AGSO Journal of Australian Geology & Geophysics, 17(4),

IS -3~

Commonwealth of Australia 1998

The hydrothermal environment

David L. Huston l
Hydrothermal mineral deposits are the products of crustal
geochemical processes that extract metals from source regions
and concentrate them at depositional sites. These processes and
the regions in which they occur constitute 'mineral systems'.
Processes that occur within source regions define the characteristics
(e.g. temperature, pressure , pH , salinity, redox, sulphur content)
of hydrothermal fluid s, which, in turn , determine the metal carry
ing capacity of the fluid. Mineral deposits that contain Cu, Zn, Pb,
Ag and/or Au can be classified into three general groupings based
on metal assemblages: (I) Zn-Pb-AgAu , (2) CuAu , and (3)
AuAg. These groupings are predicted from fluid characteristics
and the solubility of metals in the fluids. The hydrothermal
geochemistry of Sn, W, U and Mo is not considered in this discussion.
Mineral deposit diversity results from the complex interplay
of processes in source regions and depositional sites. First-order
processes that occur in source regions include devolatilisation and

degassing, circulation of surficial fluids, and expulsion of connate

fluids. These and second-order processes such as SO, dispropor
tionation result in hydrothermal fluids with diverse temperatures,
acidities , salinities, redox conditions, and, hence, metal-carrying
capacities. Many of the processes in the source region are directly
or indirectly linked to geological characteristics of the source
region, such as granitoid type and basinal lithology.
Three first-order depositional processes cause metal deposition:
phase separation, reaction with host rocks , and mixing with ambi
ent fluids. The effic iency of metal deposition depends critically
on the steepness of chemical gradients in the depositional envi
ronment. The interplay of source and depositional processes
produces the observed diversity of mineral deposits, and placing
these processes in a mineral system framework provides a power
ful tool for understanding and, potentially, for discovering mineral
deposits.

Introduction
Until thirty years ago, economic geology was essentially an
empirical science. Models of hydrothermal ore deposits, which
centred largely on empirical associations between ore deposits
and intrusions, were based on the idea that temperature increases
with pressure in the crust. Hence, ore deposits were classified
into groups directly related to the crustal level of ore deposition.
Many terms from this classification, such as 'epithermal ' ,
'mesothermal' and 'hypothermal', persist to this day.
Three decades ago, economic geology became a more genetic
and predictive science. The shift in emphasis came about for
several reasons, the most important of which was the accumu
lation of a sufficiently large descriptive database to allow the
development of ' genetic models'. The development ofanalytical
techniques (e.g. fluid inclusion and stable isotope analysis)
allowed, for the first time, insight into the conditions of metal
transport and ore deposition. The acquisition of high quality
thermodynamic data at hydrothermal temperatures allowed
quantitative modelling of depositional processes (e.g. Reed 1982).
These three factors and the study of active hydrothermal systems
resulted in great advances in understanding the many processes
involved in ore genesis.
Hydrothermal mineral deposits are ultimately the result of
chemical reactions, even though they are localised by zones of
higher penneability such as faults and aquifers. The purpose of
this paper is to present and discuss chemical processes required
for the formation of hydrothermal mineral deposits, both in the
source regime and at the depositional site.

What are hydrothermal 'ore' deposits and

mineral systems?
A metalliferous ore deposit, by definition, is a concentration of
metals that can be mined and processed at a profit. However, as
base and precious-metal prices vary considerably over the medi um
to short term, the economic viability of a particular metal
accumulation can vary greatly, even over the space of a few
years. For instance, in the 1970s porphyry Cu deposits with
grades below 0.5% Cu were economically viable, but in the
1980s and early 1990s, many of these same deposits became
uneconomic , owing to the low price of Cu. Only recently have
these deposits become economic again. Owing to short-term
economic variations in what is termed an 'ore' deposit, this
discussion will consider hydrothermal metalliferous deposits,
which might be defined as accumulations of metals that exceed
the average crustal abundance by an order of magnitude. Cu and
1

Australian Geological Survey Organisation, GPO Box 378, Canberra,

ACT 260 I, Australia

Zn accumulations exceeding 500- 1000 ppm, and Au exceeding

0.01 - 0.05 ppm fit this definition.
Hydrothermal mineral deposits form a small portion of a
larger entity, the mineral system, which Wyborn et a!. ( 1994)
defined as 'all geological factors that control the generation and
preservation of mineral deposits.' In detail, a mineral system
(Fig. I) can be divided into component parts that include:
(I) source(s) for the fluid, sulphur, ore metals, chloride and other
ligands, (2) an energy source, (3) a migration pathway, (4) a
chemical or physical trap that facilitates ore deposition, and
(5) an outflow zone. Thc sum of the chemical processes that
occur within each of these five components ofa mineral systcm
results in a great diversity of base and precious-metal mineral
deposits. The lack of one or more of these components within a
particular mineral system may preclude the fOnllation of mineral
deposits.

The solubility of ore metals: limits to ore

formation
The most fundamental control on the fOnllation of hydrothermal
mineral deposits is the ability of a hydrothermal fluid to carry
metals in solution. Roedder (1968) suggested that the concen
tration of Zn and Pb in ore solutions is 1-10 ppm. Measurements
of oil field brines (Sverjenski 1984), black smoker vent fluids
(Rona et a!. 1993; Zierenberg et a!. 1993; Binns et a!. 1993;
Fouquet et a!. 1993), active geothermal fluids (McKibben &
Williams 1989) and fluid inclusions (Bodnar 1995) have indicated
base-metal concentrations of 1-2000 ppm.
With the exception of fluids associated with porphyry Cu
deposits (Bodnar 1995), the maximum base-metal concentration
in most active hydrothermal systems is generally 100 ppm or
less. However, some hydrothermal fluids can carry much higher
concentrations of metal than they actually transport. This suggests
that the concentration of metal in a hydrothermal fluid is also
limited by its abundance and availability in the source rocks to
provide metal to the ore-forming fluid.
The ability of some ore fluids to carry metals can exceed
the supply from source rocks by several orders of magnitude.
For example, even though high-temperature (350C) black
smoker (VHMS) fluids can carry hundreds of ppm Zn (Fig. 2),
typical measured values are less than 10 ppm (von Damm 1990).
Because of this high degree of under saturation, efficient deposi
tion of such metals is impossible. In volcanic-hosted massive
sulphide (VHMS) deposits, extreme undersaturation of preexisting
Zn in high-temperature hydrothermal fluids results in the leaching
of Zn from the bases of ore lenses and redeposition at the top
when the temperature decreases, owing to mixing with seawater

16

D.L. HUSTON

Sources(s) of
fluid, chloride,
sulphur and
metals
~
Magmati~ fluid ev~ution

Energy
source

Migration
pathway

Trap

5-500 km
i

Outflow
zone

<2 km

-I

Fhlirt mixinn

Surficial fluid circulation

i

Burial,
regional
1

metamorphism

joints

and

and

magmatic

aquifers

..

Phase separation

.-

intrusion

1W-!:1
- -- -

_Ieachina
- -

"

"I
I

NO

deposition

Figure 1. The components of a mineral system (modified from Knox-Robinson & Wyborn 1997).

(e.g. Ohmoto et al. 1983). Hence, a hydrothermal fluid may be

able to cany high concentrations of metals, but it may not deposit
the metal, because of extreme undersaturation or an unfavourable
temperature- composition path.
To form significant mineral accumulations, the concentration
of a particular metal within a hydrothermal fluid must fall within
a solubility window : if the solubility is too low, the metal can
not be transported in sufficient quantities, but if the solubility
is too high, the metal will not precipitate, owing to extreme
undersaturation. For base metals in most deposit types, the
solubility window appears to be 1- 200 ppm, based on measured
abundances of modern ore-forming fluids.
For Au, the solubility window is orders of magnitude lower,
as the abundance of Au in the crust is four orders of magnitude
lower than that of base metals. The solubility window of Au in
mineralising fluid s is poorly constrained. Data from the
Broadlands geothermal fluid indicates a solubility of 1.5 ppb
(Seward 1989), which probably defines the lowest possible limit
of the gold solubility window. By analogy with base metals, the
upper limit on the window is probably around 100 ppb.

'Hardness', 'softness' and theformation ofmetal

complexes
The abundances of 'bare' base and precious-metal ions (e.g.
Zn 2+, Au+, etc) that can be dissolved into a fluid are much too
low to form viable hydrothermal fluids . To produce sufficient
metal concentrations, simple metallic cations combine with
anions in solution to form complexes. The particular type of
anion that forms complexes with a cation is dependent to a large
degree on the cation's 'hardness' (Pearson 1963). Cations such
as Au+are 'soft' bases, elements such as Zn 2+and Pb 2+are 'hard'
bases, and elements such as Cu+ and Ag+ have an intermediate
'hardness'. The hardness of the cation governs to a large degree
the type of anion with which it forms complexes. For instance,
under many geological conditions, Au preferentially forms
thiocomplexes (e.g. AuHS or Au(HS)z) with 'soft' HS-, but,

under the same conditions, Zn and Pb form chlorocomplexes

(e.g. ZnCI ~-n) with 'hard' Cl-.
Although the concept of 'hardness' of metallic ions is useful
as a guide to the type of complexes a metal will form, other
factors also govern complex formation and the solubility. The
solubility of metals in hydrothermal fluids depends on the
availability of complexing anions (or 'ligands'), temperature,
acidity, redox, pressure and the amount of reduced sulphur (H2S
and HS-). The acidity of the fluid is most commonly expressed
as pH, but the redox state of a fluid can be expressed in a number
of ways, including O2 fugacity, H2 fugacity, electrochemical
potential (Eh) and sulphate/sulphide ratios. In this discussion,
redox is expressed as sulphate/sulphide ratios because S is the
most abundant multivalent element present in most hydrother
mal fluids.

Solubility ofZn, Cu and Au

Figures 2 to 4 show the solubility of Zn, Cu and Au as a function
of temperature and salinity, which closely relates to the avail
ability of CI. The diagrams were calculated using existing
thermodynamic data (see captions for sources) for simple NaCI
solutions. Allowance was made for the formation of NaCI ion
pairs, using the data of Helgeson et al. (1981), and activity
coefficients were calculated with the extended Debye-Hiickel
equation of Helgeson (1969).
Diagrams were calculated for pH values of3.5, 4.5 and 5.5,
which correspond to strongly acid, moderately acid and near
neutral conditions, respectively. For each pH value, diagrams
are presented for oxidised fluids (redox buffered by pyrite
hematite) and for reduced fluids (LSO/ LH 2S = 10-2). The total
S concentration is assumed to be 100 ppm (_10-2.5 m) for the
acidic fluids and 300 ppm (-10-2 0 m) for the near-neutral fluid.
The above conditions are designed to illustrate solubilities of
metals in common hydrothermal fluids, but the conditions may
not be appropriate for some specific systems.

THE HYDROTHERMAL ENVIRONMENT

For reduced fluids, the solubility of Cu, Zn and Pb (not
shown) increases with increasing temperature, increasing salinity,
and decreasing pH. The solubility of gold is more complex. It
increases slowly with temperature to about 200C, where it
reaches a maximum, particularly under weakly acid to near
neutral conditions. Above 200C, it decreases until between
280 and 350C, depending on salinity and pH, where it increases
sharply again. This complex solubility results from the inter
play between Au thiocomplexes and chlorocomplexes: lower
temperature, reduced fluids 280~350C) are dominated by
Au thiocomplexes, whereas higher temperature, high salinity
and acidic fluids are dominated by Au chlorocomplexes. The
boundary between the stability fields of AuCl, and AuHS o is
characterised by low Au solubility.
For oxidised fluids at the hematite~pyrite redox buffer, the
so lubility of gold increases rapidly and consistently with
temperature as it forms chlorocomplexes. In contrast, the
solubility of zinc increases with salinity, but not as dramatically
with temperature, because LSO/ LH 2 S decreases and [H 2 S]
increases with temperature along the pyrite~hematite buffer,
partly offsetting the increase in the stability ofZn chlorocomplexes
with temperature. As in reduced fluids, Cu solubility increases
with increasing temperature and salinity and with decreasing
pH. However, if the oxidation state of the fluid is increased
marginall y so that the fluid is in equilibrium with only hematite,
the solubi lity of Cu increases rapidl y (cf. Huston et al. 1993).

A classification of mineral deposits based on

metal assemblages
Since Lindgren (1933) first classified mineral deposits according
to crustal depth, many classification schemes have been advanced
to divide mineral deposits into groups for which generalised
exploration or genetic models can be developed. Table I classifies
Cu-, Zn-, Pb- , Ag- and Au-bearing mineral deposits into groups
based on metal assemblages. Most hydrothermal deposits fall
into one of three metal associations: (I) Zn ~ Pb ~ AgAu,
(2) CuAu, and (3) AuAg. Of the deposits that do not fall
into one of these three groups, several are zoned, with individual
zones being characterised by one of these mineral assemblages.
For instance, although characterised by an overall metal assemblage
ofZn ~Cu~ Pb~AgAu , VHMS deposits are usually zoned, with
one zone characterised by a Zn~Pb~AgAu assemblage, and
the other by a CuAu assemb lage (Eldridge et al. 1983; Large
1992).
Fields showing ore fluid conditions for most deposit types
listed in Table 1 are superimposed on Figures 2-4. Fluid conditions
for Broken Hill-type (BHT) deposits are not plotted, as they
are poorly known. Fluid conditions for porphyry Cu, skarn Cu,
hypothermal Au and sediment-hosted Cu (SHCu) deposits also
are not plotted, as they lie outside the fields chosen for the
diagrams (too hot and too cool and oxidised, respectively).
Using the concept of a solubility 'window', the metal
assemblages of many ore deposits can be predicted effectively,
given the temperature, salinity, pH and redox of the ore-forming
fluid. For instance, the ore fluids for adularia~sericite, Carlin
type and mesothermal Au deposits are within the solubility
window for Au, but amounts ofCu and Zn that could be carried
by such fluids are orders of magnitude lower than the minimum
required to form a mineral deposit. Hence, these deposits are
characterised in most cases by a AuAg-only metal assemblage.
In contrast, Mississippi Valley-type (MVT) ore fluids can carry
sufficient Zn, but not sufficient Cu and Au, which results in
deposits rich in Zn, but poor in Cu and Au. Deposits which
span the Zn~Pb-AgAu and CuAu associations are characterised
by variable temperature, salinity and, possibly, pH. For example,
ore fluids that form Zn-rich zones of VHMS deposits can
transport sufficient Zn and Pb, but not significant Cu. In contrast,
higher temperature ore fluids that form Cu-rich zones can
transport sufficient Cu, but have the potential to be extremely

17

undersaturated with Zn (1 ~3 orders of magnitude), as such fluids

could carry in excess of 1% Zn.
The natural tendency for mineral deposits to be characterised
by particular metal assemblages arises directly from the solubility
of metals in solution. Ore fluids that form deposits of the Zn~
Pb~AgAu association are typically low to moderate tempera
ture, moderate to high salinity, and acidic (Table 1). Ore fluids
that form deposits of the CuAu association tend to be acidic,
high temperature, and highly saline (Table 1), although highly
oxidised (hematite stable), low-temperature fluids can also form
Cu-rich deposits (e.g. SHCu deposits, Haynes 1986; Schwartz
et al. 1995). Ore fluids that form many AUAg-only deposits
tend to be moderate temperature, low salinity and near neutral
(Table I).

Mineral deposit diversity: the direct result of

chemical processes within mineral systems
Hydrothermal mine ral deposits occur in a diverse range of
geological environments, and are characterised by an even greater
diversity in grade, size, morphology, mineralogy and geological
setting. Much of this diversity stems directly from chemical
processes in the Earth's crust. Chemical processes in the so urce
regime and depositional site, in combination with fluid conduits
(e.g. faults , shears and aquifers) define where a mineral deposit
forms. Chemica l processes at the site of deposition and the
zones in which these processes can occur define the local charac
teristics of hydrothermal mineral deposits. Based on the premises
that chemical processes within the source environment define
ore fluid characteristics, and that chemica l processes acting on
the ore fluids define the mineralogy, metal content and zonation
of mineral deposits, Figure 5 schematically illustrates how the
interplay of chemical processes at the source and depositional
sites produces the diversity present within hydrothennal mineral
deposits.

Chemical processes in the source regime

The origin of hydrothermal fluids in most hydrothermal systems
can be ascribed to one of three source environments: active
metamorphic regimes, magmatic provinces (both submarine and
subaerial), and tectonically active basins. Depending upon crustal
level, potential mineralising fluids can be derived by the general
processes of: (I) devolatilisation or degassing, (2) circulation of
surficial fluids, and (3) expulsion of connate fluids . These first
order processes can be accompanied by second-order processes
that can change the chemistry, and, thereby, the potential of
evolved fluids to produce mineral deposits in the depositional
regime. In addition, in some source regimes, potential mineralising
fluids can be generated by a combination of two or more first
order processes.
Devolatilisation and degassing. Metamorphic devolatilisation
and magmatic degassing are common processes that occur in
active metamorphic and magmatic environments, respectively.
Progressive devolatilisation ofa rock occurs as a direct result of
the crystallisation ofless-hydrous, higher temperature minerals
as the grade of metamorphism increases. For example, pelitic
rocks from ' low-grade ' metamorphic terranes contain on average
4.34% H 2 0 and 2.3 I % CO 2 , but only 2.42% H 20 and
0.22% CO 2 in 'high-grade' terranes (Shaw 1956). CO 2-rich ore
fluids in shear-hosted gold deposits have been inferred to be
produced by metamorphic devolatilisation (Phillips & Groves
1983).
The crystallisation of intermediate to felsic magmas results
in the exsolution of a separate, H 20-rich fluid into which other
volatile elements, such as Cl and S, partition (Burnham 1979).
Depending on the characteristics of the magma (e.g. redox, degree
of magma fractionation, S content), metals such as Cu, Au, Mo,
Wand Sn also partition into these fluids. Studies by Candela
(1992) and Blevin & Chappell (1992) suggest that, in oxidised
magmas, Cu, Au and Mo partition into the fluid; in reduced

ex:>

Temperature (OC)

100
20

150

200

250

300

350

Temperature (OC)

100
20

150

200

250

300

350

Temperature (0C)

150

00

200

250

CI

300

350

a
en

10

10

-i
~

o.

\\

.;

()

as

Z1

-i
~

o.

-i
~

o.

()

()

as

as

Z1

0.5

;...

o~

0.2

Zn (ppm)

pH 3.5
log I.S = -2.5
log (I.SO,vI.H 2 S) = -2.0

0.1'

0.0025 )

0.2

Zn (ppm)
0:0020

1fT (K-1)

0.1

pH = 4.5
log I.S = -2.5
log (I.SO,vI.H 2 S) = -2.0
,

0.0025

Zn (ppm)

pH 5.5
log I.S = -2.0
log (I.SO,vI.H 2S) = -2.0

0.1'

0:0025

0.Ob20

1fT (K-1)

Figure 2 (includes figure on facing page). The solubility of Zn in hydrothermal fluids as a function of temperature and salinity. Ore fluid compositional fields are taken from Table 1. Thermodynamic data
are from Johnson et at. (1992) and Ruaya & Seward (1986).

100
20

Temperature (OC)

150

250

pH 3.5
log IS -2.5
log (ISO,vIH 2 S)

0~

3:

350

100
20

=hm-py

10

-a!b

-..

300

Zn (ppm)

10

200

200

~IJ+
IIII

250

-..
0~

3:

U
CO
Z

CO

300

150

Cu-Au-Bi

10

Olympic Dam

pH 5.5
log IS -2.0
log (ISO,vIH 2 S)

-a~

0.5

"at:>o

....
g

-..
0~

U
CO
Z

0.5

0.5

....

100

0.0020
(K-1)

0.1

0.2

Zn (ppm)

1fT

=hm-py

pH 4.5
log IS -2.5
log (ISO,vIH 2S)

0.0025

- 0.01

=hm-py
1fT

0.0020
(K-1)

0.1

0.0025

300

3:

0.2

0.0025

"00

0.2

0.1

250

'0

....0
I

200

Zn (ppm)

Fe-oxide-hosted~

Temperature ( 0C)

100
20

350

"at:>a

....

Temperature ( 0C)

150

0.0020

1fT (K-1)

'--

350

Temperature (DC)

100
20

150

200

250

300

350

100

Temperature (DC)

150

200

250

300

350

Temperature eC)

100

150

200

250

I:j

300

350

20ir---------r-------r---~~--_,_r_,

t-'

e
en

o.

10

10

10

.~

cu

Z1

0.5

0.2

0.1 1

1\

....

o.

-~

o.

==

cu

cu

Z1

0.5

0.2

Cu (ppm)

pH = 3.5
log ~s = -2.5
log (~SO.vIH2S) = -2.0
0.0025

1rr (K-1)

0.5

Cu (ppm)

pH = 4.5
log ~s = -2.5
log (~SO.vIH2S) = -2.0
0.1'
__ ~

Cu (ppm)

pH = 5.5
~
log ~s = -2.0
q,.
log (~SO.vIH2S) = -2.0

0.1'

0.0025

\ 0.0020

1rr (K-1)

Figure 3 (includes figure on facing page). The solubility of Cu in hydrothermal fluids as a function of temperature and salinity. Ore fluid compositional fields are taken from Table 1. Thermodynamic data
are from Johnson et al. (1992) and Walshe & Solomon (1981).

100

Temperature (0C)

150

200

250

300

100
20

350

2o.--------.-------.-----.----.--.0

L
'\

10

10

~
o
2

0~

..:;

3:

ca

111l!

250

300

350

100
20

ca

Temperature caC)

150

200

250

300

350

Fe-oXide-hosted~

Cu-Au-Bi

10

Olympic Dam

...

'0...

0~

..:;

3:

uca

{3
Z

~t~

200

Temperature (0C)

150

0",

0.5

0.5

0.5

0.2

0.2

0.2

Cu (ppm)

pH =3.5
log IS =-2.5
log (ISO<tfLH 2 S) = hm-py

<?o"
0.1 '-----;;0:-::.0~0~25::-------------;;0:-::.0~0~20::------------'

11T (K-1)

Cu (ppm)

pH =4.5
log IS =-2.5
log (ISO<tfLH 2 S) =hm-py
0.1 '-----=0--=
.0,..,.07:
25=-------------=0-::.0,..,.0-=-20=------------'

11T (K-1)

Cu (ppm)

pH =5.5
log IS = -2.0
log (ISO<tfLH 2S)

=hm-py
0.1 '-----;;0:-::.0~0~25::-------------;;0:-::.0~0~20::--'-------'----'
11T (K-1)

tv
tv

Temperature (0C)

100

150

200

250

Temperature (OC)

350

300

150

200

250

300

Temperature eC)

100
20

350

~"'1

150

200

250

o
r-300

350

10

-'"

51-

-'#.

AuHS o

(3
CIS

0~

(0)

=3.5
log IS =-2.5

0.1

log (ISO.vIH 2S)

I

0.0025

CIS

0.5

0.2

Au (ppb)

=4.5
log IS =-2.5
pH

=-2.0
0.0020

1fT (K-1)

0.1

Au(HS)i

(3

pH

0.2

5.

0.5

Au (ppb)

i===<~ :5=:t

0~

CIS

0.5

0.21-

Au(HS)i

Z1

I ~\

...

Z1

I I

51-

\ \ ~::l

log (ISO.vIH 2S)

0.0025

Au (ppb)
pH

=-2.0

0.1

=5.5
=

log IS -2.0
log (ISO.vIH 2S)

0.0025

=-2.0
0.0020

1fT (K-1)

Figure 4 (includes figure on facing page). The solubility of Au in hydrothermal fluids as a function of temperature and salinity. Ore fluid compositional fields are taken from Table 1. Thermodynamic data
are from Benning & Seward (1996), Gammons & Williams-Jones (1995), Johnson et al. (1992), and Shenberger & Barnes (1989).

~
~

Temperature (0C)

100
20

150

200

-0;!?.

...:
3:

Temperature (0C)

150

100
20

'I"

-#-

0
0

'"

AuHS o

Olympic Dam

'"

~
oI
Z

300

350

'"

150

10

AuCI;

\I

'"
0

2
0
0

'"

og

0.5

'"

oo

0.2

Au (ppb)

pH =3.5
log I S =-2.5
log (I SO.vIH2 S) =hm-py
I --=-0.- =-00=-=2:":"5------=-0.- =-00=-=2"""0-----'
0.1 L..J....

11T (K-1)

>-<
tJ

oo
0.2

Au (ppb)

pH =4.5
log I S = -2.5
log (ISO.vIH2 S) = hm-py
0.1 '----=-0-=.0-!:-:02=-=5------=-0.-=00-!:-:2:":"0------'

11T (K-1)

>-1

S
::r:

oo

0.2

AuHS o

0
0

'"

0.5

350
I _
AuCI 2

'"

300

...:
3:

'"
0

0.5

250

"''''==

200

20r----~--~r-~~-~~~

~
0

Temperature (OC)

100

Fe-oxide-hosted~:O
Cu-Au-Bi

'"
0

250

200

~W
IIIII

10

350

II I

300

10

250

'"

:;:0

>-1

::r:
trI

Au (ppb)

pH =5.5
log I S =-2.0
log (I SO.vIH 2S) =hm-py
0.1 '----=-0-=.0-!:-:02=-=5----.l....-70.700-!:-:2=0------I

11T (K-1)

trI

<:
.....
:;:0

trI

>-1
tv

Table 1. Geochemical c1asssification and geological characteristics of Cu-Zn-Pb-Ag-Au mineral deposits.

Metal assemblage Ore fluid characteristics

Zn-Pb-Ag
Mississippi Valley
type

Lithological association

Structural association

Jgneous association

References

t;I

::r:

c:::
Vl

Zn- Pb- Ag

100- ISOC; 10- 20 eq.

wt% NaCI; H2 S-poor; acidic

Shelf carbonate .

Epigenetic, but stratabound

None

Sverjenski (1984 1986);

Anderson & Macqueen (1982)

Sediment-hosted
massive sulphide
(Selwyn type)

Zn- Pb- Ag

190- 280C; 9- 22 eq.

wt% NaCI; reduced; acidic

Pyritic shale, greywacke

and carbonate

Stratiform; commonly near

basin margins or associated
with syn-sedimentary faults

None

Gustafson & Williams (1981);

Sangster (1990)

Sediment-hosted
massive sulphide
(M t Isa type)

Zn- Pb- Ag

Not established,
but oxidised

Pyritic shale and carbonate

Stratiform; commonly near

basin margins or associated
with syn-sedimentary faults

None

McGoldrick & Keays (1990)

Broken Hill type

Zn- Pb-AgCUAu Not established

Banded iron formation,

metapelitic rocks,
metapsammitic rocks,
and metavolcanic rocks

Stratabound in high-grade
metamorphic terranes that
are interpreted as rifts

Amphibolites and
possible felsic
volcanic rocks

Walters (1998)

Zn-rich skarn
and manto deposits

Zn- Pb-AgCu

200- 400C; I- SO eq.

wt% NaCI; reduced; acidic

Carbonate

Stratabound and in veins

Beaty et al. (1990);

Proximal and distal
to granitoid intrusions Megaw et al. (1988)

VHMS, Zn-rich zones

Zn- Pb-AgAu

200- 300C; 3- 10 eq.

wt% NaCI; reduced; acidic

Stratigraphic breaks in
submarine volcanosedimentary sequences

Mainly stratiform, with

epigenetic stringer zones
rocks, subvolcanic
intrusions, and synvolcanic
faults

Volcanic,
volcaniclastic

Pisutha-Arnond &
Ohmoto (1983) ;
Franklin et al. (1981)

Acid-sulphate
epithermal Au

AUCu

200- 330C; 2- 20 eq.

wt% NaCI; reduced;
strongly acidic

Generally massive andesite

Local subvertical faults

and fractures

Spatially associated
with shallow intrusions
and hosted by coeval
volcanic rocks

Heald et al. (1987);

Hedenquist et al. (1994);
Deen et al. (1994);
Arribas (199S)

Porphyry Cu

CUMoAu

400- 800C; 3S- 7S eq.

wt% NaCI; reduced;
"boiling" ; acidic

Intermediate stocks, their

associated volcanic rocks,
and enclosing country rocks

Epigenetic; controlled
regionally by basement
faulting and pre-existing
structural fabrics

Centred and directly

related to shallow
intermediate stocks

Roedder (1984);
Titley (199S)

Skarn CuAu

CuAu

300- 600C; saline;

reduced; acidic

Carbonate rocks adjacent

to shallow stocks

Epigenetic

Centred and directly

related to shallow
intermediate stocks

Einaudi (1982)

Fe-oxide hosted
Cu-Au

Cu- Au Bi

300- 3S0C; IS- 30 eq.

wt% NaCl; oxidised; acidic

Epigenetic, massive
ironstone bodies

Late- to post-kinematic

No direct association,
but an inferred
association

Huston et al. (1993);

Khin Zaw et al. (1994)

CuAu

d
Z

Metal assemblage

Ore fluid characteristics

Lithological association

StrllclUral association

Igneous association

References

Olympic Dam-type
Cu-U-Au

Cu-U-Au-Ag

100-360C; 7-42 eq.

wt% NaCl; oxidised; acidic

Syenogranite

Epigenetic in breccias

Deposit has
indistinguishable age
to the host granite

Oreskes & Einaudi (1992);

Johnson & Cross (1995)

Mt Isa-type Cu

Cu

280- 350C; 3- 20 eq.

wt% NaCl; reduced ; acidic

Dolomitic and pyritic shale

Cross-cutting zone floored

by folded thrust fault

None

Heinrich et al. (1989)

VHMS , Cu-rich zones

CUAu

300- 350C; 3- 10 eq.

wt% NaCl; reduced;
acidic to strongly acidic

Stratigraphic breaks in
submarine volcano
sedimentary sequences

Mainly stratiform, with

epigenetic stringer zones

Volcanic,
volcaniclastic rocks ,
and subvolcanic
intrusions

Pisutha-Arnond
& Ohmoto (1983);
Franklin et al. (198 I)

Sediment-hosted Cu

Cu-Ag-Co

50-250C; 7-25 eq.

wt% NaCl; strongly
oxidised; acidic

Reduced sediment s
stratigraph ically
above red beds

Stratabound

None

Schwartz et al. (1995)

Adularia-sericite
epithermal Au

Au- Ag

200- 300C; 1- 3 eq.

wt% NaCl; reduced;
near neutral

Mainl y subaerial,
massive volcanic rocks

Veins, commonly in
structures associated with
calderas, doming or folding

Temporally associated Heald et al. (1987)

with waning volcanism

Carlin-type Au

Au

200-250C; 0-4 eq.

wt% NaCl; reduced ; acidic

Mainly silty carbonate rocks

and other clastic
sedimentary rocks

Commonly in the footwall

to thrust faults ; may be
associated with high-angle
normal faults

No direct association

Bagby & Berger (1985);

Kuehn & Rose (1995);
Presnell & Parry (1996)

Shear-hosted Au

Au

250- 350C; 0.5- 5 eq.

wt% NaCl; reduced;
near neutral

Fe-rich sedimentary and

igneous rocks, with
lesser felsic igneous
and ultramafic rock s

Veins in lower order

structures associated
with major shear zones

No direct association

Groves et al. (1989) ;

Ho et al. (1990)

Hypothermal Au

Au

220- 450 C; 5- 55 eq.

wt% NaCl; reduced; acidic;
poorly constrained

Carbonaceous sedimentary
rocks ,banded iron formation,
and calcareous metasedi
mentary rocks

Shear-hosted and stratabound;

associated with anticlines

Commonly closely
associated with
granitoids

Goellnicht et al. (1989);

Lawrie & Hinman (1998)

AuAg

26

D.L. HUSTON

Source
Processes in the
Ore fluids I Depositional
environment source environment
processes
First order

First order

Second order

Second orden

Deposit types
Deposit A
Deposit B

Active meta
morphic regime

Devolatilisation

Deposit C
hase
separation

Deposit D
Deposit E
Deposit F
Deposit G
Deposit H

Magmatic
provinces

Deposit I
Deposit J
Deposit K

Surficial water
circulation

Deposit L
Deposit M
Deposit N

Amagmatic,
tectonically
active basins

Deposit 0
Deposit P
Conna!e brine
expulsion

..

Fluid I

Deposit Q
Deposit R
Deposit S

Figure 5. Generalised diagram showing the interplay between source processes, depositional processes and the formation of mineral
deposits.

magmas, Wand Sn partition into the aqueous phase.

After a magmatic-hydrothermal fluid ex solves from a magma,
second-order processes can change its character within the source
region. In magmatic-hydrothermal fluids, S occurs in two forms:
H2S and S02' As the fluid cools, S02becomes unstable at 350400C (Ohmoto & Rye 1979). If the fluid exsolved from an
oxidised melt, S02 disproportionates into H 2S04 and H2S,
whereas for a reduced melt, S02 in the fluid is reduced to H2S by
reaction with H2. This process produces magmatic- hydrother
mal fluids with a large range in LSO/ LH2S (Whitney 1988) and,
potentially, pH. Magmatic- hydrothermal fluids can also unmix
to form a high-salinity brine, and a low-salinity vapour (Henley
& McNabb 1978). As a result of these second-order processes,
magmatic-hydrothermal fluids within a magmatic source regime
can have large variations in LSO/ LH2S, pH and salinity, and
these fluids will have distinct metal transporting capabilities.
Another second-order process, which may be important in
environments dominated by devolatilisation and/or degassing,
is the leaching of metals and S from wall rocks after the relevant
fluids are produced. This process is essential to form potential
ore fluids in active metamorphic regimes and may be important
in some hybrid magmatic- hydrothermal fluids (e.g. Mt Bischoff,
Tasmania; Halley & Walshe 1996).
Circulation of surficial fluids. Isotopic studies of VHMS
(Ohmoto et al. 1983) and adularia-sericite gold deposits (Field
& Fifarek 1985) indicate that the dominant origins of the ore
forming fluids are seawater and meteoric water, respectively.
Even in porphyry copper deposits, isotopic studies implicate
the circulation of meteoric fluids in the formation of some
alteration zones (Sheppard et al. 1971). Circulation of surficial
fluids driven by anomalously high heat flow is an important
process whereby hydrothermal fluids are produced in the mag
matic/volcanic environment and in tectonically active basins.
The resulting hydrothermal fluids have low to moderate tem
perature and salinity, and are generally buffered by the rock

through which they pass to moderately acid or near-neutral pH

(4-6).
Metals and, in some cases, Sand CI can be introduced into
circulating surficial fluids by second-order processes such as
leaching of wall rocks or incorporation of magmatic- hydrothermal
fluids. For instance, most evidence suggests that metals in Zn
rich VHMS deposits are leached, but the incorporation of
magmatic- hydrothermal fluids into seawater-dominated hydro
thermal fluids may provide metals and S to Cu-rich VHMS
deposits (Ohmoto et al. 1983 ; Huston et al. 1995).
Other second-order processes that may affect the character
istics of circulating seawater include thermochemical sulphate
reduction (Ohmoto et al. 1983), evaporation (Beaty et al. 1988),
and sub-seafloor boiling (Butterfield et al. 1990). The first process
is important as it produces H 2S, which is essential for sulphide
mineral deposition on the seafloor. The second and third processes
can increase the salinity of the resulting hydrothermal fluid, and
the third process can produce an H 2S-rich, low-salinity fluid
that could effectively transport Au.
Expulsion of connate waters. During burial and diagenesis,
fluids trapped within sediments are progressively expelled as
the confining pressure and temperature increase. Pore water is
released during initial burial for up to several hundred metres.
When the temperature increases to 90C, expandable clays such
as montmorillonite recrystallise to form clays such as illite
(Lydon 1983), which releases higher temperature fluids . As the
process of dewatering proceeds, the salinity ofthe expelled fluids
increases through processes such as membrane filtration (Graf
1982).
During or after expulsion, these fluids undergo second-order
processes such as leaching metals and S from wall rocks,
thermochemical sulphate reduction, and reaction with wall rocks
to buffer pH and redox. The resulting low to moderate tempera
ture, moderate to high salinity fluids can be potent ore fluids.
Oilfield brines, which form by such processes, carry up to

THE HYDROTHERMAL ENVIRONMENT

300 ppm Zn and 100 ppm Pb (Anderson & Macqueen 1982).
Ore fluids produced in such a manner are then forced out of their
source basins by hydrostatic fluid pressures, overpressuring or
gravity-driven fluid flow (Lydon 1983; Sverjenski 1986). Ore
fluids potentially travel hundreds of kilometres from the source
basin to form MVT deposits (Garven 1985).

Chemical processes in the depositional regime

Chemical processes in the source regime determine only the
metal-carrying capacity of a hydrothermal fluid. Processes in
the depositional regime determine if that fluid will precipitate
its metal load to form a mineral deposit. As ore metals are
commonly undersaturated in hydrothermal fluids, highly efficient
and rapid processes are required for precipitation. Such processes
include broadly: (1) phase separation, (2) mixing with other fluids,
and (3) interaction with reactive rocks. These first-order processes
are important in the formation of most if not all mineral deposits,
but second-order processes in the context of these broad processes
are varied and can produce strikingly different mineral deposits.
Phase separation. 'Phase separation' is a general term that
describes processes whereby a single homogeneous fluid separates
into two fluids of different composition and/or physical charac
teristics. Three processes fall under this broad category: (1) boil
ing, (2) effervescence, and (3) condensation. Boiling, a process
whereby a fluid separates into a low-salinity vapour and a high
density liquid, occurs when the vapour pressure equals the
confining pressure, either as the result of pressure decrease or
temperature increase. Effervescence is a process whereby dissolved
gas (not including water vapour) is rapidly lost as the result of
pressure decrease (e.g. the opening of a bottle of champagne).
Condensation is a process whereby a high-density liquid condenses
from a lower density fluid, generally as the result of tempera
ture decrease.
A fourth mechanism to generate a gaseo us phase in the
hydrothermal environment is interaction of acidic fluids with
reactive rocks such as carbonates. This interaction could evolve
CO 2gas, just as limestone fizzes, owing to CO 2 evolution, when
it interacts with hydrochloric acid.
Boiling, effervescence and fluid-rock interactions resulting in
the evolution of a gaseous phase cause significant changes to the
chemistry of the residual brine. The most important effect is the
loss of volatile components such as H2S, CO 2 and H 2 A second
important effect of boiling is the cooling of the residual brine, as
boiling is an endothermic process. The loss of volatile H 2S causes
Au deposition in adularia-sericite epithermal systems:
Au(HS)2 + 0.5H2 (g) ~ Au + 2H 2S (g)

(1).

For dilute, low to moderate temperature, near-neutral fluids,

characteristic of adularia-sericite epithermal systems, boiling is
an efficient mechanism for depositing Au and other metals
transported as thiocomplexes (e.g. Reed & Spycher 1985). Simi
larly, effervescence could also efficiently deposit metals transported
as thiocomplexes (e.g. some mesothermal Au deposits).
The condensation of vapour produced by boiling into shallow
ground waters can result in an aqueous fluid characterised by
high concentrations of H2 S04 Advanced argillic alteration zones
above adularia-sericite epithermal deposits (Buchanan 1981)
and modern subaerial geothermal systems are inferred to form
from these 'steam-heated' waters (Reed & Spycher 1985). At
the Axial Seamount vent field, vapour formed by sub-seafloor
boiling has condensed to form a fluid rich in H2S and CO2, but
poor in Cu and Zn. These fluids are actively producing chimneys
consisting mainly of anhydrite, whereas the residual brine is
actively forming sulphide-rich chimneys (Butterfield et al. 1990).
Although condensed vapour in adularia-sericite epithermal
and VHMS environments does not appear to carry enough metal
to form a metalliferous mineral deposit, Heinrich et al. (1992)
have suggested that metals such as Cu and Au could be trans
ported by thiocomplexes in a vapour, and that condensation of
this vapour would produce a fluid capable of forming Au deposits

27

such as Kidston, in Queensland.

Reaction with host rocks. Many types of mineral deposits,
such as skarns, are restricted to particular rock types, which
indicates that the interaction between hydrothermal fluids and
rocks such as carbonates, carbonaceous sediments and Fe-rich
rocks is an effective depositional mechanism. However, the
specific mechanism whereby metals are deposited varies accord
ing to the rock type with which the fluids interact.
Carbonate or carbonate-bearing rocks are by far the most
important hosts to skarn, manto, MVT, Mt Isa-type Cu, and
Carlin-type deposits. When a fluid interacts with a carbonate
bearing rock, the most important effect is an increase in pH :
CaCO J + 2W ~ Ca2+ + HFOJ

(2).

Increasing pH is a very effective mechanism for depositing

metals transported as chlorocomplexes, such as Zn, Cu, Ag and,
under some conditions, Au. Another possible consequence of
fluid--carbonate interaction is effervescence of CO2 The increase
in the concentration of H 2CO J leads directly to an increase in
the partial pressure of CO 2 according to reaction (3), which can
lead to effervescence:
H 2C0 3 (aq) ~ Hp + CO2 (g) i
(3).
The resultant increase in fluid pressure could lead to
hydrofracturing of the rock, enhancing both the passage and
reactivity of the hydrothermal fluids. A second possible effect
of effervescence would be H 2S loss, which would deposit metals,
such as Au, that are transported by thiocomplexes.
Interaction of oxidised, sulphate-rich hydrothermal fluids
with reduced lithologies such as carbonaceous sedimentary rocks
or reduced Fe-rich rocks (BIF, ironstone or mafic volcanic rocks)
also can be an effective depositional process. This interaction
decreases LSO/EH 2S according to the reaction:
2C + SO!- + 2H+ + 2Hp ~ 2H 2C0 3 + H 2S
(4), and
8Fe 30 4 + SO!- + 2W

12Fe 20 3 + H 2S

(5).

Both reactions cause deposition of metals transported as

chlorocomplexes, because H 2S content and pH increase. These
processes have been inferred to have been important in ironstone
hosted Cu-Au (Huston et al. 1993) deposits. Interaction of
relatively oxidised fluids (H 2S or SO!- dominant) with carbon
aceous sediments could result in CO 2effervescence according to
reaction (4) and:
C + 2Hp ~ CO 2 (g)

i + 2H2 (g)

(6).

As discussed previously, effervescence can result in the

deposition of metals transported as thiocomplexes.
Reduction of oxidised fluids by reduced rocks is likely to
occur only at temperatures above 300C, owing to sluggish redox
kinetics. Ramboz et al. (1985) have demonstrated that the Hp
CO 2-CH 4-graphite system is 'blocked ' below 370C, and
Ohmoto & Lasaga (1982) have demonstrated that sulphate
sulphide interaction is slow below 300C.
Interaction of H2S-rich fluids with Fe-rich rocks can result
in a decrease in the concentration of H 2S in the fluid through
wall rock 'sulphidation':
FeO (rock) + 2 H 2S ~ FeS 2 + Hp + H2 (g)
(7).
The drop in H 2S concentration leads to destabilisation of
thiocomplexes and Au deposition (reaction 2). This mechanism
has been suggested for shear-hosted Au (Phillips & Groves
1983) and ironstone-hosted Cu-Au deposits (Skirrow & Walshe
1994).
Fluid mixing. The mixing of hydrothermal fluids with am
bient fluids has been inferred to be a significant depositional
mechanisms for a range of deposits . Most surficial fluids are
characterised by low temperature 25C), low salinity
(<3.5 eq. wt % NaCl) and near-neutral pH. Hence, mixing with
surficial fluids cools, dilutes and neutralises upwelling hydro
thermal fluids. Because all three mechanisms destabilise

28

D.L. HUSTON

chlorocomplexes, mixing of metalliferous fluids with seawater

causes ore deposition in SHMS (Sangster 1990) and VHMS
(Ohmoto et al. 1983) deposits, and mixing of magmatic volatiles
with meteoric fluids causes deposition in acid-sulphate deposits
(Hedenquist et al. 1994).
At deeper levels in the crust, mixing of metalliferous fluids
with H2 S-rich ambient fluids would provide reduced S so that
initially H 2S-poor metalliferous fluids could deposit metal
sulphides. Such a mechanism has been proposed for MVT
deposits, where metalliferous, H2 S-poor oilfield brines mix with
H2 S-rich 'sour gas' to deposit base-metal sulphides (Sangster
1990). At temperatures above 250-300C, the kinetics of sulphate
reduction are sufficiently quick to allow thermochemical reduction
of sulphate in an oxidised fluid to form ~S (Ohmoto & Lasaga
1982). Hence, high-temperature mixing of sulphate-rich, oxidised
fluids with a reduced fluid may also result in deposition of base
metal sulphides.

Conclusions
Over the last three decades, rapid improvements in technology
and geochemical knowledge have significantly improved our
understanding ofthe ore-forming environment, which has resulted
in better genetic and empirical models of ore formation to guide
mineral exploration. As processes leading to mineral deposition
are well documented in many classes of mineral deposits,
emphasis is shifting to other parts of the hydrothermal environ
ment in order to understand 'mineral systems' as a whole.
As discussed above, chemical processes govern whether a
particular hydrothermal fluid will form a mineral deposit.
Processes within the source environment determine if the fluid
can transport enough metal, and processes in the depositional
environment determine ifthe fluid can deposit metals. The large
range of processes in both the source and depositional environ
ments produces the great diversity of mineral deposits observed
in the Earth's crust. More importantly, the interplay of these
processes may produce a greater diversity of mineral deposits
than that known regionally or globally.

Acknowledgments
This contribution is the result of discussion with colleagues at
the University of Tasmania, the Geological Survey of Canada
and the Australian Geological Survey Organisation, including,
most recently, Kevin Cassidy, Dick Henley, Ken Lawrie, Terry
Mernagh, Roger Skirrow, and Lesley Wyborn. Early drafts were
reviewed by David Cooke, Greg Ewers, Terry Mernagh (twice)
and Doone Wyborn. However, the interpretations (and misin
terpretations) ultimately are the responsibility of the author.

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