Economic Geology

Vol. 71, 1976, pp. 1533-1548

SulfurIsotopes
in thePorphyryCopperDeposit
at E1Salvador,Chile
C:lUS W. FmL) N) LEWS B. GUSTFSON
Abstract

Sulfur isotopeanalyseshave been performed on 64 monomineralicconcentratesfrom

37 samplesthat are representativeof mineralization in time and spaceat E1 Salvador.

The hypogenesulfates(mean +10.75o; range +7.3 to +17.05o) are enrichedin s4S

relative to supergenesulfates (--0.75; --4.6 to +3.67oo) and to hypogenesulfides
(--3.05; --10.1 to --0.37oo). Coexisting hypogenesulfidesare increasinglydepletedin
a4S in the order molybdenite,pyrite, chalcopyrite, and bornite. The isotopic data suggest that sulfur in the supergenesulfates was largely derived from the oxidation of
hypogenesulfidesand that supergene"chalcocite"probably replaced hypogenechalcopyrite or bornite, but not pyrite. Isotopic temperature estimates from sulfate-sulfide
fractionationpairs range from 400 to 570C and are only in crude agreementwith
temperatures(<300 to >600C) indicated by other geologic evidence. Those estimated from pyrite-chalcopyritefractionationpairs (95 to 185C) are nmch too low.
Fractionation between 13 coexistinghypogenesulfate-sulfideassemblages(21 mineral

pairs) definesa rather narrowbandin /o-pH-T spaceand suggests

that [o and pH
acted as internally controlledvariables throughout mineralization. Mass balance estimates of s4Szsindicate a value of about +6 per mil for the sulfate zone and a value
probablysignificantlyheavier than 0 per mil for the entire depositas presentlyexposed.
The s4S per mil values of coexistinghypogenesulfate and sulfidepairs approximate
linear trendswhen plottedagainsttheir respectivedelta (/x) values. These trends suggest that Early anhydrite-chalcopyrite-bornite
assemblageswere formed from a sulfur
reservoir having $a4Szsof approximately+1.6 per mil whereas Late anhydrite-pyritechalcopyrite assemblagesformed from a reservoir +6.8 per mil $a%.s. Speculative
interpretation suggeststhat Late sulfur was derived either from remobilizationof Early
assemblages
belowthe deepestlevelsof exposureor from volcanicwall rockssurrounding
the deposit,rather than from continuedemanationsfrom the underlying magma chamber
that was the sourceof Early mineralization. However, at least one totally different
interpretationof these data is possible. Recent experimentalwork by Ohmoto and Rye
(1975, written and oral commun.)indicatesthat our $a4Sper rail valuesfor pyrite may
require a correction factor, which would reduce both Early and Late sulfate-.sulfideassemblagesto approximatelysingle linear trends. This would imply that the underlying
magma chamber continued to be the predominant source of sulfur ($sSzs +2%)
throughoutthe entire sequenceof alteration-mineralization.The isotopicdata do not
show any consistenttrendsof s4Sdepletionwith either paragenesisor zoning that would
suggesta restricted reservoir of sulfur in the hydrothermal system. More questions
than answersare providedby thesedata.
Introduction

and mineralizedintrusive complex. Inferencesas

T comprehensive
studyof the porphyrycopper to the pressure,temperature,and chemical condidepositat E1 Salvador,Chile, by Gustarsonand tions at various stagesof this evolutionaryprocess
Hunt (1975) has revealedthe systematic
evolution havebeenpresentedby Gustafsonand Hunt (1975).
Stable isotope investigationshave been undertaken
of mineralization and alteration that culminated a
to
supplementand perhapsto quantify these interlonghistoryof vol.canism
and plutonismin the Indio
pretations.
Many of the mineralsusedin this sulfur
Muerto district. A variety of geologicarguments
isotope,
investigation
are from samplesalso studied
were presentedto supportthe contentionthat Early
for
hydrogen
and
oxygen
isotopic variations by
mineralization
wasaccomplished
very closein space
and time to the final consolidation
of certain por- Sheppardand Gustarson(1976).
Data have been publishedfor the distributionof
phyry magmasand by hydrothermalfluidsthat were
derived from t,he magmas. The transitionto Late sulfur isotopesin many ore deposits. In most cases
nfineralizationtook placeas convectingmeteoricwa- only sulfidemineralswere analyzedand interpretaters collapsedinward and reactedwith the cooling tions havebeenlargelyconcernedwith fractionation
1533

1534

C'. 14z. FIELD AND L. B. GUSTAFSON

effectsbetweensulfideminerals,isotopictrends and
zonations,and the questionof whether or not the
sulfur was of "magmatic"hydrothermalor of "biogenic" sedimentaryorigin. Relatively few studies
have been directedto the porphyry-typedepositsor
their related fissureand replacementdeposits(Field,
1966a, 1973; Field and Moore, 1971; Lange and
Cheney,1971; and Petersen,1972). Moreover, the
limited availabilityof appropriateexperimentalcalibration curveshas restrictedthe applicationof sulfide-sulfidefractionationeffectsto temperatureestimates in porphyry-type environments. Our interpretations of the E1 Salvador data have benefited
enormouslyby the recent contributionsof Sakai
(1968) and Ohmoto (1972) who have demonstrated
from theory the potentialsystematicisotopicvariations between sulfate and sulfide minerals as a func-

Early disseminated"background"mineralization

in the deepcentralzonecontains
the assemblage
chalcopyrite-bornite-an,hydrite
asrepresented
by samples(ES: 1910R,8230R,and2699R) of hostrocks
subjectedto K-silicate alteration. Host rocks altered

to sericite-chlorite
containthe Late assemblage
pyrite-.chalcopyrite-anhydrite
in samples(ES: 8237
and1116)fromthedeepintermediate
zoneandpyrite-anhydrite
in samples
(ES: 8238and1173)from
the deepperipheral
pyriticfringezone.

Vein mineralization
is represented
by samples
of
the Early "A" veins(ES: 1910Vand8230V), the
Transitional"B" veins (ES: 2699V and 7536V),
and the Late "D" veins (ES: 7525V and 7576V,
and its sericitichalo 7576H). All of these vein
samplesare froin the deepcentralzone and they

contain hypogene sulfate-sulfide assemblages.

Upward and outwardbeyondthe top of the sulfate
zonethe anhydritehas beenremovedby hydration
anddissolution(Gustarsonand Hunt, 1975). Thus,
other samplesfrom abovethe top of the sulfatezone
mometryand for internalcheckson isotopicequi- do not containprimary .hypogene
sulfate-sulfide
aslibrium. In addition,the overall patternsof isotopic semblages. Samplesof sulfate not associatedwith
fractionationbetweencoexistingsulfateand sulfide sulfidesincludegypsum(Gyp-2) from the hydrated
minerals, consideredin time and space, offer the cappingat the top of the sulfatezone and selenite
possibilityof placingsomeconstraints
on massbal- gypsum(Gyp-l) and jarosite (E.S-7466) from the
ancesof sulfur and on the isotopiccompositionof leachedcappingof the peripheraland intermediate
total sulfur (Sa4Szs)in the hydrothermalsystem.
zones,respectively.

tion of acidity (pH), oxygen fugacity (fo.o), and

temperature(T). The study of mixed sulfideassemblages
containingsulfatemineralsat E1 Salvador
providesadditionalfractionationpairs for geother-

SamplesES-1855, DDH 65, DDH 599, and ES-

SampleSelectionand Presentation

1809are from locationswithin or immediatelybelow

assemblages
representative
of the major mineralization typeswithinthe mineand with respectto both
theirzonalandparagenetic
distributions.The reader
is referred to the article by Gustarsonand Hunt

logic evidenceindicating that coarselycrystalline

alunites(ES: 5827 and 6573) of the advancedargillic assemblage
are hypogenewhereasfinelycrystalline
varieties (ES: 7486V, 1450, and 8233) associated
with secondaryenrichmentare of supergeneorigin.
Mineral pairs from two of these samples,alunitepyrite of ES-7486V and alunite-jarositeof ES-5827,
do not represent contemporaneous
or equilibrium
assemblages. Samples ES: 1855 and 1809 and
DDH 65 containsupergene"chalcocite"(quotation

the zone of supergene sulfide enrichment. The

The principalobjectiveof the samplingprogram alunite-bearingsampleswere selectedto determine
(conducted
by L.B.G.) wasto obtainsulfate-sulfidewhether or not the isotopicdata supportedthe geo-

(1975) for a description

of the geologyof the E1
Salvadordepositand for an explanationof the terminologyusedherein.
Detailed information concerning the location,

geology,
paragenesis,
andmineralogy
of eachsample
is givenin Appendix1. The orderof samples
listed
in Appendix1 is repeated,
whereapplicable,
in Fig- marks are used for any mixture of chalcocite,di-

genite,and djurleite).
sulfurisotopedata. This ordergenerallyrepresents Eleven samplescontainingpyrite and listed at the
theparagenetic
sequence
fromEarly,through
Transi- end of the tabulations(App. 1, Fig. 1, and Table 1)
tional, to Late mineralizationevents. Becausethe were collectedfrom the outer and uppermostparts
Late eventscollapsed
inwardand downwardon the of the sulfidezoneas presentlyexposed,where nearly
Early events,the tabulatedsequence
represents
at all of the remaining sulfur residesin pyrite. Reprebesta crudethree-dimensional
progression
from deep sentationamong these samplesincludesthe outer
centralto shallow
peripheral
zonesof mineralization.pyritic fringe of the propylitic alteration zone at
However,thissequence
is onlygenerally
followedas relativelylow elevations(DDH 570 and ES: 5470
varioussamplescontainingmineralsof supergene and 5472); the main pyritic fringe at the highest
originarelistedabove
pyrite-bearing
samples
formed elevationsof exposure(ES: 5709, 5715, 2541, and
duringtheLateperiodof hypogene
mineralization.3196); andpyriticwaste-rockoverlyingchalcopyriteure 1 and Tables1 and 3 for variousgroupingsof the

SULFUR ISOTOPES AT EL SALVADOR,CHILE

pyrite protore at high elevationsin theintermediate
zone (ES: 2079, 2087, and 3977). The latter
three samplesrepresenta very late event of pyritic
mineralizationthat appearsto have flushedout earlier higher grades of coppermetallization. Sample
DDH 129A is from high-levelpyritic ore that overlies the central zone of mineralization.

Sample Preparation, Analysis, and

Data

Presentation

fur from the reduction

1535
of sulfate minerals

and the

combustionof sulfideswas at least 90 percentand

usuallygreater. Sulfur isotopeanalysesof the sulfur dioxide gaseswere performedboth at the University of Utah, under contractwith Professor3I. L.
Jensenof the Laboratoryof IsotopeGeology,and in
Denver where facilitiesof the U.S. GeologicalSurvey were used under the directionof Dr. Robert O.
Rye.
The isotopicdata are presentedin terms of conventionalper rail deviations(3a4S)as obtainedfrom
the relationship

Sulfur isotopeanalyseshave beenobtainedon 64

concentrates
of sulfate (anhydrite13, gypsum 4,
alunite 5, and jarosite 2) and sulfide(molybdenite
1, pyrite 23, chalcopyrite9, bornite4, and "chalcocite" 3) mineralsseparatedfrom 37 rock samples. where R, and R represent the measuredand asMineral separationsusingstandardmethodsof con- sumedaS/a2S ratios of the sampleand standard,
centrationwere performedby Judy Montoya of the respectively.Positiveand negativeper rail deviations
AnacondaGeologyLaboratory. Where necessary, indicateenrichmentand depletionof S in the sam-

3%0o
=(R
--1)-103

concentrates

of the sulfide minerals

were leached in

ple relative to the meteoritic standard for sulfur

cold dilute hydrochloricacid to remove crystalline isotopeanalyses(0 per rail by definition). The
intergrowthsof sulfate. Prior to subsequentprep- standarddeviationof the analyticalerror is slightly
aration for isotopicanalyses,the purity of all con- lessthan --+0.2per rail as determinedfrom multiple
centrateswas further checkedby examination with preparationsand analysesof the O.S.U. secondary
the ,binocularmicroscopeand, for many, by X-ray standard. Analysesof this standardat both the Unidiffractometeranalyses. With the exceptionof py- versity of Utah and the U.S. GeologicalSurvey
rite and "chalcocite"from two samplesas described (Denver) agree by less than 0.1 per mil and thus
below, the concentrateswere essentiallymonomin- affirm the equivalencyof data betweenthe two labby threeanaeralic and purities were 95 percent to, more com- oratories. This inferenceis supported
lyses
of
pyrite
in
sample
ES-5470,
based
on the two
monly, 99 percentor better. However, the purity
of pyrite and "chal.cocite"
concentrates
from two sam- different methodsof sulfide preparation and mass
analysescited above,that providedreples (ES-1855 and DDH 65) rangedfrom 80 to 90 spectrometer
percent. The isotopic data for these four concen- markablyuniform values of --10.06, -10.13, and
trates represent "adjusted" values derived from --10.11 per mil respectively. Although the tabulated
algebraicequationsusingthe raw analyticaldata and per mil valuesare given to the hundredthplace as
estimates of contamination from both microscopic calculatedfrom the instrumentalrecord,they and the
examinationand yieldsof sulfur dioxideduring sub- derived delta values as discussed in the text are
with the
sequentpreparationsfor massspectrometer
analysis. roundedto the nearesttenth for consistency
Sulfate and sulfidemineral concentrateswere pre- measuredanalyticalerror.
Isotopicdifferencesbetweentwo coexistingsulfurpared and isotopicallyanalyzed by standard procedures. The majority of nfineral concentrateprep- bearingmineralphasesmay originatefrom temperaarations,prior to isotopicanalyses,were conducted ture-dependentfractionationeffects of isotopicexat Oregon State University (by C.W.F.). Sulfate- changeequilibria. For the purposesof geothermomsulfur of anhydrite, gypsum, alunite, and jarosite etry, the isotopicdifferencebetween two minerals
concentrateswas reduced to hydrogen sulfide in a (A and B) is normallyexpressedas a delta
valuethat is derivedfrom the measured3a4Sper mil
boiling solutionof hydrochloric-hydriodic-hypophosphorous acid as describedby Thode and others values. The equation
(1961). Silver sulfide,derived from the reduction
x_: 3aSxo- 8a%o- 1,000 In a
(2)
of sulfate minerals, and most of the sulfide minerals

were oxidizedto sulfurdioxidegasusinga modifica- relatesthe delta (A_s) value, or differencebetween

tion of the nitrogen-oxygen combustion method the measured8aSper rail values,to the fractionation
developed
by Sakaiand Yamamoto(1966). Eleven factor (). Provided variationsof the fractionation
sulfide concentrates were oxidized tto sulfur dioxide
factor with temperature are known either from
gas by the cupric oxide combustionmethod at the theoryor experiment,the .deltavaluemay thusserve
IsotopeGeologyBranchof the U.S. GeologicalSur- as an estimateof the temperatureof mineral deposi-

vey,Denver,Colorado.31easured
recoveries
of sul-

tion.

1536

C. W. FIELD AND L. B. GUSTAFSON

TABIg 1. Analytical Data Given as $a4SPer Mil Values for Mineral Concentratesof the
E1 Salvador Sample Suite
Cursory geologicdescriptionof sampleslisted in approximate order of district zonationand (or) paragenesis.

Sample
ES-1910R

Description
Andesite; central, 2,400 m; wall rock of "A" vein;
K-silicate

ES-1910V

"A" vein

Sulfide

Sulfate

a4S5

a4S

Cp --3.56

Ah 77.64

Bn --4.21

Cp -5.25

Ah 79.09

Bn -5.71

ES-8230R

"K" porphyry; central, 2,400 m; wall rock of "A" vein;

K-silicate

ES-8230V

"A" vein

Cp --3.20

Ah 77.31

Bn - 4.79

Cp - 3.08

Ah 79.38

Bn -4.76

ES-2699R

"X" porphyry; central, 2,400 m; wall rock of "B" vein;

ES-2699V

"B"

ES-7536V

Andesite; central, 2,400 m; "B" vein; K-silicate

ES-8237

Andesite; intermediate, 2,400 m; sericite-chlorite

ES-1116

"X" porphyry;intermediate, 2,400 m; sericite-chlorite

ES-8238
ES-1173

Andesite; peripheral, 2,400 m; sericite-chlorite

Andesite; peripheral, 2,400 m; sericite-chlorite
"L" porphyry; central, 2,400 m; "D" vein
"L" porphyry; central, 2,400 m; halo of "D" vein

Cp --3.94

Ah 79.69

K-silicate

ES-7525V
ES-7576H
ES-7576V

"D"

vein

vein

Mo
Py
Cp
Py
Cp
Py
Cp
Py
Py
Py
Py
Py

--0.82
- 1.66
-4.65
-0.79
-4.14
-2.11
-5.21
- 1.56
-1.21
-3.13
- 5.05
-4.06

Ah + 10.09
Ah +9.90
Ah +9.88

Ah + 10.65
Ah q- 10.05
Ah q- 10.54
Ah +11.77

Gp q- 11.40
Ah q- 12.39

Gp 711.01
ES-7486V
ES-1855

DDH

65-182m

DDH

599-24m

Pyroclastic; peripheral, 2,875 m; "D" vein with finely

crystalline supergenealunite
Andesite; peripheral, 2,710 m; enriched ore with
"chalcocite" replacingchalcopyrite
Andesire; intermediate, 2,630 m; enriched ore with
"chalcocite" replacing chalcopyrite
Andesire; intermediate, 2,570 m; protore below DDH 65
Andesire; central, 2,710 m; enriched ore with "chalcocite" replacing chalcopyrite-bornite
Rhyolite; peripheral, 3,250 m; capping with coarsely
crystalline hypogenealunite; advanced argillic
Pebble dike; intermediate, 2,990 m; capping, coarsely
crystalline hypogen'ealunite; advanced argillic
Pebble dike; central, 3,100 m; capping with vein of
finely crystalline supergenealunite

ES-1809

ES-5827
ES-6573

ES-1450

Py -3.52
Py -1.19
Cc -3.59

Py -0.34
Cc -4.14

Py - 1.08
Cp -3.23
Cc -4.35

AI + 17.00
Jr -1.58
A1 q- 14.80

A1 +3.64
AI - 1.48

"X" porphyry; central, 2,710 m; vein of finely

crystalline supergenealunite
Leachedcapping; intermediate,2,875 m; jarosite
Hydrated upper sulfate zone; central, 2,600 m; gypsum

ES-8233

ES-7466

Gyp-2

AI +3.33

Jr -3.34
Gp +10.51

vein

Gyp-1
DDH 570-84m
ES-5470
ES-5472
ES-5709
ES-5715
ES-2541
ES-3196
ES-2079

Leachedcapping; peripheral, 2,600 m; gypsum vein

Andesire; peripheral, 2,550 m; propylitic waste rock
Pyroclastic; peripheral, 2,660 m; unaltered, waste
Pyroclastic; peripheral, 2,660 m; sericite, waste
Pyroclastic; peripheral, 2,930 m; sericite, waste
Pyroclastic; peripheral, 2,930 m; sericite, waste
Pyroclastic; peripheral, 2,875 m; sericite, waste
Rhyolite; peripheral, 2,930 m; sericite, waste
Pyroclastic; intermediate, 2,930 m; advancedargillic,

Gp -4.63
Py
Py
Py
Py
Py
Py
Py
Py

- 1.23
- 10.10
-3.94
- 1.05
-- 1.83
-1.77
-2.20
- 1.58

waste

Quartz porphyry; intermediate, 2,930 m; advanced

argillic, waste
Pyroclastic;intermediate, 2,875 m; advancedargillic,

ES-2087
ES-3977

Py - 1.54

Py --1.37

waste

DDH

129A-105m

Andesire; central, 2,840 m; sericite-kaolin, enriched ore

Py - 1.49

ing mineral phasesof a singlesample,is graphically

Isotopicdata for the 64 sulfur-bearing
mineral summarizedin Figure 1. Means and rangesof the
concentrates of the E1 Salvador suite are listed in isotopicdata are given in Table 2 for various mingroupingsof
Table 1. The distributionof all 8a4Sper mil values, eralogic,genetic,zonal,and paragenetic
of 18 hypowith horizontallinesconnecting
valuesfor coexist- the samples.The mean8a4Scomposition
Results and Interpretations

SULFUR ISOTOPES AT EL SALVADOR,CHILE

1537

Petersen,1972). Thus, on the basisof conventional

geologicand isotopiccriteria, E1 Salvadoris a typical magmatic hydrothermaldeposit. The discussions that follow concernthe isotopictrends and
zonationsrelated to the mineralogyand origin and
to the spatialand temporaldistributionof the samples and minerals. Imperfectionsin some trends
1974; Jensen,1971; Langeand Cheney,1971; and listedin Table 2 are presumablyattributablein part

gonesulfatesis + 10.7 per rail and valuesrangefrom

+7.3 to q-17.0 per mil. Analysesof the 37 hypogene
sulfidesrange from -10.1 to -0.3 per mil and the
mean value is -3.0 per rail (Table 2). Our data
are generallycomparableto those previouslypublishedfor the porphyry-typedeposits(Field, 1966a,
1966b,1973; Laughlinet al., 1969; Field et al., 1971,

i S"%0

LIG#T '--'"

#EAVY

10

ES 1910R, aahy-cp-bn
ES1910V, anhy-cp-bn

-10

Kosdiaateattered"K" Parph (2400,central)

'A"vein

K- ilioatealiared"X"Porph (2400,cenlral)

ES
R,anhyanhy
-(p)
ap(bn)
ES 2699
2699V,

"8" vein

ES 7516V, Qnhy-mo-py-cp

ES 8237,

-20

blot,zeal andeSall (2400, central)

"A" veto

ES 8250R, anhy-cp-bn
ES 820 V, althy-cp- bn

-15

onhy- py- cp

ES 1116, onhy-py-cp

aar-chl altered andelite (2400, peripherol)

let altered,pyrilic andelite (2400,periMtorol}

ES 117:5, onhy-py

(2400,canItel)

ser-chlaltered'XUPorph(2400,inlermediote)

"8"vain in blohzed andollie

ser-chl oilarea andesde (2400, inlermediole)

ES 82:58, anhy-py

'D" vein (2400, central)

ES 7525V, anhyopy

"D" vein (2400,centrol)

ES ?$76V, onhy-gyp- py
ES 7576 H, gyp-py

"D" vein hatein'l' Porph.

ES 1855, py-"cc"

enriched pyrrha ore (py-cp) (2?tO,peripheral)

DDH65,

enrichedore (py-cp) (263)0, inlermediote)

pratore belowDDH6:5 (2570, inlermedmte)

DDH 599,

py-ap

1809,

enrichedore (cp- bn) ( 2710, central)

ES 7486 at (f.g.)-py

"D"veinwith supergone
alanitc (2875, perilMerol)

ES 5827

el(c.g.)-ior

ES 6573,

el (c.g.)

ES 1450,

el (f g.)

qtz-ol-oltored rhyolite (coppeg)(:52:50,peripheral)

cg al in pebble dike (copping) (:)990, intermediate)

f g. a in pebble dike (coppng) (:5100,central)

ES 82:5:5, el (f.g.)
ES 7466,

ier

Gyp-2,

gyp

euporglne al vein

jar in leochid copping

gyp in leachedcapping (2600 peripheral)

IDOH 570, py

propylilc andcalla

ES 5470,py

0
o

'

"

ES

2541, py

"

""'

ES

:5196, py

"

"

"

2079, py

/ chalcopyrite (cp)

ES

E] planils

bornils

(bn)

$ericitic volcanice (2660, perleVeret)

highlevelbarre.*lpyrlle; soriclllcto advancegrotIlia alllroliorl

in mixed rock types.
(:)9$O,periphorol)

5709, py
o

gypsum (gyp)

( 25 SO,periphMol)

frelh volco/iCl (2660, peripheral}

ES 5715, py

onhydrite (anhy)

iQroeite ( tar)

(py)

(2600,central}

Gyp- 1, gyp

ES 5472, py

pyrite

(287:5,intormedieta}

hydrated upper cutfate zohe

ItS

(ot(

(2710,central}

""

""

ES 2087,py

'

"

ES :5977, py

'

DOH129-A,py

"

( 29:50,plripherol}

(2875,peripMral}

"

(2950, porlpherM
)

'

(29:50, inlermedmla)

"

"

"

(29O, inlermediate)

'

(2875, inllrmldioll)

"

"

0 "choicecite"(ca)
4) motybdlflite (me)

2'o

;:5

hgh-level pyrihc ore

-;

_:o

( 2840,central

.,

Fro. 1. Summaryof the E1 Salvador sulfur isotopedata with sampleslisted in general order
of orebodyzonationand (or) paragenesisand with cursory descriptionsof lithology, geologic
occurrence,and locationwithin the deposit.

1538

. W. FIELD

AND L. B. GUSTAFSON

TABLe,2. Means and Ranges of (ll4S

Per Mil Values for

dration. The mean valuesfor anhydrite (Table 2)

exhibit small incrementsof progressive3S enrichGroupedwith respectto origin (hypogeneversussupergene),
ment for groupingswith respectto both district zona'mineralogy,orebodyzonation, and paragenesis.
tion (+9.7, +10.3, and +10.35/ofor central, interMean
Range
mediate, and peripheral zones respectively)and to
Grouping
n
/i4S
/54S
oo
paragenesis(+8.2, +9.2, +10.0, +10.3, and +12.1/o
for Early disseminated,"A" vein, "B" vein, Late
Sulfates--all
24
+7.9
--4.6
+17.0
sericite-chlorite,and "D" vein occurrencesrespecHypogene
18 +10.7
+7.3 +17.0
Supergene
6
--0.7
-4.6
+3.6
tively).
Hypogene sulfates
Perhaps t.he simplest and most straightforward
Central
12
+10.0
+7.3
+12.4
Intermediate
3
+11.8
+9.9
+14.8
interpretationof the sulfur isotopedata is in the disPeripheral
3
+12.5
+10.1 +17.0
tinction betweensulfatesof hypogeneand supergene
Anhydrite
13
+9.9
+7.3 +12.4
Central
9
+9.7
+7.3
+ 12.4
origin. Isotope fractionationtheory predicts that
Intermediate
2
+10.3
+9.9
+10.7
hypogenesulfate,equilibratedwith sulfide,shouldbe
Peripheral
2 +10.3
+10.1 + 10.5
distinctlyenrichedin aS relative to the sulfideand
Early K-silicate
3
+8.2
+7.3
+9.7
Early "A" veins
2
+9.2
+9.1
+9.4
to any supergenesulfatederivedfrom the quantitaTransitional "B" veins
2
+10.0
+9.9
+10.1
tive unidirectionaloxidation of sulfide-sulfur (Field,
Late sericite-chlorite
4
+10.3
+9.9
+10.7
Late "D" veins
2
+12.1
+11.8
+12.4
1966b;Jensenet al., 1971; and Field and Lombardi,
Gypsum--Late "D" veins
2 +11.2
+11.0 +11.4
1972).
Consistentwith this rationale, values for
Sulfides--all
40
-3.1
-- 10.1
-0.3
coarsely
crystalline
hypogenealunitein samplesESHypogene
37
--3.0
-- 10.1 --0.3
Supergene
3
-- 4.0
-- 4.4
-- 3.6 5827 (+ 17.0o) and ES-6573 (+ 14.8) are markMolybdenite
1
--0.8
edly enrichedin 3% relativeto thosefor the finely
Pyrite
23
--2.3
--10.1
--0.3
crystallineor "earthy" supergenevarieties in samChalcopyrite
9
--4.0
--5.3
--3.1
Sulfate and Sulfide Minerals

Bornire

--4.9

--5.7

--4.2

Chalcocite(supergene)

-- 4.0

- 4.4

- 3.6

5
7

--3.1
-1.3

-5.1
-2.1

- 1.5
--0.3

11

--2.7

--10.1

--1,1

--2.1
--5.1

--0.8
--3.1

Pyrite

Central
Intermediate

- -

Peripheral

Transitional "B" veins

Late sericite-chlorite
Late "D" veins

Pyritic "fringe"

1
5
4

--1.7
--1.4
--3.9

11

--2.6

--10.1

-1.1

3
2

--3.6
--4.2

--3.9
--5.3

--3.2
--3.1

Chalcopyrite

Early K-silicate
Early "A" veins

,Transitibnal "B" veins

Late sericite-chlorite

1
3

--4.7
--4.2

ples ES-7486 (+3.354o), ES-1450 (+3.654), and

ES-8233 (-1.5o).
The isotopicallylight alunite
in sampleES-8233 (-1.5Zo), gypsumin sample

Gyp-1 (-4.65/0) and jarositesin samples

ES-5827
and ES-7466 (-1.6 and -3.35/o) appearto have
derivedtheir sulfurthroughoxidationand redeposition of sulfide-sulfurin the leachedcapping. We at-

tributethe isotopically
intermediate
valuesof alunites
from samplesES-7486 and ES-1450 (+3.3 and
+3.65/) to mixing and redepositionof both hypo-

gene sulfateand sulfidesourcesof sulfur in the

supergene
environment.
However,theseintermediate
values might also originatethrough low-temperareactionsaccompanying
the
to retrograde
effeatand to the relativelysmall ture disproportionation
samplerepresentation
that emphasizes
the temporal surficial oxidation of sulfides that have been proevolution,
rat.herthanthe spatialdistribution,
of min- posed
byGranger
andWarren(1969). Theisotopieralization at E1 Salvador.
cally heavygypsumof sampleGyp-2 (+10.5),
from the uppermostcappingof the sulfatezone,
Hypogene
andsupergene
sulfate
minerals
formedsimplyby supergene
hydrationof hypogene
anhydrite,
as
did
gypsum
in
the
"D" vein (+ 11.05/)
The distinctionbetweensulfatesof hypogeneand
and
halo
(+
11.454o)
of
sample
ES-7576.
supergene
originwasbasedongeologic,
mineralogic,
Jarosite
in bothsamples
ES: 5827and7466conand textural criteria established
during field investirespectively).
gations.In accordance
with equilibrium
fractiona- tainslightsulfur(-1.6 and --3.354o,
Coarsely
crystalline
alunite
and
jarosite
in a few
tiontheory,thehypogene
sulfates
are distinctly
and
samples
similar
to
ES-5827
are
intergrown
in optical
variablyenriched
in aS relativeto associated
hypocontinuity.
This
texture,
and
other
geologic
infergenesulfides
(Fig. 1 andTables1 and2). Temthe speculation
that jarosite,
perature-dependent
fractionation
is suggested
by the ences,oncesupported
datafor hypogene
sulfates
that shownear-surfaceas well as alunite,might haveformedin equilibrium
in a verylatestageandshallow
alunite(range+14.8 to +17.054o)
to be distinctly withpyrite-covellite
environment
thatwastransitional
between
enrichedin a4Srelativeto deeperan.hydrite (range hot-spring
environments
+7.3 to +12.454o). In contrast,gypsum(range hypogeneand "classic"supergene
and Hunt, 1975). The isotopicevi+10.5 to +11.4%o)is compositionally
similarto an- (Gustarson
dence,
however,
indicates
that the jarosite,unlike
hydritefromwhichit wasderived
bylate-stage
hy-5.2

-3.2

SULFUR ISOTOPES AT EL SALVADOR, CHILE

1539

the alunite,hasnot undergone

ractionation
relative (ES: 1855 and 1809 and DDH 65) to that for the
to any sulfidemineral. Jarositehasderivedits light hypogenesulfides,especiallyprotore in DDH 500
sulfur froln the oxidation of a4S-.depleted
sulfides that directly underliesDDH 65, showsthe "chalcoand was formed later than the hypogenealunite cite" to be isotopicallymore similarto chalcopyrite
(+17.0o) with whichit is associated.
and bornitethan to pyrite (see Fig. 1, Tables 1 and
2). Supergene"chalcocite"(mean -4.0
is deHypo#ene and super#enesulfideminerals
pletedin aS relativeto the majority of pyritesanaBoth individual834Sper rail valuesfor coexisting lyzed from this suite. Although this isotopiceffect
with predictionsbasedon theory (Sakai,
sulfideassemblages
(Table 1) and mean valuesfor is consistent
1968;
Bachinski,
1969) it is unlikelyto haveformed
thesemineralsof the hypogenesuite (Table 2) exby
sulfide-sulfide
equili.briaat the low temperatures
hibit withoutexceptiona preferredorderof increasing a4S depletion in the sequencemolybdenite that prevail in supergeneenvironments..Thus, in
spite of small samplepopulations,the isotopicevi(-0.8Z0), pyrite (-2.3o), chalcopyrite(-4.0o),
observations
and bornite(-4.9Z,).
This orderis attributedto a denceis consistentwith the microscopic
which
suggest
that
"chal.cocite"
replaced
chalcopyrite
primary fractionationeffectinvolvingisotopicequi- or bornite.
libria and it is readilyevidentfrom comparisons
of
tabulated (Tables 1 and 2) and plotted (Fig. 1)
Isotopic equilibriumand 7eothermometry
data for the coexistingassemblages.
The temperaturedependency.of
isotopicfractionaThe hypogenesulfidesshow weak and imperfect
phasesis well documented
isotopictrends for mineral groupingsbasedon 9ara- tion betweencoexfsting
geneticoccurrence(Table 2). For example,mean and is a potentiallyusefulmethodof geothermometry.
8aSper rail valuesfor pyrite of "B" vein, Late seri- For sulfur-bearingmineralsthe fractionationeffect
cite-chlorite,"D" vein, and pyritic "fringe" assem- at constanttemperature is largest between sulfateblagesare - 1.7, - 1.4, - 3.9, and -2.6 per mil, re- sulfidepairs, with aS preferentiallyconcentratedin
spectively. Mean values for chalcopyriteof Early the sulfate, and is smallest but measurable between
disseminated,"A" vein, "B" vein, and Late sericite- many sulfide-sulfidepairs (Sakai, 1968; Bachinski,
1969; Kajiwara and Krouse, 1971; Czamanskeand
chloriteassemblages
are -3.6, -4.2, -4.7, and -4.2
per mil, respectively.It mustbe emphasized
that for Rye, 1974; and referencescitedtherein). For most
the fractionationfactor (,), which is
many parageneticgroupingsthe samplepopulations investigations
are small and that the ranges of the per mil values
overlap. The apparentlack of isotopictrends with

respectto the district zonationof hypogenesulfide

mineralsis probablyrelatedboth to the limited sample representationand to the inward collapseand
superposition
of late mineralizationeventsupon earlier ones.

At E1 Salvador,as is the casefor many deposits

that are characterizedby appreciablesecondaryenrichment, it is difficult to determine whether or not
pyrite, or other hypogenesulfides,servedas the
dominanthostfor the supergenesulfides. Geologists
of the Anaconda Company have concluded,on the
basisof extensivemicroscopic
examinations,that the
great bulk of the supergenesulfidesreplaceprimary
Cu-Fe sulfidesand not pyrite. Moreover, the textures displayedby supergene"chalcocite",and prestonablyindicativeof pyrite replacement,
are simply
those inherited froin their nonpyrite hypogeneprecursors.

a measure of the isotopic separation between two

coexistingminerals,is more convenientlyexpressed
as a delta (/x) value that is readily derivedfrom the
measuredaais per mil values of the mineral pair
(see Eq. 2). However, the application of delta
values (or fractionationfactors) to geothermometry
necessitates
a knowledgeof their variation with temperature, which is obtained either indirectly from
calculationsbasedon theory or preferably from direct experimentalcalibrations. With the exception
of the pyrite-chalcopyritecurve derived experimentally by Kajiwara and Krouse (1971) andthe sulfatepyrite curve predictedfroin theory by Sakai (1968)
and Ohmoto (1972), precise fractionation effects
betweenmineralscommonto porphyry-typedeposits
are largely unknownalthoughthey may be qualitatively estimatedfrom thermochemicaldata as suggestedby Bachinski(1969).
The validity of isotopictemperatureestimatesis
predicatedon the existenceof equilibrium between
coexistingmineral phasesat the time of deposition,
the preservationof this isotopicequilibrium thereafter, and the accuracyof the calibrationcurves by

Sulfide concentratesfrom four sampleslocated

vithinand beneaththe zoneof secondaryenrichment
have beenanalyzedto determinewhetheror not the
supergene
"chalcocite"
is isotopically
distinctiverela- which the calculated delta values are reduced to temthat
tive to the hypogenesulfidesand as an attempt to peratures. The coexistingmineral assemblages
identifyisotopicallythe primary hostmineral. Coin- we haveanalyzedwere free of any evidenceof superparisonof the data for the three supergenesulfides imposed Late events, although even in the best

1540

. Pl/. FIELD AND L. B. GUSTAFSON

TAm,. 3. Delta (/x) Values of Sulfate-Sulfideand Sulfide-SulfideMineral Pairs

Includingisotopictemperature(C) estimates(after data of Sakai, 1968,and Kajiwara and Krouse,1971)for coexisting

hypogeneassemblages
of El Salvador, groupedaccordingto mineralogy.

Sample

Description

ES-1910R
ESo1910V
ES-8230R
ES-8230V
ES-2699R

Early
Early
Early
Early
Early

ES-7536V
ES-8237
ES-1116
ES-8238
ES-1173
ES-7525V
ES-7576H
ES-7576V
DDH 599

Transitional "B" vein

Late sericite-chlorite
Late sericite-chlorite
Late sericite-chlorite
Late sericite-chlorite
Late "D" vein
Late "D" vein halo
Late "D" vein
Late sericite-chlorite

AGyp-py

AAnhy-py

AAnhy_Cp AAnhy_Bn APy_Cp

11.2 (550)
14.3 (465 )
10.5 (570 )

K-silicate
"A" vein
K-silicate
"A" vein
K-silicate
11.6
10.7
12.8
1.6
11.8
14.9
16.5 (400 )
15.1 (430 )

(520 )
(545 )
(485 )
(515 )
(510 )
(435 )

12.5 (510 )
13.6 (485 )
14.6 (460 )

14.0 (475)
15.9 (435 )

11.9
14.8
12.1
14.1

ACp_Bn
0.7
0.5
1.6
1.7

3.0 (115 )
3.4 (95 )
3.1 (110 )

16.5 (400 )
2.2 (185 )

samplessome recrystallizationof Early anhydrite evidence(Gustafsonand Hunt, 1975). The single

occurred during su,bsequent
mineralization. Only samplefrom our suitethat hasalsoyieldedan aprarely are the Early high-salinityand low-density parently valid oxygen isotopictemperatureis ESfluid inclusionspreserved (Gustafsonand Hunt, 2699R. Isotopicfractionation
amongquartz,plagio1975). Late assemblages
representa metasomatism clase,and biotite indicatesa minimumtemperature
and recrystallization
of Early assemblages.
As pre- of about 525C (Sheppardand Gustafson,1976)
viouslynoted,the isotopicdata show without ex- comparedto that of about485C from anhydriteceptionrelative s4Senrichments
amongcoexisting chalcopyritefractionation(Table 3).
Temperatures of 400 to 515C obtained from
minerals(Fig. 1, Tables 1 and 2) that are entirely
consistentwith those establishedfrom theory or ex- gypsum-pyriteand anhydrite-pyritepairs of Late

periment(Sakai,1968; Bachinski,1969; Kajiwara "D" veinandperipheralsericite-chlorite

assemblages
and Krouse,1971.The deltavaluesgivenfor various are 'not much different from thoseobtainedfor the
sulfate-sulfide
pairs from sampleslistedin Table 3 Early assemblages,
and they are considerably
higher
showa generalbut imperfecttendencyto increase than the valuesof lessthan 350C inferredby Gusamongthe Early to Late and the centralto peri- tarsonand Hunt (1975). Moreover, there is subwith the isotopicgeothermompheral assemblages.These trends are consistent stantialdisagreement
with isotopicfractionation
effectsthat accompaniedetry basedon pyrite-chalcopyritepairs from these
temdecreasing
temperatures
duringthe paragenetic
and samesamples. Althoughthe anhydrite-sulfide
zonal evolution of metallization-alteration.

Thus,

peratures appear to be too high, the 95 to 185C

pairs
theisotopic
andgeologic
evidence
collectively
support range calculatedfrom four pyrite-chalcopyrite
our contentionthat leastan approachto equilibrium utilizing the experimentally derived fractionation
wasattainedin our samplesoverthe time and space curvereportedby Kajiwara and Krouse (1971) appearsto be too low. Lastly, data for the groupof 11
of hypogene
mineralization
at E1 Salvador.
Isotopictemperatures
(see Table 3, parentheses) pyrite samples(Table 1 and Fig. 1, bottom) suggest
have been determinedfrom the delta values for ap- further evidenceof disequilibrium. With one excepare repropriatemineralpairsby utilizingthe theoreticaltion, their compositions(--3.9 to -1.1)
fractionationcurve for sulfate-pyrite(Sakai, 1968) markablyuniform and relativelyenrichedin s4Sfor
and the experimental
fractionation
curvefor pyrite- sulfidesdepositedat relatively low temperaturesin
chalcopyrite
(Kajiwaraand Krouse,1971). Tem- the outer and upper parts of the pyritic "fringe" and
peratures
rangefrom about460 to 570Cfor an- beyondthe sulfatezone as presentlyexposed.
hydrite-chalcopyrite
pairs of the Early K-silicate, Although severalof the foregoingproblemswill
"A" vein, and Transitional"B" vein assemblages,be consideredat greater length, the causesof these
and from 400 to 545C for gypsum-pyrite
and an- anomaloustrendsand high and low temperatureestihydrite-pyrite
pairsof theLate sericite-chlorite
and mates are uncertain. Isotopic disequilibrium is
probably t:he dominant factor, but further experi"D" vein assemblages.
mental work is needed on the various common minIsotopictemperatures
of the Early assemblages
(465 to 570C)are withinthe 350 to >650C eral pairs of sulfate-sulfideand sulfide-sulfidesys-

rangeindicated
byfluidinclusion
andothergeologictems.

SULFURISOTOPESAT EL SALVADOR,CHILE

154I

Implicationas to 1o2
and pH
Recent papers by Sakai (1968) and Ohmoto

(1972) havedemonstrated
a needfor cautionin applyingthe widelystatedgeneralizations
that sulfides
derivedfrom a deep-seated
sourcenecessarily
have
isotopiccompositions
closeto that of meteoriticsulfur ("S =0), and that wide variationsfrom this
value are diagnosticof biogenicfractionation. As
elegantlydevelopedby Ohmoto (1972), the
per rail valuesof individual sulfateor sulfideminerals

are indicativeof source,or the composition

of total
sulfur($a4Szs)
in thesystem,
onlywhenotherparameters suchas T, /%.o,and pH are known, as these
control the types and abundancesof the various

sulfurspecies
in solution.The 13 samples
for which
we have isotopicanalysesof sulfate-sulfide
pairs
representthe wide rangeof depositional
conditionsin

]50

250

TC

350

FIG. 2. Apparent regions of (A) [o._,-pHfor coexisting

sulfate-sulfideassemblagesat 250C as defined by the ranges
of S per mil values (sulfates +5 to +15%; sulfides --5 to
--1%o) after Ohmoto (1972, fig. 5), and (B) Io..-T as defined by the range of 15'Sper mil values for pyrite (--10 to
0o) over the pH range from 2 to 6 and after Ohmoto (1972,
figs. 4, 5, 6, and 7) in part.

the diagramsas might be expectedif acidity,oxygen

time and spaceat E1 Salvador;from early to late fugacity,and temperaturehad beenindependentor

externally controlledvariables during the evolution
and from centerto periphery. Early assemblages
were formedat pressuresand temperatures
closeto
thosethat prevailedduringfinal consolidation
of the
porphyry magrnasand in equilibrium with fluids
that were in equilibriumwith the magmas.The Late
assemblages
were formed at much lower pressures
and temperatures
and in equilibriumwith fluidsthat
were largely heated meteoricwaters then reacting
with t.hecooling,mineralized,and altered intrusive

of mineralizationat E1 Salvador. On the contrary,

our dataindicatethat two of thesevariables(presumably/o.o
and pH) were internallycontrolledor buffered. Becausethe hydrothermalsystemwas satu-

rated with respectto both anhydriteand someCu-Fe

sulfide throughoutits evolution,this conditionmay
have servedas the effectivebufferingcontrol. However, many other controlling reactionsare possible
center.
and particnlarly thoseinvolving iron-bearingoxides
Althoughchemical
parameters
suchas/o.o
andpH and silicates. Presumablythe actualmechanismsof
presumablyvaried considerably
throughoutthe min- buffering and mineral reaction were very complex
systemsconsideredby
eralizationepiso.de
in both time and space,the ob- as in the multi.component
servedmineralassemblages
are not sufficientlyre- Helgeson(1970).

strictive to define these variableswith certainty.

However,the/o.o-pHregiondefinedby isotopicassemblages
of snlfate(+5 to +15Zo) andsulfide(--5
to -1/,o) mineralsof the E1 Salvadorsuiteis given
in Figure 2A. T.he illustrationis adaptedfrom
Ohmoto(1972; fig. 5, p. 559) anduseshispredicted
isotopiccontoursfor sulfateand pyrite with changing fo2andpH at 250Candotherassumptions
(including a4Ss= 0) cited therein. The /o.,-pH
regionpermittedby our isotopicdata formsa relatively narrow band acrossthe diagram. At higher
temperatures,the isotopicallyequivalentband remainsalmostas narrowbut shiftsto regionsof higher
fo2 This isotopiceffectis shownin Figure 2B for
temperaturesranging from 150 to 350C. Again,
the illustrationis adaptedfrom Ohmoto (1972; figs.
4, 5, 6, and 7) and the narrowbandis derivedfrom
the data for E1 Salvadorpyrites (-10 to 0%o) assuminga pH range from 2 to 6. Although thermochemicaldata are not yet adequateto computethe
stabilityfield acrossthe rangesof temperatureand

Reservoirand composition
ol total sulfur
The occurrence of sulfate-sulfide assemblages
throughoutthe mineralizationsequenceat E1 Salvador renders the depositwell suited to the study of
two commonassumptions.These are (1) the compositionalsimilarityof "magmatic"hydrot.hermal
sul-

fur to meteoriticsulfur (00 by definition)and (2)

the conceptof an "infinite" sulfur reservoir in hydrothermalsystems.
On the basisof theoreticalpredictionsdeveloped
by Sakai (1968) and Ohmoto (1972), the systematics of sulfate-sulfidefractionation in porphyry-type
environmentscan be summarizedas in Figure 3. For

any populationof coexisting sulfate-sulfideassemblagesformedunderequilibriumconditionsand over

a range 'of temperatures,fractionationtrends portrayed by the graphicaldistributionof the sulfate
and sulfide$aSper mil valuesversustheir respective
delta valueswill plot as two straightlinesprovided
t.he hydrothermal
reservoirfor sulfurwas of infinite
pressureappropriate to our mineral assemblages,it supplyand maintaineda constantisotopiccomposiis clear that the isotopicdata .definea rather narrow tion and a constantproportionof oxidizedto reduced

of sulfurthroughout
mineralization.Because
regionin/oz-pH-Tspace.Theydonotscatteracross species

1542

i "?-'"'"'

C'.W. FIELD AND L. B. GUSTAFSON

XSO-XH

& ANHYDRITE
(GYP.)
' S042+20-

PYRITE
'H2S
EL

sulfateand sulfidespeciesin the solution. As illustrated in Figure 3, a mineralexhibitsisotopicsimi

larity to 8aSzsof the systemonly as its aqueous
precursorbecomesthe dominantsulfur speciesin the

SALVADOR

system,

The 8a4Sper rail valuesof coexistingsulfate-sulfide

assemblages
from E1 Salvador (Table 1) are plotted
with respectto their delta values (Table 3) in Figure 4. Various symbolsrepresenting
the data points
indicate different paragenetic-alteration
occurrences
of the samples.For manyof the samplestwo sulfide
or sulfatemineralswere analyzed,and thesesamples
are representedby two points in both the sulfate
and sulfideregions. Data pointsfor pyrite-bearing

[] SULFATES

+15-

,:

[] SULFIDES

+10 -

assemblages
from the Late "D" veinsand fringing
zone of sericite-chlorite alteration exhibit remark-

ably goodlinearity. However,thosefor bornitechalcopyrite

assemblages
of t.heEarly background
Ksilicateand "A" vein occurrences
of the deep central
zone showconsiderablymore scatter.

10

15

20

/ sulfate-sulfide
Fro. 3. Theoretical variations in the S

per mil values of

.2oj

coexistinganhydrite and pyrite in responseto changingT

:and ratios of aqueous SO, - to H2S. Isotopic trends and
temperatures determined from sulfate-sulfidefractionations
calculated by Sakai (1968), compositionof iSx, assumed
o be 0 per rail, and shadedareas representingisotopicrealms
defined by E1 Salvador sulfatesand sulfides.

,of the temperaturedependency

of the isotopicfrac':tioaation,extrapolationof the two linesto infinitely
hgh temperatureleadsto their convergence
at the
'0 delta value. The point of convergence
at high
temperature(fi, = 0) theoreticallymarksthe isotopic
composition
of total sulfur (8aSzs)in t.he system.
Isotopicvariationsbetweencoexistinganhydriteand
pyrite are shownin Figure 3 as a functionof differ-

(1)

. ..

ing temperatures and mole fractions of aqueous

oxidized(SO --) and reduced(HS) sulfur species

in a hydrothermal system for which 8aSz is assumed to be 0 per rail. The shadedareas mark the
measured isotopic reahns of coexisting sulfates
and sulfidesfrom E1 Salvador. Although fractionation effectsbetweenthe coexistingsulfateand sulfide
mineralsare relatively large, thosebetweenthe sulfur-bearing minerals and their aqueousprecursors
are presumablynegligiblefor the sulfatesand very
small (less than 1,) for the sulfidesaccordingto
Sakai (1968). As emphasized
'bybothSakai (1968)
and Ohmoto (1972), the isotopiccompositionof
sulfateand sulfidemineralsdependsnot only on temperatureand 8aSzof the system,but also on o.o
and pH whichcontrolthe mole fractionsof aqueous

300"

I I

10

15

20

Z sulfate-sulfide
Fro. 4. Estimatesof S

for the E1 Salvadorhydro-

thermalsystem
as determined
from convergent
linesof regression
for plotsof sulfateandsulfide
15'S
permil values
versus
delta(/x) values
of coexisting
sulfate-sulfide
mineral
pairsfor paragenetic
sample
populations
of EarlyK-silicate

background
and"A"veinassemblages
(1) andLatesericitechloritebackground
and"D" veinassemblages
(2).
Anhy--Cpor Bn; Early K-silicate
background

(1) O Anhy--Cp
orBn;Early"A"veins

[] Anhy--Cpor Py; Transitional

"B"veins
Anhyor Gyp--Py; Late"D" veins

(2) Anhy--Cp
orPy;Latesericite-chlorite
background.

SULFUR ISOTOPES AT EL SALVADOR, CHILE

1543

The lines of regressiondesignated2 in Figure

4 are for the per mil-delta value points of sulfatesulfide pairs from pyrite-bearing assemblagesof
Late "D" vein and "background' sericite-chlorite

stages of mineralization. Gustarson and Hunt

mineralization.

contained sulfur derived from these and the under-

Both lines intersect the vertical iso"-

(1975) haveportrayedEarly mineralizationas having been closelyrelated to the emplacementof porphyry magmas,with the hydrothermalfluids and

topic axis (where /x _-0) at +6.8 per rail. It may lyingmagmachambers.In supportof their interprebe inferred from the intercept and slopesof these tation, the indicated bulk compositionof sulfur
in the Early fluids is closeto the 0 per rail
two lines that the aSzswas -I-6.8 per rail and the (+1.6)
mole ratio of aqueous SO42- to H2S was about value that is commonly acceptedfor "magmatic"
70:30 in the late-stagehydrothermalsystemat E1 hydrothermalsulfur (see Rye and Ohmoto, 1974).
Salvador. Correlation coefficientsfor the per rail This similarity also arguesagainstspeculationthat
sulfate-deltavalue (r = 0.746) and per rail sulfide- the abundanceof sulfate at E1 Salvador might be
delta value (r---0.938)
lines of regressionon attributableto remobilizationof evaporitesthat conthe 10 mineral-pair populations are statistically ceivablymay 'bepart of the Jurassicor Lower Cresignificant
at the 95 and99 percentconfidence
levels, taceousmarine sectionunderlyingthe Indio Muerto
respectively. The excellentlinearity and converg- district. Gustafsonand Hunt (1975) have interence expressedby these data are rather unexpected pretedthe Late fluidsas .havingconsistedlargely of
in view of the apparentlack of isotopicequilibrium meteoric water, but the source of the abundant and
sulfur that was fixed
previouslydescribedfor the Late pyrite-bearingas- isotopicallyheavy (+6.8)
semblageswhich mostly formed at temperaturesbe- during Late mineralizationis not as clearly indicated
low 350C. The two pointsthat deviatemost from by the geologicevidence. Possiblesourcesmight
linearity are the anhydrite-ehalcopyrite
pairs from include (1) the underlyingmagma chambersthat
samples(ES: 8237 and 1116) of fringing sericite- continuedto provide sulfur and aqueousfluids, (2)
chlorite mineralization. Is it possiblethat there is a additionalsulfur derivedfrom surroundingwall rock
syscloser approach to isotopic equilibrium, or post- by the Late convectingmeteoric-hydrothermal
was redepositionalpreservationof that equilibrium,in the tem, and (3) Early sulfur that subsequently
anhydrite-pyritepairs than in the anhydrite-chalco- mobilizedand emplacedat ,higherelevationsduring
pyrite (or bornite) pairs? The extent to which the Late hydrothermalactivity. The isotopicevikinetic factorsmay have contributedto this linearity dencemay indicatea choiceamongthesealternatives.
Isotopicevidencefor the apparentchangein
is unknown, but they are probablyminimal as the
assemblageg
were formed over a wide range of tem- betweenEarly and Late stagesof mineralizationsuggeststhat the Late sulfur was not simply derived
perature, time, and space.
from
fluids continuingto emanatefrom the underlyData points for anhydrite-chalcopyriteand anhydrite-bornite pairs from Early disseminatedK-sili- ing magmachambersand that (2) or (3) are more
cate backgroundand "A" vein assemblages
shown in probableinterpretations. Although we have no isoFigure 4 do not form tight linear groupings. Lines topic data for tracesof sulfur containedin the volof regression(designated1 in Fig. 4) for the per mil canic wall rocks that surround the E1 Salvador oresulfate-delta value and per rail sulfide-delta value bodies, the +6.8 per rail value indicated for Late
sulfur is within the range measuredfor igneousrocks
data convergeon the vertical isotopicaxis at +1.5
and +1.7 per rail, respectively. Nonetheless,cor- (Ault, 1959; Thode et al., 1962; Smitheringaleand
relationcoefficients
(r) for theselinesbasedon nine Jensen,1963; and Sasaki,1969), and sucha source
mineral-pairpopulations
are 0.808 and -0.763, re- cannot be excludedby the presentdata.
A mass balance calculationfor sulfur now prespectively,and t'helinearityis statisticallysignificant
at confidencelevels of 95 percentor higher. How- served within the sulfate zone indicates that t.he bulk
ever, other groupingsor line "fits" may be postu- isotopiccompositionis approximately+6 per mil belated for thesescattereddata. The slopesof t,hetwo causethere is roughly 5 to 6 times more sulfur conregressionlines suggestthat the ratio of aqueous tained in aS-enriched anhydrite than in the
SO42- to HeS was slightly more than 40:60. Ac- a%-depletedsulfides.It is thereforetemptingto intercordingly,the isotopicdataindicate6hanges
in a4Sz, pret the relatively heavy sulfur of Late mineralization (+6.8) as havingbeenlargely derivedby re(from +1.6 to +6.8,) and xSO42-: xI-I2S (40:60
to 70:30) during the evolutionfrom Early copper- mobilization of sulfur fixed during the period of
and Hunt (1975)
bearing to Late pyrite-bearing assemblagesat E1 Early mineralization.Gustafson
Salvador.
.have noted the removal of Early copper from the
It is temptingto interpret the two points of con- halosof Late "D" veinsdeepin the deposit,and the
vergencein Figure 4 as representinga real difference enrichmentof chalcopyrite,bornire,and enargite in
in aSzsof the reservoirbetweenEarly and Late these veins at higher elevationsis presumablythe

1544

C. W. FIELD AND L. B. GUSTAFSON

redepositionof this copper. However, additional

sulfurwasfixed as bothanhydriteand pyrite in these
veins and halosat even t,he .deepestlevels of exposure. If there was leachingof anhydriteby the Late
mineralizationfluids,presumablyit was confinedto
the deeperparts of the deposit.
Other difficultiesare inherentto thisinterpretation.
The apparentagreementbetweenestimatesof a4Szs
derived from mass balance calculationsfor Early
sulfur (+6y4o) of the sulfatezoneand that from regressionline convergencefor Late sulfur (+6.8o)
of the "D" vein and sericite-chloriteassemblages
is
probablycoincidental. This is becausethe relative
abundanceof anhydrite versus sulfideswas largely
controlledby the relative activitiesof calcium ions
versusthose of iron and copperduring mineralization and had little to do with the isotopiccomposition of the sulfur. Althoughit is difficultto estimate
closelythe total mass and proportionsof sulfurbearingmineralsdepositedin the E1 Salvadorhydrothermal system,now that much of it has been relnovedby erosionand supergeneactivityand much
lies hidden at depth, Gustason
and Hunt (1975)
have indicatedth/t up to 10tons of sulfur may have
been originally deposited. Probablyabout one-half
of this amount was emplaced during Late stage
alteration-mineralization.

Unless

this estimate

for

in 1 kma of rock,a volumeof 20 kma wouldprovide

enoughpotentialreducingcapacityto form the re-

quiredamountof sulfidesulfur. However,simple

reactionssuchas the .directsulfidationof magnetite
or biotite are not adequateto provide the necessary
reducingpotential,and thus roughlyone-halfof the
ferrous iron in 20 km a of rock would have to have

been oxidized. Although we do not have definitive

data for the ferrous:ferric ratios of mafic silicates,
the lack of visualevidencein theserocksfor the pervasive oxidation of any element,other than sulfur,
arguesagainstthis model.
If the Late sulfur had beenderivedfrom country
rocks beyondthe limits of obvioussulfur addition,
mostof the previouslymentionedproblemsmight be
avoided. The sulfur from a sourcein the country
rockspresumablywould have beenreducedand possibly isotopicallyhomogeneous. However, there is
no direct

evidence that

sulfur

has been removed

from theserocks,or that it ,hadthe appropriateisotopic composition.

Other groupingsand associatedline "fits" may be
postulatedfrom the data plotted in Figure 4 and
theselead to markedlydifferentinterpretations.For
example,threepartly overlapping"isotopic"populationsare suggested
by the distributionsof thesedata.
They consistpredominantly,but not exclusively,of
assemblages
representingEarly .disseminated,
Early
"A" vein and Transitional "B" vein, and Late sericite-chloriteand "D" vein mineralization. Regression
linesfor all threepopulations
convergeat about +6
per rail. They suggestan isotopically
heavyand constant value for aSzsthroughoutthe mineralization
sequenceand isotopicvariations resulting largely

the quantity of Late sulfur is far too large, or the

amountof Early sulfuris far morethan is projected
below the deepestlevel of exposure,there was not
enoughEarly sulfur to accountfor all that was depositedin the Late event. It is also difficultto envisage a mineralizationprocess,which derived its
sulfur by the leachingof mixed sulfateand sulfide
assemblages
havingdifferentsolubilitiesand isotopic from changingmoleratiosof aqueousSOa2 to H=S
compositions,
that wouldmaintaina constanta4Szs (90:10 to 65: 35) with paragenesis.This interpreand a constant ratio of oxidized to reduced sulfur
tation, however,is entirely speculativebecauseof the
speciesover the parageneticinterval represented
by small numberof samplesin the earlier populations
the Late samples. Perhapsthe mostseriousproblem and becauseof isotopicand parageneticoverlap
is the reductionpotential required for converting amongthe dataand samplescomprising
thesepopularge amountsof sulfatesulfur, derivedfrownanhy- lations.
drite, to sulfide sulfur forming Late pyrite, and
On the basisof recentunpublishedexperimental
especiallyat temperaturesextending well below studiesby Ohmotoand Rye that indicateisotopic
300C. Althoughthe indicatedmoleratio of oxidized similaritybetweenchalcopyrite
andcoexisting
HeS,
to reduced sulfur increasedparageneticallyfrom and of the inordinatelylarge fractionations
we have
Early to Late assemblages,
the isotopicshiftof $aSz. measured
betweenpyrite-chalcopyrite
pairs,Ohmoto
and mass balanceconstraintspreviously noted re- (1975, writ. and oral commun)has suggested
that
quirethat sulfurderivedfrom Early anhydritebe the corrections
of our pyrite data may be warranted.
dominantsourcein this model. Approximately10s The correctioninvolvessubtracting--3 permil (Table
tons of sulfate sulfur would have to have been re-

3, average
Apy--ep
value)fromeachof theaSpermil

ducedwit.hin a relativelysmallvolumeof rock that valuesfor ,pyrite(Table1). Hence,thiscorrection

was probablyless than 20 km. The apparently transformsthe per mil valuesfor pyriteto thoseof
dominant chemical trend to oxidation of sulfur dur-

"chalcopyrite"
equivalents.
Although
thevalidityo

ing both Early and Late periodsof mineralization these transformations are uncertain at best, the cor(Gustafsonand Hunt, 1975) would have to have recteddata whenplottedon a diagramsimilarto
geologic
interpretabeenreversed. Estimating10 tonsof ferrousiron Figure4 permita verydifferent

SULFUR ISOTOPES AT EL SALVADOR, CHILE

1545

tion. Positions
of thecorrected
anhydrite(gypsum)- their originalproportions
beyondthe top of thiszone
pyrite data,whichoriginallyformedthe majorityof or l?hroughout
the entire deposit. The sulfate:sulthe data pointsfor the regressionlines designated2 fide mineral ratios presumablywere lower toward
in Figure 4, are shiftedto the right or downward the outer limits of anhydrite.deposition
and in the
and to the right by three units. As a consequence, fringing zone of abundantpyrite. Moreover, it is
the correcteddata plot more closelyas singlelinear possiblethat there were large volumesof rock in the
trends that are aligned with the anhydrite-copper upper and outer zonesin whichonly sulfideswere
sulfide data points (regressionlines designated1, deposited. The bulk isotopiccomposition
of sulfides
Fig. 4), and the entire set of isotopicdata points in thesezoneswould presumablybe lighter than 0
more nearly approximatesa singlepopulation. Con- per mil, especiallyif therehad beenany effectof
vergenceand slopesfor the lines of regressionsug- depletionduringformationof Early sulfate-riehasgest a value of about +2 per mil for a4Szsand a semblagesof the deep central zone becauseof a
moleratio of about50:50 for aqueousSO42-to HaS finite sulfur reservoir.
in the hydrot.hermal
system. This modelimpliesa
Elevensamples
werecollected
from the uppermost
single sourceof sulfur, rather than two sources,for and outermostparts of the pyritic zone as presently
Early through Late stagesof mineralization-altera- preservedto determinethe existenceof any such
tion. The implication is that sulfur continuedto isotopic treads. With one exception (ES-5470,
emanatefrom the underlyingmagma chamberas -10.1), the 3S valuesrangefrom -3.9 to -1.1
meteoric waters invaded the cupola region of the per rail (see Tables 1 and 2) and thus they are isomineralizedintrusivecomplex. To what extent there topicallynot as light as wouldbe expectedhad these
may .havebeenremobilization
of heavysulfurorigin- pyritesequilibratedwith anhydriteat t,helow temally depositedas Early anhydrite, and later con- peraturespostulatedfor fringingmineralization.This
tributed to the apparent+2 perrail compositionof isotopicuniformity and small a4S depletionof the
8a4Szsfor the total hydrothermalreservoir, is in- pyrite is puzzlingin that the outer and upperparts
determinatefrom our data and the present state of of the depositare wherethe effectsof low temperathe "art." A further implicationof the singlelinear ture and changingEh and pH should,producethe
trends, if real, is that the ratio of oxidized to reduced largestisotopicvariationsin the sulfides. We cannot
sulfur in solutionremainednearly constantover the offer any plausiblereasonfor this constancy
of comtime and temperaturerangeof mineralization. Suc.h position other than to suggestthat it represents
a condition might have prevailed if foo.was exter- some kind of "frozen" equilibrium from a higher
nally controlledby conditionsin the underlyingfrac- thresholdtemperatureand failureto re-equilibrateat
tionating magma chamber,but it conflictswith the subsequently
lower temperaturesof deposition.
previousargumentthatfo2wasprobablyan internally
The exceptionally light pyrite of ES-5470
controlled variable.
(-10.1%) is from a nearly unaltered ignimbrite.
The availabledata do not warrant further specula- SampleES-5472 (-3.9%o) representsa similarvoltion. Doubts remain concerningboth the extent of caniclithologywith more localsericitization
only 40
isotopic equilibrationamong the pyrite-bearingas- metersfrom ES-5470,andthis pyrite is alsodepleted
semblagesand the true meaning of the linear con- in a4Srelative to other sulfidesof the fringe zone.
figurationsshow in Figure 4. The scatter of data We interpret t,he aS-depletionof thesedisseminated
points for the anhydrite-coppersulfide assemblages pyritesto somelocalphenomenon,
0erhaps
fractionaallows other groupings and interpretations. This tion accompanying
diffusion,rather than to a broader
scatter probably indicates that the a4z of the mass 'balance effect related to a limited reservoir
reservoirand the ratio of oxidizedto reducedspecies of sulfur.
of sulfur did not remain constant throughout the

complex series of events that accompaniedEarly

alteration-mineralization (Gustafson and Hunt,
1975). The changefrom Early to Late environments
was probablyevolutionaryrather than abrupt between the two separatestagesof mineralization,and
someretrogradeeffectsmight be expected.
The assumption
of an effectivelyinfinitereservoir
of sulfur,whichis implicit in constructions
by Sakai
(1968), Ohmoto(1972), and our Figures3 and 4,
must be questioned. Although the sulfate zone as
presentlyexposed.containssubstantially
more sulfate than sulfide minerals, we have no measure of

Conclusions

The speculativeinterpretationsofferedhereinmust
be consideredmore as questionsthan as answers.
Clearly we have a need for additionalsamplesand
analytical data. Nonetheless,our results illustrate
the potentialwealthof informationthat may be derived from sulfur isotopestudiesof coexistingsulfate-sulfideassemblagesin depositsfor which t,he
spatial and temporal complexitiesof mineralization
are known. In addition, there is a need for further

experimentaldeterminationandcorroborationof frac-

1546

C. W. FIELD AND L. B. GUSTAFSON

tionation effects between

sulfide minerals.

the common

sulfate and

Acknowledgments
We have benefittedfrom discussionswith many

Field, C. W., and Moore, W. J., 1971, Sulfur isotope study

of the "B" limestone and Galena fissure ore deposits of
the U.S. mine, Bingham mining district, Utah: ECON.
G.o% v. 66, p. 48-62.
Field, C. W., Jones, M. B., and Bruce, W. R., 1971, Sulfur
isotopic compositionof Cordilleran hydrothermal sulfides
and the role of Eh-pI-t (abs.): Geol. Soc. America, Abs.
with Programs, 1971, v. 3, n. 2, p. 118.
1974, Porphyry copper-molybdenum deposits of the
Pacific Northwest: Am. Inst. Mining Metall. Petroleum
Engineers Trans., v. 255, p. 9-22.
Granger, H. C., and Warren, C. G., 1969, Unstable sulfur
compoundsand the origin of roll-type uranium deposits:
Ecoa. G.ot.., v. 64, p. 160-171.
Gustarson,L. B., and Hunt, J.P., 1975, The porphyry copper depositat E1 Salvador, Chile: EcoN. G.o% v. 70, p.

colleagues,particularly John P. Hunt of Scripps

Institutionof Oceanography,
Harold C. Helgesonof
the University of California (Berkeley), Hiroshi
Ohmotoof the Pennsylvania
StateUniversity,Hugh
P. Taylor, Jr., of the California Institute of Technology,J. JulianHemleyand RobertO. Rye of the
857-912.
U.S. Geological
Survey,and NicholasF. Davis of
H. C., 1970,A chemicaland thermodynamicmodel
the AnacondaCompany. Preliminaryreviewsand Helgeson,
of ore deposition in hydrothermal systems: Mineralog.
valuable criticismsof this manuscriptwere kindly
Soc.America Spec.Paper 3, p. 155-186.
givenby N. F. Davis,H. Ohmoto,and R. O. Rye. Jensen, M. L., 1971, Provenance of Cordilleran intrusives

We are particularlygratefulto H. Ohmotoand R.

O. Rye for bringingtheir unpublished
work to our
attention.

The senior author wishes to acknowl-

and associatedmetals: EcoN. G.ot..,v. 66, p. 34-42.

Ashley, R. P., and Albers, J.P., 1971, Primary and
secondary sulfates at Goldfield, Nevada: EcoN. Gso.., v.
66, p. 618-626.

Kajiwara, Y., and Krouse, H. R., 1971, Sulfur isotope

partitioning in metallic sulfide systems: Canadian Jour.
Earth Sci., v. 8, p. 1397-1408.
Lange, I. M., and Cheney, E. S., 1971, Sulfur isotopic reconnaissanceof Butte, Montana: EcoN. Gso.., v. 66, p.

edgeboththe NationalScience
Foundation,
under
the auspices
of its InternationalDecadeof Ocean
ExplorationProgram(t.he NazcaPlate Project),
for the opportunity
of visitingChilein 1974,and 63-74.
Dr. AlvaroTobarB., Superintendent
of Geology
for Laughlin, A. W., Rehrig, W. A., and Mauger, R. L., 1969,
K-Ar chronology and sulfur and strontium isotope ratios
Compania
de CobreSalvador,for an outstanding at the Questa mine, New Mexico: ECON. Gso.., v. 64, p.
tourof theE1Salvador
property.Finally,weextend 903-909.
Hiroshi, 1972, Systematics of sulfur and carbon
our thanksand appreciation
to the Anaconda
Com- Ohmoto,
isotopes in hydrothermal ore deposits: EoN. Gso.., v.

panyfor thefinancial
support
of thisstudyandfor

permission
to publishtheseresults.
C. W. F.
DEPARTMENT OF GEOLOGY
OREGON STATE UNIVERSITY

CORVALLIS,
OREGON
97331
L. B. G.

RESEARCHSCHOOLOF EARTH SCIENCE

THE AUSTRALIAN NATIONAL UNIVERSITY

C^NBERRA,
A.C.T., AUSTRALIA
2600

July17,1975;July29,1976
REFERENCES

67, p. 551-578.
Petersen, Ulrich, 1972, Nuevas investigacionesde yacimientos
Peruanos: Soc. Geol. Peru Bol., v. 42, p. 37-52.
Rye, R. O., and Ohmoto, Hiroshi, 1974, Sulfur and carbon
isotopes and ore genesis--a review: EoN. Gso.., v. 69,
p. 826-842.
Sakai, Hitoshi, 1968, Isotopic propertiesof sulfur compounds
in hydrothermal processes: Geochem.Jour. (Japan), v. 2,
p. 29-49.

and Yamamoto, Masahiro, 1966, Fractionation of sulfur

isotopesin and preparation of sulfur dioxi.de--an improved
technique for the precision analysis of stable sulfur isotopes: Geochem.Jour. (Japan), v. 1, p. 35-42.
Sasaki, Akira, 1969, Sulphur isotope study of the Muskox
intrusion, district of MacKenzie: Canada Geol. Survey
Paper 68-46, 68 p.

Sheppard,S. M. F., and Gustarson,L. B., 1976,Oxygen and

hydrogen isotopesin the porphyry copper deposit at E1
Salvador, Chile: EcoN. GEOl..,v. 71, p. 1549-1559.
Smitheringale,W. G., and Jensen,M. L., 1963, Sulfur isotopic compositionsof the Triassic igneousrocks of eastern
241-259.
United States: Geochim. et Cosmochim.Acta, v. 27, p.
Bachinski,D. J., 1969, Bond strength and sulfur isotope
1183-1207.
fractionationin coexistingsulfides: ECON.Grot.., v. 64, p.
Thode, H. G., Monster, J., and Dunford, H. B., 1961, Sul56-65.
phur isotopegeochemistry: Geochim.et Cosmochim.Acta,
Czamanske,G. K., and Rye, R. O., 1974, Experimentally
v. 25, p. 159-!74.
determinedsulfur isotopefractionationsbetweensphalerite
H. G., Dunford, I-t. B., and Shima, M., 1962, Sulfur
and galenain the temperaturerange600 to 275C: EcoN. Thode,
isotopeabundancesin rocks of the Sudbury district and
Go-., v. 69, p. 17-25.
their geologicalsignificance:EcoN. G.ot..,v. 57, p. 565Field, C. W., 1966a,Sulfur isotopeabundance
data, Bingham
578.
district, Utah: Ecoa. G.o-.,v. 61, p. 850-871.

1966b,Sulfur isotopicmethodfor discriminatingbetween

sulfatesof hypogeneand supergeneorigin: EcoN.
APPENDIX

Ault, W. U., 1959,Isotopicfractionationof sulfur in geochemicalprocesses,

in Abelson,P. H., ed., Researches
in
geochemistry:New York, John Wiley and Sons,Inc., p.

v. 61, p. 1428-1435.
1973, Sulfur isotope abundancesin hydrothermal sul-

fate-sulfideassemblages
of the American Cordillera (abs.):
Geol. Soc. America, Abs. with Programs, 1973 (Ann.
Mtg.), v. 5, n. 7, p. 619.
and Lombardi, G., 1972, Sulfur isotopic evidence for
the supergeneorigin of alunite deposits,Tolfa district,
Italy: Mineralium Deposita,v. 7, p. 113-125.

Descriptionof the E1 Salvadorsampleslisted in

approximate
orderof .orebody
zonation(deepcentral
to shallowperipheralzones) and or 1aragenesis
(Early to Late mineralassemblages),
including
host
rock,minecoordinates
and elevation(meters),rain-

SULFURISOTOPESAT EL SALVADOR,
CHILE

1547

halo of vein containsminor chalcopyriteand aneralogy of alteration and vein assemblages,

parahydrite; anhydritelargelyhydratedto gypsum.
geneticoccurrence,
and mole ratiosof sulfateto sulES-7486:
Pyroclastic;19,340N-8,740 W, 2,875m;
fide sulfur (see text for detailedelaborationof samperipheral;sericitichostin the pyritic fringe cut
ple groups).
by Late "D" vein of quartz and pyrite; finely
ES-1910: Andesite; 19,894 N-8,160 W, 2,400 m;
crystalline
supergenealunite fills vugs.
central; Early disseminatedanhydrite-borniteES-1855: Andesite; 19,580 N-8,519 W, 2,710 m;
chalcopyritewith strongbiotiticK-silicatealteraperipheral;pyritichostwith seri.cite-kaolinite
altertion; cut by "A" veinsbearingquartz,K-feldspar,
ation;
supergene
"chalcocite,"
with
pyrite,
replaces
anhydrite,bornite,and chalcopyrite;mole ratio
original hypogenepyrite-chalcopyrite
assemblage.
sulfate/sulfidesulfur approximately7:1, somewhat lower in the veins.

DDH 65-182m: Andesite; 20,400 N-8,610 W, 2,630

m; intermediate; strongly enriched "chalcocite"-

ES-8230: "K" porphyry;19,706N-7,829 W, 2,400

pyrite ore in host alteredto kaolinite-sericite
asm; central; low intensityEarly disseminated
ansemblage.
hydrite-chalcopyrite-bornite.with
K-silicatealtera- DDH 599-24m: Andesite;20,385 N-8,630 W, 2,570

tion; cut by Early "A" veinsbearingquartz,'bornm; intermediate;host with biotite-chlorite-sericite

ite, chalcopyrite,and anhydrite.
alteration containschalcopyrite-pyriteprotore beES-2699: "X" porphyry;19,875N-8,200 W, 2,400
low DDH 65.
m; central; Early disseminated
anhydrite-borniteES-1809: Andesite; 19,752 N-7,597 W, 2,710 m;
chalcopyritewith moderateK-silicate alteration;
central; host wit,h kaolinite-sericitealteration concut by Transitional"B" veinbearingquartz,an,hytains strong "chalcocite"enrichmentof hypogene
drite, and chalcopyrite;mole ratio of sulfate/sulchalcopyrite-bornite
assemblage.
fide sulfur approximately6:1 in the wall rock,
somewhat lower in the vein.

ES-7536: Andesite; 19,950 N-7,613 W, 2,400 m;

central; biotitic K-silicate alteration of host with

ES-5827: Rhyolite; 19,832 N-7,535 W, 3,250 m;

peripheral;j arositicleachedcappingwith quartzalunite alteration; coarsely crystalline hypogene
alunite.

disseminated
chalcopyrite-bornite
cut by TransiES-6573: Pebble dike; 20,118 N-8,875 W, 2,990
tional "B" vein bearingquartz, anhydrite,chalcom; intermediate;j arositicleachedcappingin which
pyrite, molybdenite,and pyrite.
coarselycrystallinehypogenealunite associated
ES-8237: Andesite; 19,808 N-8,530 W, 2,400 m;
with pyrophyllite-diaspore-quartz
in sandypebble
intermediate; intenseLate sericite-chloritealteradike
cuts
quartz
porphyry
host
that
has beensubtion, and residual sodicplagioclase,with pyritejected to advancedargillic alteration.
chalcopyrite-anhydrite(magnetite)mineralization; ES-1450: Pebbledike; 19,707 N-7,849 W, 3,100 m;
mole ratio sulfate/sulfidesulfur approximately
central; jarosific leachedcappingthat contains
1:1.
vein of finelycrystallinesupergene
alunitein dike
ES-1116: "X" porphyry;19,720N-8,420 W, 2,400
cutting
"K"
porphyry
host
with
sericite-andalusitem; intermediate; intense sericite-chloritealterapyrophyllitealteration.
tion, and residualalkali feldspar,with Late anhyES-8233:
"X" porphyry;20,044N-7,830 W, 2,710
drite-chalcopyrite-pyrite
mineralization;
moleratio

of sulfate/sulfide
sulfuris approximately
2:1.
ES-8238: Andesite; 19,500 N-8,750 W, 2,400 m;

m: central; enriched and kaolinized host cut by

veinof finelycrystalline
supergene'alunite.

peripheral;intenseLate sericite-chlorite
alteration, ES-7466: Rhyolite; 19,804N-9,040 W, 2,875 m;

intermediate;coarselycrystallinejarosite filling
cracks in leachedcapping formed by sericitized
with weak anhydrite-pyriteveinlets;mole ratio of
hostover pyritic fringe mineralization.
sulfate/sulfidesulfur is approximately3:1.
Gyp-2:
Gypsumvein; 19,814N-8,390 W, 2,600 m;
SE-1173: Andesite; 19,502 N-8,748 W, 2,400 m;
central;
massivegranfilar gypsumin vein within
peripheral;moderately
biotizedwith Late sericiteupper hydratedcappingof the sulfatezone.
chlorite alteration and numerouspyrite-anhydrite
and residualbiotite and tracesof sodicplagioclase,

veinletslacinghost; mole ratio of sulfate/sulfide Gyp-l: Gypsumvein; 20,640N-9,560 W, 2,600m;

peripheral;selenitegypsumfillingcracksin leached
sulfuris approximately
0.5: 1.
cappingover outer pyritic fringe.
ES-7525: "L" porphyry;19,946N-7,742 W, 2,400
m; central;weaklymineralizedhost cut by Late DDH 570-84m: Andesite; 21,500 N-9,650 W, 2,550
m; peripheral;propyliticalterationin wasterock
"D" vein of pyrite-an,hydrite
whichhasa sericitecontainingdisseminated
pyrite.
pyrite halo.
ES-5470:
Pyroclastic;
18,106
N-7,738 W, 2,660 m;
ES-7576: "L" porphyry;19,950N-7,920 W, 2,400
peripheral; disseminated
pyrite in nearly fresh
m; central;very weaklymineralizedhost cut by
Late "D" vein of pyrite-anhydrite;
sericite-pyrite ignimbritethat containstracesof sericite;outer-

1548

C. H/. FIELD AND L. B. GUSTAFSON

most pyritic fringe with nearbypropyliticaltera-

intermediate;strong pyritic waste mineralization

in host altered to an advancedargillic sericiteES-5472: Pyroclastic;18,145N-7,744 W, 2,660 m;
andalusite-pyrophyllite
assemblage;sample overperipheral; disseminated
pyritic in host near ESlieschalcopyrite-pyrite
protoreand secondarily
en5470 that locallycontainszonesof sericitealterarichedpyrite-bornitemineralization.
tion.
ES-2087: Quartz porphyry; 19,464 N-8,133 W,
ES-5709: Pyroclastic;19,100N-7,981 W, 2,930m;
2,930 m; intermediate;strongpyritic wasteminperipheral; strong pyritic waste mineralizationin
eralizationin host alteredto an advancedargillic
sericitizedhost from the upper level of the pyritic
sericite-andalusite-pyrophyllite
assemblage;residfringe.
dual sulfidesin relictpyrite-bornitezoneof leached
ES-5715: Pyroclastic;19,100N-7,891 W, 2,930 m;
capping (see ES-2079) probably representlate
peripheral; strong pyritic waste mineralizationin
pyritic copper-flushing
mineralization.
sericitizedhost from the upper level of the pyritic ES-3977: Pyroclastic;19,838N-8,553 W, 2,875 m;
fringe.
intermediate; strong pyritic waste mineralization
in host altered to an advancedargillic sericite-anES-2541: Pyroclastic;19,400N-8,691 W, 2,875 m;
dalusite-pyrophylliteassemblage;overlies secondperipheral; strong pyritic waste mineralizationin
arily enrichedore and pyrite-chalcopyriteprotore.
sericitizedhostfrom the upper level of the pyritic
DDH 129A-105m; Andesite; 19,950 N-7,610 W,
fringe; collectedaboveES: 1173and 8238.
ES-3196: Rhyolite; 19,950 N-7,233 W, 2,930 m;
2,840 m; central; secondarilyenriched pyrite"chalcocite" ore with traces of enargite in host
peripheral; strong pyritic waste mineralizationin
altered to an advancedargillic sericite-alunitesericitized host t,hat contains traces of diaspore,
kaolinite assemblage;overlieschalcopyrite-bornite
alunite, enargite, and corellite.
ES-2079: Pyroclastic;19,580N-8,076 W, 2,930 m;
protore.
tion.