Geo&imi~~et~oahi1~I~Ao~,1978,Vol.

87.~p.379toS99. Pergsmonti.

Printedin NorthamIr&r&

Thio compkJxesof gold

ang;et

of gold in m

T. M. SEWARD Chemistry Division, D.S.I.R., Private Bag, Petone, New Zealand

(Received 14 FebtuMy 1972; acc@d in reviued fom 11 July 1972)

-The wlubility of gold in aquwue wlphide wlutiona hes been de&m&d from pH*c Y 4 to pHm*~ (cf 9.6 in the prewnoe of a pyrite-pphotito redox bu%r at temperatfrom 160 to 3OOCand 1000bar pFesaure. Maximum wlubiliti~ wem obtained in the neutral region of pH as, for example, with mNms = 0.16 m, pH#rc - 6.96, T - 30QC, P = 1000 bar where a gold wlubility of 226 mg/kg wae obtained. It wee wncluded that three thio gold oomplexee oontzibuted to the wlubility. The complex Au#S)#predominated in alkaline wlution, the Au(HS),- oomplex owurred in the neutral pH region, and in the aeid pH region, it ww wneluded with lese wrtainty that the Atl( oomplex was pmnt. Formation oonstsntecelouletedforAu,(HB),S~~dAu(H6)~~emp~theirhighetsbiiity. In thetiperature renge from 176 to 260C, valuea of p@ for AuJHS),Ss vary from -63-O to 47.9 (&-l-6) and from -23.1 to -19.6 (&l-6) for Au(HS),-. Equilibrium con&ante for the diswlution rewtiom, Au0 + B$ and 2Au + H&J + 2HE- tr Au#tS&Ss + H, vary from pK, - +2*14 to +2.66 (f0.10) for Au@S)#and from pK_ = +I.29 to +l.lQ (&O-IO) for Au(HS),- over the temperatrange 176 to 26OC. Enthdpier, of theee dimolution reactiona were calculated to be AH, - -6.2 f 2-Okcal/moland AH,, P + 1.7 f 2.0 kcal/m& respeotively. It was wnoluded that gold is probably traneported in hydrothermal ore whitiona BB both thio and ahlow wmplexea and may be deposited in reeponw to ohangeain temperature, preawre, pH, oxidation potential of the sy&em and total wlphur oonoentzation. INTBODUCTION + HSP Au(HS),+ @I,

of transport and deposition of gold in hydrothermal ore solutiona hae long aroused the curiosity of geologists. Experiments and caloulationa by previous workem have taken ease&ally two btic lines of approach, one involving the transport of gold as chloride complexes and the other suggesting that gold could be oar&d as sulphide oomplexes in alkaline sulphide eolutione at elevated temperat-. Early experimenta by Oo~a~o (1936) at temperatures up to 300C indioated that gold was soluble in aoid chloride and alkaline sulphide solutions. Further work by LINDNER and GRUKER (1939) suggested that gold wae insoluble in aoid aulphide (H&J) eolutior~ at 300C, and experiments by Zvlaa~~cxv and PAULSEN (1940) on the solubility of gold in alkaline sulphide solutions at temperatures to 80C confirmed Ogryxlos I-eslalti. Based on the experimental data available at the time, SMITH (1944) favoured the transport of gold in alkaline sulphide solutions; however, KRATJ~K~PF (1961) calculati that gold, in addition to being soluble in alkaline sulphide solutioxu~ (probably aa AuS-), oould also be transported as a chloride oomplex in aoid chloride solutions. More recently, WEISSBERG (1970) demonstrated experimentally that gold exhibited much higher solubilitiee in high temperature alkaline sulphide solutions
THE MODE 379

380

T. M. SEWARD

than those c&n&ted for chloride solutions by HEL~ESONand GARRELS(1968). Clearly, these two competing hypotheses beg the question as to which mechanism is the more important and to what extent. HELQESON and GARRELS(1968) concluded from thermodynamic calculations based on extrapolation of low temperature data that hydrothermal gold ore deposits are formed from acid solutions in which gold is transported only as chloride complexes. However, their model must be treated with caution because the possibility of transport of gold as thio complexes wa.s not considered. HEL~ESON and GARRELS (1968) conclusions have been criticised by BOYLE (1969), who suggested that complexing of gold by chloride ligands and the transport and deposition from hydrothermal solutions of low pH was not in agreement with geologic evidence exhibited by many gold deposits. Studies of wall rock alteration a.ssemblBges(MEYER and HEXLEY, 1967), fluid inclusions (ROEDDER, 1967), coexisting sulphides and sulphide-oxide mineral associations (BARNES and KULLERUD, 1961) and of hot springs (WHITE, 1967) suggest that the majority of naturaJ hydrothermal ore solutions do not vary more than approximately two units either side of neutral pH. The object of this study has, therefore, been to determine the solubility of gold at elevated temperatures and pressures over the near neutral region of pH with the intention of elucidating the stoichiometry of the complexes contributing to the solubility. This may permit conclusions as to the transport of gold in hydrothermal solutions as well as to the factors causing its subsequent deposition. EXPERIMENTAL METHODS
The experiments were conducted in a gold bag bomb similar to that described by Wzuss~a~o ( 1270). The solutions were contained in B flexible gold container having s total volume of 460 ml and could be sampled by means of a gold capillary which extended from the gold-bag through pressure tubing to a valve outside the pressure vessel and its surrounding resistance furnace. The stem within the sampling valve was gold plated in order to retard the corrosion which ocourred with lower pH solutions (concentrated in H&J). The temperatures were controlled to within &I% of the steted values and pressures were maintained to within &20 bar. Sodium bisulphide solutions were obtained by bubbling HsS through N&H solutions which had been prepared with freshly boiled distilled water and stored in e flask under a nitrogen etmosphere. The required volume of solution was then pumped from the flask with a smnh nitrogen preesnre into the previously evacuated gold-bag. In this wey, the solutions did not come in oontact with air and the formation of polysulphides and oxyanions of sulphur wae suppressed. During the experiments, the volume of solution in the gold-bag was monitored such th8t its conclentration and pH could be adjusted by pumping in the sppropriete volume and concentration of HCl, N&l or NaHS solution. This was facilitated by means of a separator whilemeinthe bomb at elevated temperature and pressure. As a check against errors having ocmrrred during the numerous adjustments to the solution compositions and to ensure thtat leaks hed not developed in the gold-bag, aliquots of solution were regularly extracted and analysed iodometrically and by the Mohr method for sulphide and chloride concentrations, respectively. In addition, the pH of solutions bled from the bomb wss determined with 8 glass electrode at 20%. However, at pH values less than about 7.6 the measured values were erroneous due to exsolution of HsS at room temper&m-e and pressure. Thus, all pH values less than 7.6 have been calculated from the relationship

(1)

Thio complexes of gold rend the transport

of gold in hydrothermal

ore solutions

381

where rn~s- CLnd rn~,~ 8re the molelities of HS and H$, If,, (20%) of HrS is taken from RLLIS and GIWENBACE (1971), end the appropriate value of ~n,s is from GABBJ&+ICBend SCEINDLEB (1969). The HS- ion is aonsidered to be simil8r to the Cl- ion and ~a-( =y~s-) data ere from ROBINSON and Srcnues (1966). Two lines of approach were followed in the solubility experiments. In one, the total dissolved, reduoed sulphur, mstor, ~8s m8intained constant while the bisulphide ion concentration and pH were veried and in the other, the bisulphide ion concentration ~8s held constant while vsrying PH. In 8ll ~8888, the ionic strength ~8s kept at 0.60 by addition of NaCl. Since the dissolution of gold is a function of hydrogen fug8city. 8 pyrite-pyrrhotite redox buffer (see for ex8mple RAYMUX.UHAY 8nd HOLLAND, 1969) was present in 8ll experiments in order that the jJ& WBBm8int8ined et a known v8lue. Samples were taken at two-day intervals, although the equilibrium gold solubility ~8s ettained in lees thau 24 hr for 8ll temper8tures end pressums. A few millilitres of solution were extmcted into a flask containing aqueous bromine solution with a drop of Ccl, 8nd then enslysed for Au via atomic absorption spectroscopy. The veriabihty of replicate gold analyses ~8s never Some of the solutions were enelysed for iron greater then 2 per cent of the stated concentration. (using atomic absorption) in order to determine the concentration of dissolved iron in equilibrium with the pyrite-pyrrhotita buffer. The precision on these sn8lyses wa8 approximately f 16 per cent of the stated ooncentration. EXPERIMENTAL Con&ant RESULTS

bisulphide ion concentration

These experimenti were concerned with the effect of intensive parameters such as and pH on the solubility of gold at constant bisulphide ion temperature, pm concentration. The solutions were maintained at oonstant ionic strength by employing N&l as an essentially inert component (i.e. r))N&s + ??&NaCI = 040).The data of Pig. 1 indicate that the solubility of Au in mNtis = O-16 (I= O-16) w&8 unaffected by
10

N&IS-O.lSm 0

0 T (C) Fig. 1. The affect of Nail on the solubility of gold @g/kg of solution) in high temperature solutions where rnxas = 0.15 (molal); the velue of pH ( - Q-60) refers to the pH of the solution at 20C and 1 her pressure.

the addition of &Cl suoh that mN&s = 0.16 and )rzN&c1 = 0.36 (1 = 0.60). The ooncentration of gold in 0.60 m N&l solutions up to 300C and P = 1000bar was below the limit of deteotion of the clsalytical method (i.e. < O-1 mg/kg). Furthermore, HELWWN and GABEELS(1968) calculrttions also emphaske the low solubility of Au

382

T. M.

SEWARD

in sodium chloride solutions. Chloride complexes of gold are therefore considered to be present in negligible concentrations relative to thio gold species. The solubility of Au as a function of NaHS concentration, PH and temperature is clearly illustrated by Figs. 2, 3 and 4. Rising temperature quite dramatically 240 e 22op
t zoo/L P-1000 = bar

NaHS-O.lSm
NaCl -0.35-n

@+ZOT -

9.35 I:350 1

,801

b
C

P+I,,~,-~*LZ (L.11)
(1.60) 6.44 (0.43)

~H,~~-7.01 pHZvC-

160. L

d e

~~~~~-5~96

(0.15) !
P

T (C)

Fig. 2. The effect of temperature and pH on the volubility of gold @g/kg of solution) at 1000 bar preaaure with rn~ds = 0.16 and mN&] = 0.38; the pH velues are those at 20% end 1 bar preraure; odculati v&w of the ratio, HW/H$ are in parentheses. increases the solubility and a similar trend may be observed as pH decreases towards neutrality (where the ratio HS-/H,S M 1). In addition, an increase in the bisulphide ion concentration at constant pH (or HS-/H,S ratio) leads to higher gold solubilities. An interestii anomaly exists in the progression towards increasing solubility with decreasing pH. For solutions in which mNgs = 040 (Fig. 4), this trend is broken at T < 23OC and a subsequent decrease in gold solubility occurs with fur%herdeereases in pH,, from 7.65 to 7.47. One experiment conducted at 238% and 1000 bar pressure with ?,&Nas = 0.50, pH,, = 6.20 (i.e. total dissolvedsnlphur, %t.t m 3.9) and mN.Cl = 2.6 yielded a very high gold solubility of 546 mg/kg. The reproducibility and reversibility of the experimental runs was very good. For example, the gold sohrbihty for mua- = 0.30, pHWp, = 7.46, T = 224C and P = 1000 bar was found to be 16.8 mg/kg. After four weeks of temperature and

Thio complexes of gold end the tranqort

70

1
N&l

of gold in hydrothermal ore solutions

333

NaHS-0.3Om -O.ZOm

60 50 G . E LOE

P - 1000 bar

a
b
C

pHzOoC - 9.55 pHzOeC - 8 -41 pHwc - 7.45

(555) GO*21 (4.Ll)

a 30-

Fig. 3. The e&f& of t.emper&u.re and pH on the mlubility of gold (mg/kg of eolution) at 1000 b8r pzwsure with mNaS = 0.30 end mN@j - O-20; the pH valuea are those et 20% end 1 bar pmmsure; oalouzated vahm of the ratio Hf3-/H&3 am iuparantha3e8.

-11

NaHs-o~xRn

I&O-

NaCl-0
P-1000

bar (5551

%,=935

b &,-7.95 C pHmT= 7.65 d pH,,-7.47

(13.9)
(6.39) (4.611

T (C)

Fig. 4. The effect of temperature end pH on the Bolubilityof gold @g/kg of solution) at 1000 b8r preamre with mNdif5 = O-60 and mNa = 0; the pH vehm c8lculated v8luea of the r8tio ES-/H# a30 methomat20Caud1baxpremure;

inpalmthe.

384

T. M. SEWARD

let-

NatiS-C.lSm N&i -'I

.35m

1. 160

I 180

I 200

2al

2&a T ('C)

26(,

280

360

I i

Fig. 5. The &&etof pFeeaure on the variation of gold eolubility @g/kg of solution) with mxa8 = O-16 and rnxa = O-36 the pH valuesare thoee et 20% and 1 bar
preeeure; csltit-sd valuea of the ratio HS-/Ef# LUW in perentheees. refers to ourvea m and n. Soale at right

pressure cycles (up to 3OOC and 1600 bar) using the same pressure vessel, the conditions were returned to T = 224C and P = 1000 bar. A new aliquot of solution when aaalysed gave a gold solubility of 16-9 mg/kg. Sii reproduaibility and reversibility in gold aolubilitieawas demonstrated over the entire range of solution compositions, temperature and pressure. Concentrations of iron in alkaline solutions in this system were lea than O-3 mg/kg at T < 200C but rose to a maximum of 5 mg/kg at 3OVC. In near neutral solutions, concentrations increased from 0 to 13 mg/kg &8temperatures rose from 100 to 300c. These experiments were designed in order that the variation of gold volubility, mA,_,, a~ a function of pH could be determined while the total amount of reduced sulphur iu solution was m&Wned con&ant. The resulta of one set of experiments in Fig. 6. A pro~ouncad solubility maximum where WJ~,,* = 040 are ill-M occurs in the region of pH - 7 with lower solubilities being obtained in the acid and more alkaline regions. The vahzea of pH plotted in Fig. 6 are the true once for each part&k temperature and for pressure = 1000 bar aad have been calculated from the relation pHTvP = ~9:;~ + log (z) + log (ET?

(2)

Thio complexes of gold and the transport

of gold in hydrothermal

ore solutions

386

P-loo0

bar

mStot - 0.50 I-O.50

Fig. 6. Veriation of gold SolubiJity, mAntot (mom) with pH at temperatmw from 176 to 250C; the experimante pointa oorreepond to the gold solubilitiea at the pH of the eolution at the swed tan-and P - 1000 bsr.

where XzP is the &st dissociation coustant of H&3at a giveu temperature and preesnre. As previously mentioned,NaHS is consideredto be similarto NaCl and the values of&Z heve thereforebeen taken from LINDSAY and Lru (1968). It haa been assumedthat m,s doas not vary greatly with temperatureand preemuw and hence, ~~,s values are taken from GAMSJLQER and SOXIND~ (1969). !l%e ratio, m-/mg will not reqond greatly to chauges in temperature and pressm~ but small correctionshave been made in znus-to account for the formation of NaHS ion pairs (as will be discussedlater).

Effed ofpvmtwe
A few experimentswere performed to elucidate the effect of pressure on the solubility of gold, and these data &FB given in Fig. 6. In the region of a5line pH, the effect of decreasing the preesarefrom 1600to 6od bar is to inoreeeethe solubility of gold, particularlyat highertemperatures. Wheu T < 200C,the effect of presanre on the solubility of gold is relativelyminor. Iu the neutraJ pH region, a similaxeffect of ina solubility with decre&ng pxwsureoccurs at high tempera&- (i.e. T > 2SOOC). However, wheu T < 250C, ed-inpreesnrefkom1OOOto600bardethe gold solubility.
NATI~ZEOFTI~ECO~XES The variation of gold solubility with changiug pH reflects the presence of a number of thi+gold complex~, each having a characte&tic pH stability range. It is therefore of interest to determinethe composition and stoichiometryof the gold complex contributingto the maximumsohbility in the pH region of about 7 as well aa the nature of the aqueous gold species in the more acid end alkake @ens a& elevated temperatureand pressure. of the threepossiblespecies,HS-, H,S and S-, which might be consideredto act aa ligands in this system, the HS- ion is likely to be the most important candidate

386

T. A?&. &SWARD

for compkx formation. The uncharged species, H,S, will be of only minor importance beeax~seof its weak compiexing properties, whereas the concentration of SF- ions in the pH range invest g&xl can be considered to be too fow to play any direct role in completing (GIWENBACEX, 1971). The formation of sulpbide ligands is considered to be due to hydrolysis reactions similar to Au(HS);-~ + Au(S!R$_, (S);-z-V -I- xH+ (3)

The equilibria which define the conditions under which gold complaes form in this system s2x given as fallows: Au + H+ F; Au+ + &H,

The formation of rnm~~~~Aeargold species may be described by tk generaMd eqnation, Au+ -+ yHS- f Au(HS),, (S);++ -f- zH+

If it is aeaumed that ths total dissolved gold pre~nt in solution, mcAnhol, is the sum of 8ll such complexes, then we.osn szrangsaquation (7) (approximating mA,,,, SZI aAuto,)
to give, @%*t C--y4--t ah,+ a&- s+- =.z* B ,r(t~3w a I M

where WBhsve summed avar 8ll possibie stoichiometries of 5 and y, the only restriction being that the maximum oo-ordimbtion number of ligands about ti An+ ion is 4. The total dissolved sulphur present may be defined M -k na,&l, =%?t = @&Eswhere the sulphur oomplexed with gold is neglected otig P)

to the small gold solubility compared with the total dissolved aulpha concentration. It should be noted that the presence of thio-iron complexes resulting &om th,s dissolution of pyrite and pyrrhotite is also neglected, b&g in mind the very low solubility of these two phases_ Under the reducing aonditions of these experimfm& gold is CXBU&S&4~ be present p~orn~~tl~ In the 8urous st&te. Setting activity coeflkients equal to u&y such tb& metotm asto, and combking equ8tions (0) and (9), the expression 00) %s- =z ama,,,

Thio oomplexes of gold and the transport

of gold in hydrothermaJ

ore solutions

387

is obtained, where

a=a~+ +Kal
i.e. for pH < pKal, a = K&E+ and for pH > pKb,, a = 1.

=a1

(11)

However, if we delineate two regions of pH for consideration, then a may be somewhat simplified.

The acid-base dependence of these gold complex equilibria may be expressed in terms of the single variable, pH, this approach resembling that taken by other ACH and WIDMER, 1963 ; G-ELI and ST&&RXIE, 1967) workers (e.g. S~~~AXZZEXB in dealing with spsringly soluble sulphides. From (6) and (lo), we may obtain
aH,S =

a rnstot

%+

=a, a-l/a
%i+-

(12)

If equation (12) is combined with (5) to yield an expression for&, and this result subsequently introduced into (4), the following relationship for (IA,+may be written as Kill2 rn%ot aA,+ = K* P@ 01
1 2
(13)

Substituting (10) and (13) into (8), we finally obtain

For 8 given tempersture and pressure!and fixed matot,equation (14) describes the solubility of gold (i.e. ??&&,&as a function of the single variable, pH. For a particular region of pH, one obtains, by employing the appropriate value of a, taking logarithms and differentiating, a general expression for the slope of the gold solubility versus pH curve within the stipulated pH region. Thus, for pH c pKa,,

d 1%mAutot
dPH and for pH > pKol

=z+y-1 *J~mntot
=

(16)

d logmA%t
dPH

*.P.aratot

i*

(16)

If pH ia con&ant and mstot is varied, then a similar relation may be derived: d log
mAutot >

d p%t

T.P.pH = ' -"

(17)

The slopes of the solubility curves for hypothetical complexes of diverse stoichiometries may, therefore, be determined and compared with the experimental solubility

388

T. X. SEWARD

data. When the slope of a calculated solubility curve for a particular complex is coincident with that of the experimental solubility curve, then it is concluded that m.4O, is due to this particular compIex. This approach is applicable to mononuclear complexes, although the possible presence of some binuclear species may also be tested. Table 1 gives the calculated slopes of the solubility curves for a selection of possible gold complexes which could occur in this system at elevated temperature and pressure. In Fig. 7, a number of these calculated solubility curves have been fitted
Table 1. Calculated slopes for solubility curves for a selection of gold complexes Complex d log mAntot
dp= d %I mAutat d p&t

PH < PK,, AU+ AUHP Au(HS),Au(HS), Au(~) AuCH8S);+ AUP AUS, AuJHS),S&Au(OH) Au(HS)(OH)Au(S)(OH)% -1 0 +1 +2 -1 -1 +1 +3 +1 0 +1 +2

PH P&, -0.5 -0.5 -0.5 -0.6 -1.5 -2.5 +0*5 +1.5 0 $0.5 +0.6 +1.5

AuHS

2 Fig.

I 3

I 4

I 5

I 6 PH

10

I 11

7. calotited Solllbility l3urves for three thio-gold camphy~ compered isotherm for T = 225 C and P withthee xperimatadly de&mhedso;~~ty

Thio complexes of gold end the trauaport of gold in hydrothermal ore solutions

389

to the experimentalvolubilitycurve for 22bOC.The same treatmentmay be equally applied to the other volubilityisothermsshown in Fig. 6. !Lhiacomparison of c&ml&d and experimentally derived volubility curves indicatesthe presenceof three dominantthio-gold speck. In the neutralpH region, the complex Au(HS)$- is postulated and in the alkalineregion, the deproton&ed binuckr complex, Au#XS)&Y- predominates. Verificationof these resultsmay be found in Fig. 8 and 9 wherelog r@AatO, has been plotted versus -log ?a+ at con&ant pH and temper&are. In the neutral pH region, such a plot should yield a line of

t 250C\

0.2

0.4

0.6

0.8

Fig. 8. The &&i&y of gold, ma,,, (mom), 86 8 function Of redated enlphur concentr8tion, p&t ( = -log m&, 8t elevated tem~turea and P - l()QO bare the v&e of pH ia for 20C and 1 bar.

-6*OO& 0

0.2

Oe4

0.6

0.8

1.0

PStot. Fig. 9. The taolubility of gold aAUtot (mow), BB e function of reduced eulphur concentration, pS,, ( = -log m,,), at elevated temperf&turee and P = 1000 b8r; the value of pH ie for 20C and 1 bar.

390

T. M. SEWARD

slope - 14 if the Au(HS),r- complex predominates, whereas in the alkaline region, a line of slope -1.0 is due to the Au,(HS)&?- complex. Figures 8 and 9 confirm this, the slopes obtained at each temperature being well within the limits of experimental error. In the acid region of pH, the complex AuHS is assumed to be present but the paucity of experimental data for different total dissolved sulphur concentrations adds a degree of uncertainty to this conclusion. A plot of log n~*,,~~ versus -log mstot would confirm the presence of AuHS but, unfortunately, these experiments were prematurely terminated before these data were obtained, due to the catastrophic failure (by corrosion) of the valve containing the low pH sulphide-chloride solutions at elevated temperature and 1000 bar pressure. As previously noted, the existence of appreciable concentration of the Au(H,S)r+ complex would be unlikely and would at any rate, give rise to a solubility curve with a slope of -1.0 where pH < pKal. In addition, simple complexes involving the S*- ion are apparently absent, there being no evidence for the presence of the frequently postulated complex, AuS-. SABIN (1971) has suggested (on the basis of ab initio calculations) the existence of the strongly hydrogen bonded adduct, (H,SHS)l-; however, the presence of complexes of the type Au(H,S.HS)~-~, particularly at elevated temperatures, is considered to be rather unlikely. A derivation was performed in order to determine if any simple hydroxo complexes or mixed hydroxo-thio complexes of Aul+ might be formed. The calculated slopes of solubility curves for a few such species are given in Table 1, indicating that they are not present at significant concentrations. There is, in fact, a possibility of the uncharged Au,(HS)(OH) complex existing at much lower temperatures (i.e. at T -c lOOC), but this would not be of geological importance with respect to hydrothermal ore solutions.
DETERMINATIONOF HYDROGEN FUUAC~ES AT ELEVATED

TEICPERATURES ANDPRESSURES The dissolution of gold involves a redox equilibrium liberating hydrogen. We may describe the solubility of gold in terms of a reaction of the type pAu + QH,S + rHS- + Au,(HS);;,9- f hH2 .
(18)

In order to calculate an equilibrium constant for this reaction or a formation constant for the complex, Au,,(HS):;,Q-, it is necessary to know the hydrogen fugacity, fn*. For this reason a pyrite-pyrrhotite assemblage was present in these experiments, such that the fx, was buffered to a constant value which could be calculated from available thermochemical data. In the calculation of fn,, the equilibrium constant, K,,, for the reaction FeS + H+ + HS- f FeS, + H,(,, may be initially determined from AG values obtained for the four equilibria, Fe&,, + QS2(,)+ H&,, + H,f,, + HS,,, = H&&q) = FeS2(,, H,,,, + 4S,W H&W H&G,, (19)

Thio complexes of gold and the trenaport of gold in hydrothermal ore solutions

391

The pertinent thermodynamic data are &om TOULMIN and BARTON(1964), KUBASCEEWNZI and EVANS(1966), ELLISand GIQ~ENBACH (1971) and KOZINT~EVA (1966). Values for log I&,, at four temperatures from 175 to 25OC are listed in Table 2. However, these data must be adjusted to aeeount for P = 1000 bar, the pressure under which the experiments were performed. This correction was facilitated by using the relation

(
Table 2. Valueaof ass,
l& Of log q#.

ahl9,

ap

~~~ T=-RT~

where WV,,, = partial molal volume change for reaction (19). Values for partial molal volume6 of the H+ and HS- ions are taken from ELLISand MCFADDEN (1972) and the partial molal volumes of FeS, and FeS are from ROBIE et a2. (1967) and TOULAUN and BUXTON (1964), respectively.
the pfbrti8lmolal volume cb8nge for re8otion (19) the log8ritbm of the equilibrium oonstuat fOr the spme reMtiOll, 8t eleveted ~perStUl@l.

&

log 4,s

zQ@m%nol-1) -3.74 +3*17 + 11.77 + 22.77

log K,,(P

- 1000 bmr)

176 209 226 26Q

+ 10.06 + 9.89 +9+0 + 9.77

+ 10.09 + 9*86 + 9.73 + 9.64

For example, at 260C,~~

= +22*77 cma mol-l, and, hexme, = -2~27 x 10-r bar-l.

Value8 for log Kn (at P = 1090 bar) are given iu Table 2. The hydrogen fugaeity at elevated temperaturw and 1090 bar prwsure may now be determined from the following expre&on
lgfH, =

log rr,, -pH

+logaHs-,

(21)

where pH and czus-are the true values for a given elevated temperature and 1090 bar P==n= The approach taken in obtaining es- at elevated temperature and.preasure involvea &mating es- from the relation,
mH,_

- K-WyH.S
_

%+YHS-

(22)

the assumption being made that

maa--F ncH,s

0.50 - rnStot .

(23)

392

T. M, SEWARD

However, the formation of NaHS ion pairs must be considered ak elevated ~rn~~t~. i.e. NaHS ~1 Na+ f HSR diss= aNe+aHS-= tis-7J*a, aNaE[Se rmNF%FW
(24)

whereyN=0 is f& eqIUb1 to unify. EqU&tiOn (24) is SObd for ?%N&S, thus &owing equation (23) to be more murately expressedas
%a+ ?x*s = 0.60 mNm80 . (25)

Using this relation, equation (22) is again solved for mge-. Thb iteration is repeated w&l essentblly constant v&w for %a_ and w sre oMa$ned. Because of the simikrity in solute propertiesof NaHS rend X&Cl(e.g. variation in partid molal vohzmes with temperature up to 250C),valuesof meanionic activity co~ffi&nti for GHS we therefore taken from LTKDasy and we (1968) data for NaCl. Data for ya,8 are from CW&X& and S-m (IS@), and rwe cotid not to change greatly with increased temperatureand p-. In addition, values of K, (di8aooisti~ constant) of NaHS are taken as similar to those for NaCI. The variation of Ir,, (NaCl) with ~rn~a~ is given in Fig. 10 and has been by the method outlined by l&xs aad MCFADDEN adju&ed to 1000 bars pm
(1972).

$ -.?*oo
s"

-3.00 v

-8
t

0 Wr$ht
b D

etai

1961

DInnarldt+iafe~l1969 sill&l and Mutall 1964

Fig. 10. V&&ion of log ICw for NaCi with temperature.

Using equation (21), log fH,data have been cakulated for high temperature-high pressure values of pH corresponding to pHs (at 20C; 1 bar) of 7.10, and lo-00 and satisfying the condition that total dissolved sulphur, mstot is equal to 0460. These cakulated data are presented in Table 3. Eg-am
CCWSTABTS END

Em-s

OF TE~E ~~SS&WOX

REACTIONS

We have concluded that three thio-gold complexes predominate in this system, AUKin the neutral pH region, Au,(HS)$P- in the alkaline region, and in the

Thio complexes of gold and the transport of gold in hydrothermal ore solutions Table 3. Values of hydrogen fugacitiee at elevated temperatures as calculated from equation (21) for a solution in which m,,, = 0.60 and two different pHs (8t 20% and 1 bar). The corre&onding valuea of pH at elevated temperatureaand P = 1000 bar are also given

393

P~~moa

bar

lWfH,

176 200 226 260

pH = 7.10 (at 20%; 1 bar) 6.73 +2*71 6.76 + 2.40 6.97 +2.07 7.01 + 1.76

pH = lO@O (at 20%; 1 bar) 9.43 +0*13 -0.26 9.66 9.80 -o+Io 9.87 -0.94

aoid region, the AuHS species probably exists. The followiug discwsion will be ooncernedwith the flrst two species sinw there is some degree of uncertainty as to the presenceof the AuHS complex. The dissolutionreactionsdasoribedby equation (18) giving rise tothe above complexes may thus be written, Au0 + HI&!3 +.HS- + AUK+ )H; (26) 2Au + H,S + 2HS- v=Aus(HS)JP- + He . (27) The equilibriumconstantfor reaction (26) arisingfrom the dissolutionof gold in the neutral pH region may be given as
p& = log
aH@ %SaAnUSS)I --If..:

(28)

have been taken as the maxima on the various solubility whsaevdu- of aA,,( isotherms depicted $n Fig. 6. The hydrogen fugacitiea (listed in Table 3) and the appropriateaotivitiesof H,S and HS-havebeen calculaf~Iforthehightemperature+ high pressumpHs oorreqonding to these solnbility maxima (e.g. pHwo = 7.01), the only stipulationbeing that total dissolved sulphur, msto,= O-60= a oonstant. Defaileofthe~~tionof~,,anda~,-aregiveninthepreviononhy~~ fngacities. The approximationis ti made that (lA,,(ns,-) = mA,,(ns),-. h a Similar manner, the equilibrium son&ant, 9, for reaotion (27) may be derived. Table 4 tabulates the values determiwd for pII,,, and pK,. Enthalpiss for the dissolutionreactions in the temperaturerq 176 to 26OoC and at 1000 bar prewmre were obtained from a graphic&l solution of the van% Hoff isochore aud are AE,O = +1*7( f2*0) kcaljmol and AH, = -&2( f2.0) koal/mol.
Table 4. Values of equilibrium con&ants for renctiona (26) and (27) end form&&m con&ante for the two complexes, Au(HS),*- and Au#B)$when nag,,, = 0.60, end ionic &en@h = 0.60 et elevated temper&m and 1000 bar preenwe (& 176 200 226 260 p&( f0.10) Au(HS),$-l-29 + 1.28 + 1.22 + 1.19 -23.1 -21.1 - 20.3 -19*6 + 2.14 +240 + 2.60 + 2.65 P&S( 9~1.5) pR,( f0.10) p/9,( 9~1.6) -63.0 -60.7 -49.3 -47.9

Aua(HS)P-

394

T. M.

SEWARD

FOEMATION CONSTANTS AI~DCOMPLEX STABILITY Formation con&ants for the t&o-gold complexes are expressed by

PI2=

aAu(HS a,,+

),-I

a&-

(29)

as in the case for Au(HS)%-, or with the appropriate substitution of equation (3), the formation constant may be written Par f -log aAn(u1 - 4 log&, - px* - pH + 2 log %w
.

(30)

Approximate values of pK* have been derived from HEI&ESOES (1960) oaloulated (and extrapolated) log H data for the equilibrium, Au + tO,(,, + H+ + Au+ + ~H&+u,,
l

(31) de(32)

The effeot of 1000 bar pressure on this reaction has not been considered. Inasimilar manner, a formation constant for the complex, Au&I&S-~, scribed by @au =
aAa,,(HS),S-

may be o&ulated. Utilising equations (3) aud (6), one obtains

%+ ags- aa:-

PBst1= -lOgaAn,(Es),sb- log&, - 2 pg* - pH - p%,

+ 310g

aHS-e

(33)

Data on pK,, the second dissooiation constant of H&3, at elevated temperatures have been extrapolated &om GIWEEEACH( 1971). Table 4 lists the o&ml&d values The unoertainties in these values are given as fl.5 pfi units. of ~/%a and PL. This allows for considerable error in the evaluation of K* as well as for the laok of preoision inherent in the other parameters such as K,,, at elevated temperatures. It is worth noting that the formation of the complex, Ar@S),@-, by a hydrolysis reaotion similar to 2Au+ + 3HS- + Au,(HS),S*- + H+ is probably more likely than the one implied by equation (32). The f&e 8% ion is not considered to play an important role in the formation of A%@@$*-. The large p#? values obtained emphasise the high stability of the An(H and Au,(HS)#species. Strong complex formation would in faot be expected since Au+ is a typical class B or soft acceptor and as such, would form very stable complexes with ligands having high polarizabilitiea (e.g. HS- and Sa-). Sueh metal-ligaud bonds would exhibit a large degree of covalent character. The complexes present exemplify the preference of Au+ for 2-fold coordination. The Au(HS)*- will exhibit a linear configuration; however, the stihemistry of the binu&ar A%(HS)#complex will probably be determined by a sulphur-bridge similar to

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

396

The extent of condensation (polymerization) would depend upon such factors as temperature, pressure, pH and activity of reduced sulphur.

Considerable quantities of gold may be transported in hydrothermal ore solutions as thio complexes, particularly in the near neutral pH region where the Au(HS),complex predominates. These experiments did not extend past 3OOC; however, it may be concluded that very stable thio complexes would also exist in the temperature interval from 300 to 350C, giving rise to solubilities in excess of 500 mg/kg. .Deposition of gold would be in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration. Decrease in temperature of an ascending ore solution quite obviously leads to deposition of gold and associated sulphides. Since the gold solubility maxima at the temperatures investigated approximately coincide with the pH range of the majority of hydrothermal ore solutions, any process which results in a shift of pH to either acid or more alkaline conditions would cause the precipitation of gold. Progressive acid dissociation (e.g. H&JO,) with decreasing temperature would effectively lower the pH although this effect would be antipathetic to the consumption of hydrogen ions by wall rock alteration reactions. Increasing oxidation of the system as might occur when ascending hydrothermal solutions meet oxygenated meteoric waters (e.g. conversion of H,S to H&JO,); may also cause deposition of gold by lowering the pH and decreasing the activity of reduced sulphur. Further decrease in reduced sulphur activity (and hence decreasing gold solubility) may be accomplished by precipitation of other metal sulphides and by wall rock alteration reactions forming pyrite. An ore solution of approximately neutral pH encountering a dilatant zone would precipitate gold in response to the drop in pressure at temperatures less than 260C! but this effect would not be great. At T > 250C, a decrease in pressure would enhance the solubility and deposition of gold would not occur. In more alkaline solutions (see Fig. 6) gold would not precipitate as pressure dropped. A comparison of gold solubilities obtained in the presence of a pyrite-pyrrhotite buffer with those obtained by WEISSBER~ (1970) demonstrates the effect of hydrogen fugacity on the solubility of gold in sulphide solutions. The higher hydrogen fugacities associated with the pyrite-pyrrhotite assembla,geconsiderably depress the solubility (1970) determined a solubility of 200 ppm at 25OC for NaHS = of gold. WEISSBPRCJ 0.32 m and pH = 8-l (at room temperature). An approximate comparison may be drawn with data given in Fig. 3 for NaHS = 0.30 m and pH = 8.41 (at 2OC) where the gold solubility was found to be about 13 ppm. At 250C, the estimated Pa, for NaHS = 0.30 and pH = 8.41 in equilibrium with pyrite-pyrrhotite is about 2 atm and WEI~SBERQ (1970) estimates PH, = O-02 atm at 25OC for his solution. The comparison of these data at least illustrate the magnitude of the effect despite the fact that Weissbergs estimate of Pa, = 0.02 atm will be somewhat in error, because his calculation rests on the assumption that only AuS- is present. One may Bpeculate that as the oxidation of an ascending ore solution proceeds, the gold will be initially stabilised in solution but with further oxidation (and lowering of fu,), the activity of reduced sulphur will be lowered by conversion to sulphate, thus causing precipitation of gold. In order to evaluate the significance of thio-gold complexes in the transport and

396

T. &I. SEWARD

deposition of gold, it is necessary to determine the solubility of gold in hydrothermal solutions containing geologically reasonable total sulphur concentrations. The total sulphide content of the majority of hydrothermal ore solutions falls in the range from 1O-3 to 5 x 10d2 m as evidenced by fluid inclusion compositions (expressed as sulphate, ROEDDER, 1967) and analyses (for sulphide) of geothermal bore waters (WEISSBER~,1969). The solubility of gold in hydrothermal solutions containing 10-a and 1O-3m total dissolved sulphur (as sulphide) have therefore been calculated, the assumption being that gold is present as thio complexes. The calculations were performed using equation (28) and the appropriate values of fir, [calculated from equation (21)], m&s, mns- andYHIs, Yus- (yB,sfrOmGAMSJ&XERandScHIND~~I%, 1969; pus- from LINDSAY and LIUS 1968 data for NaCI) such that mu,s + mus- = 10m2 and 10-3. The calculated curves showing the solubility of gold as a function of temperature are given in Fig. 11 (curves I and II). In both cases, the solutions are in equilibrium with pyrite and pyrrhotite with P = 1000 bar, PH,,~, = 7.1 and ionic strength = 0.50.

1
OGQOI

/
200

225

250 T caC)

275

300

Fig. 11. Celc&ted eolubility of gold (ppm) 8s a fun&ion of tempez8ture. Curves

I and II refer to solutions heving sulphide concentretiona of 10ea m and 10m3 m, respectively. Curvea III and IV are HELGESON and GABBEIS (1968) c8kmlst&d only for rnxa = 3-Oand pH = 3.0 and 2.5, respectively. Curvea V and VI give &LGlBsON snd GARRBLS(19tH) eatimetee of gold aolubility bawd on geologial considerations.

Also included in Fig. 11 are the calculated solubility curves (III and IV) of HELC)ESOET and GARRELS (1968)) whose model involves the transpork and deposition of gold in acid chloride solutions in which gold is complexed only by chloride ligands. Curves V and VI give HELCEBON and GARRELS(1968) estimates of the solubility of

398

T. M. SEWARD

transport mechanism. At more extreme supercritical conditions where T > 4OOC, chloro complexes will be of importance (ANDERSON and BTJRNHAM,1967 ; HENLEY, 197 1) ; however, gold will also be soluble in supercritical sulphide solutions but there are at present no experimental data available to indicate the magnitude of such solubilities. It is also interesting to note the higher stability of thioaurate (I) complexes as compared with chloroaurate (I) species. Comparison of the formation constants in Table 4 with those given by HELGESON (1969) for the AuCl,- complex (e.g. p@ = -6.2 at 25OC) illustrates this. The widespread occurrence of gold tellurides in many gold deposits such as those in Colorado, Transylvania, Kalgoorlie and South Porcupin+Timmins (Ontario) to name but a few, suggests that telluro gold species may also be important in some ore solutions. Since the ditelluride ion, Te,s- is the only stable reduced tellurium species, complexes of the type, Au(Te,)-, Au,(Te,) and the Au(Te,),a- probably occur. Similar telluro complexes of Ag+ and to a lesser extent, Cu+, probably exist also as evidenced by the silver tellurides, mixed silver-gold tellurides and more rarely, copper tellurides which occur in nature. The geochemical association of gold with arsenic and antimony, especially in epithermal gold deposits, suggests that arsenothio and antimonothio complexes [e.g. Au(A&,)~, Au(AsSJ2-, Au(Sb,S,)-, etc.] may also be of importance in the transport of gold in some hydrothermal ore solutions.
Acknowledge mmc8-I would like to thank my colleagues, Drs. A. J. ELUS, W. GIOOENBACE, A. J. READand B . G.WEISSBERO for many interestingdiscussionsand for their comments on the manuscript. REFERENCES ANDERSON G. 116. and BunC. Wayne (1967) Reactiona of quartz end oorundumwith aqueous chloride and hydroxide solutions at high temperatures and pressures. Amer. J. Sci. 866, 12-27. UD G. (1961) Equilibria in sulphur-containingaqueous solutions in BARNESH. L. and KULLB;R the system Fe-S-O, and their oorrelationduring ore deposition. Econ. Geoi. 56.648-688. BOYLER. W. (1969) Hydrothermal transport and deposition of gold. Eccm. t&d. 84,112-116. B~OWNE P. R. L. and ELLIB A. J. (1970) The Ohaki-Broadlands hydrothermal ares, New Zealand: mineralogy and related geochemistry. Amer. J. Sci. EQB, 97-131. DUNN L. A. and MaasW. L. (1969) Electrical conductances and ionizetion behaviour of sodium ohloride in dioxane-water mixtures at 100C. J. Phye. Chem. 78,2619-2622. ELLISA. J. and GI~OENBACE W. (1971) Hydrogen sulphide ionization and sulphuxhydrolysis in high temperature solution. Geochim.Cosmochim. Acta 85, 247-260. ELLISA. J. and MCFADDIEN I. M. (1972) Partial molal volumes of ions in hydrothermalsolutions. awchim. Coemochim. Acta 86,413-426. LER P. (1969) Liisli&keiten und AktivitiitskoefBxientenvon I&S GAXSJ~~~ER H. and SCHIND in Elektrolytmie&ungen. H&v. C&m. Acta u, 1396-1402 GI~~ENBACH W. (1971) Gptieal spectra of high alkaline eulphide solutions and the second dissociation constant of hydrogen sulphide. Inorg. Cirem. 10,1333-1338. G-ELI A. 0. and STE-MUUE J. (1967) Con&antes de stabilite de thiocomplexes et produits de solubiliti de aulfuresde m&aux. Can. J. C&m. 45, 2101-2108. HELQESON H. C. (1969) Thermodymamicsof hydrothermal systems at elevated temperatures and pressures. Amsr. J. Sci. W?, 729-804. BELOESON H. C. and GELS R. M. (1968) Hydrothermal transport and deposition of gold. Econ. Qeol. 68, 622-636.

Thio complexes of gold and the transport of gold in hydrothermal ore solutions
HENLEY

399

R. W. (1971) personal communioation. KOZCNTBEVA T. N. (1966) The solubility of hydrogen sulphide in water and solutions under higher temperate. In Qecchsmical In~tigdion in the l%&i of Higher Preaawea and lempe.~&ww (editor N. I. Khitarov) pp. 121-134. Nauka. Kr~~asomcwazu0. and EVMVSE. Ll. (1965) Mstollurgiccrl Thawnochun&q/. Pergamon. Ka~usnopa K. B. (1961) The solubility of gold. Ecun. &oZ. 46,868-870. LINDNEBJ. L. and GBUNEEJ. W. (1939) Action of alkali sulphide solutions on minerals at elevated temperatures. Econ Geol. 84,637-660. LINDSAYW. T. and Lrn C. T. (1908) Vapour pressurelowering of aqueous solutions at elevated temperatures. Office of Saline Water, Reseamh and Development Progress Report No. 347. United States Department of the Interior. MARION W. A. J. and F~LAYSON J. B. (1972) The chemistry of the Broadhmds geothermal area, New Zealand. Amer. J. Sci. W&48-68. M~YEE C. and HEMLEY J. J. (1967) Wall rock alteration. In &o&emi&y of Rydrdhbnnal Ore Depouite (editor H. L. Bsrnes), 166-236. Holt, Rinehsrt and Wiuston. Oa~vzno 6. P. (1935) Hydrothermal experimente with gold. 1Cccn.@sol. 80.400-424. C. S. end BENSONS. W. (1963) The electrical oonduotauoeof aqueous PEARSON D., COsodium chloride in the range 300 to 383. J. Amer. C&m. Sot. 85, 1044-1047. RAYMAHASEAY B. C. and HOUAND H. D. (1969) Redox reactions accompanying hydrothermal wall rock alteration. Econ. @ad. 64,291-306. ROBE R. A., Ble~~9a: P. M. and B~b~~srzv K. M. (1967) Selected X-ray arystahographicdata, molsr volumes, and densitiesof minerals aud related substances. U.S. @e&. SUTV.B&L 1248. ROBINSON R. A. and STOKES R. H. (1966) E&ctrolyte. eolutione. Butterworths. ROEDDE~ E. (1967) Fluid inclusion ae samples of ore fluids. In Uwchemiatryof Hgd&hwmd 0~ Deposits (editor H. L. Barnes), pp. 615-674. Holt, Rinehart and Winston. SANN J. R. (1971) Hydrogen bonds involving sulphur. II. The hydrogen sulphide-hydrosulpbide complex. J. Chem. Phys. 54,4676-4680. SCEW-AOE G. and WXD~ M. (1963) Die Lbslichkeit von Metallsulflden I. Schwarxee Queoksilbersulfld. Helv. Chim. Acta 46,2613-2628. SXLLEN L. G. and l&s!rszn A. E. (1964) St&i&y Con&z& of Metal&m Compi%xee. The Chemical Society (London), Special Publication. No. 17. Sxrrn F. G. (1944) The alkali sulphide theory of gold deposition. E&on. &oZ. 88,661-690. Touqr~ P. III and B-TON P. B. (1964) A thermodymsmic study of pyrite and pyrrhotite. &ochim. C&im. Acta 2&641-671. W~~SSBEBO B. G. (1969) Gold-silver ore-grade precipitates from New Zealand thermal waters. Ewn. t&d. 64,95-108. WICISSS~~~O B. G. (1970) Solubility of gold in hydrothermal elkaline sulfide solutions. Eoon. &oZ. 66,661-656. Wm D. E. (1967) Mercury and base-metal deposits with eeaoaieted thermal and mineral waters. In &c&cmof Hydndhermal Ore Depotits (editor H. L. Barnes), pp. 576-631. Holt, Rinehart end Winston. WBJOETJ. M., hNDSAY W. T. and DBUGA T. R. (1961) The behaviour of electrolytic solutions at elevated temperatures as derived from conductance m easurements. USAEC Bcport WAPD-TM-204. Z~IA~INC~CP 0. E. and PAUUEN I. A. (1940) Contributionto the theory of formation of vein gold deposits. Dokl. Akud. Nauk SSSR M, 647-661.