Economic

Geology
Vol.91, 1996,pp 289-301

Gold Mineralization

in the Ashanti Belt of Ghana:

GeneticConstraints
of the StableIsotopeGeochemistry
THOMAS OBERTHOR,

Bundesanstah
fiir Geowissenschaften
undItohstoffe,
Stilleweg
2, D-30655Hannover,
Germany
ANDREAS SCHMIDT MUMM,

Institutfiir Geologische
]Vissenschaften
undGeiseltalmuseum,
Domstrafle
5, D-06108Halle(Saale),Germany
ULRICH VETTER,

Bundesanstah
fo'r Geowissenschaften
undItohstoffe,
Stilleweg
2, D-30655Hannover,
Germany
KLAUS SIMON,

Geochemisches
Institutder Universitiit
GSttingen,
Goldschmidtstrasse
1, D-37077GSttingen,
Germany

ANDJOEA. AMANOR
AshantiGoldfields
Company
Ltd., Obuasi,Ghana
Abstract

The Ashantibeltof Ghanaisthekeydistrictof goldmineralization

in thePaleoproterozoic
terraneof West
Africa.Theareaconsidered
in southwest
Ghanaiscovered
bylithologies
of thevolcanic-sedimentary
Birimian
Supergroup
andtheoverlying
elastic
sedimentary
Tarkwaian
Groupwhichwerejointlyfoldedandmetamorphosedundergreenschist
faciesconditions
duringthe Eburneanteetonothermal
eventat about9..1Ga.
Regional
fotiation
mdsubparallel
shearzoneshosting
mesothermal
goldmineralization
developed
during
deformation
coevalwithmetamorphism.
Fourmajortsoes
ofprimary
goldmineralization
arepresent
in theAshanti
belt:(1)mesothermal,
generally
steeplydippingquartzveinsin shearzonesmainlyin Birimiansedimentary
rocks,(9,)sulfideoreswith
auriferous
arsenopyrite
andpyrite,spatialty
doselyassociated
withthequartzveins,(3) sulfide
disseminations
andstockworks
in granitoids,
and(4) paleoplaeers
of theTarkwaian
Group.
Thisstudyconcentrates
ontypes(1) and(9,)ofthehydrotherlnal
goldmineralization.
Stable
isotope
analyses
of host-rock
andorecomponents
wereperformed
withtheailnof obtaining
parameters
relevant
to theorigin
andevolution
of the fluidsthatproduced
goldmineralization.

Carbonaeeous
matterin theBirimian
metasediments
displays
93Cvalues
ranging
from-11.4 to -9,8.3
permilrelative
to PDB,indicating
anorganogenie
origin.
Carbonates
display
a unimodal
distribution
of 9aC
valuesrangingfrom -9.9 to -17.0 per rail relativeto PDB. COz extracted
fromfluidinclusions
in the

auriferous
quartzveinshas93Cvalues
ranging
from-9.5 to -15.7 permilrelative
to PDB.It isproposed
thatthesecarbonisotope
compositions
of carbonates
andCOzreflectextensive
interaction
of theCO,2-rieh
hydrothermal
fluidswith reducedcarbonin Birimiansediments
in the deeperpartsof the hydrothermal
systems.

Carbonates
andauriferous
veinquartzhave6Sovalues
ranging
from19,.9
to9,9,.9,
and19,.8
to 15.6permil
relativeto SMOW,respectively.
Carbonates
andquartzweredeposited
in nearisotopic
equilibrium
with
respect
to 6So,indicating
fluid-dominated
conditions
duringoreformation,
fromfluidsof metamorphic
or
magmatie
origin.Suchanoriginis corroborated
by SDvaluesof waterextracted
fromfluidinclusions
in vein
quartz(-37 to -53% relativeto SMOXV).
Pyriteof synsedimentary-diagenetie
originin Birimianschists
displays
sulfurisotope
compositions
ranging
from+7.3 to -9,0.9perrail(median
ca.-10% relative
to CDT). Similarcompositions
andwideranges
are
usually
attributed
to sulfidegeneration
bybacterial
sulfatereduction
fromseawater.
Arsenopyrite
andeogenetie
pyritefromthesulfide
oresgenerally
have534S
values
in therange-5.3 to
-10.9,perrailrelative
to CDT.Thetightunimodal
distribution
of 534S
values
indicates
a large,homogeneous

fluidreservoir.
Thelow(534S
values
areinterpreted
assource-inherited,
notrelatedto unusual
pH, Eh,
temperature,
or depositional
conditions.
Sulfidesin Birimiansediments
represent
the mostlikelysulfur
reservoir
tappedby the fluidsystems.
TheC, O, H, andSisotope
compositions
of ore-related
hydrothermal
minerals
andfluidinclusion
componentsindicatethatthe mineralizing
fluidsinteracted
extensively
withthe Paleoproterozoie
rocks,especially
Birimiansediments,
at deepercrustallevelsandat hightemperatures.
The isotopic
compositions
aremost
compatible
withthe formation
of fluidsfromdevolatilization
reactions
invoMngBirimianstrataduringprogrademetamorphism
at depth(metamorphic
fluids).

0361-0128/96/1815/289-1355.00

289

290

OBERTHOR ET AL.

Introduction

tationagesof 2132 _+3 and 2135 __+

5 Ma, respectively,
whereas
Birimianvolcanics
yieldedanSm/Ndageof 2166+_
GOLDmineralization
constitutes
animportanteconomic
fac- 66 Ma (Tayloret al., 1992;DaSset al., 1994).
tor in the Paleoproterozoic
Birimianterratieof WestAfrica. Thesupracrustal
sequence
wasfoldedandmetamorphosed
The largestandmostprominent
mines,with a cumulativeundergreenschist
faciesconditions
duringthe ca. 2.1 Ga
pastproduction
in excess
of 1,500metrictons(t) of thenoble Eburnean tectonothermalevent (Leube et al., 1990; Hirdes
metal,arelocatedin Ghana.Amongthese,theAshantiGold- et al., 1992;Tayloret al., 1992).Structural
investigations
refieldsmineat Obuasiis a world-class
golddeposit,
having vealed that Birimian and Tarkwaian rocks were deformed
produced
morethan800t of goldhistorically,
withanoutput jointlyduringa singleprogressive
event.Northwest-southof 26,551kg in 1994.
east-directed
crnstalshortening
produced
majorthrustsand
Lightstableisotope
studies
havegainedincreasing
impor- shears,commonlycloseto the basin-beltcontacts,
which
tancein the description
andinterpretation
of geologic
pro- actedas channelways
for mineralizing
hydrothermal
fluids
eesses.
Thesestudiesnowadays
form integralpartsin the (Eisenlohr,
1989;Blenkinsop
et al., 1994).Goldmineralizaformulation
of metallogenetie
modelsfor golddeposits
and tionin theAshanti
beltis largelysynkinematic
andsynmetawereintensely
employed
formesothermal
Archcan
(e.g.,Ker- morphic,
i.e., coevalwiththe Eburneanevent(Oberthiiret
rich,1987;Colvineet al., 1988;Colvine,1989;Goldinget al., al.,1994).Theintrusion
oftwomajordistinct
suites
of granit1989;de Rondeet al., 1992) and epithermalPhanerozoicoids,theDixcoveorbelt-type
granitoids
whichoccurwithin
(e.g., Rye, 1993)gold deposits
(seealsocontributions
in the volcanicbelts,and the late kinematicCapeCoast-or
Barnes, 1979, and Ohmoto, 1986). In contrast,little work
basin-type
granitoids
in thesedimentary
basins
(Fig.1),took
has been done in the Proterozoic terrane of West Africa.
placeat differenttime intervalsbetweenca. 2180 to 2170
Exceptions
arestudies
on the stableisotopecompositions
of Ma and2116to 2088Ma, respectively
(Hirdeset al., 1992).
carbonin Birimianargillites
andchertsfromGhana(Leube
Gold Mineralization
et al.,1990),anda stableisotope
studyonthetourmalinized
sandstones
andgoldoresfromLouloin Mall (Fouillacet al.,
The deposits
investigated
in this studyare situatedin a
1993).
northeast-southwest-trending
goldbelt whichstretches
for
Thepresent
workcomprises
thefirstcomprehensive
stable about250km fromsouthof Prestea
to Konongo
in thenorth
isotopestudyon hostrocksandore components
fromthe (Fig.1).Thefoilroving
fourmajortypesof primarygoldminAshantigoldbelt in the Birimianterraneof Ghana.Special eralization
arepresent:(1) generally
steeplydippingquartz
emphasis
isplacedona distinction
between
original,
synsedi- veinsin shearzonesmainlyin Birimiansedimentary
rocks,
mentary-diagenetic
isotopic
signatures
andthosedueto hy- withfree-milling
goldandfluidinclusions
in veinsdominated
drothermal
inputandoverprintrelevantto goldmineraliza- by CO.(Fig. 2C and D); (2) sulfideores,with auriferous
tion.The studyis basedon samples
collected
undergroundarsenopyrite
+ pyrite,closely
associated
withthequartzveins
at the AshantiandPresteamines,andin the openpitsof (Fig.2B); (3) sulfidedisseminations
and/orstockworks
with
Bogosu
and Konongo.
Drill corewasmadeavailable
from freegold,arsenopyrite,
andpyritein granites
(e.g.,Ayanfuri);
the Ayanfuriconcession
andfromObenemase
northof Ko- and(4) palcoplacers
of the Tarkwaian
Group.
nongo.
Thesamples
fromtheoldBokitsiminenearAyanfuri Thisstudymainlydealswiththefirsttwotypesof mineralwerecollected
fromminedumps.
ization,whichweredescribed
by Junner(1932,1935,1940),
Cooper
(1934),
and
Hirst
(1941).
Theseauthors
stressed
the
RegionalGeology
structural
controlof the epigenetic
mineralization
andtheir
The relativetimingof volcanism,
sedimentation,
emplace- location in Lower Birimian strata close to the contacts with
rocks.Epigenetic
quartzvein
mentof variousgranitoidsuites,andtectonism
in the vast UpperBirimianor Tarkwaian
Birimian terrane of West Africa is still controversial and beandsulfidemineralization
wasalsofavoredby laterstudies
yondthe scopeof thispaper.The following
description
fol- of Eisenlohr (1989), Hirdes and Leube (1989), Milesi et al.

lows
concepts
recently
developed
fortheGhanaian
sector
of

(1989, 1991, 1992), Leube et al. (1990), and Oberthiir et

the terrane (Leube and Hirdes, 1986; Eisenlohr,1989; Leube

et al., 1990; Eisenlohrand Hirdes, 1992; Hirdes et al., 1992;

al. (1991,1994).In contrast,Ntiamoah-Agyakwa

(1979)put

forward
a syngenetic-metamorphic
concept
byproposing
that

Tayloret al.,1992;Blenkinsop
et al.,1994;Daviset al.,1994). goldandsulfides
of volcanic-exhalative
originwereinitially
in theBirimiansediments
andsubsequently
redisLargeareasof southern
Ghanaarecovered
by Paleopro- deposited
to oresby metamorphism.
Simiterozoielithologies.
The supracrustal
rocksare subdividedtributedandconcentrated
thatat leastsomeof the
into the volcanic-sedimentary
BirimianSupergroup
andthe larly,Leubeet al. (1990)postulated
sulfidelodeoresaresyngenetic.
overlying
elastic
sedimentary
Tarkwaian
Group.Theclassicaldisseminated
subdivisionof the Birimian into Lower Birimian (voleanielasThe Ashantimine(Junner,1932;Hirdes,1989;Leubeet
ties,waekes,
argillites,
chemical
sediments)
andUpperBiri- al., 1990;Oberthiiret al., 1991, 1994)can serveas a type
formostofthedeposits
studied
because
it illustrates
mian(basalts
withsomeinterflow
sediments),
asproposed
by example
betweenhostrocksandores.
Junner(1935,1940),wasreinterpreted
by LeubeandHirdes the interrelationships
mine,goldmineralization
ishosted
in tightly
(1986)and Leubeet al. (1990).The latter authorsregard AttheAshanti
Lowerand UpperBirimianas a coevalsequence
with the folded,steeply
dippingandnortheast-southwest-striking
BiriThe greenschist
faciesrockscomprise
sedimentary-voleanielastie
assemblage
(sedimentary
basins) mianmetasediments.
representing
a distalfaciesof volcanic
belts.Detritalzircons alternating
argillites(muscovite
schists,
muscovite-chlorite
fromBirimianandTarkwaian
stratagavemaximum
sedimen- schists
andcarbonate-spotted
schists,
all variablygraphitic)

ASHANTI BELT, GHANA,Au MINEBALIZATION

291

VOLTAlAN
TOGO
SERIES
TARKWAIAN

basintype

granitoids

belts
[ volcanic
sedimentary
basins
granitoids
belttype

BIRIMIAN

SunyaniO

__

DAHOMEYAN

++++

(,O''

+
+

+
+

+
+

+
+

+
+

+
+

+
+

+
+

+ ++

+
+

+
+

+
+

+
+

Wnneba

Cape
Coast

GUL

S,ko.d,G 3\ t

0 2340 60Kin
I

Fc,.1. Geolo' of southern

GhanaafterLeubeandHirdes(1986),modifiedafterHirdesandLoh (pers.commun.,
1995).Alsoshoxm
are majorgoldmines:A = AyanfuriandBokitsi,B = Bogosu,
K = Konongo,
O = Ashantimineat
Obuasi, P = Prestea.

arevariablein the differentmine

andfeldspathie
metasandstones.
Irregularboudins
andinter- whoserelativeproportions
layersof "metavoleanie"
or "dyke"rocks(in mineterminol- sections:
ogy)arelocallypresent.
Theserocks,hoxvever,
generally
are
1. Quartzveins,locally
withspectacular
showings
ofvisible
intensely
metasomatized
or earbonatized
andhavethusbeen
gold
and
minor
Pb-Sb-Cu
sulfides
(galena,
bournonite,
tetrainterpreted
to represent
earbonatized
metasediments
(Oberhealrite;
Fig.
2C).
Single,
massive
or
laminated
veins,
0.2
to
thiir et al., 1994).Thisinterpretation
maybe extended
to
5
m
wide
but
locally
reaching
25
m
in
width,
or
multiple
similar
rockunitsatPrestea
(Adjimah,
1988).Possibly
concor- quartzveinswithintercalated,
sheared,
andcommonly
sulfiddant Birimianmetavoleanies
and unmetamorphosed
dikes
ized
wall
rocks
are
present.
Selvages
in
the
form
of
intensely
(dolerites),
however,
arealsopresent
in subordinate
amounts sheared carbonaceous schists are common. Wall-rock alterat the Ashanti mine.

ation takes the form of sulfidization and carbonatization.

Goldmineralization
is exposed
in mineworkings
forabout
goldhosted
in arsenopyrite
8 km alongstrikeanddownto ca. 1,650m belowsurface. 2. Sulfideores,withrefractory
as
the
main
ore
mineral
(Fig.
2B).
This
mineralization
forms
The orezoneconsists
of several
steeporebodies
subparallel
either
envelopes,
up
to
some
meters
wide,
around
quartz
to the regionalstrike,whichmeasure
up to somehundred
veins,or disseminations
in metasediments
or "dyke"rocks.
metershorizontally
andverticallyandattainthicknesses
of
Ore
minerals
besides
arsenopyrite
include
pyrite,
pyrrhotite,
upto 50 m.Theorezoneisfurthercharacterized
byintensive
andmarcasite,
andrarechalcopyrite
andsphalerite.
shearing,
pronounced
sulfide
mineralization
of country
rocks,
multipleto massive
quartzveining,
andthecommon
presence Petrographic
and structural
investigations
haverevealed
andsynkiofearbonaeeous
schists.
Twodistinct
oretypesarerecognizedthatbothore typesare largelysynmetamorphic

292

OBERTHORETAL

bou

tet

' '

sph

cpy

FG.2. A. Carbonate
spottedschistconsisting
of augenof monocrystalline
Mg sideritein a fine-grained
matrixof
quartz,sericite,
andcarbonaceous
matter.Transmitted
light,onepolarizer,
horizontal
width= 1.2cm.Ashanti
mine.B.
Well-developed
crystals
of arsenopyrite
(white)andminorhypidiomorphic
pyrite(white)in sulfide
orefromPrestea.
Note
abundant
carbonates
(lightest
gray).Reflected
light,in air,onepolarizer,
horizontal
width= 1.4min.C. Sulfide
paragenesis
in the goldquartzveinsof the Ashantimine.Bournonite
(bou),chalcopyrite
(cpy),galena(ga),gold(white),sphalerite
(sph),andtetrahedrite
(tet).Gangue
is quartz.Reflected
light,oilimmersion,
onepolarizer,
horizontal
width= 700tim.
D. Primarygaseous
CO +__
N +__
CH4inclusions
in quartz,Ashanti
mine.Transmitted
light,horizontal
width= 250tim.

nematicand were depositedfrom hydrothermal

solutions relativeto arsenopyrite
occurat Prestea,
Bogosu,
andBokitsi
duringonesingleprogressive
deformational
event,in thePT (meanabout50/50)compared
toAshanti
andKonongo
(mean
rangeof 2 to 5 kbarsand400 _ 50C(Blenkinsop
et al., about 15/85).
1994; Oberthiir et al., 1994).
Mineralization
at the Ayanfuriconcession
comprises
imThegeneral
geologic
setting,
typesof ore,mineralogy,
and pregnations
of arsenopyrite
andfreegoldin graniticstocks

thephysicochemical
conditions
of oredeposition
at theKo- which
nongo,Bokitsi,Bogosu,
and Presteaminesare remarkably

were intruded into Birimian metasediments.

AnalyticalMethods
aremainlyhostedby Birimianmetasediments,
closeto conCarbonisotope
compositions
of carbonaceous
matter,and
tacts with Birimian volcanics or Tarkwaian sediments to the
carbonandoxygen
isotope
compositions
of carbonates
were
east,(2)theorebodies
dipsteeply
andtrendnorth-northeast-determined
on whole-rock
samples.
For carbonates
in veinsouth-southwest
to northeast-southwest,
i.e., subparallel
to lets,handpicked
concentrates
wereanalyzed.
Oxygen
isotope
theregional
strikeofthesedimentary
lithologies,
(3)goldhas compositions
of quartzfromthe auriferous
veinswereoba bimodaldistribution
in quartzveinsandsulfideores,and tainedfromcoarse,cleanveinquartz.Sulfideconcentrates
(4) fluidinclusions
of the quartzveinsareunusual
withCO.2 wereproduced
fromsulfideoresamples
andpyritein schists
asthedominant
phase(Schmidt
Mummetal.,1996,inpress). by crushing
of the samples
andsubsequent
mechanical
conDifferences
area highermetamorphic
gradeat Konongo centration(panning).
(biotite,garnet;Hirst, 1941),whereasthe otherminesare
Isotopic
anyses
wereperformedby GCA Lehrte,Ger13
18
located
in greenschist
facies
rocks;
largerproportions
ofpyrite many(6 C, 6 O; carbonaceous
matterandcarbonates)
and
similarto thoseat the Ashantimine: (1) the mineralizations

ASHANTIBELT,GHANA,Au MINERALIZATION

293

of Carbonaceous
Matter(c.m.)
Geochron
Labs,Cambridge,
UnitedStates
(834S),
using
stan- TABLE1. CarbonIsotopeCompositions
Carbonates
(earb),Oxygen
Isotope
Compositions
of Carbonates,
Total
dardmethods.
Analytical
reproducibility
was+0.2 per rail and
Organic
Carbon
(C....), andCarbonate
Carbon
(Cc.,rb)
Contents
of Rock
foroxygen
andcarbon
and+ 0.4perrailforsulfur.
The
Samples
fromtheAshanti
Beltin Ghana

values
of quartzweredetermined
at G6ttingen
University
by
reactionwith C1F3,the liberatedoxygen
wasconverted
to Sample
Rock
Locality type (93C
CO2by reduction
ongraphite
at 600C;/Dvaluesof water no.
extracted
fromquartz(grainsize6-12 ram)weredeterminedGH 042
sps
-24.5
afterdegassing
adsorbed
waterat 140C
for24 h in vacumn. GH 101 Ashanti
Ashanti
carb
-26.6
carb
Thequartzwassubsequently
deerepirated
at800C,
theliber- GH 107 Ashanti
atedwaterwasreducedto H2 by reactionxvithhot (800C) GH 111 Ashanti sps -25.8
142 Ashanti
sps
-24.9
uranium,and immediately
analyzedfor D and H isotope GH
GH 199 Ashanti
cs
-25.3
compositions.
Typicalanalytical
errorsof themethodare+_2 Glt 209 Ashanti sps -22.7
perrail.COzfroinfluidinclusions
vasextracted
bymechani- GH 338 Ashanti
cs
-25.7
cs
-25.2
calcrushing
of quartzat roomtemperature
followed
by its GH 346 Ashanti

14.9
15.3

-12.9
-12.6

16.3
18.8

0.41
0.58

-14.6

15.9

2.20

1.29

-15.6

15.6

0.63

2.16

15.3
15.1
21.2

1.43
2.01
0.45

1.29
1.23
0.19

5.03
0.69

0.62
3.58

0.23
0.37
0.33
0.62
0.62
4.16

1.54
0.49
0.91
0.21
1.25
1.75
0.69

3.64

0.62

2.66
4.67

0.85

GH

368

Ashanti

-25.6

obtainedCO.2wasmeasured
directly.Goldcontents
were
analyzed
by instrumental
neutronactivation
analysis
(INAA,

GH

380

GH

382

GH

384

Ashanti
Ashanti
Ashanti

mv
mv
cs

-12.7
-11.4
-24.6

-12.3
-10.9
- 13.0

12.9
14.6
15.3

Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti

s
cs
s
sst
sst
sst
v
s
s
cs

- 15.5
-23.8
-15.7
-16.3
-17.9
-15.7

- 13.1
- 13.0
-14.8
-14.4
-13.7
-14.3
- 13.5
-17.0
-15.5

14.5
22.2
14.5
16.2
16.4
16.2
14.1
13.5
14.3

Ashanti
GH017
144
Ashanti

cs
cs*
cs

-28.3
-25.1
- 25.1

cs*
cs
s

-24.5
-23.8
-23.6

es
cs
cs*
cs
cs
cs
cs
my*
my
my
my*
my
cs
cs

-24.3
-28.2
-25.2
-20.7
- 18.3
-23.2
-20.5
-24.8

s*

-28.3

s
s
Mn-cb

-20.9
-20.1

cs

-28.1

cs
cs

-28.8
-19.9

cs

-22.8

sps
gt
cs
cs

Isotopic
compositions
aredenoted
asfollow:
1513C
......
carbonaceous
matter,
in permilrelative
toPDB;/5t3C = GH
GH
carbonate
carbon,
in per rail relativeto PDB;/9SO = GH
carbonate
oxygen,
inperrailrelative
toSMOW,a4s: sulfide GH
cal'[)

sulfur,in perrailrelative
to CDT, and/D= waterhydrogen,GH
in perrailrelative
to SMOW.Results
arepresented
in Tables GH
GH

1, 2, and3.

604
634
664
684

701
709
710

GH 711

Results

GH

Ashanti

Carbon
isotope
compositions
GH
152Ashanti
GH 217
Ashanti
Elemental
carbon
ispresent
ascarbonaceous
matter
inthe GH
237Ashanti
GH 251

various
schists
(locally
called
"graphitic"
or"graphite
schists")GH25SAshanti

andconcentrated
in the shearzonesasgraphitic
gougeor as GH324 Ashanti
selvages
to the veins.The carbonaceous
matteris extremely GH187 Ashanti
finegrained(1-3 by 10-20/m), flaky,andis oftenconcen- GH330 Ashanti
Ashanti

trated
inirregular
schlieren
parallel
tobedding
and/or
schis-GH
GH 667
703 Ashanti
tosity.Coalpetrographic
investigations
byKoch(1991,1992) GH765 Ashanti
characterized
the carbonaceous
matteras semigraphite
of GH201 Ashanti
originally
sedimentary
origin,which,in tectonized
rocks,was GH232 Ashanti
Ashanti

concentrated
along
shear
planes
conspicious
arecrys- GH
Less
GH 375
387 Ashanti
tallites
andsmallaggregates
ofcarbonaceous
matterongrain GH407Ashanti

boundaries
of coarser
hydrothermal
carbonates.

Carbonaceousmatter from the Ashanti mine has/93C val-

GH881 Ashanti
GH 927

Ashanti

uescovering
a considerable
rangefrom-11.4 to -28.3 per GH009 Bogosu
Nsuta

rail.Thedataoverlap
withvalues
ofBirimian
argillite
and Nsutal
Nsuta
Nsuta2

chertsamples
fromGhana(range-18.3 to -30.2%) given OH019 Nsuta
by Leubeet al. (1990).Isotopic
compositions
fromtheother OH045 Prestea
occurrences
in the Ashantibelt (Table 1 and Fig. 3) are OH04S Prestea
Prestea

similar
tothose
fromtheAshanti
minebutdisplay
a smaller OH
046Obenemase
GH 039
variation
and tend towardlower:xCcontents
(mean GH420Ayanfuri
-23.1%o).Collectively,
theisotopic
coinpositions
ofcarbona- On436 Ayanfiri
ceous
matterfallintotherangeof organic
carbon(Schidlow-6009 Obuom
ski et al., 1983;Hoefs, 1987).

1-40

Huntado

-20.1
-16.4
-21.7

1.98
1.50

16.0

-12.4
-9.9

separation
fromH20bycryogenic
methods.
The/93Cofthe

GH 405
GH 510

C.b

-11.3

-14.2
-15.0
-15.4

ACTLABS, Canada).

C....

4.73
3.41
2.92
0.50
0.58
-13.8
- 13.0
- 12.4
- 13.9
- 13.1

1.82
1.10
0.38
0.34

13.5
12.4
12.8
13.8
13.6

-27.1
-27.5
0.43
0.93

-5.5

14.6

- 15.3
-12.5

15.3
16.0

-23.3

- 18.6
- 16.6

11.9
14.4

-18.6
-20.3

-12.8
-21.0

14.4
19.1

3.79
5.18

5.84
0.29

1.32

2.59

Carbonates
areubiquitous
in all rocksstudied.
Mg siderite
53C
in permilrelative
to PDB,5SO
in permi]relative
to SMOW
of diagenetic
originconstitutes
the carbonate
augenof the
Abbreviations:earb = late carbonatevein, es = earbonaeeousschist,s =
carbonate-spotted
schists
(Fig. 2A), whereasankeritewith schist,
sps= carbonate
spotted
schist,
sst= sandstone,
nw = metavoleanie,
(dolerite),
Mn-eb= manganese
carbonate,
gt = granitoid,
=
varyingMg/Feratios(MgCO3:20.05-36.98
mole%; FeCO3: v = volcanic
sample(sulfideore)
8.32-28.51mole%) is typicalfor the variousschists
and mineralized
metasomatized rocks. Ankerite in late carbonate veins is do-

lomitic(MgCO3:31.53-42.91
mole%) andhaselevated
contents of SrCOa (mean 0.60 mole %; Oberthfir et al., 1994).

294

OBERTHOR ET AL.

TABLE2. Oxygen
IsotopeCompositions
of QuartzandMuscovite
Samples,
Hydrogen
IsotopeCompositions
of WaterExtracted
fromQuartz,andof Muscovite,
aswell asCarbonIsotope
Compositions
of CO2Extractedfi'omQuartz

Sample

Locality

SJSO

SD(H20)

GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH

145
159
160
172
191
239
255
269
931
952
970

GH

914
GH 915
GH 916

Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti
Ashanti

14.6
15.6
12.8
15.0
14.2
14.1
14.9
15.4
14.1
14.7
15.5

Prestea

15.4

Prestea
Prestea

15.1
14.6

GH 367
GH 368
GH 802

Ashanti
Ashanti
Ashanti

-9.8
- 10.7

per railat 350Cand9.7 to 12.5per railat 450C,indicating

a fluidof metamorphic
or magmatic
origin.

-37

- 10.8

(Fig.5) reveals
closely
matching
median
values
atapprox15.0
per railanda widerrangeof/SOvalues
of thecarbonates

Comparison
of the/SOvalues
of carbonates
andquartz
compared
to thefightdistribution
of/SOvalues
obtained
for quartz.
SDof waterextracted
from veinquartz
Quartzsamples
fromauriferous
veinsof the Ashantiand
-39

-15.7
-9.5

D
-43
-60

11.4

-58

9SoandSDin per mil relativeto SMOW,(13C

in per mil relativeto
PDB

to5 kbars.
Accordingly,/SO
values
ofthewater,calculated
from/lSO
of quartz(Clayton,
1972),rangefrom7.4to 10.2

-53
-42

Muscovite

Jso

the Ashanti mine (Oberth/ir et al., 1994) showedthat ore

tookplacein the PT rangeof 400 _ 50Cand2

53C
(COs) deposition

Fluid inclusions

Quartz

tween12.8and 15.6per mil (mean= 14.6%o;

n = 11) for
the Ashantimineand 14.6to 15.4per rail (mean= 15.0%o;
n = 3) for the Presteamine (Fig. 5, Table2). Studiesat

Presteamineswereinvesfigated
(Table2). Onlyfour out
of ten samples
yieldedsufficientH20for analysis
as most
inclusions
contain
mainlymixtures
of COs-+N,2,andaqueous
inclusions
are rare;however,up to about15 molepercent
of waterin gaseous
inclusions
mayremainmicroscopically
undetected.
Theobtained/Dvaluesrangefrom-37 to -53
per mil,indicating
magmatic-metamorphic
fluidswhenplot-

tedagainst
therespective
values
of/sO (Fig.6).
Hydrogen
isotope
coinpositions
of muscovite
frommineralized muscoviteschists(sulfide ores) at the Ashanti mine

rangefrom-43 to -60 per rail (Table2). Recentworkby

Ojalaetal.(1995)indicates
thatA(D) values
offluidinclusion
SampleGH 019 is a chemicalsedimentary
Mn carbonate, water and coexistent alteration muscovite should be on the
orderof 10to 20 per railat temperatures
between
300and
theprimaryoreof Nsutamanganese
mine.
Carbonates from the Ashanti belt have/aC values from 350C,
whichis in generalagreement
withtheabovedata.
-9.9 to -17.0 (meanabout-14.0%o)anddisplay
a unimodal
5Cof COsextracted
fromveinquartz
distribution
(TableI and Fig. 3). Exceptions
are the nearThreesamples
fromtheAshanti
minegave/3Cvalues
of
surfacesamplesGH 420 (-18.6%o)and 1-40 (-21.0%o),
and the Mn carbonatefrom Nsuta (-5.5%0).
-9.8, -10.7, and-10.8 per rail,andavosamples
fromPreCarbonisotopeinterrelationships
betweencarbonaceoussteayielded-9.5 and -15.7 per rail (Table2 andFig. 3).
compositions
ofCOsfromfluidinclusions
matterandcarbonates
in individual
samples
are depictedin The'C isotope
(mean= -10.9%o)thusoverlap
xviththecarbon
isotope
comFigure4. Theplotof26pairsof/3Cvalues
ofcarbonaceous
matterand carbonates
versusA(3C) indicatesthat a sub- positions
of carbonates,
especially
from the Ashantimine
groupof dataclosely
corresponds
to isotopic
equilibrium
be- (range-9.9 to - 17.0,mean- 13.6%o).
tweenthe carbonaceous
matter-carbonate
pairsin the temSulfurisotopecompositions
peraturerange200 to 350C.Anothersubgroup
is clearly
outofisotopic
equilibrium;
mostofthesesamples
arecharac- The sulfide concentrates obtained from the sulfide ores
contained
between
terizedby low ratiosof carbonaceous
matterto carbonate andmarked"aspy"in Table3 generally
theothercomponents
being
carbon(cf. Table 1) indicating
a certaindegreeof isotopic 50 and80 percentarsenopyrite,
andmarcasite.
Sulfideconcentrates
overprint
andexchange;
however,
theinterceptof theregres- mainlypyrite,pyrrhofite,
andhandpicked
concentrates
of
sionlinesthroughall samples
(thicklines)is interpreted
as withlargerpyritecontents
aredenoted
accordingly
in Table3, whichalso
thecarbon
isotope
composition
ofthewholesystem
(/3C= othersulfides
dataof sphalerite
andpyritefromthe Perkoa
volca- 15%o).
Withrespect
to thosesamples
closely
approximatingcontains
massive
sulfidedeposit
in BurkinaFasoandofpyrite
isotopicequilibrium(thin regression
lines),a meancarbon hOgchic
mine in
isotopecomposition
of about-20 per rail is indicatedin a veiningBirimiantuffs at the Nsuta manganese
of the concentrates
system
dominated
bya largeamountof carbonaceous
matter. Ghana.Table3 alsolistsgoldcontents
obtainedby INAA.
Oxygenisotopecompositions
Pyriteof synsedimentary-diagenefic
originin variablycarBirimianschists
displays
a widescatterof sulfur
Carbonate
5sO
valuesrangefrom12.9to 22.2per rail bonaceous
(median 15.5%o)at the Ashantimine and data from the other isotope
composifions,
from +7.3 to -20.9 per rail (median
occurrences
closely
matchthisrange(Table1).Thetotaldata ca. -10%o,Fig. 7). Pyriteandsphalerite
fromthe Perkoa
volcanogenic
massive
sulfidedeposit
andpyriteveiningBiriset(Fig.5) approximates
a normaldistribution.

Quartzfromtheauriferous
veinsdisplays
sO values
be- miantuffsat Nsutahavemagmatic
values
closeto 0 permil.

ASHANTIBELT,GHANA,Au MINEP,
ALIZATION

295

TABLE
3. SulfurIsotope
Compositions
andGoldContents
of Various
Sulfides
fromtheAshanti
Beltin Ghana

Oretype/
Sample
no.
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH
GH

002
120
124
131
165
202
202 m
219
231
231 m
301
302
307
308
343
355
368
387
391
407
460
518
520
721
733
891
947
950
956 A
958
959
961 B
962
967
969 A
43-1

GH 357
GH 405

Locality

hostrock

64S
Mineral

Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine
Ashanti mine

Sulfide ore

mine
Ashanti
Ashantimine

Carb.schi. py
Schist
in ore py + cpy

aspy

Au

Oretype/

(%0) (ppm) Sample

no.
-6.4

396

-6.3

-6.3
-7.0
-6.0
-6.4
-7.3

323
167
134
150
86

-6.3

222

-6.5

134

-10.4
-6.2

-6.6
-8.9
-5.3
-7.5
-8.5
-6.6
-6.0
-6.3
-7.0
-6.4
-6.8
-7.6
-8.9
-8.9
-10.1

82
253

-6.9

294

-8.0
-6.3
-7.1
-6.9
-7.7
-8.0
-8.9
- 10.2
-5.8

93
72
201
306
154
248
164
32

-16.0
-9.0

245
100
175
295
268
182
79
198
214
197
55
285

17

Locality

GH 888
GH 927
GH 306
GH 780

Ashantimine
Ashantimine
Ashantimine
Ashantimine

hostrock
Carb.schi.
Carb.schi.
Qtz vein
Qtz vein

534S Au
Mineral
py
py
galena
galena

(%o) (ppm)
-20.9

0.4

-19.5

0.3

-12.0
-12.6
-6.9

86

GH

005

Presteamine Sulfideore

GH

858

Prestea

mine

-6.8

35

GH

860

Prestea mine

-7.5

195

GH

918 A

Prestea mine

-7.1

32

GH

918 B

-7.8

10.1

GH

006

Presteamine
Presteamine

GH

10-1

Prestea mine

GH

048

Prestea
mine Carb.schi.

py

-11.7

GH

046

Presteamine

py

-10.8

py

-8.2

93

aspy

-8.5

137

py > aspy

-7.7
-16.8

169

0.7

92

aspy

py
aspy

-4.6

-4.7

Sulfideore

31

9.7
31

GH 912 A
GH 912 B
GH 920
6181WH

Bogosu
Bogosu
Bogosu
Bogosu

Carb.schi.

py

GH 785

Ayanfuri

Granite

aspy

GH
GH
GH
GH

Bokitsi
Bokitsi
Bokitsi
Bokitsi

Schist

py

-6.5

PY

-9.6

aspy

-11.4

7.7

PY

-11.2

29.8

GH 873

Konongo

Sulfideore

aspy

-3.1

GH 036
GH 037

Obenemase
Obenemase

GH 035

Obenemase Carb.schi.

GH 039

Obenemase

6009WH
6040WH
6041WH

Obuom
Bilpraw
Bilpraw

1-44/45
1-49 WH

Huntado
Huntado

Perkoa
Perkoa
Nsuta

Perkoa
Perkoa
Hill B

420
422
869 A
869 B

Schist/ore

Schist
Carb.schi.

py
py

24

-0.5

32
156

-2.8

122

-10.9

1.0

-10.1

0.4

-4.4
-12.4
-14.1
5.5
7.3

VMS
VMS
"TufF'

py
sphalerite
py

1.2
1.4
1.2

34Sin permil relative

to CDT
Abbreviations:
carb.schi.= carbonaceous
schist,
qtzvein= quartzvein;aspy= arsenopyrite,
cpy= chalcopyrite,
py = pyrite

fallintotherangeof organic
carbon(Schidlowski
et
Arsenopyrite
fromthe sulfideoresat the Ashantimineis grossly
with the petroconsiderably
depleted
in 34S(range-5.3 to -10.2%).The al., 1983;Hoers,1957),and in accordance

studies
(Koch,1991,1992),lendsupport
to anorigidatadisplay
a tightnormaldistribution
(Fig.7) indicative
of graphic
nallyorganogenie
derivation
of the earbonaeeous
matter.
a large,homogeneous
source.
Carbonates from unmineralized and mineralized litholoThearsenopyrite
samples
fromPrestea,
Bogosu,
andBokidepleted
in 3C.The3C values
range
tsi conform
with andslightlyextendthe totalrangeof data giesareconsiderably
a unimodal
distribuwithrespect
totheAshanti
mine.However,
arsenopyrite
from from-9.9 to -17.0 permilanddisplay
uniformgroup,
withthe
Konongo
markedlyrangesfrom -0.5 to -3.1 per rail, and tion(Fig.3).Alldataforma eoherant
ofthesynsedimentary
Mn carbonate
fromNsutaat
oneconcentrate
fromgranite-hosted
mineralization
at Ayan- exception
-5.5 per mil.
furi has0.7 permil.
Furthermore,
cogenetic
arsenopyrite
andpyriteseparated Anapproach
toward
isotopic
equilibrium
between
earbonafromthesamesamples
of sulfide
oresdisplay
nearlyidentical eeous matter and associated carbonates was identified in one

634S
values
(arrows
in Fig.7;Table3). Galena
fromthegold subgroup
of samples
(Fig.4), whereas
a second
subgroup
quartzveinsat theAshanti
minehas634S
valuesof -12.0 appears
to be outof equilibrium.
Samples
of thelattersuband-12.6 per rail.
Discussion

Carbonisotopes
Carbonaceous
matterin Birimianmetasediments
isisotopi-

callylight(6aC= -11.4 to -28.8%).The data(Fig.3)

grouparemainlycharacterized
byratios
ofearbonaeeous
matter to carbonate
carbonbelowunity,indicating
an overprint
of carbonate
carbonisotopecompositions
on thoseof the
associated earbonaeeous matter.

Thelightcarbon
isotope
compositions
of carbonates
from
the Ashanti belt are in distinct contrast to those of carbonates

296

OBERTHORETAL.

co
2mdds)1-'] JJJd

5n iiiD
quartz

n-

carbonate

carbon

lO

,,FI

o
-20

lO-

-15

-10

organic carbon

car.at

20

80

Fi. 5. Histogram
of oxygen
isotope
compositions
(6]SO
in permilrelativeto SMOW)of quartzandcarbonates
fromtheAshanti
mine(stippled)
-30

-25

-20

and other localities in the Ashanti belt. For data sources see Tables 1

-15

and g.

FIG.3. Histogram
of carbon
isotope
compositions
(6]aCin per]nilrelativeto PDB)forcarbonaceous
matter(organic
carbon),
carbonates,
andCOs
extracted
fromfluidinclusions.
DatafromtheAshanti
mine(stippled)
and
other localities in the Ashanti belt. For data source see Table 1.

-24.9%0).Kontaket al. (1990)proposed

thatthe verylow

613C
values
reflect
abiogenic
origin
forthiselement,
probably
fromoxidation
of graphite
in the sourceregion.

Ios,>
dso.
ssd
oaon
sooph

fromchemical
sediments,
whichdisplayrelatively
constant
andstatedthatin gene , 6t3Cval s of
values
closeto 0 permilthrough
earth's
history(Schidlowskiveincarbonates
vein
carbonates
are
dependent
ontemperature,
Eh, andpH
et al., 1983).Furthermore,
theydifferfromcarbonisotope
aswellasthecarbonisotope
composicompositions
of carbonates
associated
withArchcan
goldde- duringprecipitation,
tion
of
the
carbon-bearing
species
in
solution
(Ohmoto
and
positsin Australia,
Canada,and SouthAfrica,whichrange
Rye,
1979).
The
fluids
depositing
hydrothermal
carbonates
from+2 to -9 witha meanof about-4 per rail (Kerrich,
golddeposits
aregenerally
considered
to be
1987;Colvineet al.,1988;Golding
et al.,1989;de Rondeet in mesothermal
by conditions
offo.closeto the QFM buffer,
al., 1991,1992).However,similarandevenlightercarbon characterized
isotopecompositions
of carbonates
like thosein the Ashanti above COs-CH4, at T > 270C (Kerrich, 1987). At these

beltarereported
fromthe Homestake
goldminein South
Dakota(-5.6 to -11.2%<RyeandRye,1974)andfromgold
deposits
in thelowerPaleozoic
Meguma
terrane,NovaScotia
(Kontaket al., 1988,1990;mean-21.5, range-13.5 to
equilibrium temperature
620

450

340

200

-10

conditions,
carbonisotope
fractionation
attributable
to redox

/c13t
-ieffects
13 or ternPeraturedifferencesis minor
o o,ont
' ' = --

6 Cn,,a;OhmotoandRye,1979;Kernch,1987).The above
conditions
alsoholdtruefortheAshanti
beltgoldmineralization, as indicated
by the mineralassemblages
(pyrrhotitepyrite-arsenopyrite;
no magnetiteor sulfates)and the fluid
inclusion
inventory
(mainlyCOs,tracesof CH4).
Oxidized
carbon
species
in hydrothermal
fluidsmayorigi-

20

..-1

-20

OY

-40

-0

'

metamorp
water
(300- 600C)

-24

r -oo

(C
-28

60-100

'''
-2

10

12

14

a(13C)carbonate
-carbonaceous
matter[%]

16

,,,,o
7

....

,'

I.' I

magmatic
/

-120
/
water
-140

-160

-20

-10

10

20

ceousmatterand carbonates.
Equilibriumtemperatures
after Bottinga
a"o(o)
(1969).Thesubgroup
of samples
withequilibrium
fractionation
closeto and
exceeding
ca.10permil (thinlines)depicts
a system
witha meanisotopic FIe. 6. Plotof 6D for aqueous
fluidsextracted
fromquartzvs.sO of
composition
near-20 permildominated
bycarbonaceous
matter.Thetrend thefluidscalculated
from60 of thehostquartzat 400C. 6D and6]SOin
of all samples
(thicklines)indicates
a carbonate-dominated
system
witha per mil relativeto SMOW.Opencircles= Ashantimine;11edcircle=
Prestea mine.
meanisotopic
composition
of about-15 per mil.
18,

ASHANTI BELT, GHANA,Au MINERALIZATION

297

produce
a COs-bearing
fluidcapable
of precipitating
carbon

1989). In the same contextof Archcanvein carbonates,Ker-

rich (1987)warnsthat the assumption

that the correspon-

i []Konongo
[] Ayanfuri

[] 8ogosu

'

[] Prestea

-15

-10

-5

:'::::
:;:[-]I II,,[Al:::.::iil]
,,lad,r-'l
-20

ates,with43Caround-3 to -5 per mil (Golding

et al.,

:i Ashanti

-15

-10

-5

+5

[--I 1 [--I
0

+5

+10

denceof carbonate
3C values
to themagmatie
rangealso
impliesa geneticequivalence
is an unwarranted
generalization,especially
since3C values
around
-5 permilaredifficultto interpretwith regardto the carbonsoume,because
magmatic,
sedimentary,
andmetamorphic
rocksareall characterized
byaverage
l'3Cvalues
in thisrange.
The abovediscussion
is of greatvalueto the situation
in
the Ashantibelt,wherepervasive
carbonatization
resulting
fromvoluminous
streaming
of CO2-rich
fluidshasbeenidentified.Also,Eh andPT conditions
of goldmineralization
are
largelyin concordance
with thosecharacteristic
of Archcan
mesothermal
deposits.
Theuniformandlightcarbonisotope
compositions
of car-

FIG.7. Histogram
ofsulfur
isotope
coinpositions
(634S
inpermilrelative bonatesin the Ashantibelt (medianabout- 14%o),therefore,
to CDT) of arsenopyrite
concentrates
froingoldmineralization
(a, top), cannot
resultfromunusual
localfluidor depositional
condiandpyrite(b, bottom),frombothgoldmineralizations
andunmineralized
tions,
which
in
any
case
would
only
have
small
effects
on
Birimian
schists.
Arrovs
indicate
isotopic
compositions
of coexisting
arsenofractionation.
Instead,the obtaineddatapointto a
pyritemdpyrite.Samplelocalities
are indicated;
for datasources
seeTa- isotopic
ble 3.

specific
source
of the carbonate
carbon,
whichappears
less
prominentand underestimated
in Archeanenvironments,
namelyreducedcarbonin sedimentary
rocks.Ohmotoand
hatefromthedecarbonation
ordissolution
ofpreexisting
car- Rye(1979)suggest
thatcarbonaceous
materialmaybecome
bonateminerals,from magmatie
sources,
and/orfromthe a source
of hydrothermal
carbonthroughhydrolysis
andoxioxidation
or hydrolysis
of reduced
carbon
in sedimentary
or dationat elevated
temperatures
of metamorphism,
andthat
metamorphic
rocks.Eachof thesesources
maycontribute the resultant
CO2wouldprobably
have413Cvalues
below
carbonof differingisotopiccompositions
to hydrothermal- 10 per mil.
In the Ashanti belt of Ghana, sufficient reduced carbon
solutions
(OhmotoandRye,1979).
The majorcarbonreservoirs
considered
possess
distinct with43Cvalues
in therange-11 to -28 permilispresent
carbonisotopecompositions:
(1) seawater-derived
carbonate in the form of carbonaceous matter in Birimian metasediischaracterized
byaverage
13Cvalues
doseto0 permil,(2) ments(cf. Table 1). Completeinorganic
oxidation
of that
magmatie
CO.2mainlyshows
13Cvalues
between
-5 and carbon
(C + 0.2 CO2)wouldresultin isotopic
compositions
-7 perrail(Pineauet al., 1976;CoMneet al., 1988),and(3) of theCO.2similarto thoseof thestarting
material(Ohmoto
reducedcarbonin sedimentary
or metamorphic
rockshas andRye,1979).On theotherhand,CO2produced
byhydromean13Cvalues
of about-25 permil(Sehidlowski
et al., lysisreactions
(e.g.,2C + 2H20 -* CO2+ CH4)at tempera1983; Hoers, 1987).

tures between 350 and 600C would have 13C values be-

The source
of carbonin carbonates
of Archcan
lodegold tween3 and 12 per mil heavierthanthat of graphite,dedeposits
hasbeena matterof muchdebate(Burrowset al., pendingon whetherthe graphiteis completely
consumed
1986;Kerrieh,1987;Groveset al., 1988;NisbetandKyser, and whetherisotopicequilibriumis attainedbetweenthe
1988;Golding
et al., 1989).Thediscussion
wastriggered
by remaining
graphite
andtheCO2produced
(OhmotoandRye,
thefinding
thatcarbonates
fromArehean
golddeposits
with 1979).
carbon
isotope
values< -3 permilareunlikely
to originate In conclusion,
the lightcarbonisotopecompositions
of
from seawater-derived
carbonate,becausedissolutionand/or carbonates
in the Ashantibeltareinterpreted
to resultfrom
deearbonation
ofthissource
wouldleadtoisotopically
similar, CO2-rieh
hydrothermal
fluidswhichattainedtheir 3C-dei.e.,43C= __0 permil (Ohmoto
andRye,1979;Golding,pletedcharacter
throughintensive
fluid-host
rockreactions.
1989),or evenslightly
13C-enriched,
CO.2(byabout3-5%o; Thesetookplaceat lowfluid/rock
ratiosin the deeperparts
Burrows
et al., 1986).Therefore,Burrows
et al. (1986)sug- of the hydrothermal
systems.
Bothoxidation
andhydrolysis
gestedthatthe isotopic
signatures
of Archcan
gold-relatedof carbonmayhaveplayeda role,andcontributions
of CO2
carbonates
ratherreflectmagmatie
carbonreservoirs.
How- from other sources cannot be ruled out.
ever,Groveset al. (1988)andGoldinget al. (1989)argue Indeed,dewatering
anddeearbonation
of (Birimian)rocks
that the relationships
derivedby Burrowset al. (1986)are atlowercrustal
levelsundergoing
progressive
metamorphism,
notsostraightforward.
Instead,
theyidentifyanother
carbon andpossibly
magmatie
input(basin-type
granitoids),
mayall
reservoir,
namelyfault-controlled
regional
alteration
thought havecontributed
to the hydrothermal
systems
whichformed
to reflectmantleoutgassing
of CO2alongcrustal-scale
fault the golddeposits
in the Ashantibelt.The ultimatesourceof
systems.
In the Norseman-Wiluna
belt of Australia,
thisear- theCO2in thefluids,however,
ismasked
bythemetamorphic
bonation
produced
carbonated
rockswitha median13Cof carbonisotopecompositions,
whichwereattainedduringthe
about-5 permil(Groves
et al.,1988;Golding,
1989).Meta- passage
of the fluidsthroughthe crust.
morphic
dissolution
of thisregionally
extensive
soume
would The3C values
of CO2extracted
fromthequartzveins

298

OBERTHOR ETAL.

(range-9.5 to -15.7%o)arein accordance

withknownisoto- tantly,primordial
sulfurbecomes
partitioned
betweena repicfractionation
betweencarbonates
andCO2(Ohmotoand duced(sedimentary
sulfide)
andanoxidized
reservoir
(marine
Rye,1979),whichindicates
thatcalciteanddolomite
which plusevaporite
sulfate)
in theexogenic
environment,
whereby
formedattemperatures
aboveabout250Cshould
beisotopi- substantial
isotopic
shiftstakeplacedueto kineticandequicallysimilaror slightly
lowerbya fewpermilthancoexistinglibriumisotopic
reactions.
The samebasicprincipleholds
CO2,and alsoin equilibrium
with graphite(t93Cabout truein hydrothermal
systems
wheresulfate
isgenerally
more
enrichedin 34Sthan is the associated
sulfide(Ohmotoand
-25%0) at temperatures
between300and500C.
Rye,1979;LambertandDonnelly,1990).Threemajorsulfur
Oxygenandhydrogen
isotopes
reservoirs
withdistinct
sulfurisotope
signatures
canbedistinOxygenisotopecompositions
of quartzclusterbetween guished:
12.8 and 15.6per mil (median14.7%o),whereasthoseof
1. Mantle-derived
sulfur
witht534S
values
close
to0 permil.
carbonates
displaya widerscatterandrangefrom 12.9to
Pyrite
and
sphalerite
from
the
Perkoa
volcanogenic
massive
22.2at a medianof 15.5per mil (Tablesi and2, Fig.5).
sulfidedepositandpyritefromNsutapossess
mantlet534S

Thet9SOvalues
of quartz
correspond
tothenarrow
range values(Table 3).

of data(10-16%o)typicalforveinquartzfromhydrothermal 2. The oxidation of mantle-derived sulfur to sulfate will

golddeposits
ofallagesincluding
theArchcan
(Kerrich,1987;
producea positive
isotopic
shift(OhmotoandRye,1979),
Colvineet al., 1988;Goldinget al., 1989;de Rondeet al.,
irregardless
of
whether
the
process
isinorganic
orbiologically
1991,1992).Kerrich(1987)pointsoutthatthedistinct
uniformediated,
leading
to
the
resultant
sulfate
sulfur
in theoceans
mityof t9SOvalues
of quartz
in Au-Agveindeposits
implies andin evaporites
with
(534S
=
18
_+
6
and
19
+ 6 per mil,
a corresponding
isotopic
homogeneity
of the hydrothermalrespectively.
fluids,andsimilarambienttemperatures
of mineralization.
3. Tappingof the oceanic
sulfatereservoir
by sulfate-reKerrich(1987)furtherremarks
thata gross
covariance
exists
ducing
bacteria
leads
to
the
generation
of
HaS
andsubsebetween
average
t51SO
values
ofquartz
anddolomite.
Oxygen quentprecipitation
of sulfidesulfurin sediments
witht534S
isotope
compositions
of Fe dolomites,
however,
aregenerally = -15 _+12 per mil (Schidlowski,
1987).
dispersed
incontrast
totherestricted
rangeofthoseofquartz,
effectinherentin bacterial
sulfatereafinding
paralleled
bythepresent
setofdatafromtheAshanti Thekineticisotopic
belt.Kerrich(1987)interprets
thedispersion
in Fe dolomites duction
thusbringsaboutanaverage
fraetionation
of30to35
to reflectvarying
degrees
of reequilibration
at temperaturespermil andisregarded
asbeingresponsible
for theisotopic
belowthe ambientthermalconditions
of quartz-dolomitedisproportionation
ofterrestrial
sulfurintolight,reduced
sulfideandheavy,oxidized
sulfate(Schidlowski,
1987).
precipitation,
duringlatermineral-fluid
interaction.
in Archcansedimentary
(andigneous)
rocksare
Oxyg
en isoto
ositions
of waterin theore-forming Sulfides
Pe coms
by sulfurisotopecompositions
markedly
confluid,calculated
fromt5 O valuesof quartzafterClaytonet characterized
al. (1972),rangefrom5.8 to 8.6 per rail (300C)and8.7 to centrating
in the range-4 to +4 per mil (mantleor mag11.5permil (400C)
in theAshanti
belt.Thisrangeissimilar matic),whichimpliesa generalpaucityof oxidized
relative
tofluidt51SO
values
(6-10%o)obtained
forArchcan
goldde- to reducedsulfurspecies
in thehydrosphere
duringtheArposits(Kerrich,1987;Colvineeta]., 1988;Goldinget al., chcan,in a mantle-bufferedocean(Schidlowski,1987; Lam1989;deRonde,1991,1992).In anology
withArchcan
hydro- bert andDonnelly,1990).
thesituation
changes
afterabout2.4 to 2.0 Ga,
thermalgoldsystems,
the oxygen
isotope
datafromquartz However,
and carbonates in the Ashanti belt indicate fluid-dominated
wherewidespreads
oftSa4S
values
(-40 to +30%0)arecharacteristicof sulfides
in sedimentary
andexhalative
strata.This
conditions
duringoreformation.
In combination with the tSD values of water extracted from
pointsto the globaltransitionto a largelyoxidizedhydroquartz(-37 to -53%0;Fig.6), the Ashanti
beltoxygen
and sphere,
increasing
oxygenation
oftheatmosphere,
andprolifhydrogen
isotopecompositions
indicatefluidsof metamor- eration
ofsulfate-reducing
bacteria
(Schidlowski,
1987;Lamphicor magmatic
origin.However,
t93Cvalues
of CO2ex- bert andDonnelly,1990).
tractedfromfluidinclusions
(-9.5 to -15.7%o)unequivocally Theobserved
range
oft534S
values
ofpyritein theBirimian
pointto a metamorphic
originof thisfluidcomponent.
Fur- metasediments
(-20.9 to +7.3%0;
Table3 andFig.7) corrobthermore,the largeuniformity
of isotopic
compositions
on oratesthe statementsof Schidlowski(1987) and Lambert and
the scale of the whole Ashanti belt indicates that the same
Donnelly(1990)andaddsanotherexample
to theevolutiongiantfluidsystem
or fluidsystems
of similargenesis
pervaded arypathof the terrestrial
sulfurcyclein the timespanbethe Ashanti belt structural zone.
tweenabout2180Ma (oldestbelt-typegranitoid)
and2116
Ma(oldest
basin-type
granitoid).
Notably,
theblacksandminSulfurisotopes
eral assemblage
of the Tarkwaian
palcoplacers
(<2135 Ma
Two distinctgroupsof sulfides,
whichwill be dealtwith and > 2116 Ma; Daviseta]., 1994) indicatesthat the atmoseparately,
arepresent
in theAshanti
beltof Ghana:synsedi- spherewasoxygenated
duringsedimentation
of the Tarkmentary-diagenetic
sulfides,
mainlypyrite,in Birimianmeta- waian(HirdesandNunoo,1994;Kruppet al., 1994).Therethattheneccessary
ingredients
(freeoxygen,
sediments,
andsulfides
relatedtohydrothermal
goldmineral- fore,it appears
ization.
sulfatein seawater,
sulfate-reducing
organisms)
wereavailIn thefirstgroup,theexogenic
geochemical
cycleofsulfur able
inBirimian
times
to
conduct
biological
mediated
sulfur
appears
to be basically
controlled
by lifeprocesses
overmost isotope
fractionations.
Thewiderangeoft5a Svalues
ofpyrite
of the recordedearthhistory(Schidlowski,
1987).Impor- andtheoverall
trendtowardlightisotopic
compositions
(me-

ASHANTI BELT, GHANA, Au MINEPtALIZATION

299

dianabout-10%o) manifestan originof the sulfides

via lightsulfurisotopecompositions,
theirdepositional
environbiogenie
(earbonaeeous
matterin Birimiansediments)
reduc- ment,andsoume,
the following
statements
canbe made.
tionof sulfatefromcontemporaneous
seawater
and,further- Mineralogieal,
geochemical,
andfluidinclusion
studies
of
more,pointsto variably
dosedsystems,
whereby
moreposi- theAshanti
beltmineralization
(Oberthiir
et al.,1994)suggest
tive634S
values
indicate
environments
withlimitedreplen- a generalsimilarito Archcanhydrothermal
golddeposits.
ishment
of sulfate(LambertandDonnelly,1990).
In the Ashantibelt,ore deposition
waslargelysynmetamorIn thesecond
group,sulfurisotope
compositions
of sulfides phicandtookplaceundergreenschist
faciesmetamorphic
in hydrothermal
oredeposits
arecontrolled
by the isotopic conditions
in the temperature
rangeof 400 _+50C.Fluid
composition
ofthefluids,aswellastemperature,
Eh andpH oxygenfugaeityconstraints,
as delineated
by Mikuekiand
atthesiteofmineralization
(Ohmoto
andRye,1979;Kerrieh, iRidley(1993),alsoindicatethat the oxidation
stateof the
1987).Vhereasthe firstparameter
is a characteristic
of the fluid was above the CO/CH4 buffer, but below the SO,,/
soume,
theothersrelateto theenvironment
of deposition. H,Sequalconcentration
boundary.
Thisisindicated
byfluid
With regardto sources,
sulfurmayoriginate
frommag- inclusion
analyses
(CO,>>CH4),the paragenesis
arsenopymatiefluidsdirectlyor fromtheleaching
or desulfidation
of rite-pyrrhotite-pyrite,
thepresence
ofapowerful
redoxbuffer
minerals
in igneous
rocks,hydrothermal
sediments
or elastic in the form of ubiquitous
earbonaeeous
matter,and at the
sedimentary
rocks(Kerrieh,
1987).Equilibrium
isotopic
frae- same time the absence of hematite and sulfates in the host
tionationbetween H,S and most sulfidesis small (max _+ rocksand ores (Oberthiir et al., 1994).

2%0)at temperatures
above250C(OhmotoandRye,1979). The light sulfurisotopecompositions
of sulfides
in the
Constraints
on ambienttemperature,
Eh, andpH canbe majorityof the Ashanti
beltgolddeposits,
therefore,
appear
obtained
fromalteration
andmineralization
parageneses.
Mi- neithertobetheproducts
ofunusual
localdepositional
condikuekiandRidley(1993)concluded
fromtheinvestigation
of tionswith respectto pH or temperaturenor a reflection
oreandalteration
assemblages
in Arehean
golddeposits
that of oxidized fluids relative to the SO,/H2Sbuffer. Indeed,
thepH of theorefluidswasnear-neutral
to slightly
alkaline, mineralogieal
andgeoehelnieal
dataof hostrocksandores
neverfar fromequilibrium
withserieite-albite,
at tempera- pointto fluidproperties
characteristic
of reduced
greenschist
turesof low to mid-greensehist
fadesconditions.
Further- fadeslodegolddeposits
in thesense
of MikuekiandiRidley
more,thefluidinclusion
inventory
andoreparageneses
indi- (1993).
catethat mostdeposits
formedfromrelatively
reducedore
Therefore,
thelightsulfurisotope
compositions
of sulfides
fluids(Phillips
andGroves,
1983;MikuekiandRidley,1993), in the Ashantibelt ratherreflecta spedfiesoume.Tapping
the fluid redoxstategenerallybeingbelowthe SO.2/H2Softhissoume
byhydrothermal
fluidsleading
toleaching
and/
boundary(Kerrieh,1987)and abovethe COz/CH4buffer or desulfidation,
uptakeinto andtransport
by the fluidsas
(MikuekiandIRidley,
1993).
wellaslaterprecipitation
ofsulfides
wouldresultin negligible
equilibrium
isotopic
fraetionation
if the assumed
process
Sulfides
(mainly
pyrite,
pyrrhotite,
arseno4Yrite
) ininmost
Archcan
mesothermal
golddeposits
display
6 Svalues
the takesplaceat elevatedtemperatures
(>300C)andif only
range+7 to -3 permil (Lambertet al., 1984;Kerrieh,1987; reduced
sulfurspedes
areinvolved
(OhmotoandiRye,1979).
Colvineet al., 1988;de iRondeet al., 1991, 1992). The rela- Themost
likelycandidate
foralight6a4S
reservoir
isthesuite
tivelytightclustering
of6a4S
values
isinterpreted
toindicate of synsedimentary-diagenetie
sulfides
present
in theBirimian
thatthefluidredoxstatewasbelowtheSO/H2S
equalcon- metasediments.
Thesesulfides
display
a widerangeof 6a4S
centration
boundary
andthatthe sulfursoume
wasisotopi- values
(+7.3to -20.9%0),butpossess
a similar
median
6a4S

callyuniform(Kerrieh,1987).A directderivation
ofthesulfur value(-10%o)compared
to thatof sulfides
relatedto hydrofrommagmas
orindirectly
bydissolution
and/ordesulfidationthermalgoldmineralization
(about-7%0). Thelatterarealso
of magmatie
sulfides
is indicated
(Lambertet al., 1984;Ker- characterized
bya tightunimodal
distribution
of 6a4S
values,
rich, 1987).
indicating
a large,homogenous
fluidreservoir.
Thedepleted
However,exceptions
to the abovemainrangeof sulfur lightisotopic
signatures,
therefore,
areinterpreted
asinherisotopecompositions
are alsoto be accounted
for and are ited fromtheirsoume;
i.e., theyresultfromremobilization
exemplified
bytheGoldenMilein Western
Australia
(range andisotopic
homogenization
duringtransport
of preexisting
-4 to -10%o;Phillipset al., 1986)andthe Hemlodeposit sulfides in Birimian metasediments.
in Canada(range0 to -17.5%o;Cameron
andHattori,1985).
The near-magmatie
6a4Svaluesof gold-related
sulfides
Theabove
unusual
lightsulfurisotope
compositions
andthe fromKonongo
mayberelated
toslightly
different
mean6a4S
presence
ofvarious
sulfates
and/or
hematite
in thesedepositscompositions
of the sulfides
leached(ef. spreadof dataof
wereinterpreted
topointtotheinvolvement
ofoxidized
fluids sulfidesin Birimian metasediments;Table 3). Fluids with
or extensive
fluid-wall
rockreactions
leading
to anoxidation magmatie
signatures
maybe impliedfor the granite-hosted
ofthefluids(Cameron
andHattori,1985;Phillips
etal.,1986; Ayanfurideposit.
Kerrieh,1987;LambertandDonnelly,1990).
Conclusions
In theAshanti
beltof Ghana,sulfides
relatedto hydrothermalgoldmineralization
areisotopically
lightwith634S
ranging The soumeof mineralizing
fluidsof (Archcan)
mesotherfrom-4.6 to -11.4 permil (Ashanti,
Bokitsi,
Bogosu,
and malgolddeposits
is underdebate,andthe following
major
Prestea
mines;Table3 andFig. 7). Exceptions
aresulfides hypotheses
are in vogueat present:(1) strueturally
focused
fromKonongo
(-0.5 to -3.1%o)andonesample
fromthe metamorphic
dewatering
andoutgassing
at the greensehistgranite-hosted
Ayanfurideposit(0.7%0).
amphibolite
facies
transition
ofgreenstone
piles(e.g.,Phillips
Considering
the mostimportant
factors
fortheseunusual andGroves,1983),(2) mantledegassing
andgranulitization

300

OBERTHORET

AL.

at deep crustallevels(e.g.,Colvineet al., 1988),and (3)

Acknowledgments
magmatie
derivation
fromfelsieintrusions
(e.g.,Burrows
and
The presentworkis a contribution
of the Bundesanstalt
Spooner,1987).Notably,one mustalsotake into account
ftir
Geowissenschaften
und
Rohstoffe
(BGR)
project"Metalthat the sources
of the fluids,solutesandvolatilesmaybe
logenesis
of
Gold
in
Africa."
Sincere
thanks
go
totheGeologiindependent
(Kerrieh,1987).
cal
Survey
Department,
Accra,
Ghana,
especially
itsdirector,
Theisotopic
fingerprints
ofthesystems
studied
(6:3C,
6sO,
G.
O.
Kesse,
for
providing
logistic
assistance
in
Ghana.
The
6D, 634S)
in theAshanti
beltof Ghana
leadto thefollowing
management
of
the
Ashanti
Goldfields
Company
Ltd.
actively
interpretations:
supported
the workthroughgenerous
hospitality,
access
to
mine
data,
and
guidance
on
surface
and
underground,
su1. Carbonate
615C
andgold-related
sulfide
654S
values
indiby ourcolleagues
of the Geology
Departcatemetamorphic
fluidsin thesenseof PhillipsandGroves perblyorganized
ment.
The
State
Gold
Mining
Corporation,
Cluff
Minerals,
(1983),originating
fromoratleastequilibrating
withBirimian
andCanadian
Bogosu
allowedaccess
to theirproperties
and
strataat deepercrustallevels.
usefulinformation.
JoeAreanor,
RogerKumi,Wyl2. Quartzandcarbonate
61sOand6D valuesof waterin provided
(Ashanti),
andJeffNichols(Cluff)deserve
spefluidinclusions
pointto fluidsources
of metamorphic
ormag- lie Gyapong
cial
thanks
for
their
continuous
cooperation.
The
manuscript
maticorigin.Massive
streaming
of CO2ismanifested
in perby A. Techmer,Hannover,
vasivecarbonatizationand the CO2-dominantfluid inclusions benefitedfrom criticalreviews
and
two
Economic
Geology
reviewers.
G. GOdecke,
Hannoin the auriferous
quartzveins.CO2mayhavebeenexpelled
ver,
ably
typed
the
manuscript.
by granulitization
of thelowercrustwhich,however,
appears
unlikelyin theBirimianterraneof Ghanadueto thefactthat
onlyjuvenilecrustis present(Tayloret al., 1992).Alternatively,CO mayoriginate
fromthedecarbonatization
of Birimianlithologies
at depth,or mayhavebeencontributed
from
the mantledirectly.Certainmagmatic
contributions
to the
fluid systems
maybe indirectlyinferredfrom the at least
temporally
closelink betweenbasin-type
granitoids
(21162088Ma) andgoldmineralization
(2120-2070Ma).

October 2,5, 1994; November 6, 1995

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Structural
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andisotopic
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gold
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