Chemical Geology, 11 (1973) 73-87

© Elsevier Scientific Publishing Company, Amsterdam - Printed in The Netherlands

SOLUBILITY OF GOLD IN HYDROTHERMAL CHLORIDE SOLUTIONS

R.W. HENLEY
Department of Geology, University of Otago, Dunedin {New Zealand)
(Accepted for publication November 20, 1972)

ABSTRACT

Henley, R.W., 1973. Solubility of gold in hydrothermal chloride solutions. Chem. Geol., 11 : 73- 87.

The solubility of gold has been determined in chloride solutions in the temperature range 300-
500°C corresponding to the inferred range for the formation of "hypothermal" gold deposits. The
solutions were buffered with respect to HC1 by a K-feldspar-muscovite-quartz assemblage, and to
oxygen by the assemblage haematite-magnetite. Solubilities increased rapidly with temperature from
about 10 p.p.m, at 300°C, to 500 and 1000 p.p.m, at 500°C at 1000 and 2000 bar, respectively.
These results are discussed in terms of possible solution species in this high-temperature region
where molecular behaviour predominates in the solution equilibria. It is suggested that gold and other
metals may be transported to the site of ore-deposition in undersaturated high-temperature solutions.
Ore deposition may take place at lower temperatures where ionic gold chloride or sulfide species
dominate the chemistry of the ore solutions.

INTRODUCTION

Metallic gold occurs with base-metal sulfides in hydrothermal vein and replacement-
type ore-bodies, which are found most commonly in Archaean greenschist terrains such
as at Morro Velho, Brazil (Gait, 1962) and Yellowknife, Canada (Boyle, 1959) and in
areas of T e r t i a r y - R e c e n t volcanic activity (e.g., in the circum-Pacific and Alpine belts).
Solubility information is a prerequisite to the understanding of the genesis of these ore-
bodies. In the Archaean group of deposits wallrock alteration assemblages, developed
adjacent to the ore, are often indistinguishable from those produced by greenschist facies
metamorphism, while in the Tertiary group of ores, propylitic wallrock assemblages are
often developed which are similar in character to greenschist or a l b i t e - e p i d o t e - h o r n -
blende hornfels facies assemblages. This suggests that, although ore-deposition may have
occurred at lower temperatures, the ore-transporting solutions at some stage in their
evolution were at temperatures appropriate to the development of these facies. Thus, for
a study of the chemistry o f gold-transport a broad P-T field is outlined coincident with
that for the development o f the greenschist facies, with temperatures in the range 3 0 0 -
500°C and pressures up to 10000 bar (Turner, 1968).
Current evidence (White, 1968) suggests that ore-bearing solutions are, in general,
brines with total chloride concentrations up to 5 M. Similar but less concentrated
74 R.W. HENLEY

solutions are well-known in active geothermal areas (e.g., Taupo, New Zealand), but these
have low sulphur contents, and it is uncertain whether their low sulphur concentration is
also representative of that in ore-forming systems. In the Salton Sea geothermal system
(White, 1968) the total molal metal content is well in excess of the sulphur molality
suggesting that the metals are dissolved as chloride rather than sulfide complexes. Some
authors (e.g., Barnes, 1967) suggest, however, that the sulphur content of ore-forming
solutions was higher than that of the geothermal systems, so that total base metals
equalled total sulphur content; metal-sulphur complexes could then account for ore
transport.
Above 300°C the self-ionization of water is about one-thousand times greater than at
room temperature (Quist, 1970) but due to the breakdown of the liquid structure at the
higher temperature, the dielectric constant is only equivalent to that of organic solvents
at room temperature (Quist and Marshall, 1965). For this reason the ionization constants
for strong electrolytes, such as sodium chloride, decrease rapidly with increasing tempera-
ture so that undissociated solute molecules become more and more abundant and
"molecular" rather than ionic equilibria predominate in the hydrothermal solution.
Because of this behaviour, for example, chloride occurs largely as the undissociated HCI,
KCI, NaC1 monomeric or dimeric molecules while sulphur occurs as molecular H2S, SO2,
or as undissociated species such as NariS. Solution species will therefore be quite different
in their chemical nature and structure than the species which account for solubility at
lower temperatures. In deference to the few studies carried out in this region, it would be
unwise to apply the genetic term "ion-pair" to the high temperature species; the writer
prefers at this stage to use the term "molecular complex" to describe the undissociated
solution species, which may have little or no ionic behaviour.
Weissberg (1970) and Seward (1972) have studied the solubility equilibria of gold up
to 300°C in sulphur and sulphur-chloride solutions, and Seward (1972) concluded that
complex ionic species such as [Au (HS)] o, [Au (HS)2]- or [Au2 (HS)2S]-2 (depending
on pH) allow gold solubilities in hydrothermal solutions much higher than those computed
for gold-chloride species by Helgeson and Garrels (1968). At higher temperatures, how-
ever, metal complexing with the very abundant and strongly-bonding chloride species may
be favoured more than with sulphur species.
This paper reports the results of an experimental study of the solubility of gold in
alkali chloride solutions at temperatures in excess of 300°C and up to 2000 bar pressure.
The dissolution reaction of a metal involves both oxidation and complex formation,
and for gold a formal reaction may be written:
Au + aHC1 + bO2 ~ ~Aucomplex] + c H 2 0 (1)
In this study an attempt was made to determine the stoichiometry of such a reaction
and to determine the variation of the equilibrium constant, K, over a range of tempera-
tures and pressures. In order to experimentally determine solubility equilibria it is
convenient to buffer the activities of both oxygen and ligands by reaction with solid
assemblages. Hemley (1959) has calibrated the useful HC1/KCI buffer assemblage quartz-
SOLUBILITYOF GOLD IN CHLORIDE SOLUTIONS 75

muscovite-K-feldspar while Eugster and Wones (1962) give data for the useful redox
buffer, haematite-magnetite. Both these assemblages occur in the earth's crust and limit
the activities of 02 and HC1, although the haematite-magnetite pair may represent an
upper limit to the range of possible oxygen activities in ore-forming systems.
The activities in these buffered systems may represent extremes in the ore-forming
environment, but the use of other more realistic assemblages is prohibited by the addition
of extra components, kinetics of the buffer reactions, and scarcity of well-calibrated
assemblages in the temperature range considered here. The use of the buffer systems
described above allows the determination of the equilibrium constant (K) for the dissolu-
tion reaction so that for other conditions gold solubilities can be calculated thus:

log a(Au species) = log KTp + a lOg aHC1 + b log f o 2 - - c logfH~O (2)

EXPERIMENTAL APPROACH

The solubility of gold in buffered chloride solutions was measured directly by analysis
of an extracted solution sample, using a technique especially developed for this study.
The solid buffer assemblages and solution (about 0.5 g) are weighed into a 0.5 cm diameter
gold capsule (5 cm long) together with an open-ended tube, 2 cm long, consisting of
Teflon, silica glass or alumina, depending upon the temperature of the run. On temperature
quenching at constant pressure, about 0.1 g of solution becomes trapped in the tube as the
gold capsule collapses around it. The tube is then removed, wrapped in aluminium foil,
weighed, carefully dried and reweighed to determine the mass of trapped solution (by
evaporative weight loss).
The runs were carried out in large stainless steel pressure vessels (O.D. = 5 cm, I.D. =
1.25 cm), so that two or three capsules could be run simultaneously. Temperatures were
measured using an external thermocouple and, where possible, with an internal sheathed
thermocouple in contact with the capsule.
The quartz-muscovite-K-feldspar solid buffer assemblage was prepared by fine-
grinding (to < 200 mesh) natural materials (crystalline quartz, adularia and muscovite).
In some runs synthetic assemblages were used, crystallized from gels (either of muscovite
or K-feldspar composition of a 1 : 1 : 1 quartz-muscovite-K-feldspar composition)
prepared by the method of Hamilton and Henderson (1968). Potassium chloride solutions
were used (2.0, 1.0 and 0.5 M at N.T.P.), and in some cases a solution was used in which
the mole ratio KCI: HC1 was initially approximately equal to that of the buffered solution.

ANALYSIS

The small solution volume and low solubilities limited total gold content and necessi-
tated the use of neutron activation analysis for the determination of gold in the aluminium
wrapped tube. The analyses were performed by the Joint Manchester-Liverpool
Universities Research Reactor Analysis Service, using a Bendix Multi-channel X-ray
76 R.W. HENLEY

TABLE I

Experimental results for gold solubility at 1 kbar

A. 2 MKC1

Run Temperature Solubility Run Temperature Solubility

No. (° C) (p.p.m.) No. ( o C) (p.p.m.)

E 50 305 38 P 42 266-308 67
E51 305 31 P 43 266-308 18
17 310-325 18 S 49 295-340 23
20 305-308 87 S 50 295-340 19
39 313 7 S 46 311-342 21
41 313 46 S 27 402 61
63 507 936 96 512 298
64 507 114 97 512 348
65 507 328 98 512 83
61 485-509 507 99 499 14
68 509 2113 100 499 30
69 509 484 101 499 3
66 495-504 196 130 504* 133
67 495-504 68 132 517 414
81 500 65 133 489-508 60
84 513 263 134 502-506* 159
85 513 133 135 487 68
86 513 592 136 504 18
87 513" 2987 137 503 26
88 513" 87 151 456* 67
89 513" 818 162 400 H 42
163 504 H 17
164 508 H 38
165 450 H 20

B. 1MKC1

Run Temperature Solubility

No. ( oC) (p.p.m.)

14 295 2.9 S
15 295 6.9 S
18 310-325 60 S
25 430-454 22 S
28 400 63 S
62 485-500 260
70 485 - 5 0 0 2968
156 493-499 H 1778
157 556 15
TABLE I (continued)

C. 0.5 M KCI

Run Temperature Solubility

No. ( ° C) (p.p.m.)

16 295 5
19 310-325 35
29 420-450 11
26 400 81
79 507 795
159 556 H 40
160 461H 31
161 508* 76

Notes: Duration of runs 1 0 - 2 0 days. Collection thimble was alumina except where indicated:
P = PTFE (Teflon); S = silica glass. Temperature measurement: cold seal b o m b s with external thermo-
couple except where marked: * internal sheathed thermocouple; H = hot-seal bomb. The thermocouple
temperature was measured by potentiometer to -+ 2 C. Mixture was synthetic quartz, muscovite and
K-feldspar. Mixture of natural silicates was used for runs 96 et seq. Consecutive run No. at the same
temperature indicate that these runs were held together in the same pressure vessel.
60C

500 ~" ,~i,iI i

r~
1000

800
/ v
E
c~
40C

3OC
i ii !i¸¸ i ¸¸ ?
ill~i!ii ~ i

~ ? i~?~ii~i !i¸
i

~5
6O0
2 kbar 03
~3
20(2
o
v1
"1 r
40C

10£

0
_i ~ / ~ "/I c
300 400 500 480 500 520
Temperature*C Tern perQt u re *C

Fig.1. Some experimental data for gold solubility in the range 3 0 0 - 5 0 0 ° C at 2000 bar total pressure
in 2 M (at N.T.P.) potassium chloride solutions, buffered by the assemblages q u a r t z - m u s c o v i t e - K -
feldspar and haematite-magnetite.
Fig.2. Experimental data for gold solubility in 2 M (at N.T.P.) potassium chloride solutions at 1000 bar
total pressure at 4 8 0 - 5 2 0 ° C. Q u a r t z - m u s c o v i t e - K - f e l d s p a r and h a e m a t i t e - m a g n e t i t e buffer
assemblages present. Errors in temperature measurement are indicated by the bar length.
78 R.W. HENLEY

spectrometer. Radiochemical separations were unnecessary. The standard'deviation of

these analyses was very much less than the variance of the gold solubilities determined in
these experiments.

ERRORS

Precipitation of solute during the quench is always a danger in solution studies, but in
these experiments no evidence was seen for crystallization of gold on the vessel walls. In
any case, provided no precipitated gold is washed into the tube, quench precipitation
should have no effect upon the results.
To test the efficacy of the method the solubility of sphalerite was determined using
both weight loss on crystal fragments and tube analysis by X-ray fluorescence, for each
run. The chloride solutions were buffered by the quartz-muscovite--K-feldspar assem-
blage and the results were in good agreement with similar solubility runs by Hemley et al.
(1967), and the difference between the mean weight loss and X.R.F. results indicated a
deviation from the mean of 16%. Neutron activation analysis may involve slightly greater
variance, so that for the gold solubility runs, variance of 16-30% was expected. A further
source of error may lie in the slow attainment of equilibrium by the buffer assemblages.
Hemley (1959) indicates that the quartz-muscovite--K-feldspar assemblage attains
equilibrium at 300-500°C, within two weeks, while the haematite-magnetite assemblage
may be very slow to react below 500°C (Eugster and Wones, 1962). Run times of between
10 and 20 days were therefore employed. Henley (1971) showed that gold + HC1 reactions
went to completion within a few hours in this temperature range. The reaction rates of
the buffer assemblages were thus the major factor controlling the attainment of solubility
equilibrium.

RESULTS

Results for gold solubility in buffered potassium chloride solutions are given in Tables
I and II for the range 300-500°C, 1000-2000 bar total pressure. These are seen to be
extremely variable within small temperature ranges and much of the time involved in this
study was devoted to trying various experimental modifications in an attempt to improve
the reproducibility of the results. In Fig.1 results at 2000 bar total pressure are seen to
have an almost exponential trend with solubilities increasing rapidly near to 500°C. Fig.2
shows solubility results at 1000 bar in the narrow temperature range 480-520°C, and
emphasizes the asymptotic form suggested in Fig.1. Small errors in temperature meas-
urement and control on the very steep part of the curve would involve marked differences
in the solubility measured at the apparent m e a n temperature.
SOLUBILITY OF GOLD IN CHLORIDE SOLUTIONS 79

TABLE II

Results at 2 kbar for 2 M KC1 solutions

Run Temperature Gold solubility Means of collection

No. (° C) (p.p.m.)

F 52 295 18 Teflon collection thimbles

F 53 293 18 Teflon collection thimbles
21 ] 17 silica thimbles
302
22 f 21 silica thimbles
24 420-450 112 silica thimbles
77-~ 886 corundum thimbles
507
78J 1070 corundum thimbles

DISCUSSION OF RESULTS

In Fig.3 the variation of the molality o f the silicate-buffered species HC1 with tempera-
ture is seen to have the same form as the solubility curve obtained for gold in similarly
buffered solutions. This parallelism suggests that HC1 may be an important species in the
gold solubility equilibrium. Fugacities of oxygen buffered by h a e m a t i t e - m a g n e t i t e also
increase rapidly with temperature and contribute to the steepness of the gold solubility
curve particularly above 450°C. As shown above (eq.2) the solubility equilibrium can be
written as a function of the activities o f the reaction species. For simple gold species such
as Au C1, Au C13 etc., the term a is-always greater than 1, while b is < 1. The solubility

20

U o

×1o ~, //
5

360 460
Tempe rat. u re °C

Fig.3. Variation of the molality of H + and HC1 in potassium chloride solutions buffered by the
assemblage quartz-muscovite-K-feldspar (calculated from the data of Hemley, 1959).
80 R.W. HENLEY

contribution of the HC1 term is therefore considerably greater than that of 02. The
decrease in the hydrogen ion molality for the buffered solution shown in Fig.3 indicates
that this ionic species may take little, if any, part in the gold-solubility equilibrium.
In Fig.4 the gold-solubility results are compared with solubility data for sphalerite in
buffered chloride solutions (Hemley et al., 1967). These show similar and parallel trends,
which are also, above 400°C, parallel to the molalities of HC1 in buffered solutions. Below
400°C ionic equilibria become more significant and account for the change of slope of the
solubility curves. For comparison, the solubility of quartz at 1000-2000 bar is shown,

-2

0
E

_J

5(~)0 460 360

T*C

Fig.4. Experimental solubility data for gold and sphalerite in quartz-muscovite-K-feldspar buffered
solutions at 300,400 and 500 ° C, together with the molality of HC1 in chloride solutions (calculated
from data of Hemley, 1959) and the solubility of quartz. Data sources: sphalerite - Hemley et al.
(1967); quartz - Weill and Fyfe (1964); gold - this study.

since quartz solubility is scarcely affected by the presence of HC1 in the solvent (Anderson
and Burnham, 1967).
The poor reproducibility of the solubility results did not allow direct determination of
the equilibrium constant or the stoichiometry of the reaction; however, the important
contribution of the HC1 species was demonstrated and is further discussed below.
Barnes and Ernst (1963) showed that at high temperatures (about 500°C) hydrothermal
solutions tend toward the behaviour of ideal mixtures. This suggests that the solution
species can be considered as molecular species which have minimum interaction with one
another.
SOLUBILITY OF GOLD IN CHLORIDE SOLUTIONS 8l

Using this as a model system, equilibrium solubilities can be calculated for gold on the
basis of known gaseous gold chlorides, Au C1, Au2 C12, Au C13, Au2 C16. High-temperature
thermodynamic data (compiled in Henley, 1971) show that the dimeric species, Au2 C16,
is likely to be the most stable in a high temperature gas phase, as was demonstrated
experimentally by Landsberg and Hoatson (1970) in vapor pressure studies. Solubility
reactions for each of these species can be written in the form of eq.1 and equilibrium
constants calculated. Insertion then of data for a HCI~,fo~, fH20 into solubility functions
like eq.2 allows the calculation of an equilibrium solubility for gold. Thus at 500°C, with
data for the buffers used in the experiments, the solubility of gold in this model system is
10 -6 p.p.m, at 1 kbar rising to 10 -4's p.p.m, at 5 kbar for the species Au2CI6, while the
contributions of the other gold species are insignificant. The writer is aware of the dangers
of this approach; however, until quantitative data is available for solution chemistry in
this very high-temperature field, no better method of calculation is feasible.
The trend of the calculated solubility curves is also similar to those obtained exper-
imentally and demonstrates that very large solubility variations are to be expected over
small temperature ranges in the vicinity of 500°C.
The experimental work demonstrated gold solubilities up to 1000 p.p.m, in the
buffered system at 2 kbar 500°C, while the calculated solubility for the same conditions
is less than 10 -4 p.p.m. Anderson and Burnham (1967) also noted high experimental gold
solubilities up to 1000 p.p.m, in unbuffered HCI and KCI solutions at 600°C, 3 kbar and
Burnham (from H.L. Barnes, personal communication, 1972) has also found solubilities
up to 3000 p.p.m, in 0.58 M HCI in contact with "granite" at 600°C up to 4 kbar.
The very large discrepancy between calculated and experimental solubilities for gold
may offer some clue to the nature of the solution species. In the thermodynamic calcula-
tions above, no account was taken of solvation of the gold chloride solution species. Water
is still a polar solvent at these high temperatures and pressures, so that solvated chloride
species will certainly occur. Copeland et al. (1953) noted very high molar volumes for
sodium chloride in dilute solutions, above the critical point, and they ascribed this
observation to extensive hydration of the solution species, and Crerar and Anderson
(1971) have studied the hydration of silica species in high-temperature solutions.
In order to account for the difference between the observed and calculated solubilities
two possibilities are apparent:
(1) The assumption that the high-temperature species is based on the planar Au2 El6
molecule may not be valid. Thermodynamic data favours the assumption of auric species,
but monomeric auric species, or perhaps higher order polymers may occur (Brewer, 1958).
(2) Extensive hydration of the simple gold chloride species may involve sufficient
solvation free energy to account for the higher experimental solubilities. The asymmetric
bond polarity in gold chlorides favours weak co-ordinate bond formation between water
molecules and the complexed gold, and similarly hydration of the complexed chloride
atoms would occur, by hydrogen bonding. Furthermore, in this high-temperature region
where ionic equilibria are insignificant, the availability of undissociated HC1 and alkali
chloride molecules suggests that these too may take part in solvation equilibria. The gold
82 R.W. HENLEY

solubility equilibria considered in this temperature region take place in a complex mixed
solvent consisting of reactive dipolar species, i.e., H20, HC1, KC1, (KCI)2 all of which can
take part in solvation equilibria with the gold species.
Marshall and Quist (1967) have stressed that such ion-ion-pair-solvent equilibria
play a major role in solution chemistry, and must be taken into account in determining
complete solubility equilibria constants. These authors suggest that ion-pair-solvent
equilibria involve dipole-dipole interactions, but it would be unwise at this stage to
speculate too much on the precise nature of the gold species-solvent bonding in the
high temperature and pressure region under consideration.
If gold chloride-HCl solvation does occur, then substitutional solvation equilibria will
be involved in gold solubility, of the form:

[Au2CI 6 (H~O)a (Hfl)b] + cH20 ~ [Au2C16 (H20)a+c(Hfl)b-c] + cHCI

Up to twelve possible "inner-sphere" co-ordination positions would be available to

HC1 for direct coordination, but the actual solvation numbers of HC1 and H20 would be
expected to be sensitive to both temperature and pressure. Further experimental work
(Henley, 1971) in the system A u - H 2 0 - H C I - 0 2 has suggested that at 500°C, 1000 bar,
the solvation number for HCI is six, while at 2000 bar this decreases to two.
Similar solvation equilibria can be written for the dipolar KC1 and other species in ore-
forming solutions.

SOLUBILITYOF GOLD IN ORE-FORMINGENVIRONMENTS

The primary object of a study of this kind is to follow the solution behaviour of metal
species in order to attempt to understand the physical and chemical controls which cause
the deposition of the metal in an ore-body.
The experimental work and its interpretation demonstrate that gold is readily soluble
in hydrothermal solutions and that about 1000 p.p.m, of the metal may be transported as
chloride species at 500°C, 2 kbar under the conditions of the haematite-magnetite buffer.
In buffered systems at temperatures where the solution approaches an ideal mixing model,
the presence of other components can have little effect upon the solubility of gold. The
solubility could be decreased, however, if other species are present which also involve
solvation by chloride ligands (HC1, KC1, NaC1... ), and this includes most of the ore-
metals. The ZnS solubility (Hemley et al., 1967) shown in Fig.4 demonstrates that
[ZnCI2 (HCI)n ] complexes may occur, and similarly pyrite solubility may involve a
complex such as [Fe2C16(HC1)n] in this temperature field.
The variation in the type of solution complexes and their stoichiometry makes the
draughting of solubility curves for gold over wide temperature ranges extremely difficult.
In Fig.5 a generalized solubility curve is shown for chloride complexes only, calculated
from an equilibrium constant obtained from the experimental data at 500°C, 2 kbar,
assuming the presence of the species [Au2C16 (HC1)2 (H20)n] • Three fields are indicated,
characterized by the dominance of ionic or molecular behaviour in the solutions.
SOLUBILITY OF GOLD IN CHLORIDE SOLUTIONS 83

3
2 Ionic -~- --~ M o l e c u l o ~

7 1
C Brines derived P~I kbo~/ /
+~

____ -2
0
Wo~roke~!r?"?"~..................
-e~tT°~'~'h-!~-~ C
~t°W_rm~J _b_"_'_~'?_ . . . . J. . . . . . . . . . . . . . . . . . . . . . . . . . .
__1
-,4

6 ~6o 26o 36o 46o 56o 6&

TemperotureOC
Fig.5. General solubility curve for gold in 3 M potassium chloride solution, The curve beiow 300°C is
that of Helgeson and Garrels (1968) for solutions in contact with quartz and pyrite. The curve for
T > 300°C, P = 1 kbar is calculated from solubility data (this study) for solutions where mHC 1 is
buffered by the quartz-muscovite-K-feldspar assemblage. Oxygen fugacity is buffered at values
intermediate between those on the quartz-fayalite-magnetite and haematite-magnetite buffers,

Helgeson and Garrels (1968) have computed the "sub-critical" solubility of gold for a
3 M sodium chloride solution in equilibrium with quartz, pyrite and gold. Their data
showed that a u r o u s chloride complexes [Au C12] are most important up to about 300°C,
although gold-sulphur species were not considered. Their chloride solubilities are shown
in Fig.5, region A, where it is evident that falling temperature rapidly reduces the
equilibrium solubility of gold.
Seward (1972) has demonstrated that, in the temperature range below 300°C pH-
dependant thiocomplexes of gold exist in solution and that the resulting solubilities are
considerably higher than those calculated by Helgeson and Garrels (1968) for chloride
complexes. The HS- stability field may exist well above 300°C (Ellis and Giggenbach,
(197 l)so that gold thiocomplexes (terminology used by other workers, e.g., Seward
(1972)), may be stable in this region. The rapidly increasing oxygen fugacity buffered by
natural assemblages may,however,oxidize sulphur in solution to sulphate species, less
suitable for gold complexing.
The temperature region B (Fig.5) is highlighted, where three important phenomena
occur:
(1) Redox transitions between aurous and auric chloride complexes favoured by the
higher buffered fo2 in this region.
(2) Transition between low temperature ionic thiocomplexes and high-temperature
molecular chloride complexes.
(3) General trend from ionic to molecular solution chemistry.
84 R W. HENLEY

The general higher temperature solubility (region C) is shown for a gold chloride
complex, e.g., [Au2 C16(HC1)2], at 2000 bar in a 3 M chloride solution with fo2, buffered
by an assemblage between quartz-fayalite-magnetite and haematite-magnetite. The
solution considered is buffered with respect to HC1 by a quartz-feldspar-muscovite
assemblage, so that the solubility curve (C) corresponds to that for a hydrothermal
solution passing through a granite (e.g., at the Mazoe gold mine, Rhodesia (Henley, 1971)).
The solubility curve shows that gold may be rapidly deposited from a saturated solution
due to falling temperature. Similar curves will apply to solutions in contact with other
HCI or O2-buffer assemblages (e.g., chlorite-biotite, amphibole-chlorite, etc.).
For the Tertiary-Recent gold deposits (of "epithermal" character) lower fluid
pressures prevailed during ore-deposition. Low pressure (< 1 kbar) favours molecular
species, so that the solubility curve may have a pronounced inflection in region B (Fig.5).
For these deposits the higher acidity (as HC1) due to wallrock assemblages such as
kaolinite-prophyllite, may allow higher gold solubilities than indicated in the diagram,
but the very low unbuffered oxygen content of solutions at shallow depths in the crust,
may reverse this trend. The inflection in the curve would allow two stages of ore-deposition.
The first deposition occurs at about 450°C, and "late" gold precipitates below 300°C.
Some of the early gold may be redissolved as cooler solutions pass, particularly if gold
thiocomplexes can form.
At higher pressures (> 1 kbar) ionic equilibria are important up to higher temperatures,
so that the solubility curve has a less pronounced inflection, and this curve would apply
to the Archaean group of deposits. Gold deposition in response to falling temperature
occurs only below 300°C, so that only "late" gold would be observed in these ores. With
falling temperature gold, pyrite, quartz, etc., will coprecipitate, so that for a quickly
cooling solution, rapidly deposited fine-grained pyrite would correspond to high gold
values as is the case at the Mazoe mine, Rhodesia (Henley, 1971). An intermediate
colloidal phase may occur during rapid deposition, and the distribution of gold in quartz
veins has often been discussed in terms of colloidal transport. Replacement relationships
showed sometimes by gold (e.g., gold commonly replaces pyrrhotite) may be accounted
for by the competition between gold and the displaced metal for HC1 ligands or compli-
mentary redox reactions between the two metals if the solution is not effectively buffered.
In the above discussion the possibility was mentioned that thiocomplexes allow higher
gold solubilities in the subcritical ionic region A. Incorporation of this possibility into
solubility schemes for gold must, however, be made with caution because, although
chlorine-containing species are known to be abundant, it is by no means certain that the
species of sulphur are equally so. The stoichiometry of the reported sulphur-metal
complexes indicate that for a hydrothermal solution the total molality of metals must be
equal to the total sulphur molality, so that this condition must be fulfilled before
consideration of hydrothermal thio-complexes can be made. Furthermore in low sulphur-
high metal solutions, the metals must compete for the available sulphur ligands and this
will result in substantial modification of the equilibrium solubilities of metals in this
region. Seward (1972) further discusses this problem and has indicated that thiocomplexes
SOLUBILITYOF GOLD IN CHLORIDE SOLUTIONS 85

can account for the gold content of present-day geothermal solutions.

Tile transition region B, between dominantly ionic solutions and the higher temperature
molecular solutions is stressed here because of the lack of quantitative understanding of
solution behaviour within it and its obvious importance in ore-metal transport and
deposition. It is important to obtain solubility information in this region (300-450°C)
and to correlate this with a thermodynamic study, possibly combining an extension of
Helgeson's (1964) methods and incorporating a correction for the transition to molecular
behaviour.
In the high-temperature region C (Fig.5) very high equilibrium solubilities are to be
expected for most ore-metals, on account of the ideal mixing behaviour of the solution
species, where species interaction is at a minimum and therefore does not limit solubilities.
With high equilibrium solubilities, it is unlikely that hydrothermal solutions above 400°C
are ever saturated with respect to the metals. If the hydrothermal solutions responsible
for mineralization in the Morro Velho gold mine, Brazil (described by Gair, 1962), for
example, were derived by metamorphic dehydration reactions in the P-T range of the
greenschist-amphibolite facies transition, and all the trace gold in the country rock
affected by these reactions was leached out, a solution with a maximum gold content of
0.1 p.p.m, would result. A similar estimate of the geological "solubility" was made by
Helgeson and Garrels (1968). These estimates are well below the experimentally deter-
mined equilibrium solubilities of gold at temperatures above 350-400°C. This suggests
that an efficient transport and concentration mechanism can be envisaged for gold to
account for the formation of ore-bodies (where the metal content is commonly well in
excess of 10 p.p.m.). Gold would be readily transported as chloride species in high-
temperature solutions derived from a widely dispersed source (such as a metamorphic
pile) to the ore-zone, in undersaturated solutions and then efficiently concentrated to
form an ore-body by deposition as the solution cooled below 300°C.
Particularly important in ore deposition are the relative rates of change of the solution
parameters, fo2, fHC1 etc., in determining the paragenesis of the ore-minerals and their
disposition through the ore-body. These aspects of ore-formation have been discussed by
Helgeson (1970a, b) who provides a powerful model for base-metal ore-deposition. At
this time, however, there is insufficient information available concerning the solubility of
the other ore-components, let alone the kinetics of their deposition, to allow the devel-
opment of a quantitative geochemical model for the formation of a gold deposit.

ACKNOWLEDGEMENTS

The experimental work reported in this paper was carried out at the Geology Depart-
ment, University of Manchester, during the tenure of an N.E.R.C. Research Studentship.
I am grateful to Professor W.S. Fyfe for suggesting and encouraging this field of research.
Mr. B.L. Goodwin (Joint Universities Research Reactor, Risley) carried out the neutron
activation analyses rapidly and efficiently. I am also grateful to Professor Fyfe, Professor
D.S. Coombs, Dr. T.M. Seward and the many others at the Chemistry Division, D.S.I.R.,
86 R.W. ttENLEY

Wellington and the Chemistry Department, University of Otago, for critical reading and
discussion o f the manuscript. The author accepts the entire responsibility for any
deficiencies o f this paper.

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