
4SO2 + 4H2O = 3SO42 + 6H + + H2 S (2)
ermal deposits and via pyrite formation by a reaction with
In sedimentary environments in which dissolved sulfate Fe-bearing wallrock in orogenic-gold deposits.
(in basinal brines and other formation waters) encounters
Although the above four parameters explain most precipita-
hydrocarbons at about 100C to 160C, sulfate is reduced
tion phenomena, recent data may open new perspectives.
inorganically by hydrocarbons (a process called thermo-
The last five years of hydrothermal research were marked
chemical sulfate reduction, or TSR). In a simplified form,
by the recognition of a new form of aqueous sulfur in
TSR can be represented as follows:
hydrothermal fluids: the trisulfur radical ion, S3 (Pokrovski
2H + + SO42 + CH4 = CO2 + H2 S + 2H2O (3) and Dubessy 2015). The omission of S3 in current models
of hydrothermal fluids is due to its very rapid breakdown to
KEY PARAMETERS CONTROLLING SULFIDE sulfate and sulfide in aqueous solutions when the solutions
PRECIPITATION IN HYDROTHERMAL cool below 200150C, which means that S 3 in experi-
SYSTEMS mental and natural fluid (and melt) samples is not detected
at room temperature. Pokrovski and Dubessy (2015)
Sulfide precipitation from hydrothermal fluids is governed
demonstrated the stability of this ion over a wide tempera-
by four main physico-chemical parameters across various
ture (T = 200700C) and pressure (P from saturated vapor
ore deposit types: (1) temperature, (2) acidity (pH), (3)
pressure to ~30 kbar) ranges. Significant amounts of S3
salinity, and (4) fO2 f S2 . Of key importance is the nature
(>10100ppm S) may be contained in fluids typical of
of the metal-transporting agents: base metals and Ag
magmatichydrothermal and metamorphic environments,
are commonly transported as chloride complexes, Mo as
which are characterized by elevated total S concentrations
(alkali-)oxyhydroxide and possibly oxychloride complexes,
(>1,000 ppm), slightly acidic to neutral pH (3 to 7) and
and Au mainly as sulfide complexes. Figure 3 shows the
redox conditions enabling the coexistence of sulfate (or
influence of these four parameters on the solubility of
sulfur dioxide) and hydrogen sulfide (Fig. 4). Furthermore,
chalcopyrite, pyrite, sphalerite, molybdenite, argentite,
Pokrovski et al. (2015) have shown that S3, together with
and native gold under conditions typical for a wide range
HS , can form stable complexes with Au, enabling transport
of hydrothermal ore deposits. The solubility of all sulfides
of this metal in aqueous solutions at 10100 times higher
decreases with decreasing temperature. For instance, with
concentration than by traditional sulfide complexes. By
other parameters constant, a temperature decrease from
analogy with Au, other sulfur-loving, economically critical
350C to 250C triggers a solubility decrease of two orders
metals, such as Mo, Re, and the platinum-group elements,
of magnitude for Cu and Ag, and one order of magni-
might also form stable complexes with S3. Such complexes
tude for Zn (Fig. 3A). Similar effects on the solubility of
would enhance metal mobility and focus the deposition
metals transported as chloride complexes are caused by
upon destabilization of the radical ion. This hypothesis
a salinity decrease (base metals and Ag), in contrast to
awaits further study.
that of Au (Fig. 3B). The solubility of base metals strongly

USING SULFIDE
105
105
3001000 bar,10 wt. % NaCl eq., pH = 5 400 C, 500 bar, pH = 5 MINERALS TO
sulfur and O2 buffered by pymthm sulfur (0.017m H2S), redox = pymthm
104
104 RECONSTRUCT
103
PHYSICO-CHEMICAL
metal in fluid (ppm)

metal in fluid (ppm)

103
102
PARAMETERS OF ORE
10 102
FORMATION
1 10
Ag2S Mineral assemblages can
10-1 Au 1 be used to reconstruct the
CuFeS2
10-2
FeS2
10-1
physico-chemical parameters
10-3 MoS2

10-4
AA ZnS
10-2
BB that prevailed during the
150 200 250 300 350 400 450 500 550 0.1 1 10 formation of an ore deposit.
Temperature (C) Salinity (wt. % NaCl eq.) The term mineral assemblage
signifies a group of minerals in
105 105
400 C, 500 bar, 10 wt. % NaCl eq. 400 C, 500 bar, pH = 5 chemical equilibrium (Einaudi
sulfur (0.017m H2S) 104 redox = mthm
104
redox = pymthm et al. 2003). The sulfidation
metal in fluid (ppm)

state (Fig. 5A) of hydrothermal

metal in fluid (ppm)

103 103
fluids as a function of log S2
102 102
and temperature determines
10 10 the stability domains of key
1 1 sulfide, sulfosalt and oxide
minerals (Einaudi et al. 2003).
10-1 10-1

10-2
CC 10-2
DD The typical environments of
3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 0.0001 0.001 0.01 0.1 the main ore deposits types
1
pH H2S (mol/kg) can vary in terms of S2 and
temperature (Fig. 5B). Cross-
Solubility of metals in hydrothermal fluids in equilib- cutting relationships between
Figure 3
rium (i.e. saturated) with major sulfide minerals as a
function of the four parameters (A) temperature, (B) fluid salinity, successive mineral assemblages allow the sulfidation-
(C) pH, and (D) H2S concentration. In each case, a number of state evolution of the hydrothermal system to be traced.
physical and chemical parameters of the fluid are fixed (as indicated Mineralogical and metal zoning of sulfide- and sulfosalt-
in the figure). Galena solubility, not shown, is slightly lower than bearing assemblages can be used for exploration purposes
that of sphalerite. Abbreviations: hm (hematite); py (pyrite);
mt(magnetite). Modified from Kouzmanov and Pokrovski (2012). because they may act as prospection guides towards the
center of the mineralizing system.

E lements 100 A pr il 2017

 Magmatic-hydrothermal uid
(0.22.0 kbar)
2 wt% S, H2S:SO2 = 1 at 700 C, 2 kbar
T-P gradient = 278 C/1 kbar
sulfur concentration, wt% S
Metamorphic uid
1 (210 kbar)
10
Pyrite-Pyrrhotite-Magnetite
10 0 T-P gradient = 75 C/1 kbar
so, in turn, metal-sulfide complexes to be destabi-
lized (e.g. responsible for much gold precipitation).
S3- Progressive cooling, due to boiling and/or mixing,
away from the heat source explains much of the

1 H2S 10 -1 metal zoning observed in different deposit types.

SO2
(H)SO4 SO2 10
-2
H2S
For example, at a similar temperature, chalcopy-
-3
rite is much less soluble than sphalerite or galena
10
S3- HS- (Fig. 3A). This results in metal zoning (at the ore
10 -4 body to deposit scale) of Cu in proximal locations
0.1 10 -5 and the deposition of ZnPb and AgMn in distal

4
SO
H)
-6 locations, as commonly observed in many types

(
10
S2 -

-7 of deposits (porphyry copper, skarn, carbonate-

10
-8
AA BB
10
0.01
200 300 400 500 600 700 200 300 400 500
Temperature, C Temperature, C
Concentrations of the different forms of sulfur,
Figure 4
including the sulfur radical ions, in two typical types
of fluids as a function of temperature (T ). (A) Magmatic
hydrothermal fluid. (B) Metamorphic fluid. The sulfur species
concentrations were predicted using the stability constants of sulfur
forms reported in Pokrovski and Dubessy (2015) and in Pokrovski et
al. (2015). The concentration of S2 is tentative. The S3, and,
potentially, S2 ions may represent a significant part of dissolved
sulfur content over a wide TP range. Direct experimental data are
currently limited to <500C (gray areas).
The abundances of minor and trace elements in some
sulfides and sulfosalts can also be used as indicators of
physical and chemical parameters of ore formation. For
example, the iron content of sphalerite strongly depends
on temperature and f S2 (Fig. 5A) and has been extensively
used in ore deposits research, together with other mineral
thermometers and thermobarometers (e.g. Sack and Ebel
2006). Recently, using in situ LAICPMS analyses, Cook
et al. (2016) established the partition coefficients for trace
elements between different base-metal sulfides, thereby
opening new possibilities in the use of these sulfides as
tracers of paleo-physicochemical conditions.
PROCESSES CONTROLLING SULFIDE
PRECIPITATION IN HYDROTHERMAL
OREDEPOSITS
Processes such as cooling, phase separation (boiling),
mixing, and fluidrock interaction are key for sulfide
precipitation in hydrothermal systems because they influ-
ence the four main parameters of the fluids (temperature,
salinity, pH, and fO2 fS2). Because sulfide solubility strongly
depends on temperature, cooling of hydrothermal fluids
is the most efficient process leading to ore deposition. A
main cause of cooling is boiling and the removal of the
high-heat vapour phase during depressurization events.
This causes H 2 S to fractionate to the vapour phase and
replacement, epithermal, and VHMS).
Mixing between two fluids with contrasting
600 700 temperature and composition can also cause
mineral precipitation, particularly in basinal
settings. For example, mixing between hot saline
fluids and cold meteoric waters is an efficient mechanism
to decrease both the temperature and salinity of metal-
bearing fluids, and so favour sulfide precipitation. Mixing
of metal-bearing but H 2 S-poor fluids with fluids rich in
H 2 S can also trigger sulfide precipitation. The key factors
in forming a hydrothermal sulfide deposit are not only
the availability of metals but also the presence of reduced
sulfur.
Metal-bearing hydrothermal fluids are typically not in
equilibrium with their host rocks. The resulting water
rock interactions produce alteration in the wallrock
and influence the solubility of metal sulfides in the fluid.
Neutralization of reactive fluids through interaction with
carbonates and feldspars increases the pH, which can lead
to sulfide precipitation (e.g. Fig. 3C). Redox conditions are
also strongly influenced by fluidrock interaction (e.g. fluid
reduction by Fe 2+ -bearing silicate minerals or by rocks
rich in organic matter, or oxidation by Fe3+ -rich detrital
continental sediments). Interaction of metal-bearing fluids
with rocks containing pyrite is a common sulfide precipita-
tion mechanism for elements like copper that have a high
affinity for reduced sulfur (iron from pyrite may in this case
re-precipitate as oxide). The opposite process scavenging
of H2 S by the host rock via Fe sulfidation reactions desta-
bilizes metal-sulfide complexes, leading to gold precipita-
tion in orogenic gold deposits.
SELECTED EXAMPLES OF PROCESSES
CAUSING SULFIDE PRECIPITATION
INHYDROTHERMAL DEPOSITS
The analysis of the occurrence of sulfides in porphyry
copper, VHMS and sediment-hosted deposits and of the
associated precipitation mechanisms helps to unravel the
formation of hydrothermal ore deposits.

(A) Log fS2 versus temperature

A B Figure 5
diagram, illustrating various sulfida-
tion states (in green) of the hydrothermal fluids,
based on stable sulfide mineral assemblages (from
Einaudi et al. 2003). FeS (mol%) content of sphal-
erite is also plotted (in red; from Barton and
Toulmin 1964); sphalerite is a common mineral in
many hydrothermal ore types and its FeS content
can indicate the temperature or sulfur fugacity.
(B) Log fS2 versus temperature estimated for
various hydrothermal ore deposits. Colours are
visualization aids only. Abbreviations: asp (arseno-
pyrite), bn (bornite), cp (chalcopyrite), cv (covel-
lite), dg (digenite), lo (loellingite), po (pyrrhotite),
py (pyrite). Ore deposit abbreviations as in Table 1.

E lements 101 A pr il 2017

 Table 1 MAJOR SULFIDE AND SULFOSALT MINERALS IN HYDROTHERMAL DEPOSITS RELATED TO BASE AND PRECIOUS METALS.

Metal Major sulfides Minor sulfides/sulfosalts Deposit types

chalcopyrite* CuFeS2, covellite CuS, enargite Cu3AsS 4,
Porphyry Cu(MoAu) deposits, HS and
Copper Cu bornite* Cu5FeS 4, chalcocite* tennantitetetrahedrite Cu12 (As, Sb) 4S13 ;
IS epithermal, skarn, VHMS, SHMS, IOCG
Cu2S >180 sulfide and sulfosalt species
sphalerite ZnS wurtzite ZnS (rare); >20 Cu, Tl, and HS and IS epithermal, skarn, VHMS,
Zinc Zn
(common host ofFe, In, Cd) Ag-bearing sulfosalts SHMS,MVT
galena PbS HS and IS epithermal, skarn, VHMS,
Lead Pb >160 sulfosalt species
(common host of Ag) SHMS,MVT
acanthite Ag2S LS epithermal AuAg deposits, IS poly-
Silver Ag >120 sulfosalt and sulfide species
(also selenides, etc.) metallic epithermal deposits
Fe-bearing sulfides are not mined for
pyrite* FeS2, pyrrhotite FeS, marcasite* FeS2, arsenopyrite* FeAsS; iron. Pyrite, pyrrhotite, and marcasite,
Iron Fe
chalcopyrite* CuFeS2 >110 sulfide andsulfosalt species are ubiquitous in hydrothermal ore
deposits as gangue minerals.

Abbreviations: HS, IS, LS (high, intermediate, low sulfidation); IOCG (iron oxideCuAu); MVT (Mississippi Valley type);
SHMS (sedimentary-hosted massive sulfide); VHMS (volcanic-hosted massive sulfide); * these minerals may contain economically
recoverable gold.

Porphyry copper deposits are among the largest sulfur
anomalies on Earth. These low-grade, high-tonnage
deposits are related to shallow intrusions in volcanic arcs,
with both metals and sulfur released from the magmas via
hydrothermal fluids. Porphyry copper deposits consist of
quartzsulfide stockwork veins and disseminated sulfides
in large volumes of hydrothermally altered porphyritic
stocks and country rocks (Fig. 1A). In the early stages of
porphyry copper deposit formation at depths of 23 km,
the minerals bornite, chalcopyrite and magnetite precipi-
tate from the magmatic fluid. In subsequent lower tempera-
ture stages, the proportion of reduced sulfur increases and
pyrite progressively becomes more abundant. At shallow
(<1 km), epithermal depths where there is sharp cooling ,
the sulfides are dominated by intermediate- to very high-
sulfidation assemblages of enargite, digenite and covel-
lite (Fig. 5A). In porphyry systems, temperature decrease,
accompanied by vapor-liquid separation, as well as fluid
rock interaction and more distal mixing, causes a general
mineral, and hence metal, zonation over a scale of a few
kilometers: one often observes a core of Cu ( Mo), an inter-
mediate zone of ZnPbAg veins, and more distal AsSb
(AuHg)-dominated margins.
Volcanic-hosted massive sulfide deposits consist of high-
grade, low-tonnage ore bodies, built up by 10s vol% of
fine-grained base-metal sulfides (Fig. 1E). The sulfides
precipitate at the interface between the oceanic crust and
seawater and as replacement assemblages in the subsurface.
Cooling and neutralization of hot, reactive and reduced
H 2 S- and metal-bearing fluids with seawater is regarded
to be the main process that governs sulfide precipitation
in VHMS deposits.
In the sedimentary rockhosted environments that occur
in basins, several deposit styles are related to the flow of
basinal brines. In general, stratiform Cu deposits, clastic
sediment-hosted massive PbZn Cu sulfide (SHMS), and
carbonate-related Mississippi Valley type (MVT) PbZn
deposits are all formed by fluids of intermediate sulfida-
tion state at temperatures of ~100C to 250C (Fig. 5B).
The SHMS deposits form in passive margins, back-arcs

TYPICAL METAL GRADES, SIZE OF ORE BODIES, AND MAIN ORE-FORMING HYDROTHERMAL FLUID MENTIONED IN
Table 2 THEARTICLE. See Figure 5 for sulfidation state and fluid temperature; see text for precipitation mechanisms. Mt = million tons;
other abbreviations as inTable 1. Sources and additional data on the deposit types in Hedenquist et al. (2005).

Deposit type Typical metal grades Typical size (ore) Origin of main metal-bearing hydrothermal fluid
0.4% 1.5% Cu
Porphyry Cu(Mo Au)
0.04% 0.15% Mo 5005,000 Mt Magmatic
deposits
( Au, <0.11 g/t)
1% 2% Cu ( Au)
Cu /ZnPb skarns 10150 Mt Magmatic
2% 10% Zn + Pb
0.55 g/t (Au) ( Ag)
HS and IS epithermal 1% 2% Cu 10150 Mt Magmatic
4% 8% (Zn + Pb) ( Ag)
LS epithermal Au 0.55 g/t Au, ( Ag) 10100 Mt Meteoric waters mixed with magmatic fluids
1.0% 1.8% Cu
Evolved seawater (extensional setting) mixed with
VHMS 0.8% 4% Zn 1050 Mt
magmatic (magmatic arc)
0.1% 1% Pb
~3% 8% Zn 1040 Mt (MVT)
SHMS/MVT 1% 2% Pb Basinal brines
<0.3% Cu (Ag) 20200 Mt (SHMS)

2% 3% Cu
Stratiform Cu 2003,000 Mt Basinal brines
<0.4% Co (Ag) ( ZnPb)
CO2-rich, low salinity fluids. Metamorphic component
Orogenic Au 28 g/t 440 Mt
with magmatic? / evolved meteoric? / mantle degassing?
IOCG 0.5% 2% Cu ( Au) 20200 Mt Magmatic basinal brines

E lements 102 A pr il 2017

and continental rifts; sulfide precipitation is caused by CONCLUSIONS
mixing fluids that ascend along basin margin faults and
The key processes that govern sulfide precipitation in
so vent into basins with anaerobic conditions where they
hydrothermal systems are common, to varying degrees,
encounter H 2 S-rich waters. This process is the root of the
across many ore deposit types, and can be used to formu-
term sedex (sedimentary exhalative), which is frequently
late genetic models. These models, in turn, can be used to
applied to SHMS deposits, although researchers now avoid
refine methods of exploration for mineral resources (e.g.
this term because most sulfide precipitation takes place
Sillitoe 2010). Windows of understanding are being opened
by subsurface replacement of already deposited sediments,
on the true nature of ore-forming processes via analytical
where reduced biogenic sulfur is also available as diagenetic
and experimental developments for measuring the metal
pyrite. Fluid mixing is also important in epigenetic base-
and sulfur contents (and their speciation) in hydrothermal
metal deposits that have been formed by basinal brines on
fluids, via experiments on the stability of metal-bearing
carbonate platforms: the largest MVT deposits form when
sulfur complexes in high TP liquids and vapours, and via
metal-bearing basinal brines mix with fluids rich in H2 S
determining the trace-element contents and their struc-
(generated by TSR, Eq. 3) or with fluids containing biogenic
tural state in sulfide minerals. This improved knowledge
H2 S in organic matter and/or hydrocarbons. Precipitation
contributes to better exploration models and on how to
is also related to salinity decrease during fluid mixing.
optimize mineral processing. This will help ensure that
Interaction of oxidizing metal-bearing basinal brines with
our technology-hungry society will have a supply of metals
black shales and other sediments containing biogenic
long into the future (Arndt et al. 2017) and it will lessen
reduced sulfur, mostly in the form of framboidal pyrite, is
the environmental impact of mining and ore processing
the main process at the origin of stratiform Cu deposits and
operations. All these aspects rely on an understanding of
other sedimentary rockhosted deposits. As noted above,
sulfide minerals and their stabilities.
copper is less soluble than zinc and lead, and, it can only
be transported by oxidizing fluids (buffered by hematite),
devoid of H 2 S. The lithologic contact between red beds ACKNOWLEDGMENTS
(oxidized clastic sediments) and black shales controls the We thank J. Hedenquist, D. Smith and Guest Editors Marie
stratiform morphology of these copper deposits. Sulfides Edmonds and Kate Kiseeva for their reviews, which greatly
commonly are zoned with native copper, chalcocite and improved the manuscript, and to Jodi Rosso and the Elements
covellite, bornite, chalcopyrite, sphalerite and galena in a staff for the careful editing. We acknowledge financial
sequence from the oxidized to the reduced H2 S-rich part support from grants SNF 160071, 162415, 165752, Soumet
of the redox profile. ANR-11-BS56-0009 and RadicalS ANR-16-CE31-0017.

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