ECONOMIC GEOLOGY

AN'D THE

BULLETIN OF THE SOCIETY OF ECONOMIC GEOLOGISTS

VOL. 67 AUGUST, 1972 No. 5

Systematicsof Sulfur and Carbon Isotopesin

HydrothermalOre Deposits
HIROSHI OHMOTO

Abstract

The effects of the chemistry of ore-forming fluids on the sulfur and carbon isotopic
compositions of hydrothermal minerals are quantitatively evaluated from available
thermochemical data and isotopic fractionation factors.
The isotopic composition of both sulfur and carbon in hydrothermal minerals is
strongly controlled by the fo2 and pH values of hydrothermal fluids as well as by the
temperature
and the isotopiccomposition
of sulfurand carbonin the fluids(bSaz•s
and
•C•acvalues).For example,at 250ø C and within geologically
importantfo2-pH regions,
an increasein foa value by 1 log unit or in pH by 1 unit can causea decreasein bSa4
valuesof sulfur-bearingmineralsby as much as 20 per mil. An increasein foa by 1 log
unit or in pH by 2 units can causea decreaseof about 30 per mil in bCn valuesof carbon-
bearingminerals.Large variation in the •Sa4valuesor in the •C •avaluesof hydrothermal
minerals, which often have been interpreted as an indication of biogenic sulfur or car-
bon, could also be causedby slight variation in the foa and/or pH of ore-formingfluids
during ore deposition.
The concentrationsin an ore solutionof sulfur (or fs•) and of carbon (or fco2) place
limits on possiblebSatand bCtavaluesfor hydrothermalminerals.Sulfur-bearingminerals
and carbon-bearing minerals precipitating from sulfur- and carbon-rich solutions can
have wider rangesof bSat and •C la valuesthan thosemineralsprecipitatingfrom sulfur-
and carbon-poor solutions.
Sulfide minerals which precipitated in equilibrium with magnetite, hematite, or sul-
fate minerals, and carbonate minerals which precipitated in equilibrium with graphite,
could exhibit isotopic compositionsmarkedly different from those of the depositing
fluids. Therefore, sulfideswith bSat values near zero per mil or carbonateswith bCTM
values near --6 per mil do not necessarilyindicate a magmatic origin for the sulfur or
the carbon.
The mode of variation on the bSa4values of sulfide minerals and in the bCla values of
carbonate minerals in a given deposit may indicate the relative oxidation states of ore-
forming fluids: variable •Sat q- uniform •C •a values may suggestthat the mineralswere
precipitatedunder relatively high foa conditions;uniform bSa4
q- uniform bCTMvalues,
under intermediatefoa conditions;and uniform bSat q- variable bCta valuessuggesting
depositionunder relatively low foa conditions.
Sulfur and carbon isotopic data, combined with geologicaland mineralogical data of
ore deposits,may define the physico-chemicalparameters (T, foa,fs2,fcoa,mzs,mzc)and
the origin (bS?sand •C•%values)of ore-formingfluidsas well as the mechanisms
of ore
deposition.

Introduction ing the originof ore deposits. Sulfidesof magmatic-

T•E isotopicratiosof sulfur (Sa•/S
TM)in sulfide hydrothermal
originwereassumed
to havesulfur
minerals,and thoseof carbon(Cta/C•2)in carbonate isotopiccompositions
similarto thoseof sulfidesin
minerals, have been increasinglyusedfor interpret- meteorites. Ore deposits in which sulfides show
551
552 HIROSHI OHMO TO

a wide variation in isotopic compositionor possess isotopic fractionation factors and thermochemical
•Sa4values• far removed from zero (i.e., more than data on minerals and solutions, the effects of
ca. 7 mil deviation from zero), on the other hand, physico-chemicalstates of ore-forming fluids (T,
have generally been interpreted as of biogenicor pH, for fs•, fcov and concentrationof sulfur,
sedimentaryderivation (e.g., Jensen,1967). Simi- carbon and salts) on the sulfur and carbon isotopic
larly, the carbonates of magmatic-hydrothermal compositionsof hydrothermalmineralsare quanti-
origin were believed to show /•C•a values• around tatively evaluated. Possible mechanismsto pro-
-5 to -8 per mil, compared with biogenic car- duce large variations in the sulfur and/or carbon
bonates of often more negative and variable /JC•a isotopiccompositionof hydrothermalmineralsare
values. presented, and the potential of sulfur and carbon
The basesof these interpretationswere: (1) the isotopic ratios in limiting the chemical states and
observation that sulfides and carbonates in many the origin of ore-forming fluids is demonstrated.
igneous rocks show the isotopic compositions,
/•Sa4= • 0% (e.g., Jensen, 1967) and/•C •a = - 5 Sulfur Isotopic Equilibria in
to -8•00 (e.g., Taylor et al., 1967), (2) the observa- Hydrothermal Systems
tion that the most effective means of isotopic The compositionof fluid inclusions(e.g., Roed-
fractionation at low temperatures is by biologic der, 1967; Rye and Hafty, 1969; Ohmoto, 1971)
processes(e.g., reduction of sulfate to sulfide by showsthat ore-formingfluids are essentiallycon-
sulfur-reducingbacteria), and (3) the assumption centrated alkal-chloride solutions. Aqueous sulfur
that the hydrothermal minerals accurately reflect specieswhichmay becomeimportantin thesesolu-
the isotopiccompositionsof hydrothermalfluids. tions at temperatures below about 500øC are
The latter assumptionwas first challengedby Sakai HaS, HS-, S2-, SOl-, HSO[, KSO[ and NaSO[.
(1968) in a paper which must be regarded as a Other sulfur species, suchas CaS0•, MgSO•,
turning point in sulfur isotopicgeochemistry.Based KHSO•, NaHSO•,H2SO4,HaSO3,HSO• and S22-, o o

on the calculatedisotopicfractionation factors2 be- can be neglectedin most geologicconditions.

tween aqueoussulfidespeciesand sulfideminerals, The mean isotopiccompositionof sulfur in the
Sakai has suggestedthat the isotopiccomposition solutions,•S34 •s, therefore, can be closely approxi-
of sulfide minerals may be influenced by the tem- mated by
peratureand pH of hydrothermalfluids. Although
his calculationsare semi-quantitative and his dia- = \ H•S + \ HS-
grams (e.g., pHvs. /•Sa4valuesof pyrite, Fig. 5 in + (/•S•,•-.X s•-) + /(•S34, Xso¾)
• so,-'
Sakai, 1968) are not directly applicableto natural q- (/•S•sor'XHsor) q- f/•S
• 34•sor'X•so;)
systemsbecausehe did not considerother important
q- \(•S34
NaSO•' XNaSO;) (1)
aqueoussulfur speciesin his systems,his paper has
indeed pointed out the importanceof considering in which/•S• 4 is the isotopiccomposition of a sulfur
the chemistry of ore-formingfluids in interpreting species i, and X• is the molefractionof the sulfur
sulfur isotopic data. speciesi relative to total sulfurcontent:
The present paper is essentiallya continuation
and extensionof Sakai's approach. Using available
X•- m• _ m• (2)
• The 15S
a4or the 15C
•avalue of a speciesi is definedas: mzs mx-hsq-mx-•s-q-ms•-q-msol
-
(s,4/s,,),- + rnusor+m•:sor q-mNasOr
•sl(•) = (s,,/s=), x 1,ooo,
or
where ml is the molality of the speciesi.
(c•,/c•,),- (c•,/c•,)
•c?(•)= (c•,/c•,), ' x 1,ooo, When the /•S3•
H•S value is taken as a reference,
in which (Sa4/S
a2),is the sulfur isotopiccompositionof troilite /iSa4values of other sulfur speciesin the solutions
of the Cation Diablo meteorite, 0.0450045 (Macnamara and and of minerals which precipitate from the same
Thode, 1950; Ault and Jensen,1963), and (C•a/C•% is the
carbonisotopiccompositionof the Chicagostandard (PDB), solutionsat the sametemperaturecan be expressed
0.0112372 (Craig, 1957). as
2The isotopicfractionationfactor between speciesA and
B is defined as •S•4 = •Sms
34 + • (3)
a• -- R•
R-• = 1,000
1,000+
+ in which/x• is the relative isotopicenrichmentfactor
in which R is the isotopicratio, (Sa4/S
a•) or (C•a/CX•). between a sulfur speciesi and H•S. Using Eqs.
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 553

(1) and (3), we can write as Relativeisotopicenrichmentfactors

= o•s + •- I-(•s-.X•s-) + (•s•---Xs •--)
+ (Asol-'Xsor•) + (A•so•'X.so•)
+ (Arso;.Xrso•) + (ANaSo;'XNaso•)-I (4)
Eq. (4) indicates that the isotopiccompositionof
a sulfur species in hydrothermal systems is con-
trolled by: (1) the relative isotopic enrichment
factors among various sulfur species,(2) the mole
fractions of aqueous sulfur species, and (3) the
mean isotopiccompositionof sulfur in the solutions.
Pyrite, for example, can obtain •S34values similar
to the valueof •Szs34if the relativeisotopicenrich- the speciesare available:
ment factors among all the aqueoussulfur species
If isotopicequilibriumis establishedamongsulfur
speciesin a system,the relative isotopicenrichment
factor (A) can be shownto be related to the isotopic
fractionation factor (a) by
/x•• 1,000In OtH•
i s (5)
At the presenttime, reliable experimentaldata are
not available for the isotopic fractionation factors
among theseaqueoussulfur species. However, the
isotopicfractionationfactorscan be estimatedusing
statistical mechanicsif the vibrational spectra for
• (Q•/Q•)•
! !

and pyrite are small, or if the sulfur in the fluids is (6)

dominated by one species(e.g., H•S) and the rela-
ams (Q•/Q•)a•s ! !

tive isotopicenrichment factor between pyrite and in which (Q•/Q•) is a thermodynamicfunction

the aqueousspeciesis small. called the "reducedpartition function ratio" (for
(øC)
600 400 2.00 I00 50 2.5

+SO
/ I • I •/ I I ! '

o --•--- [ZnS]

-•o[ ...................
-15/
0
[PbSJ
'
S•_ I
2
, I
4
• I
6
, I
8
, I
I0
[
2.

(I/T •) xlO6
Fro. 1. Isotopic enrichemnt factors for important sulfur species(basedon the data by Sakai, 1968;
Rye and Czamanske, 1969; Kajiwara and Krouse, 1971).
554 HIROSHI OHMOTO

TABLE 1. Isotopic Enrichment Factors for Sulfur Species His partition function ratios for solid phases,par-
asp - aS•2s(•0)
ticularly for pyrite and galena are, however, less
accurate compared to those for aqueous species,
Species 150 ø C 200 ø C 250 ø C 300 ø C 350 ø C Ref.
becauseof the large uncertainties in the available
HS- --1.9 -1.6 -1.4 -1.4 --1.3 a spectroscopicdata and in the assumptionsused in
S •'- --8.2 -7.1 -6.2 -5.5 -4.8 a
SO •'- and other the statistical mechanicalcalculationsof the parti-
sulfates 39.0 32.0 26.5 22.0 19.0 a tion function ratios of solid phases.
ZnS, FeS --0.9 --1.2 -1.4 --1.5 --1.0 a,b
FeS• q.0.8 q.0.1 --0.3 --0.6 --0.2 c Since Sakai's calculations,several sets of experi-
PbS --5.1 --4.5 -4.1 --3.8 --2.9 d mental data have been published for the isotopic
fractionation factors amongst pyrite-sphalerite-
• Sakai (1968).
b'Kajiwara and Krouse (1971). galena (see Fig. 2). The agreement among the
• Avu = A,v q-1,000 lnafvu, in which the values for 1,000 various experimental data are, however, not satis-
lnaf• are taken from Kajiwara and Krouse (1971).
a Aan = A• q-1,000 lna•,0s in which the values of 1,000 factory, and experimental data for the isotopic
lnaf• are the average of Rye and Czamanske (1969) and fractionation factors between the sulfide minerals
Kajiwara and Krouse (1971).
and aqueousspeciesare few. The A values for the
sulfide minerals in Figure 1 and Table 1 are tenta-
detailed discussion and the methods of calculation
tively assignedas follows:
of reducedpartition function ratios, seeUrey, 1947;
Bigeleisen and Mayer, 1947; Sakai, 1968). The with ams sP values of Sakai (1968)
reduced partition function ratio of a species is
A•p = 1,000In ams,
•P (8)
mainly a function of temperature and has been
calculated at various temperaturesfor H•.S (Tudge with Ogsp
pyvalues of Kajiwara and Krouse (1971)
and Thode, 1950; Sakai, 1957, 1968; Ault and Kulp,
Apy= A• q- 1,000In ofpy
$p, (9)
1960; Thode et al., 1971), for HS- (Sakai, 1968)
and for S•- • and SO2• - (Tudgeand Thode, 1950; and with the average asp g• values• of Rye and
Sakai, 1957, 1968; Ault and Kulp, 1960). Czamanske (1969) and Kajiwara and Krouse (1971)
A• valuesfor HS-, S•'- andSO2•
- in Figure1 and gn (10)
Ag• = A•v q- 1,000 In a•p
Table 1 are basedon Sakai's (1968) reducedparti-
tion function ratios. The reduced partition func- The valuesof AsoF-- Apyin Figure 1 and Table 1
tion ratios calculated by other authors may differ at temperatures between 250 and 300øC agree to
from Sakai's values by as much as 4-5 percent, within 4-5 percent of the isotopic fractionation
becauseof the differencesin the assignedvibrational factors experimentally determined by Nakai
frequenciesof isotopic molecules and in the ap- (1970a). Comparison of temperatures derived
proximations used in computations. The reduced from fluid inclusion studies and the isotopic com-
partition function ratios are not available for positionsof coexistingsulfideminerals from various
HSO•, KSO• and NaSOT. However, when the locations (Rye and Czamanske, 1969; Kajiwara et
small isotopic fractionation factors (i.e., less than al., 1969; Groves et al., 1970; Ohmoto et al., 1970;
3 per mil at room temperature)betweenSO2• - Greig et al., 1971; Robinsonand Ohmoto, in prep.)
and various sulfate minerals (summarized in Sakai, also suggest that the Apy- A•p and A•p- Agn
1968) and the uncertainties in the calculated parti- values in Figure 1 and Table 1 are probably good
tion functionratios for H•.S and SO2• - are taken to within 4-5 percent of the assignedvalues. Tak-
into account, we can assume at present that all ing all uncertainties into account, the A values in
the ionic sulfate specieshave similar A values: Figure 1 and Table 1 appear to have an uncertainty
of 4-10 percent.
AsoF"• A•so• "'• A}•so;---•A•sor (7)
Sakai (1968) also calculated the reduced parti- Molefractionsof sulfur species
tion function ratios for sphalerite,galena and pyrite. If chemical equilibrium is establishedin a hydro-
a The reduced partition function ratio for S•'- is 1.0 and is thermal system, the mole fractions of aqueoussulfur
not dependent on temperature, since speciesrelative to total sulfur content, X•, can be
(Qa'/Q•')sa- = (Ma/MOt. • Accordingto Rye (pers.com.), the isotopicfractionation
in which M and m are, respectively,the massof moleculeand factors between sphalerite and galena, determined in a hydro-
the massof isotope, and 1 and 2 are, respectively, the lighter thermal system containing ZnS q- PbS q- FeS q- FeS,., fall
isotope (Saa)and heavier isotope (Sa•). closeto the values estimated in this paper.
 +2 555
25O
20O
+1
(Py) (I)

(s

-4

-'5

o I
Fie
2Isot
P•c
e.
nrlchment
œ 2
,•XP•erffnental:
_ t/ca/. /• • Ctors[o
•_ ,
1•71,ex•,;•m hYdroth=•.•rooten• - PYnte(n•.:..
(1/• •
' ' 'uV
3
..... •lentalin •._•,mal Syste•e• and S•'•UVe Valu• . O
•Y systems
'?;;•(49Ka;•]•rcz, 1969•(.•aq
galena
ß w• 8chiller
•. asaet al. l•penmeata• )•egative
=tat.,197n" •, exne• ' *" arysv.•,•'k-es)
withtoo- .
Pnmental
in •?_•mdry SVs,•_(3)
'•ms. •ye
t4q an •Phalefite
evaluated
from
the
following
reactions ""yurot •-•Z•
•.....
"•
systems"
'•/iwara
•k•I•69,
r• d Czam • ß•(I)

(11)

2H+
+SO•-•
H•S(aq)
+20• (12)
(18)
HS07
• H+
+SO•- (13)

KS07
• K+
+SO•- (1•)
(19)

•XPressin=
.• .. . a + SO•-

achons
ofsulfu•P•_yely,
•½cles as
We '•, •ce the
c
556 HIROSHI OHMOTO

TABLE 2. Equilibrium Constantsfor ReactionsInvolving Sulfur

log K

Eq. 1 Reaction 150 ø C 200 ø C 250 ø C 300 ø C 350 ø C Ref.

11. H2S(aq) • H + + HS- -- 6.72 -- 6.96 -- 7.35 -- 8.06 -- 9.0 a

12. HS- •- H + q. S2- --10.62 -- 9.57 -- 8.61 -- 7.72 -- 6.9 a
13. 2H + + SOt- • H,S (aq) + 20,. --79.31 --67.13 --57.10 --48.55 --41.0 a
14. HSO• •- H + d- SOI- -- 3.74 -- 4.49 -- 5.41 -- 7.06 -- 9.2 a
15. KSO•- • K + + SOI- -- 1.60 -- 1.94 -- 2.4 -- 3.0 -- 4.0 b
30. H,S (aq) q. «O, •-• H,O (l) q. -xaS= 20.00 17.53 15.30 13.60 12.5 a
31. FeS, •-• FeS q. --10.25 -- 8.48 -- 7.03 -- 5.81 - 4.79 a
32. 3FeS= q- 20,. •-• FeaO4 q. 3S, 40.95 38.11 35.81 33.93 32.36 a
33. 2FeS, q- •O,. •- Fe,Oa q. 2S, 34.66 31.72 29.35 28.19 25.60 a
34. 3FeS q. 20,. •-• FeaO4 q. 71.76 63.56 56.91 51.39 46.74 a
35. 2FeaO4 q. xaO,.•-• 3Fe,Oa 22.07 18.95 16.44 14.35 12.08 a
37. BaSO• •- Ba '+ q. SOl- -- 9.34 -- 9.76 --10.34 --11.05 -11.9 a

Numbers correspondto those in text.

Helgeson(1969). Valuesfor 350øC are extrapolated.
Helgeson(1969). Extrapolationabove200ø C.

in which the ionic strengthcan be further approximatedby

I • (mE+) + (m•, +) (25)
C = 1+ aa+'q'as
- + aa+"}'s
a- Therefore, we can consider as

q- Ksol-'
(aa+)=!••solq-KHSO;'YHSO7 X• = f(T, fo,,pH,I) (26)
and, with Eq. (4),
mE+'Y•+
q-KKSO; q-KNaSOr
ß'YKSO;mN'+'YN'+
) (24)
''YNaSO• •S•4
i •/•c•4
= J\ oZS, T,fo,,pH,I) (27)
and rn• and y• are, respectively,the molality and The equilibriumconstantsfor reactions(11) to
activitycoefficient
of a species
i. Eqs. (17) to (24) (15) have beensummarizedfor temperaturesup to
indicate that the mole fractions of aqueoussulfur 350ø C in Table 2. The dissociation constants for
speciesrelativeto total sulfurcontentaredependent NaSO•- are not available. However,the similarity
on the equilibriumconstantsfor the reactions,the between the dissociation constants of various
activity coefficients
of aqueousspecies,the fugacity sodiumcomplexesand those of equivalent potas-
of oxygen,the pH, and the molalitiesof potassium sium complexessuggestthat the dissociationcon-
and sodium ions in the solutions. The equilibrium stants for NaSO• are also in the same order of
constantsare mainly a functionof temperature,and magnitudeas thosefor KSO7. That is,
the activity coefficientsof temperature and the
ionicstrengthof fluids. In alkali-chloridesolutions, KNaSO; •-• Kszso; (28)

TABLE3. Activity Coefficients

of AqueousSpecies

log •i

150ø C 250 ø C 350 ø C

Species I= 1 I= 3 I-- 1 I= 3 I= 1 I-- 3

H,COa(ap),
H,S,CH• q.0.08 q.0.23 q.0.13 q-0.27 q.0.35 +0.58
K+, CI- --0.26 --0.21 --0.33 --0.31 --0.52 --0.49
OH-, HS- --0.23 --0.18 --0.30 --0.25 --0.45 --0.38
Na+, HCOr,HSOr,KSO•,NaSOr --0.21 --0.13 --0.26 --0.20 --0.38 --0.29
SO•- -- 1.09 -- 1.20 -- 1.44 -- 1.62 --2.58 --2.89
CO.•- -- 1.01 - 1.08 -- 1.33 -- 1.46 --2.37 --2.59
S'-, Ba•+ -0.94 --0.99 --1.24 --1.33 --2.18 --2.34
Ca,+ -- 0.83 -- 0.84 -- 1.08 -- 1.12 -- 1.88 -- 1.95
H+ --0.01 q.0.03 --0.09 q.0.03 --0.06 q.0.13

Theactivity
coefficients
ofaqueous
species
werecalculated
according
to themethod
described
in Helgeson
(1967,1969)
usingthedataof effective
ionicradiusin GarrelsandChrist(1965).
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 557

-3O ' I ' I ' I ' I '

.-32 - / XH2S
.ox

.% X ).99
-34 _ %\

ZS04
h
-36

• .......... .99

-38

X ).99
H2S

II

-40 -
I ii Xs•_
)'99
I

I I Xst-
-4• -
I I i I
'
.9O
I
.
I
I I '
XHs , , , ',
i

.01 ,10 .50 .50 ,10 .01

-44
4 6 8 I0

pH
FIG. 3. Mole fractionsof aqueoussulfur speciesrelative to total sulfur content.
T = 250ø C and I = 1.0. ZS04 = SOl- d- HSOi- d- KSO7 d- NaSOT.

Influenceof T, fo2, pH and I on sulfur isotopic computedas functionsof /1Szs, 34 fo•., pH and I at
composition various temperatures, using the /x• values sum-
The molefractionsof aqueoussulfurspeciesrela- marized in Table 1, the equilibrium constantssum-
tive to total sulfur content and /•S34
i values were marized in Table 2, the activity coefficientssum-
558 HIROSHI OHMOTO

marizedin Table 3, and with Eqs. (4), (7), (17-25) Figure 3 showsthe mole fractions of aqueous
and (28). sulfur species relative to total sulfur content in
-30
' I

-32

-34

-26.5

-36

-38

-40
Hz
s =0-+1

-42 -

• I ß • I , I • I
-44• 4 6 8 10

pH
Fro. 4. Influenceof fo• and pH on the isotopiccompositions of sulfurspecies.T = 250øC, I = 1.0, and •S•a = 05[0.
•Sa4valuesshownin the diagramare for H•S. •Sa4valuesof othersulfurspecies
canbe easilyobtainedfrom the data in Table
1 (e.g.,•S•s = 0 contourisidenticalto •S•s- = -- 1.4or•S•oI- -- q- 26.5contourat thistemperature).In theregionbelow
O contour andto theleftof q.1 contour,•S•s -- •-• 05[0;in theregionabove-26.5 contour,•S•s = - 26.5•o0;in theregion
to the right of q.6.2 contour,•S•s = q- 6.2.
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 559

-30
' I

-32

-34 ,•, Fe304

-36
•" X ..........
•Sbor•(o)

SSpy \' .... (+.8)

....... (+6.8)

-38
FeS 2 (+26,5)
(+29.8)

(FeS)
-40
+1 I+

/ t
-42

FeS
!

-44 i
• I |, I
2 4 6 8 I0

pH
FIo. 5. Comparison
of the positionsof 8S•4 contourswith the stability fieldsof Fe-S-Omineralsand barite. T = 250ø C
and I -- 1.0.

..... : 8S•4 contours. Valuesin l- J and ( ) are, respectively,

for pyrite and bariteat 8Sa4 = 0•o0.
----: Fe-S-O mineral boundariesat XS -- 0.1 moles/kg H•O.
.... : Fe-S-O mineral boundariesat XS -- 0.001 moles/kg H•O.
.... :barite soluble/insoluble
boundaryat mBa2 +.mr.s = 10-4.
(UndertheseT andI conditions,
an increase
of rnBa2+
or mr.svalueby 1 orderof magnitude
dropsthe boundary
by about0.5
log fo• units.)
560 HIROSHI OHMOTO

a solutionof ionicstrength1.0 and temperatureof the samesolutionundera conditionof •234

o•.s-- 0•o0.
250øC, andFigure4 illustratesthe •Si34contours
in At givenT andI, the positions
of •S,3-•contours are

-42

-44 FezOS

Fe-O-

-46 -

-48 -
4

-50 -
FeS2

-52. -

/! FeS
-54 , I , I /, I/• , I ,
4 6' 8 I0 12..

pH
Fro. 6. Comparisonof the positionsof $S•4 contourswith the stability fields of Fe-S-O mineralsand barite. T = 150 ø C
and I = 1.0.
-- : 15S,
a-4
contours. Values in ( ) are for H2S at •S•s
a• = 0•.
-----: Fe-S-O mineral boundariesat •S = 0.001 moles/kg H20.
.... : barite soluble/insolubleboundary at mBd+'m•s = 10-5.
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 561

-22

-24

-26

-28

-•0

-•4

pH
FIG. 7. Comparisonof the positionsof •iS[• contourswith the stability fields of Fe-S-O minerals and barite. T -- 350øC
and I -- 1.0.
: •iS•4 contours. Values in ( ) are for H•S at •iS•s = 0/%.
--- •: Fe-S-O mineral boundariesat 2S -- 0.01 moles/kg H•O.
.... : barite soluble/insolubleboundary at rn•*.rn•,s -- 10-a.
(Becauseof the uncertaintiesin the extrapolatedthermodynamicdata at this temperature,uncertaintiesin the positionof the
a4contoursare about 4-0.5 log fo• and 4-0.5 pH units.)
pyrite-pyrrhotite-magnetitetriple point with respectto the positionsof •iS•
562 HIROSHI OHMOTO

+15
' I '

•-----. 150oc
+10 - •S $4
•s: 0%0
• ;>50
-'---- 350

+5

-30

-37

-30

\
-35
\
\
-44 -48

402 ' l•----

4 6 8
I

I0
I

pH
FIG. 8. Comparisonof the effect of changein pH on the •S•4 valuesat different T and fo2 of the fluids.
I = 1.0. •S" valuesfor H•S are where •S•s = 05[0.

the same for all the aqueoussulfur speciesin the isotopiccomposition of sulfurin the fluids,•S:•S,
34
solution, and for the minerals precipitating from is +20%oratherthan0%0,•S•4 valuesin the figures
the same solution. For example, the contour of are increased by +20.
•S34
H,S: 0%0isthesameasthatof •SHs- 34 : -- 1.4%, bS•• contoursat 150 and 350øC are shownin
4- = -- 6.2•0,
aS•2 voso,
.•342-= + 26.5%0, or Figures6 and 7, respectively.The bS•• valuesin
•S3p4y
-- --0.3%o at 250øC (see Fig. 5). If the mean Figures 4-7 probably have an uncertainty of 4-10
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 563

percent(i.e., •Sms
34 = -- 20 contour could be -18 the causeof the'observed
/•Sa4variation. Alter-
or --22•), because of the uncertainty in the /x• natively, if this mineralis stableover a large fo,-pH
values. The uncertaintyin the positionsof /•S•• region,variation in the fo• and/or pH value may be
contoursin fo•-pH diagrams,due to the uncertain- consideredas a possible mechanism to produce
ties in the assumptionsof Eqs. (7) and (28) and in variationsin the /•S,
3.•values. To illustratethis,
the equilibrium constants,is probably within 4-0.5 the relationshipsbetweenthe positionsof /•S, 3.•
log fo• units at a given pH. The ionic strength of contours and the stability fields of iron sulfides
ore-forming fluids is in many cases between 0.5 and barite are examined below.
and 3 (e.g., Ohmoto, 1971). In this range of ionic The fugacity of sulfur in aqueous solutions is
strength,the positions of bS•• contours are affected related to fo,, pH, and the sulfur concentration
only slightly (i.e., less than 4-0.3 log fo• units) by (mzs) by
the changeof ionic strength of the fluids; the effect
is small and can be neglectedat the present time.
The relative order of S a• enrichment is sulfate fs•(K•*'Xu•s'm•s'*u•s)
.....
2 fo•
C/,H•O
(29)

species>> H2S •' sulfide minerals > S2- (see Fig. in which Kh8 (seeTable 2) is the equilibrium con-
1). Therefore, in the H•.S predominant field (i.e., stant for the reaction
low fo• and low pH region),sulfidemineralsprecipi-
tating from solutionswould exhibit/•S aavalues simi- H2S(aq) q- «02 •- H20(/) q- «S2 (30)
lar to the/•S•[value;in the2:SO4 predominantfield and Xms is the mole fraction of H2S(aq) relative
(i.e., high fo• region), sulfides,if present,would to total sulfur content, which has been computed
show•Sa4valuesmuchsmallerthan the/•S• value; as functionsof both fo• and pH (seeFig. 3). Using
and in the S2- predominantfield (i.e., low fo• and Eq. (29) and the equilibrium constantsfor the fol-
high pH region), sulfideminerals, if present, would lowing reactions (seeTable 2), we can constructthe
show/•Sa4valuesslightlyhigherthan the/•S• value. stability fields of Fe-S-O minerals in solutions ef
Within eachof the three regions(i.e., regionswhere given T, I, and mzs values.
Xa•s > 0.99, Xzso4 > 0.99, or Xsl- > 0.99),
changesin pH and/or fo• will not affectthe isotopic FeS•.• FeS q- «S2 (31)
compositionof minerals. However, in regionswhere 3FeS2q- 202 •--FeaO4 q- 3S2 (32)
several aqueousspeciesare present in significant
proportions,a slight changein pH and/or fo• can 2FeS• + -•O•.•-Fe2Oa + 2S• (33)
changethe/•S•• valuedrastically. For example,at 3FeS q- 202 ,--FeaO•
--• q- •aS2 (34)
250ø C, an increasein fo• by 1 log unit, or an in-
creaseof pH by 1 unit coulddecrease/•S,
3.•valuesby 2FeaO4q- «02 •---3Fe2Oa (35)
nearly 20%0 (see Figs. 4, 5 and 8). A change of The stability field of barite can be constructedfor
fo• and/or pH value by 1 unit can cause larger selected values of the molalities of Ba 2+ and ZS
variationin the •S•• valuesat lowertemperatures using
(see Figs. 6, 7 and 8), as the isotopicenrichment rbar
factors are larger at lower temperature. Figure 8 Xsol- = (36)
m•3a
a+'mz s ß•/Ba2+'•/SO•+
alsoindicatesthat an increase
in the/•S•• valueswith
an increaseof pH, which Sakai (1968) has demon- whereXsol-is relatedto the fo• and pH of the solu-
strated, is only valid at extremelylow fo,. regions. tions (seeEqs. 20), and K•,• is the equilibriumcon-
stant (seeTable 2) for the reaction
Influenceof mzs and f s,.on sulfur isotopic
composition BaSO4•---Ba2++ SOl- (37)
Discussionof the effect of fo• and pH on the The total sulfur concentrationin ore-forming
isotopic compositionsof minerals is meaningless fluids is generally consideredto be between 0.1 and
unlessthe positionsof bS•• contoursare compared 0.001 moles/kgH20 in the temperaturerange 150
with the stability fieldsof minerals. For example,
to 350ø C, althoughsomefluid inclusionanalyses
if a sulfidemineralin a givendepositexhibitsa large (Ohmoto,1971) suggestthat the ES couldbe as low
variation in/•S a4values but if the stability field of as 0.0005moles/kgH20. In Figure5, the stability
the mineral is restrictedto the low fo• and low pH fields of iron sulfides and of barite in solutions con-
region, then the fc• and/or pH variation can not be taining 0.1 and 0.001 m ZS are comparedwith the
564 HIROSHI OHMOTO

•JS•
4 contoursof Figure4. An increase
in the mzs fluid inclusions suggest that only the sulfur of
value enlargesthe stability field of pyrite, and an around +20• (i.e., sea-water sulfur) could have
increase in the mzs or in the mBa2+ value also en- produced the observed /•S34values for the sulfides
larges the stability field of barite. It follows that under the depositional conditions of the Kuroko
both sulfide and sulfate minerals can possessa ores (Ohmoto et al., 1970; Ohmoto et al., in prep.).
wider range of/•S3•values in solutionsof higher 2;S The sulfur isotopic compositionof minerals can
concentration. For example, pyrite precipitating be used to determine the •34 o•s value and the source
at 250 ø C from a solution which contains 0.1 m of of sulfur only when the temperature,foa, and pH
:EScan vary as much as 30.5 per mil in/•S34values conditions of ore-forming fluids are known. Con-
(from +4 to -26.5•00 when T = 250øC and versely, when the value of •34 o•s is known, the sulfur
/•S•} = 0•00)comparedto 18 per mil (from 0 to isotopic compositionof minerals can determine the
-18•00) for the pyrite precipitating from a solution T, foa, and/or pH of ore-formingfluids.
containing0.001 m of 2:S. Although the valuesof
mzsand fsa do not affectthe positions of /•S•
4 Carbon Isotopic Equilibria in
contours,they define the stability fields of sulfur- Hydrothermal Systems
bearing minerals and consequentlylimit the pos-
sible/•S a• values for minerals.
As the proportions of carbon speciesin aqueous
fluids are also controlled by T, foa, pH and I of
Stability.fieldsof iron sulfidesand of barite in hydrothermal fluids, and because there are large
solutions containing pertinent 2;S are compared
isotopic fractionation factors amongst various
with/JS•4 contoursat 150 and 350ø C in Figures6
carbon species,the carbon isotopic compositionof
and 7, respectively. At temperatures up to at
carbon-bearingminerals should also be affected by
least350øC, the positions of /•S•4 contourswith
the physico-chemical conditions of hydrothermal
respect to the boundariesof mineral phasesare fluids.
similar;thefoa-pHregions wherethe/•S•
4contours
4 values Aqueous carbon specieswhich may become im-
are clustered(i.e., in the regionwhere/•S•
are highlysensitiveto changesof foa and/or of pH) portant in ore-formingfluids are CO•(aq), H•COa,
lie near the pyrite-magnetiteboundary,the pyrite- HCO], CO•-, and CH4(aq); CO and COS, which
hematite boundary, and the barite soluble/insolu- may becomeimportant at higher temperatures,and
ble boundary. This implies that pyrite or other other hydrocarbonscan be negelctedin most cases
sulfide minerals in equilibrium with magnetite, at temperaturesbelowabout 600ø C. Therefore, in
hematite, and/or with a sulfate mineral can show analogy to the sulfur isotopic balance, the mean
/•S• values much smaller than the •34
o•s value, and isotopic compositionof carbon in solutionscan be
that thesesulfidemineralsmay exhibit a large varia- closely approximated by
tion in the /•Sa• values, which may reflect a slight
variation in foa and/or pH in the ore-forming •j•13 13
-•c = (•Cco,'Xco0 + (,•C•,co,'X•,co•)
fluids. Figures5-7 alsosuggestthat pyrrhotite, or + (aC•cor.X•co_)+ (•Cco,;.Xco,-)
other sulfide minerals in equilibrium with pyr- q- (bC[•,.Xca,) (33)
rhotite, are likely to possess/•S
•4valuescloseto the
/•S•4
•s value (withinseveralper mil of/•S•} valueif in which X• is the mole fraction of carbon speciesi
T •> 200ø C) and that these sulfide minerals are
useful indicators for the •j•234
o•s value. T2•m• 4. Isotopic Enrichment Factors for Carbon Species
It follows that sulfidesof/•S a• = • 0• need not
have precipitated from solutions in which & = *Cl• - *C•,co•(,•,)(•)
/•c•4 • 0•00,and that a wide variation in /•S3• Species 150 ø C 200 ø C 250 ø C 300 ø C 350 ø C Ref.

values does not necessarily indicate biogenic or HCO•- -- 2.3 -- 4.1 -- 5.5 -- 6.6 -- 7.0 a
CO•- -- 0.9 -- 2.4 -- 3.4 -- 4.1 -- 4.6 b
sedimentaryderivationfor the sulfur. For example, CH4(g,aq) --40.5 --34.5 --29.2 --25.2 --21.8 c
/•S3• values of sulfides in the Kuroko deposits in CaCOa q- 1.5 -- 0.2 -- 1.4 -- 2.1 -- 2.5 d
C (graphite) -14.9 --14.5 --13.9 --13.2 --12.4 c
Japanare typicallybetween+8 and -6•oo (e.g.,
Clark, 1971), valueswhich had beeninterpretedas See text.
Thode et al. (1965).
an indication of magmatic sulfur. However, de- Bottinga (1969).
tailed studies of sulfur isotopes,mineralogy, and Bottinga (1968).
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 565

(øC)
000500 300 200 I00
14

12

IO

C02(g) = h2C03(ap
)

-12

-14

-16
CH4 (g)'"CH4(aq.)
-18

-2.0 I • I I I I I • I • I ,
0 2 4 6 8 I0 12 4

(I/T xlOs
FIG.9. Isotopicenrichment
factorsfor importantcarbonspecies.The datashownin the figurearebasedon the theoretical
fractionation factorsby Bottinga(1968,1969)forCO2--CH4--C--CaCO3, byUrey(1947)forCO2--COI-(curveU), byThode
et al. (1965)forCO2--CO•-(curveT), andby Malinniet al. (1967)for CO•--COI- (curveM). Experimental dataforCO•--
HCO• fractionation factors
areby Deuser andDegens (x points,1967)andby Malininet al. (opoints,1967). Thecurvesused
in this paperare (T) for COl- and (O) for HCOF (seetext).
566 HIROSHI OHMOTO

relative to total carbon content' speciesin the solutions as

mi mi • = /•Cmco,(•p)+ zX• (42)
Xi - - (34)
m•½ mco2 •- mH2coa where zX•is the relative isotopic enrichment factor
+ m}•co; + mco• + mc•4 between the speciesi and H2COa(ap). Using Eqs.
Carbon dioxide in solution is present as CO2 (38), (40), and (42) the followingrelationshipcan
be established.
molecule and as H2COa, and the sum of these two
speciesare commonly expressedas H•COa(appar- 3= + a,-
ent) in thermochemical calculations:
+ (acol-.Xcol-) + (Aca4'Xca4)• (43)
mco,(,q)+ mu,coa= mlt2COa(ap), (40)
a convention that will also be followed here. The Relativeisotopicenrichmentfactors
reduced partition function ratios are not well The relative isotopic enrichment factors for im-
established for CO•.(aq), H•COa, and H•COa(ap), portant carbon speciesare summarized in Figure 9
although such ratios for CO•.(aq) and H2COa are and Table 4. The zX•valuesfor CaCOa, C (graphite),
probablysimilar to thosefor CO•(g) and CO•-, and CH4 are based on the theoretically calculated
respectively.That is, the valueof •CH2cO,(ap
•3 ) can isotopic fractionation factors among CO•.--CaCOa
be expected to lie somewherebetween the values of --CH4•C byBottinga (1968,1969). The calculated
/•Ccoqand ,•co2(g).However,becausethe isotopic isotopic fractionation factors between CO• and
fractionation
factorsbetweenCO•- and CO•(g) at CaCOa agree well with the experimentally deter-
temperaturesabove 100ø C are relatively small (i.e., mined values by Baertschi (1957), Vogel (1961),
less than 5 per mil) compared to those between and Northrop and Clayton (1966), and those for
CO2(g) and CH4(g,aq) (i.e., •50 per rail at 100ø C, CO•--CH4 and CaCOa--C appear to be in good
see Fig. 9) and becausethe dissolvedcarbon dioxide agreement with the observedisotopic fractionation
is predominantly present as CO• molecule rather in many natural samples (e.g., Bottinga, 1969).
than H•COa (Helgeson, 1967), the following ap- The isotopic fractionation factors among CO•--
proximation can be made: HCO•--CO•- are, however,not well established.
13 13 There are significant discrepancies among the
•Cmco•(a•)• •Cco•(g) (41)
values calculated by Urey (1947), Thode et al.
Takingthe valueof •Cmco•(ap)
• as a reference,we (1965), and Malinin et al. (1967) (see Fig. 9).
can expressthe isotopiccompositionof other carbon ZXcol-curves of both Urey and Malinin et al. lie
TABLE 5. Equilibrium Constantsfor ReactionsInvolving Carbon and AI-Silicates

log K

Eq.x Reaction 150 ø C 200 ø C 250 ø C 300 ø C 350 ø C Ref.

H2COa(ap) • H + + HCOr -- 6.73 -- 7.08 -- 7.63 -- 8.86 --10.2 a

HCOE •- H + + COa•- --10.33 --10.73 -- 11.24 --11.83 --12.4 b
(--10.29) (--10.68) (--11.43) (-13.38) (-15.5) a
46. CH4(aq) + 20• • H2COa(ap) + H20(/) 98.34 86.87 77.52 69.74 63.28 c
55. CO2(g) + H•O (l) • H•COa (ap) -- 2.07 -- 2.06 - 1.98 - 1.83 -- 1.6 a
56. C q- O• q- H•O (l) •- H2COa(ap) 46.62 41.49 37.41 34.13 31.48 d
58. CaCOa • Ca2+ + COa •- --10.25 --11.37 --12.72 --14.10 --15.5 a
59. H20 (l) • H + + OH- -11.63 --11.25 --11.04 --11.03 --11.42 e
(--11.64) (--11.27) (--11.13) (-11.39) a
62. 3KAISiaO8+ 2H + -• KAlaSiaOt0(OH)2
+ 6SiO: + 2K + 9.2 8.6 8.2 f
(8.91) (8.49) (8.12) (7.82) (7.6) a
63. 2KAlaSiaO10(OH)2+ 2H + + 3H20(/)
• 3AI•Si•O( (OH)• + 2K + 7.96 7.04 6.20 5.44 4.9 a

Numbers correspondto those in text.

Helgeson (1969). Extrapolation above 300ø C.
Barnes et al. (1966).
Calculated from the thermochemicaldata on CH4 (g) q- 202 •
CO• (g) q- 2H20 (g) in Holland (1965), the solubility data of
CO2(g) in H20 (l) summarizedin Holland (1965), and the solubilitydata of CH4(g) in H20 (l) summarizedin Ohmoto (1968).
Calculated from the thermodynamicdata on C q- O2•- CO2(g) in Holland and Eq. 55.
Fisher and Barnes (1972).
Extrapolation of the data obtained by Shade (1968).
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 567

-:•21 '
I X. oo >.99 i
I ', I'I ' I ' I '
k .• 3(op.)
01 0 0 • -

'1
(•).5)
(3)1(5)(5) (4)
I . •13

I • •,•o•,.•.,
•
! Iil I I
, i I
;• ........ ,,.... ',
II __
.... I I
.• --.••-•r•);'-,,•gA I /
• ••• :. - -•.•, -...,....
-40
......
•-:-'-a-.
'"'-.
ff:/o.• ......
(29.2). - --

-42

XCH
4).99

.-441 , I , I , I , I , /
2 4 6 8 I0 12

pH
FIG. 10. Mole fractionsof aqueouscarbonspecies(relative to total carboncontent) and •C•3 contours. T = 250ø C and
I= 1.0.
-----: mole fractions of H2COa(ap).
ßmolefractionsof CH4(aq). (Althoughthe valuesof XHcoyandXco•- werecomputed,
they are not shownin the
diagram).
: •C•acontours.Valuesin ( ) areforH2COa (ap)at C•c = 0•oo.•CH•co•(,p)
•a = 20•0 contouris identicalto the contour
of (•cl]•cO•
= 14.5,•C•oi- = 16.6,•Cca4
13 = - 9.2, (•Cl
$ = 18.6, or •Cg,
c• 13= 6.1•0.

below the Ac•co:,curve. In this paper, the ZXcol-curve of Thode et al. (see Fig. 9). In this paper,
curve by Thode et al. (curve, T in Fig. 9) is used,
a curve (O) which is drawn nearly parallel to that
becausequantum mechanicspredicts that the re- of ZXcoF(T)and which passesthrough the experi-
duced partition function ratios for carbonates mentally determined points at low and high tem-
(solid) are larger than those for CO•-, that is, peratures is used, becausethe order of C• enrich-
ZXc•co,> ZXcoF. The experimentally determined ment is knownto be CO•- > HCO] throughout
zX}tco;curve of Malinin et al. intersectsthe ZXcol- this temperaturerange (e.g., Malinin et al., 1967).
568 HIROSHI OHMOTO

The errorin the 8C•3 valuescausedby the uncer-

tainties in the Aco•-and AHCO;values will be dis-
cussed later.
= Ka,
XHCO• co3'•a,
Ct'a• co•(ap)
+"YHCo• (48)
ra•coa ßKHCOr' TH•COa
(ap)
Mole fractions of carbonspecies Xcol-
= C'.(a•+)•-•co•
- (49)
The mole fractions of aqueous carbon species
relative to total carbon content can be evaluated Kca,
Xc•,- C'.
(fo•)
• (50)
from the following equilibrium relationships'
in which
H•.COa(ap)•- H+ q- HCO• (44)
HCO• •- H+ q- rOE- (45) C'=1+(Ku•co•'•n•co•{•))
CH4(aq) q- 20•. •-H•.COa(ap) q- H•.O(/) (46)
' ,HCO•aa+'*co•
+ (fo,)
2
Hence
ß

and Ku,co•, Kaco• and Kca• are the equilibrium

1
constants (seeTable 5) for reactions (44), (45) and
Xa•co3(ap)
-- C' (47) (46), respectively.
+35

+30 log fo•= -41

+25

-39
+20

+10

+5

_52: , I , I I I
I I I

4 6 8 I0 IP.

pH
FIG. 11. Comparison
of the effectof changein pH on the 8C• valuesat differentoxidationstateof the fluids.
T 250øCand I 1.0. 8C• valuesfor H2COa(ap)are at 8C•3 --- 0•00.
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 569

Eqs. (47) to (51) indicate that the mole fractions logicprocesses at temperaturesup to around 300ø C,
of aqueouscarbon speciesrelative to total carbon and thus the uncertainty in the assigned ZX•cor
content are dependent on the temperature, value may affectthe positionsof •C•3 contours.
pH and I of fluids. That is, For example, if the zX}•co;value at 150øC were
+0.5 instead of -2.3 (i.e., ZX•cor>
X• = f(T, fo•,pH,I) (52)
> Z•col-insteadof AH,.COa(ap) > ACO •- > AHCO• , see
and, with Eq. (43), Fig. 9), $C•3valueswouldshowa minimuminstead
•C!3 of a maximumat which X}•co; was maximized. In
, = f(•Czc,T, fo,pH,I) (53)
this case,the $Cn•co•(•p)values changefrom 0 at
pH = 6 to -0.5•0• at pH = 7 (cf., Figs. 11and 12).
Influence of T, f o, pH and I on carbonisotopic The salt concentration in the fluids affects the
composition
activity coefficientsof aqueouscarbon species,and
Using the zX•values summarized in Table 4, the thereforeinfluences the $C•3 values. However,its
equilibrium constantsin Table 5, and the activity effecton the positions of $C•3 contoursis smaller
coefficientsin Table 3, the molefractionsof aqueous than the uncertainties due to the uncertainties in
carbonspecies(relative to total carboncontent) and the isotopic enrichment factors and in the equi-
bC•3 valueswerecomputed as functionsof librium constants, and will be neglected for this
fo, pH and I at various temperatures. Figure 10 reason.
showsthe mole fractionsof aqueouscarbonspecies The patternsof/•C•$contours aresomewhat simi-
in solutionsof I = 1.0 and T = 250ø C, and the lar to those of the •so4Si ' 34 contours. The largest
•CI3 contours where•C• = 0•00.The changeof change in & values occur near the boundaries be-
•C•3values withrespect to pH at variousfo•values tween the reducedand the oxidized aqueousspecies,
is also comparedin Figure 11. Figures 12 and 13 and the magnitude and the direction of & change
show$C•3contours at 150and350øC, respectively.per unit change in fo,. is similar. However, the
The patternsfor contoursof $C•3 are similarat patternsof ,• contours differ from those of the
temperatures above ca. 100ø C, where the order of •S•• contours
in the following
respects'(1) Bound-
C•3enrichment
isH•.CO3
(ap)> CO•- > H CO• > CH4 aries for the reducedand the oxidized carbon species
(see Fig. 9); although the incrementalchangein lie at a lower fo,. comparedto thosefor the reduced
bC•3duetochanges in fo,.and/orpH valueislarger and the oxidized sulfur species. (2) Variations in
at lower temperatures. In high fo,. regions,where pH cancausea change in ilC•3 valuesbut onlyin
theabundance
of CH4 is negligible,
$C•3 valuesare alkaline regions, because H•.COa(ap) and/or CH4
independentof fo,. and showa maximumat slightly is the dominant carbon speciesin lower pH regions
alkaline to alkaline pH regions (see Fig. 11). In and becausethe mole ratios of H•.COa(ap)/CH4 are
the regions where both H•.COa(ap) and CH4 are independent
of pH. (3) •C•3 showsthe maximum
presentin significantproportions(i.e., low fo•. and value at low fo• conditions(i.e., CH4 predominant
lowpH region),
$C•$valuesarestrongly
dependentfield)while•S•• showsthe maximumvalueat low
on the fo•. value but not on pH. In theseregions, fo,. and high pH conditions (i.e., S•'- predominant
an increaseof fo,. by 1 log unit can causea decrease field). These differenceswill be shown later to be
in •C•3 valuesby about30 permil at 250øC(see extremely useful in limiting the geochemicalcondi-
Fig. 10). In regionswhere H•.COa(ap), HCO• and tions of ore-forming processes.
CH4 are equally important (i.e., low fo,. and inter-
mediatepH region),15C•
3 valuesare stronglyde- Influenceof mgc and fco,. on carbonisotopic
pendent on both fo• and pH values; an increasein composition
fo• by 1 log unit or in pH by 2 units can cause
a decrease of nearly30 per mil in bC•3 valuesat The stability fieldsof carbon-bearingminerals on
250 ø C. a fo,.-pH plane can be easily constructedby fixing
Becausethe mole fractionof CO32-is sosmallin either mg½ or J½o•.value in the fluids, because
geologicallyimportant pH regionsat temperatures fco,. is related to fo,., pH and m•c by
above about 100ø C, even a large error in the as- XI-I2C03(ap)' "YH2C
03(ap)' mxc
signedZXcoVvaluesdoesnot affect the positionsof f½o,.-- (54)
Kco,.'amo
C$•3 contours
seriously.HCO], however,
canbe-
come an important carbon speciesin various geo- in which Kco,. is the equilibrium constant (see
570 HIROSHI OHMOTO

-42
I I I ' I

I
-44 -
I
[coco,]
I
I
•C •$ I
H•CO$(op.
I
-46 I
(o) i (o.5) (2) (2)

-48
• (o.5)

(3) •
(IO)
(20)
(35)
-5O
(40)
[c]

mmm mm mmm mmmm m•mm

m •m m•mmm
m m mmm

'•(40.5) • \\,•
-52

\
\
-54
2 4 6 8 I0 12

pH
FIG. 12. Comparisonof the positionsof •C,1.acontourswith the stability fieldsof calcite and graphite. T = 150 ø C and
I= 1.0.
--: •C,1.a
contours. Values in ( ) are for H2COa(ap) at
ßstability boundariesfor calciteand graphiteat IIC -- 0.1 moles/kgH20.

Table 5) for the reaction which leads to

CO2(g) q- H20(/) • H2COa(ap) (55) fo•- Xa•coa(ap)'3'a2co•(ap)'mzc

--

rg. a•2o
(57)
For a given 2C, the stability field of graphite can be where Kg is the equilibrium constant for reaction
constructed from the equilibrium reaction (53) (see Table 5) and XIt•Coa(ap)has been com-
puted as functions of both fo• and pH (see Fig.
C q- O2 q- H20(/) • H2COa(ap) (56) 10). The stability field of calcite can be defined
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 571

from the first and the seconddissociationequilibria 2mca2++ mH+ • mHco;+ 2mco•-+ moa- (60)
of H2COa(ap) (Eqs. 44 and 45) together with the
following two equilibrium reactions In high fo2 regions,the stability field of calcite can
be approximated by
CaCOa•- Ca2+q- CO•- (58)
(KH,co•)2'K•coF' •ca•+'
H20(/) •- H+ q- OH- (59) (X•t2coa(•p)ß7•coa (•) ßm•c) 2
Oa+) a = (61)
and with an equation for electron mass balance, 2K•'•Hco;

-24
' I ' I ' I

-26 I
I'--,.
I
Ecoco3]
I
I
I (o) (0.5) (2) (5)
-28 •C 13 I (5)
H2CO$(ap,)
,,

-30 (o)
I

(o.5)
(5) \
'(10)
-32 - \
(20)

\
(21.8) \
\
\
\
\
\
\
\
\
-36 , I , I , I
2 4 6 8 I0 12

pH
FzG. 13. Comparisonof the positionsof •CI a contourswith the stability fields of calcite and graphite. T = 350ø C and
I= 1.0.
--: •CI a contours. Values in ( ) are for HaCOa(ap)at/iCrc = 0•oo.
.... : stability boundariesfor calciteand graphiteat 2:C = 3 moles/kgHaO. (The uncertaintyin the calcitesoluble/insolu-
ble boundaryis probablyas muchas 4-1.0 pH at this temperature.)
572 HIROSHI OHMOTO

-32

-34

-36

•+_0

-313

-40

-42:

-44

pH
14. Comparisonof the positionsof/•C}• contourswith the stability fieldsof calciteand graphite. T = 250 ø C and
1.0.
:/•C]• contours.Valuesin E -1and ( ) are,respectively,
for calciteandgraphiteat/•C[•c-- -- 5•o, a probablevaluefor
carbon of juvenile origin.
ßstability boundariesfor calciteand graphiteat I;C -- 1 mole/kg H•O.
.... stability boundariesfor calciteand graphiteat I;C 0.1 moles/kgH•O.

in which Kc is the equilibrium constant for reaction
(55) (see Table 5).
Using the equilibrium constantssummarizedin
Table 5 and the activity coefficientssummarized in
Table 3, the stability fields of graphite and calcite
are computedfor solutionscontainingvarious ZC
and are comparedwith the •i contoursin Figures
12, 13 and 14. With a decreasein the carbon con-
centration in the fluids, the stability field of calcite
moves towards higher pH regions, and that of
graphite shrinks towards lower pH regions (see
Fig. 14): the stability field of graphite disappears
when ZC becomeslessthan about 0.005 m at 150ø C,
about 0.05 m at 250 ø C and about 0.5 m at 350 ø C.
Figure 14 indicatesthat while the carbonconcentra-
tion of the fluids has little effect on the possible
/iCisrangefor carbonates,the valuesof m•c strongly
control the possible/iC•svalues for graphite.
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 573

-30

-32

co feaO•
I

,, Fe:•O
4

-34 ooI

-36
•, I,
Spy: -26
c •¾,•..'.'...'1.'•
'.;..::'...'..:'
,,.-.':
?.?.:., -..\ 34

-38 Spy: -I
I • • • iv v• v
34=+1
Spy
I /

-40 '%,.
- ß
.... .... FeSa
FeS
•/'

-42

2 4 6 I0

pH
Fro. 15. Compositediagramshowingthe fo2-pH relationships
amongthe iiSl4 contours,the iiCla contours,and the stability
fields of Fe-S-O minerals, calcite, graphite and sericite (muscovite). T = 250ø C and I = 1.0.
a4
: ifsa• contoursfor pyrite at iiSr.s = 0•v.
iiCxacontoursfor calcite at iiC[ac= -- 5•oo,a probablevalue for carbon of juvenile origin.
•-: muscovite•K-feldspar boundary at K + = 0.001 moles/kg HaO and kaolinitc--muscoviteboundary at K + = 0.!
moles/kgHaO. The field for muscovite(sericite)in the diagramis the maximumstability field, sincem•c+ in ore-
forming fluids seldomlies outsideof 0.001 to 1 m range (e.g., Ohmoto, 1970).
-----: Fe-S-O mineral boundariesat •;S = 0.01 moles/kg HaO.
.... : calcite and graphite stability fields at •;C = 1 mole/kg HaO.
The pH regionwheresericitecan be stableis divided into 5 areas: (1) aboveiiS•y = - 26f•ocontour, (2) betweenthe two
iiS•ycontoursof --26 and -- 1, (3) betweeniiS•y = - 1 and iiC[a•= -- 6 contours,(4) betweenthe two iiC[a•contoursof --6 and
+22, and (5) below •CXca• = + 22• contour.
A, B and C representthree simplepaths which a solution,I, can follow during ore deposition(seetext).
574 H1ROSH1 OHMOTO

TABLE 6. Relationshipsbetween the Chemical Environments of Ore Deposition and the

Sulfur and Carbon Isotopic Compositionsof Hydrothermal Minerals

Variation of Isotopic
Isotop. Comp. of Minerals Comp. by Changes
Relative to Fluid Comp. in fog and pH
Oxid. Possible
Area• State Min. Assoc.2 •S•4 •C? •S•4 • •C•a
1 high bar, calc. /•S•4•r
•-/•Sa•s /•C[a½
•/•C•c uniform uniform
2 bar, py, f•S•,[r >
calc. •S•y < •Sa4 •C •&• •C •a variable uniform
py,po,calc. •S•y
• •S• •C•• •C•}• uniformuniform
py,
po,
calc, gr.
•S•y• •Ss•
s ••Cg•h••> •C•c
•C•c uniform variable
5 low po •S•o -- •Szs uniform

xSee Figure 15.

2Mineralsconsidered are pyrite, pyrrhotite,barite, calciteand graphiteonly. Sericiteis stablein all the areas. Presenceor
absenceof pyrrhotitein areas3 and 4 dependon the I:S value (seetext).

At temperaturesaboveabout 100ø C, carbonate Therefore, the measurementsof isotopic composi-

mineralsprecipitatingin oxidizedconditionswould tions of coexisting sulfides, sulfate/sulfide, or
showiSC 13valueswithinseveral permil of theiSC• carbonate/graphite in ore bodiescan determine the
value. However, the carbon isotopic composition temperature of mineralization. During the past
of carbonatesprecipitating in reduced conditions few years, the sulfur isotopegeothermometryhas
and that of graphite are highly sensitive to the been applied to various ore deposits (e.g., Greig
fo•.value of fluids. Therefore,one can not assume et al., 1971; Robinson and Ohmoto, in prep.).
carbonates of iSCxa = • -- 5 to • - 8• to have Although there are still many problems in sulfur
precipitated fromsolutions inwhich bC• = • -- 5 isotope geothermometry, emphasis here will be
to • -- 8•, unlessinformation on the T, foa and placed on the complementary use of sulfur and
pH of ore-formingfluidshasbeenobtained. Large carbon isotopes in determining other physico-
variations in the carbon isotopic composition, chemical parameters.
which were commonlyinterpretedas being due to Figure 15 comparesthe positionsof •Si34 con-
biogeniccarbon,can be producedby variation in tourswith thoseof iSC• 3 contours alongwith the
fo• and/or pH of hydrothermalfluidsduring ore stability fields of Fe-S-O minerals, graphite, calcite
deposition. and sericite at 250ø C. (The stability field of seri-
Carbonatesof very negative/5C•a values can be cite can be constructedfrom the followingreactions'
formed from solutionsin which /•C• values are
3KAISi•Os q- 2H + -• KA13SiaO•0(OH)•
very negative(e.g.,carbonobtainedby dissolutions
of graphite),and neednot have formedfrom bio- + 6SiO• + 2K+ (62)
genic carbon. 2KAlaSiaO•0(OH)• + 2H+ + 3H•O(/)
Applicationsto Natural Systems •- 3A1Si•.O•(OH)4q- 2K + (63)
Chemicalenvironments
of ore deposition See Table 5 for the equilibrium constants). Be-
The temperature, of oxygen,sulfurand cause sericite is one of the more common gangue
fugacities
carbondioxide,and pH of hydrothermalfluidscan minerals in various types of ore depositsat inter-
often be deducedfrom fluid inclusionstudiesand/or mediate temperatures (• 150- • 400øC), we
and chemicalstudiesof ore and can probably assumethat a reasonablepH range
from mineralogical
gangueminerals. There are, however,many de- for hydrothermal fluids during ore deposition lies
is toosimpleor the within the stability field of sericite. This pH range
positsin whichthe mineralogy
minerals are not suitable for fluid inclusion studies. can be divided into five areas in terms of oxidation
For thegeochemical
studiesof thesedeposits, sulfur state (see Fig. 15). Each area is characterizedby
andcarbonisotopes
maybecome particularlyuseful. a specificcombinationOf iSS•
34and/5C•13valuesas well
The difference in the iSS
a4 values of coexisting as by mineral assemblage (Table 6). The rela-
sulfur-bearing •avalues tionships among the oxidation state of fluids,
minerals,and that in the iSC
of coexistingcarbon-bearing minerals,are depend- /5Sa• and bC•a values of minerals, and the mineral
entprimarilyontemperature (seeFigs.2, 3 and9). assemblageare similar at other temperatures, as
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 575

we can see from the comparisonof Figure 6 vs. stronglyon the originof the fluids. Magmatically
Figure 12 and Figure 7 vs. Figure 13. Therefore, derivedfluids,in many cases,startedin the stability
by examining the bSa4and /•C•3 values in a given field of pyrite or at near the pyrite-pyrrhotite
deposit, we can estimate the relative oxidation state boundary,as indicated by commonoccurrenceof
of ore-formingfluids without a detailed knowledge pyrite in intrusiverocks. Supposethe initial state
of the local mineralogy and the temperature of of a magmaticallyderivedfluid was T = 250ø C,
formation.
Examplesof the useof Table 6 and Figure 15 can
be taken in so-calledmagmatic depositsand in
meteorites, although meteorites may not be con-
sidered as sulfide ores. Both sulfur and carbon iso-
topic compositionsof hydrothermal minerals in
many deposits which are closely related to intru-
sires are found to be uniform throughoutthe ore
bodies,such as the Providencialead-zincdeposits
in Mexico (Rye and Czamanske, 1969) and the
lead-zinc depositsin the Casapalcamine, Peru
(Sawkinsand Rye, 1970). This suggeststhat these
depositswere formed under intermediate fo• con-
ditions, area 3 in Figure 15. In meteorites, the
/•C•3 values of both graphite and carbonatesshow
wide variation (e.g., Schwarcz, 1969) while the
/•Sa4values of sulfidesare uniform (e.g., Jensen,
1967), suggestingthat meteorites were formed in
low fo,• conditions,area 4.
Where the mineralogyof the ores is suitable for
various geochemicalstudies, combinations of these
studieswith sulfur and carbonisotopicstudiescan
provide detailed information on the chemistry of
ore-formingfluids. For example,if the pH and the
oxidation state of the fluids were known, from the
sulfur and carbon isotope studies, to lie within a
certain area, suchas area 3 in Figure 15, and if the
fugacity of sulfur in the fluids were estimated from
a sulfidemineral assemblageand/or from the iron
content of sphalerite which coexistswith an iron
sulfide, we should be able to place a limit on the
sulfur content in the fluidsusingEq. (29). Simi-
larly, the presenceor absenceof graphitein area 3
or 4 (Fig. 15) can limit the carbon content as well
as the fco• value of the fluids from Eqs. (57) and
(s4).
The chemicalstate of hydrothermal fluids during
ore depositionis controlled by the initial state and
by subsequentchangescaused by reactions with
wallrocks as well as with previously deposited
minerals. Mixing of meteoric waters or boiling
also changesthe chemical state. Changesin the
chemical state of ore-forming fluids can in some
casesbe traced in the sulfur and carbon isotopic
data as well as in the mineralogy.
The initial state of hydrothermal fluids depends
fo• = 10-a7and pH = 35 (i.e., point I in Fig. 15).
Three simplepathswhichthis solutionsmight fol-
low during the processes
of ore depositionmay be
examined.
The first path, A, is toward the right, endingin
area 3 of Figure 15. This path may be applied to
a casewhere the fluid encountersgranitic rockscon-
taining abundant feldsparsand mica, or limestone.
Both sulfide and carbonate minerals precipitat-
ing from this solution would exhibit uniform
isotopic compositions(/•Ss•des 34 r• 34 and
--/•S•.s
•3 • fica3
($Ccarbonates-- • throughout the paragenetic
Y-CJ
sequence. Occurrenceof sulfide ores in limestone
near granodioritestocks,abundant pyrite through-
out the entire stagesof mineralization, appearance
of calcite in the later stagesof mineralization,and
the uniform sulfur and carbon isotopic composi-
tions of hydrothermal minerals at the Providencia
mine (Sawkins,1964; Rye, 1966; Rye and Czaman-
ske, 1969) may be taken as an example.
Thesecond
path,B, isupward
to theright,end-
ing in area 2. This path representsa combination
of path A with an increasein fo•. The increasein
oxidation state of the fluid can be caused in various
ways, such as by reactionswith host rockswhich
contain abundant hematite and/or magnetite, by
mixing with oxidizedmeteoricwaters, by preferen-
tial lossof hydrogen,etc. Sulfate minerals may ap-
pear during the later stagesof mineralization. In
ore depositsformed from this solution, while the
/•C•avalues of the carbonates would show relatively
uniform values, a trend of decreasing/•Sa4values
toward the later stagesof mineralization should be
observedin the sulfur-bearing minerals.
The third path, C, is downward to the right, end-
ing in area 4. This path is a combinationof path
A with a decreasein fo•. The decreasein oxida-
tion state of fluid can be causedby wall rocks which
contain abundant mafic minerals (i.e., reduction by
5 The pH of hydrothermal fluids, before starting mineral
deposition,has been a focusof heated arguments. Evidence
for or againstacid transportationof heavy metals can be listed
in hundredsof pages. The pH of 3 at 250ø C for a magmati-
cally derived fluid was chosenprimarily becausethe quenched
pH of hydrothermal fluids equilibrated with granitic melts
was found to be between 1.4 and 2.2 (Holland, 1972) and
because the fluid could cool down to 250 ø C without attaining
completere-equilibrationwith wallrocksuntil the fluid reached
the depositionalsites.
576 HIROSHI OHMOTO

"FeO" component),graphite, and/or organic car- fluids moved from area 3 to area 4 during ore
bon. In ore deposits formed from this solution, deposition.
while the sulfideswould exhibit uniform •S34values, At the U-Ni-Co-Ag-Cu depositsof the Echo Bay
•C 13valuesof the carbonatesmight showa trend of mine in N.W.T., Canada, •Sa• values of sulfide
increasing •C la values toward the later stages of minerals changed from about -22ffoo in the early
mineralization. stageto about q-25ffooin the later stageof minerali-
Under natural conditions,the changesin chemical zation. The mineralogy of the ore and gangue
state of ore-forming fluids could have been more minerals also changed with time from (hematite
complex. However, combinations of these three q- quartz), (Ni-Co arsenidesq- native silver),
simplepaths can explain the variations of sulfur and (acanthite), (marcasite), (acanthite q- galena
carbon isotopicdata in many "magmatic" deposits. q- sphalerite q- chalocpyrite + bornite q- dolo-
For example, the geologyof the lead-zinc deposits mite), and to (native silver q- sphalerite q- quartz).
at the Mogul mine in Ireland (e.g., Greig et al., These changes in the sulfur isotopic composition
1971) suggeststhat the ore-formingfluidsmovedup of sulfide minerals and in the mineralogy can
through a thick sedimentary sequenceof carbon- be explainedif the fluids had sulfurof •Si•
rich Silurian shale/sandstoneunits and through = • q- 25ffoo(i.e., probably of sea-water sulfur),
hematite-rich Devonian red beds before the fluids and if the oxidation state of the fluids decreased
encountered Carboniferous carbonate units. This
continuously with time from area ! (hematite
suggeststhat the chemicalstate of the fluidschanged field) to area 4 at temperatures around 200øC
from somewherenear point (I) to area 4 and finally (Robinsonand Ohmoto, in prep.).
moved to area 2. This changein the chemistry of
fluids can explain the observed trend in the sulfur Isotopic equilibria in natural systems
isotopic composition of sulfide minerals (i.e., con- The above computations and discussionshave
tinuous decreasein the •Sa4values from around 0ffoo been made on the assumptionsthat both chemical
near the red beds/limestone contact to around and isotopic equilibria are established among
-25ffooin the peripheral parts of the ore bodiesin aqueous speciesand between aqueous speciesand
the limestone) and the observed changesin the precipitating mineral phasesduring ore deposition.
mineralogyof the ores (i.e., occurrenceof barite in These assumptions,however, may not be valid in
the peripheral parts of ore bodies) (Greig et al., somegeologicprocesses, suchas in low temperature
1971). hydrothermal conditions, or during rapid precipi-
Hydrothermal fluids of non-magmaticorigin can tation of minerals caused by sudden changes in
take entirely different paths. For example, the T, P, fo• and/or pH of hydrothermal fluids.
hydrothermal fluids responsiblefor the Tertiary Chemical and isotopic data on hot springs (e.g.,
Kuroko depositsin Japan appear to have been the Steiner and Rafter, 1966; Nakai, 1970b), fluid in-
mixture of sea water and meteoric water (Ohmoto clusions (Rye and O'Neil, 1968; Ohmoto, 1971)
et al., 1970). The changesin the mineralogy and and oil field brines (e.g., Yeremenko and Pankina,
the sulfur isotopic compositionof sulfide minerals 1962), experimental data on chemical equilibria
at the Kuroko suggest that the fluids had initial (e.g., Malinin and Khitarov, 1969; Ellis and
state at near the sericite/K-feldspar boundary in Giggenbach, 1971), and the data of isotopic ex-
area 3, moved upward to the left, and ended at near change experiments (e.g., Nakai in Cheney and
the sericite/kaolinite and the pyrite/hematite Jensen, 1965; Rye and Czamanske, 1969; Oana et
boundaries(Ohmoto et al., in prep.). al., 1970; Kajiwara and Krouse, 1971) all suggest
The lead-zinc depositsin the Pine Point, N.W.T., that the rates of both chemical and isotopic ex-
Canada occur in reef dolomite which contains change reactions, particularly between the reduced
and the oxidizedsulfur species,are extremely slow
abundant organic carbon (e.g., Jackson and
at temperatures below about 200ø C. However,
Folinsbee,1969). Although the temperaturesof ore
there are several low temperature deposits,such as
depositionwere low (about 100ø C; Roedder, 1968), at Pine Point, whoseisotopicand mineralogicaldata
constant•Sa•valuesfor sulfideminerals (Sasakiand apparently can be explained if the establishment of
Krouse, 1969) and continuously increasing •C •a both chemicaland isotopicequilibria were assumed
values for carbonates toward later stages of among aqueous speciesand precipitating mineral
mineralization (Fritz, 1969) can be explainedif the phases. It appears, at the present time, that the
 SYSTEMATICS OF ISOTOPES IN HYDROTHERMAL DEPOSITS 577

fo2-pH-/iS344C•3
diagramscan be appliedto many Y. Kajiwara (Tokyo University of Education), A.
deposits formed at temperatures above about Sasaki (GeologicalSurvey of Japan), H. D. Hol-
150øC; although both detailed studieson the iso- land (PrincetonUniversity), H. L. Barnes (Penn-
topic compositionof a numberof low temperature sylvania State University) and R. O. Rye (U.S.
depositsand controlledexperimentson the rates of GeologicalSurvey) for the benefitsof stimulating
isotopicexchangereactionsmust be carried out to discussionsof the problemsinvolved.
support this. Critical readingof the manuscriptand numerous
It shouldbe rememberedthat the changein T, suggestionsby Drs. H. L. Barnes, P. B. Barton,
fo• and/or pH may not be the only causeof iso- Jr., C. W. Burnham, H. D. Holland, R. O. Rye and
topic variation in nature. In somelow tempera- V. J. Wall are gratefully acknowledged.
ture deposits, bacteria might have played an Use of an IBM-360 computerwas made possible
important role in isotopicvariation. Variation in through funds provided by the PennsylvaniaState
the carbon and sulfur isotopic compositionsof University. The work was financedby NSF grant
hydrothermalmineralsat the Bluebelldepositsin GA-31901.
Canada (+12 to -24• and T > 300øC)cannot be DEPARTMENTOF GEOSCIENCES,
explainedby the variation in T, fo, or pH of the TaE PENNSYLVANIASTATE UNIVERSITY,
fluids. The variationappearsto be bestexplained UNIVERSITY PARK, PA. 16802,
in termsof mixingof two or severalmeteoricwaters, February 5, March 28, 1972
eachcarryingsulfurand carbonof differentisotopic
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