Economic Geology

Vol. 79, 1984,pp. $8-49

Mobility of Gold and Silverin Lateritic WeatheringProfiles:

Some Observations from Western Australia

A. W. MANN

Divisionof Mineralogy,Institute of Energyand Earth Resources,

CSIBO, Wembley,WesternAustralia6014, Australia

Abstract

Mineralogicobservations of naturally occurringAu-Ag nuggetsfrom the Yilgarn Block,

WesternAustralia,indicatethat dissolution of Ag and/or Au is a relativelyfrequentoccurrence
alongthe rim of nuggets,especiallywhen there are adjoiningiron oxides.Smallgoldcrystals
of very high purity (<0.4% Ag) have been found intimatelyassociated with iron oxidein
laterite profiles.Thesealsosuggestthat Au and Ag have been dissolved,transported,and
redeposited duringlateritization.Experimentalevidencesuggests thatveryacidchloridesolutions
generatedin lateritic profilesby ferrolysis(oxidationand hydrolysisof iron) are responsible
for the dissolution of gold and silver.Au is subsequentlyreprecipitatedby reductionof the
AuCI•-ion with Fe+•. Reductionof the AgC1 øcomplexdoesnot similarlyoccurbecause of the
relativeredoxpotentialsof Fe+•/Fe+aandAg/AgC1 ø.Thuschemicalrefinement of goldoccurs
duringlateritization.The developmentof low pH and the redistribution
of goldand silverin
lateritic weatheringprofilesappearto be more commonover graniticand gneissicbasement
and may be inhibited by the presenceof carbonatein the weatheringzone of basicrock
sequences.

Introduction coveringcleavageplanesetc., so as to representthe

TI-I•:originof alluvialgold,gold nuggets,and partic- appearanceof painted surfaces.The mode of occur-
ulate gold in the weatheredzone has long been the rence,associations, and characterof thisgoldall point
subjectof conjectureand discussion. In Australiasome to a secondary origin; this secondarygold has been
of thesediscussions (e.g.,Brough-Smyth, 1869)were deposited from solution not only in somecasesin the
committedto paperbeforethe discoveryof majorde- alluviumand other superficialand residualdeposits,
positsin WesternAustralia.Many easternAustralian but alsoin the zoneof decomposition of the bed rock"
nuggets wereknownto be finer(containing lesssilver) (p. 8). More recentlyWilson (1981) has observed gold
thanveingold(Liversidge, 1898).In manycases gold in the weathering environment of some Australian de-
in the oxidizedzone was observedto be crystalline, posits whichisfiner(lower%Ag)thanadjacent primary
vein material.
and it was thoughtto have been transportedin, and
depositedfrom, a low-temperatureaqueoussolution. Variouslaboratorystudieshave shownthat gold is
Simpson (1902)subsequently described andanalyzed soluble in chemicalsolutions whichmay occurnaturally
goldfrom severalWesternAustraliandeposits.Eight in weatheringprofiles.McCaughey(1909)showedthat
gold samplesfrom quartz veinsand alluvial nuggets solutionsof ferric saltscould dissolvegold and that
the addition of ferrous ion to these solutions inhibited
were found to contain from 8.5 to 28 percent silver
(byweight). • Twosamples--sponge goldfromtheox- their abilityto dissolve gold.Smith(1948)foundthat
idizedzoneat Kalgoorlieandcoarse goldfromironstone goldcouldbe dissolved in, and subsequently precip-
pebblesat Coolgardie--contained lessthan0.7 percent itated from, sodium sulfide solutionsat low tempera-
silverby weight. Singleoctahedrawere observedin ture. He alsonoted that thesesulfidesolutions,if left
asbolite(a cobalt-manganesewad)in soapyclayfrom to oxidize in air, formed sulfatesand thiosulfates.
Kanowna,20 km north of Kalgoorlie--thefamous The importanceof the chlorideion, low pH, and
"deeplead."Coarsegoldwith well-developed crystal oxygen content(or redoxpotential)on the solubility
faceswasalsoobservedat Bulongnear Kalgoorlieand of goldwas deduced by Krauskopf (1951)ontheoretical
Norseman.Gibb-Maitland(1919), summarizingthe grounds. A seriesof experiments at low pH with NaC1
WesternAustraliangolddeposits, concludedwith re- by ClokeandKelly(1964)demonstrated thatgoldwas
gardto goldin the weatheringzonethat:"In addition dissolved at an appreciableand observable rate when
to the undoubtedresidual(or detrital)gold,thereis crushed pyrolusite was present in acid, chloride so-
another massive,arborescent,or coarselycrystalline lutions.Lakin et al. (1974)showedthat a wide range
form which occursfilling certainirregularcracksor ofionsandagents, includingCI-, I-, Br-, S20•2,SCN-,
CN-, andorganicsubstances, coulddissolve goldunder
I All valuesin thispaperare quotedin weightpercentAg. laboratoryconditions.

0861-0128/84/261/88-1252.50 88
 MOBILITY OF Au AND Ag (39

Despitethe numerousfield observations indicating amounts of rain derived from local thunderstorms con-
solutionmigrationof gold,andthe numerous laboratory tributeto the annualtotal.Wiluna, for example(see
experimentsindicatingthe typesof solutions likely to Fig. 1), hasan annualaveragerainfall of 24 cm/yr.
be responsible for solutionmigrationof goldin nature, The annual average maximum temperatureis over
there have been few, if any, detailedattemptsto link 25øC for most of the area, and in the hot summer
closelyfield observations with laboratoryexperimen- months(December
to February)theaveragemaximum
tation. In part, this is due to the fact that suitable daily temperatureis often above$5øC. The southern
materialfor mineralogicstudyof gold in weathered andwesternportionsof the YilgarnBlockhavea milder
profilesis limited, and becausethe rate of dissolution Mediterranean-type climate, with winter rainfall
of goldin low temperaturesolutionsis relativelyslow. (April-August)beingderivedfrom subtropicallow-
Thispaperdescribes observationsmadeongold-bearing pressure
systems
and onshorewesterlywinds.Northam
materialmade availableby prospectors and company (see Fig. 1) has an annual averagerainfall of 44
geologists in weatheringprofileson the YilgarnBlock, cm/yr.
WesternAustralia.It alsodescribes laboratoryandfield Drainage over mostof the Yilgarn Block is almost
experimentsperformedin an attemptto explainsome entirelyinternal.The drainagebasinsare broadwith
of the observedmineralogicfeatures. lowgradientsandin generalarecharacterized by large
areasof colluvialand alluvialslopes--herethe water
(geology,Climate, and (geomorphology table is between 10 and 40 m below the surface. Salt
The YilgarnBlockof WesternAustraliahasan area lakesoccur in the remnant palcodrainagesystems.
of 657,$00km2 and is composed of Archcanrocksof Thesesaltlakesor playasfunctionasdrainagesumps
the EasternGoldfieldsprovince($45,100km2),the for surroundingareas,particularlyduring periodsof
Murchisonprovince(161,000km•), and the South- increased rainfall.
westernprovince(140,$00km•) andof adjoiningPro- Relict weatheredprofilesare commonover much
terozoicrocks(10,900km•). The EasternGoldfields of the YilgarnBlock.They owetheir developmentand
province constitutesthe eastern half of the Archcan preservationto tectonicstability,low relief, a long
YilgarnBlock.Intrusivegranitoidrocksapproximately subaerialhistorywith a generalabsenceof Cenozoic
2,900 to 2,500 m.y. in age compriseabout 70 percent glaciation,and a geologicallylate trend to aridity
of this province,with the remainderconsistingof (Mabbutt,1980).They provideevidenceof pastgeo-
metamorphosed igneous andsedimentary assemblages,chemicalregimesand of the evolutionof associated
or greenstonebelts, which are north or northwest land surfaces,and they have locallycontrolled,sub-
trendingandpredatetheintrusivegranitesandgneisses sequentlandformdevelopment. The weatheredprofiles
(Williams,1975).The Murchison province, comprising commonlyhave indurated upper horizonsor duri-
thenorthwest portionof the YilgarnBlock,hasa geol- crusts--ferruginous, siliceous,
calcareous,
or gypseous.
ogysimilarto that of the EasternGoldfieldsprovince Deeplyweatheredkaoliniticprofileswhichhavea fer-
with the exception thatthe granitoidrocksare usually ruginousand/or siliceousduricrustoccurextensively
youngerin age,the metasedimentary and metavolcanic over granitesand also over sedimentary,basic,and
rockshave,in general,a lowergradeof metamorphism,ultramaficsequences and are commonlyreferredto as
andthestructural trendiseast-northeast (dela Hunty, lateriteprofiles.Therearelargevariationsin the detail
1975). of individuallateriticprofilesaccordingto locationon
The majorgolddeposits, whichoccurpredominantly the YilgarnBlock,underlyinggeology,and landscape
in the EasternGoldfieldsand Murchisonprovinces, position.Figure 2 showsan idealizedlateriticprofile.
are shownin Figure 1. This is the type of profilewhichmight occurtoward
The majorgolddeposits are associated with green- the centerof the YilgarnBlock,overa granite-green-
stonebeltsandare largelyepigenetic.Primarygoldis stonecontact,a favoredgeologicenvironmentfor epi-
foundlocatedin a numberof rock types,including geneticgold deposits.
quartzveins,felsicvolcanics,volcanogenic sediments, This lateritic profile consistsof an upper pisolitic
metabasalts, and metadolerites. Pyrite is a ubiquitous layer of coarseironstone pebbles(cementedby fer-
accessory mineral.The presenceof a granitoidheat ruginousmaterial)whichmay eithercropout at the
sourceis a commonfeature--goldis alsooccasionally surface or be covered with a thin cover of soil. The
foundin granitoidmaterialadjacentto granite-green- pisoliticlayer, and ferruginouszonesin general,are
stone contact zones. usuallybetterdeveloped overbasicandmaficsequences
The climateof the northernand easternYilgarn becauseof their higheriron content.Beneaththe pi-
Blockissemiaridto arid.The rainfallisirregular;heavy soliticlayeroccursa mottledzone,whichovergranite
butinfrequentfallsof rainoriginatefromtropicallow- is usually pale to off-white kaolinitc with brown or
pressuresystemswhich mostoften occurduring Jan- orangeferruginous stainingandangulariron-richfrag-
uary to June.During Octoberand November,smaller ments.In lateriticsequences developedoverbasicrocks
40 A. W. MANN

i i
117 ø 120 ø 123 ø

Meekath,

-28 ø

,• •%• Southern

*Northam
Metredin
•
½PERTH ,
Norsem•

f /•-/• Predominantly
gramtes
,• Greenstones
• Major fault

0 50 100 150km
• Boundary of Yilgarn Block
I I I I
• Major gold deposits
I I I

FIG.1. Locationof the majorgold-producing

centerson the YilgarnBlock,WesternAustralia.

this zone may containuniformlystained(yellow, not only to the grade in parent material but to the
brown,purple,or green)kaoliniticclays.Beneaththe underlyinglithology.In many casesgold is prefer-
mottledzone,a pallidzoneof paleto off-whitekaolinite entiallyassociated
with iron oxidefragmentsand nod-
extends downward to fresh bedrock. The contact be- ules in the mottled zone, and as such it constitutesa
tweenthe pallid zoneand freshrock is gradational, majorsamplingproblemto establish gradeandtonnage.
with relicttexturesrelatingthe pallidzoneor saprolite For similar reasons, and because of the additional
to parentmaterialin somecasesextendingovertens problemof lateral transportof someof the pisolites,
of meters. gold distributionin pisoliticlayersis alsousuallyir-
Gold,characteristically,
showsan increasein grade regular,makingsurface-based explorationtechniques
andpurityin themottledzoneof suchprofiles,
although difficultto apply in this terrain.
the degreeto which this occursis apparentlyrelated Large gold nuggetshave been a feature of some
 MOBILITY OF Au AND Ag 41

Quartz
outcrop

0-1m
o
oO o o
o * o ß o- e
ø.ø o o o.
o o
•
o'o ooOoO -L.Sod
o•o oOoOo

-•Pisohtic
hayer
LMottledzone
1-10n - kaolinire
+ ferruginous
J fragments

10-40m Palhd zone

kaolimte

vvvYvvvvvv
+ + + +
++++++++ + + + + ++ +++++++++ +++ +
vvvvv¾¾vv
vvvvvvvvv
++++++++++++++++++++++
++++++++++++++
+++++++
Bedrock
vv•¾vvvvv
+++++ +++++++++ +++++++++ +
vvvvvvvv¾
vvvvvvvv
vvvvvvvvvvv
+++
+ +++++++++++ +++++
++++++++++++++ +++++
+++++++
++++++++++++++ +

FIG.2. Idealizedlateriticweathering
profileovera granite-greenstone
contact.+ = granite,v = greenstone.

partsof the residuallateriticsurfaceof the Yilgarn whichwereprobablywidespread ontheYilgarnBlock

Block,sincethe time of discovery
of goldin the 1890s. duringthe Tertiary,we mustturn to present-day hy-
The discoveryof Coolgardie,Kalgoorlie,Menzies,and drogeochemical evidencefrom the southwesternpor-
many other major gold centerswas dependentupon tion of the YilgarnBlock,whereprocesses akin to la-
the detectionof nuggetsat or near the surfaceby the teritization are believed to be still active.
early prospectors.
More recently,sincethe advent of ßThe datain Table 1 are chemicalanalyses
of ground
the modernmetaldetector,numerous nuggets(many watersfrom an activeprofile at the CSIRO Yalanbee
in excessof 1 kg wt) have been recoveredfrom just field station,near Northam(seeFig. 1); thesedata
beneaththe red-brownferruginous surfacein boththe showthat waterscontainhigh concentrationsof chlo-
Murchisonand EasternGoldfieldsprovinces.Someof rideion(in excessof 0.1 M), andmanyhavepH values
thesenuggetshavebeencloselyassociated
with quartz; below pH 4. Two sampleshave a pH value of 2.8.
most have been characterizedby adhesionsof iron Measurementsof Eh and pH of groundwater from
oxide. this same profile show the characteristicEh and pH
regimes.Eh valueswere obtainedfrom the voltage
Hydrogeochemistryduring Lateritization measuredbetweena platinumandAg-AgC1electrode,
Lateritizationon the Yilgarn Block, WesternAus- andpH wasmeasuredusinga standardglasselectrode.
tralia, is thoughtto have taken placeat varioustimes Values were obtained in situ from water in a series of
sincethe Mesozoicandextendingto the present;pro- drill holesinto the profileand are shownin Figure$.
cesses akinto lateritization
arethoughtto beoccurring The pathof oxidationand hydrolysis of Fe+2,mea-
in the drainagesof the southwestern sectionof the suredin the laboratoryusingthe sameelectrodes and
YilgarnBlockunderpresent-day conditions(Bettenay a 1 M solutionof FeSO4oxidized in air, is shownon
et al., 1979).Bowler(1976)contends that the climate the samediagram.The path of Fe oxidationand hy-
of the northernpart of the YilgarnBlockwashumid drolysisin the field can be reconstructedwith this
at sometime during the Tertiary and that there has laboratory information.Groundwater at depth(low
beena gradualtransition (withfluctuations)sincethat Eh, approximately200 mV in Fig. $) has a pH of
time to the arid climate of the present.Thus, in the nearly6.0, a highFe content(204 mg l-I), anda low
past,the northernand easternpartsof the Yilgarn A1content(0.1 mg 1-1).Asthissolutionisoxidizedthe
Blockmayhavehadclimatic,geomorphological, and Eh risesandpH falls(for the syntheticsolutionalong
hydrogeochemical conditionssimilar to thosewhich lineA-B) asFe+2is removed.The process is probably
existat presentin the southwesternareaof the Yilgarn closelyrelated to that observedfor the oxidationof
Block.To appreciate thehydrogeochemical conditions pyritein acidmineseepages (e.g.,StummandMorgan,
42 A. W. MANN

TABLE
1. Analysis
of Ground
Waters
at theCSIROYalanbee
FieldStation
(nearNortham)
Sample
number pH Mg Na K Ca SO4 CI SiO2 Fe AI
mg 1-]
549 3.5 413 3,686 37.2 13.5 454 7,094 110 8 $1
550 4.5 645 5,500 99 41.8 783 10,468 97 43 5
551 3.6 437 3,706 49.7 32.6 461 7,177 100 10 16
552 3.4 388 3,263 41.1 28.7 447 6,323 99 7 15
555 $.5 $91 $,245 40.8 28.5 455 6,$$4 99 4 15
554 3.5 308 2,942 49.3 11.0 326 5,646 102 $ 15
556 2.8 471 $,687 7.82 5.46 599 7,458 112 72 26
558 4.6 195 2,100 47.3 2.59 176 4,177 85 48 4
559 $.$ 733 5,933 118 48.9 919 11,601 115 17 16
560 3.5 666 5,800 93.0 18.0 931 11,146 116 49
561 4.5 808 $,558 55.0 202 614 8,375 79 8 1
562 $.5 726 3,338 53.6 179 556 7,802 75 1 8
566 5.3 $25 4,540 138 56.0 604 8,398 62 204 <0.1
567 $.5 393 $,545 43.1 34.7 486 6,937 105 6 17
570 2.8 856 4,189 15.7 216 764 10,052 97 96 58
571 3.2 404 3,286 42.4 29.5 462 6,531 98 4 14

1970), which is bacteriallycatalyzedby Thiobacillus processin the vicinity of gold deposits.In the caseof
ferroxidans.Pyrite is a ubiquitousaccessory mineral a deepand well-developed lateriteprofilethe oxidation
in Yilgarnblockepigenetic golddeposits,andoxidation probablyoccursas two discretereactions,the first at
of pyriteprobablycontributes stronglyto the ferrolysis the weatheringbedrockfront:

Eh-pH Measurements ß Field station measurements (Northam)

: •-_Experimental path of hydrolysis

1.5 m

Air oxidized FeSO4 + MnO2

O Air oxidizedFeSO4 solutions

Mn02 [] FeCI
3 solutions
..
Mn
2+ • X Na2S203 solutions
"• 0 Fe
3+Thermodynamic
1.0 'L,'•,• De•
'•0 • •_• oro,o,•
•,, Fe2+ values
AuCI•(10
-5M) •'/t/on

Eh Au
Fe3+
• FeCI
34 + MnO
FeSO 2
• •ater
volts Fe2+
•FeSO4
0.5 ß B
H Mn2+•

AgCI Fe2+
e• ß

Ag A X•XNa2S203
, I I I , I , I , I
0 2 4 6 8 10
pH

Fic. 3. Eh-pHdiagramshowing
somerelevantredoxpotentials,
andexperimental
datafor ferrolysis
experiments
and Au,Agmobilityexperiments.
.i

MOBILITY OF Au AND Ag 43

2FeS2+ 2H20 -{-702 '-• 2Fe+2-{-4SO•-2-{-4H+,

and the second,the oxidationof ferrousion at or near
the water table at a higheroxygenfugacity:
2Fe+2+ 8H20 + 1/202 --• 2FeOOH + 4H +.
The data in Table I clearly show that parts of the
saturatedlateriteprofilecontainappreciableconcen-
trations of ferrous and sulfate ions, and that concen-
trations
of ferrousion(ca.10-a M) areappropriate
for
the developmentof pH's in the range2 < pH < 8.
This reactionin lateriteprofileshasbeen referredto
as ferrolysis
.(Mann,1983)becauseof the similarities
with soil processes(Brinkman,1977) for which this
term has been used.
As a consequence of the ferrolysisreaction,pallid FIG.4. Opticalmicrograph of a polished
sectionof a goldnugget
zone profilesbecomeexceedinglyacid. This process fromnearAgnew,WesternAustralia. Themicrograph,200•m across,
canoccuroverlargeareas;ground-water seepages with shows incipientremobilization
of goldandsilveralongthegold-iron
pH valueslessthan2.5 arecommonalongthe western oxideboundary. The Au-Agalloyappearsasa paleoff-whitecolor;
gray = iron oxide;black= void.
edgeof the DarlingScarp(Fig. 1), andsaltlakeswith
pH values<4 arecommonasfar eastasSouthernCross
(Mann,1988).Valuesof pH nearthe watertableand
Ag by weight,comparedto 4.4 percentAg in the main
in the capillaryfringeof the actualprofilewherethe
nugget.Table 2 showsthat this phenomenonwasob-
process originatesare likelyto be evenlowerthan this.
servedin severalother nuggetsas well; whereasthe
As a corollary,it can be stated that wherever and
wheneverthe oxidationof iron takesplacein profiles
percentage of Ag in the mainbodyof the goldnuggets
was alwaysin excessof 4 percentAg, that in gold
suchas these,hydrogenion must be producedand
fragments
therewill be a tendencyfor an acidicprofileto develop.
in ironoxidesurroundingthe nuggets always
containedlessthan 0.2 percentAg.
If bicarbonateion (e.g.,fromweathering basicrocks)
Further evidencefor redeposition of gold of very
is presentthis acid productionmay be neutralized.
high finenessin the weatheringzone was obtained
However,overmuchof theYilgarnBlock,particularly
where substantiallaterite cappingsand ferruginous
froma golddepositnearSouthern Cross(forlocation,
seeFig. 1). Figure 5 showsa scanningelectronmi-
horizonsare observed,acid conditionsare likely to
have been prevalentat or aboutthe time of formation
of iron oxide. TABLE2. MicroprobeAnalysis of GoldNuggetsand Goldin
Associated
Iron Oxidesfrom Agnew,WesternAustralia
Gold--Mineralogic Observations
Figure4 showsthe polishedsudaceof a nuggetfrom Numberof Mean % Ag a
Sample analyses (by wt) (%) Fineness
Agnew,WesternAustralia(for location,seeFig. 1),
one of twelve from the surfaceof a lateritic profile Main bodyof nugget
overa basicsedimentarysequencemadeavailablefor
AGN 15 9 7.9 0.8 0.921
scientificstudy. AGN 7 14 7.6 0.2 0.924
The field of Figure 4 showsa boundarycontact AGN 81003 2 7.5 0.3 0.925
betweenthe mainbodyof the nuggetandan adhering AGN 14 15 7.5 0.3 0.925
AGN 81002 8 7.4 0.2 0.926
piece of iron oxide.Alongthe boundarya crack has AGN 1A 14 7.2 0.2 0.928
developed,probablycausedby shrinkageduringa de- AGN 16 8 6.5 0.2 0.935
hydrationphase.Insidethe iron oxidea rim of gold- AGN 19 9 6.2 0.5 0.938
bearingmaterialsubparallelto the nuggetoutlineis AGN 81001 3 5.9 0.1 0.941
AGN DB001 9 5.5 0.4 0.945
evident.The texture of this rim suggests partial re-
AGN 17 15 4.4 0.1 0.956
placementof gold by iron oxide.This in turn implies AGN 20 8 4.0 0.3 0.960
that the goldnuggetwassubjectto dissolution along
its rim, at or about the time of iron oxide formation.
GoM paRiclesinassociated
Feoxides
Throughoutthe iron oxidematrix, numeroussmall
AGN 16 4 O.2 0.1 0.9•
particlesof gold(<1-10 •m) wereobserved.
Electron AGN 17 9 0.1 0.1 0.9•
microprobeanalysisof someof the .largerof these AGN 18 6- 0.1 0.1 0.9•
fragments
showedthemto containlessthan0.2 percent
44 A. W. MANN

Dissolution of Au and Ag
A seriesof simplelaboratoryexperimentswere per-
formed in order to assessthe most likely chemical
agentsresponsible for the solutiontransportof goldin
lateritic profiles.In all of theseexperiments,a finely
dividedprecipitateof puregoldwaspreparedby add-
ing ascorbicacid to a gold-containing aqua regia so-
lution. The precipitatewas filtered and washedand
transferredto a conicalflaskcontainingthe solution
understudy.In a similarway, AgCI wasprecipitated
froman AgNO8solution. Bothprecipitates wereheld
in contactwith the appropriatesolutionat 25øC in a
waterbathwith occasional shaking,and afterthe pas-
sageof the requiredtime, the solutions were filtered
usinga 0.45-/•mfilter. The filteredsolutions
werean-
alyzedfor Au and Ag usinga Varian TechtronAA5
atomical•sorptionspectrophotometer (detectionlimits,
Ag _+0.02 ppm, Au _+0.07 ppm). AliquotsOf.each
solventwere carriedthroughthe process and usedas
blanksin the analysis.The resultsof theseexperiments,
FIC.5. Scanning
electronmicroscope of a smallgold which clearly do not indicateequilibriumsolubilities
photograph
crystal
ofhighpurity(•0.4% Ag)takenfromanironoxidevoidfrom but rather relative mobilities, are shown in Table $.
a depositnearSouthernCross.The goldcrystalis approximately
20 The datain Table$ showthat low pH's weredeveloped
/•m across.
by solutions
of FeSO4and FeCI8in the presence
of
NaCI. These solutionsdissolvedAg and, in the case
of FeCI•, someAu. SolutionscontainingFeSO4and
croscope photographof a smallgoldcrystalapproxi- NaCI did not dissolveAu. However,as shownby the
mately20/•m across depositedin an iron oxidenodule factthatAu (andAg)weredissolved in NaCIsolutions
approximately 4 m belowthe surface. containingHCI, the presenceof ferric ion is not es-
Many crystalswith perfectlyformedfacessuchas sential to the dissolution of Au in chloride solutions.
thoseshownin Figure 5 were obtainedfrom voidsin Thiosulfatewasfoundto be a goodsolventfor Au and
iron oxide--clearlya late-stagedepositionin the iron Ag in the neutral-alkalinepH range.
oxide.Smallpiecesof flakegold,somewith straight Clearly, the predictionmade by Krauskopfin his
edges,were observedwithin the adjacentiron oxide. theoreticalstudy--that solutionswith low pH, high
Thesecouldhavebeencrystallinewhen depositedbut chlorideion concentration, and high Eh will dissolve
subsequently deformedas the iron oxide precipitate gold--isillustratedherein a varietyof ways.Solutions
hardened.Electron microprobeanalysisof polished containingNaCI, with MnO2 present,only dissolve
sectionscontainingthis crystallinegold showedthat goldwhenacid is added.Solutions derivinga low pH
it had lessthan 0.4 percentAg. fromthe oxidationof FeSO4(by ferrolysis)do notdis-
The crystalsobserved by Simpson(1902)in the as- solveappreciablegold even when NaCI is present,
bolite at Kanownawere probablyanalogousto those unless thereiscompleteoxidation of Fe+2,e.g.,by the
recordedhere. Kaoliniteand ironstonegravelsat Ka- additionof MnO2. Completeoxidationof Fe+2 may
nownaare developedoverweatheredgranite,weath- alsobe achievedin natureby atmospheric oxygenbe-
ered schist,and felsiticrock (Gibb-Maitland,1919). causeof the longertime scalesinvolvedand because
Wilson(1981)notedthat octahedrasimilarto those of the alternatewetting and drying in the capillary
found by Simpsonoccurredin deeply weatheredAr- fringeabovea water tablecausedby fluctuations in
chcan metamorphicrocks near a Tertiary uncon- the water table. The importanceof Eh can be dem-
formitywith highlysalinecarbonaceous at onstratedwhen the Eh valuesof the FeSO4and FeCla
sediments
Norseman.Small,perfectlyformedgoldcrystalshave solutionsusedin theseexperimentsare plottedon the
also been observed in the mottled zone above weath- Eh-pH diagram(Fig. $).
ered gneissat the Edna May depositnear Merredin Oxygenwasfoundby Krauskopf(1951)to bea most
(J.Webster,pers.commun.), andthe phenomenon of likely oxidantfor gold, and the solubilityof gold at
redeposition of smallgold crystalsof high purity is varyingconcentrations of H + and CI- in equilibrium
probablyrelativelywidespreadin depositswith a sim- with air (02 with a constantpartial pressureof 0.2
ilar type of lateriticweatheringprofile. atto) wascalculated.Thesecalculations showedgold
 MOBILITY OF Au AND Ag 45

TABLE 3. Mobilities of Gold and Silver in Various

in excessof 0.1 M and had pH's closeto pH 3. Such
Solutions at 25øC
solutionswoulddissolvegoldprovidingsufficientox-
Time Ag Au
ygenwaspresentin solution.Near the water table,or
Solution (days) pH (ppm) (ppm) above it in the capillary fringe, oxygenfugacities
> 10-5 mightreadilyoccur.Lowerin theprofile,where
Chloride+ manganese
oxide groundwaterscontainsignificantconcentrations of
1 M NaCI + MnO2 14 0.6x 6.7 0.3 ferrousions(and concomitantly, little oxygen),gold
1 M NaCI + MnO2 14 3.4x 7.6 0.1 couldbe expectedto havelimited solubility.
I M NaCI + MnOz 14 6.2 8.2 <0.1
Preferential Leaching of Ag from Au/Ag Alloys
Bicarbonate,sulfide Figure 6 showsthe scanningelectronmicroscope
0.01 M Na2S + 0.1 M NailCOs 14 9.3 0.02 <0.1 imageof a portionof the exposed
outeredgeof one
0.1 M Na2S + 0.1 M NailCOs 14 11.8 0.01 0.2 of the nuggetsfrom the Agnewarea.
1 M Na2S + 0.1 M NailCOs 14 13.4 0.07 0.7 This image,takenfrom a surfacenot boundedby
iron oxide,showsa pockmarkedand corrodedarea of
Thiosulphate highercontrast(higherpurity Au) than the internal
0.01 M Na2S2Oa 14 9.8 53 <0.1 section,which containsa higher percentageof Ag.
0.1 M Na2S2Os 14 11.2 104 0.3 Figure 7A and B showsthis effecton electronmicro-
1 M Na2SzO• 14 10.5 165 0.4 probescans acrosstheedgesof nuggetAGN 14 which
hasa matrixcomposition of 7.5 weightpercentAg.
Ferrous sulfate
The perimeterof thisnuggetboundedby ironoxide
0.1 M FeSO4q- 0.01 M NaCI 14 1.9 0.2 <0.1 (thesimilaredgeshownin Fig. 4) shows a sympathetic
0.1 M FeSO4q- 0.1 M NaC1 14 1.9 0.3 <0.1 declinein both Au and Ag at the iron oxide/nugget
0.1 M FeSO4q- 1 M NaC1 14 1.9 6.8 <0.1
1 M FeSO4q- 0.01 M NaCI 14 1.6 0.02 <0.1
boundary.By contrast,the exposedouteredgeof this
1 M FeSO4+ 0.1 M NaCI 14 1.7 0.12 nugget(Fig. 7B; no Fe oxidecontact)showsa 50
1 M FeSO4+ 1 M NaCI 14 1.6 4.6 depletionof Ag in from the Au rim. Thisboundaryis
0.1 M FeSO4q- 1 M NaCI 140 1.9 6.0 <0.1 sharp, not diffuse; the silver content just inside this
0.1 M FeSO4+ 1 M NaCI boundaryis equivalentto that of the main bodyof the
+ MnO2 14 1.9 6.0 0.4
nugget.Clearly, there is preferentialleachingof Ag
Ferric chloride
from the Au/Ag alloy,nearthe surfaceof the nugget.
This raisesthe moregeneralpossibilityof preferential
0.1 M FeCIs 20 1.4 0.7 0.5 dissolutionof Au-Agalloysin naturalsolutions, com-
0.1 M FeCIs + 1 M NaCI 20 1.4 9.2 1.9
0.1 M FeCIa + 1 M NaCI
paredto that of pure Au, or pure Ag, as reportedin
Table 3.
0.1 M FeCIs + 1 M NaC1
q- MnO2 20 1.2 13 39 Furtherevidenceregardingthe dissolutionof Au-
Ag alloyswasobtainedby measuring
the galvanicelec-
Hydrochloricacid tromotiveforces(and current)generatedbetweena
0.03 M HC1 14 1.4 0.1 0.8
0.03 M HCI q- 0.1 M NaCI
+ O2 14 1.4 0.4 1.4
TABLE4. Solubilityof Gold in Solutions with Different
0.03 M HCI q- 1 M NaCI q- O2 14 1.4 3.8 1.4 Activitiesof H + and CI-, and DifferentFugacitiesof Oz
Dataarecalculated
frominformation
in Krauskopf
(1951).
Acidaddedto attainthispH
a.+ acl- fo• a^•cn Au(ppm)
10-2 10-x 10-• 10-o75 35,032
to be solubleat low pH andhighchlorideion activity 10-5 10-z25 1,107
(e.g.,Au = 200 ppm at pH = 2 and act- = 10-2). 10-7 10-s 75 35
10-ø 10-5 25 1.1
However, as shown in Table 4, with data calculated
usingconstants from Krauskopf(1951),Au solubility 10-s 10-• 10-a 10-s 75 35
is criticallydependenton oxygenfugacity,fo2 aswell 10-5 10-5 25 1.1
10-7 10-6 75 0.035
asa.+ and act-. At pH = 3 and act- = 10-1, gold is 10-ø 10-s 25 0.001
relativelysolubleatfo2> 10-s andrelativelyinsoluble
at fo2 < 10-s if an activity of 10-s Au is usedas the 10-4 10-• 10-s 10-6 7s 0.035
10-5 10-8 25 0.001
criterionfor goldsolubility. 10-7 10-o 75 <0.001
Groundwatersfrom the active laterite profile at 10-ø 10-n 25 <0.001
Yalanbee(Table 1) containedchlorideconcentrations
46 A. W. MANN

highpurity(0.9999fineness)
Auelectrode
andsynthetic
Au-Agalloys,asshownin Table5.
Thesecrudeelectrochemical experimentsshowthat
in a solutionof 0.08 M HCI and 1 'M NaCI, alloysof
Au-AgarelessstablethanpureAu. In all cases
a
galvanic
current(or the orderof 1-10 •A/cm•) was
observed
to flow,withthe Au-Agelectrode
always
beinganodie.In a sodiumthiosulfate
solution
theresults
are a little ambiguous:
the generatedelectromotive
forces are less than 0.1 V and there is little consistent
variationwith alloy composition.
Althoughthere is
dearly roomfor furtherexperimentation
in this area,
theseresultsindicate that in an add chloride medium,
Au-Agalloysare potentiallylessstablethan pure Au.
Whetherdissolutionof an Au-Agalloyreleases silver
or bothgoldand silverto the solutionremainsto be
considered.

Discussion

The chloridecorrosionof gold-containing casting

alloyswasinvestigated by Brugirardet.al. (1973)and
Sarkaret al. (1979) in connectionwith their studies
FIG.6. Scanning electronmicroscope
imageof a polished
section
of a nuggetfrom the Agnewarea. The silver-depletedouter rim on dental alloys.Polarizationcurvesshowedthat, in
appearsasa palergraycolor.The micrograph
is approximately400 general,the higherthe goldcontent,the greaterthe
pm across. resistance to corrosion. In some cases a variation in

A I 2ø'•mI •'

'External
surface
•/
] Au
nugget
(7.5%
Ag)
' •-- f• I 20•m
I B
Fro. 7. A. E!•tron micropro• •an acres the •dary •tw•n an Au-AgM!oyand iron oxideo[ a
nu•et, AGN ]4, [romthe Angewarea.B. E!•tron micro•o• • acres the ex• outer•ge o[ the
same nu•et.
 MOBILITY OF Au AND Ag 47

TABLE 5. Galvanic Electromotive Forces Generated between a

sponsiblefor the observedmigrationof goldandsilver,
High-PurityAu Electrode,and Au/Ag Alloy Electrodes,
in 0.03 M HCI-1 M NaCI and in I M Na•S•Oa
except possibly at the weatheringbed-rockinterface,
where freshsulfidespersistand thio- speciescouldbe
Atomic emf emf insufficientconcentrations to redistributelocallygold
percent Fineness (HCI, NaCI) (Na•S•Oa) and silver. In laterite profilesgold has clearly been
remobilized well above the bed-rock zone, where the
90 0.94 -0.15 V -0.04 V
80 0.88 -0.19 V 0.0 V
mineralogyindicateslate-stageoxide precipitatesof
70 0.81 -0.24 V +0.02 V iron ratherthan sulfides(e.g.,Fig. 4). Furthermore,
60 0.78 -0.25 V -0.09 V thiosulfates and sulfides are not stable under acid con-
50 0.65 -0.29 V ditions,and the likelihoodof laterite profilesbeing
-0.09 V

acidicowingto ferrolysishasbeen discussed. Humic

acids(e.g.,Baker,1978)and cyanidecannotbe real-
the rate of dissolutionwith time was noted; this was istically consideredbecausein most laterite profiles
attributedto a residueof almostpure goldformingat organicmatter is extremelyrare if not absent.In other
the surface.However none of the alloysstudiedcon- typesof weatheringenvironment,for examplethose
tained just Au and Ag. described by Pitul'ko(1976)and Fisher(1945),thio-
Potter(1961)discussed thecorrosionandelectrolysis sulfate,organicmatter, and/or cyanidemay play an
of alloysand pointedout that the simultaneous release important part.
of two or more metal ionsfrom a corrodingalloy de- Low pH and a high concentrationof chlorideion
pendson the individual current potentialor polariza- appearto be requisitefor goldandsilverremobilization
tion curves of the metals. The two main variables which in lateriteprofiles.In acidchloridesolution,goldforms
affectthe disposition of polarizationcurvesare quoted chloride complexes,the most important being
aselectrolytecomposition and temperature.In the case AuCI•-(Sillenand Martell,1964).Silversolubilityin-
ofnaturalcorrosion of Au-Agalloys,it appears therefore creases withincreasing chlorideionconcentration (e.g.,
that somenatural electrolytesolutionswill be capable seeTable 3), despitethe limited solubilityof AgC1,
of dissolving bothAu andAg froman alloy,andsome, becausesilver alsoformssolublechloridecomplexes,
lesspotent,will preferentiallyremoveAg only. Min- e.g.,AgCIø, AgCI•, and AgCI• -2 (Sillenand Martell,
eralogicevidencefor the formerappearsin Figure 4, 1964). Storageof solublesalts,principallyNaC1,has
andmineralogic evidencefor the latterappearsin Fig- beenshown(Dimmocket al., 1974)to be in excess of
ures 6 and 7B. I X 105kg/hain lateriticprofiles
of theYilgarnBlock
Laterite profilesin WesternAustraliain the vicinity ofWesternAustralia.
Hingston andGailitis(1976)have
ofgolddeposits
(asdemonstrated
byFig.5) oftenshow shownthat mostof this salt is derivedfrom the pre-
an enrichmentof very pure gold.This hasalsobeen vailingonshorewesterlywind systemwhichbringsthe
observedelsewhere,for exampleby Mackay(1944)in bulk of present-dayrainfall to southwestern Australia.
AfricaandEvans(1981)in the UnitedStates. During If similarsystemsare responsible for rainfall during
periodsof lateritization,conditionsconduciveto the the developmentof lateriteson the YilgarnBlockdur-
mobilizationof Au and Ag are obviouslydeveloped. ing the Tertiary, then largeamountsof chloridehave
Becauseof the more extremeconditionsrequired to probably residedin laterite profilessincethat time.
dissolvepure gold ascomparedto an Au-Ag alloy,in For oxidationof goldby oxygen,in the presenceof
many lateritic profilesconditionswill prevail where the chloride ion, the reaction is:
an Au-Ag alloy will dissolvemore readily than pure
4Auø + 16C1- + 302+ 12H+
Au. In suchcaseschemicalrefinementof gold may
occur--dissolution of an Au-Ag alloy followedby re- • 4AuCI•-+ 6H20. (1)
precipitation of almost pure Au from solution. It is
implicitthat underconditions in whichgold is only Whereasthe dissolution of gold via this reaction
marginallysoluble,a small changein any chemical requireshigh oxygenpartial pressures,preferential
parameter(e.g., by dilution)couldcauseits precipi- dissolutionof silver(orleaching)of silverfroman Au-
tation.Similarly,nucleationof pure gold couldoccur Ag alloy, as shownin Figure 7B couldtake placevia
preferentiallyon the surfacesof specificminerals. a similarmechanism but at loweroxygenpartialpres-
The actualchemicalspeciesresponsible for the so- sures.This wouldbe possible,for example,in solutions
lutionmigrationof goldhaslongbeena problemfor containingsubstantialconcentrationsof ferrousion,
thegeochemist. differentcomplexing sincethe oxidationpotential of silver is well below
In all probability,
ions are responsiblefor gold migrationin different that of the ferrous-ferric
couple(seeFig. 3). The re-
environmental situations. In the case of the laterite action for dissolution of silver in an acid chloride so-
lution can be written:
profilesconsidered here,it isdifficultto envisage
thio-
sulfate,sulfide,or any thio- speciesbeingwidelyre- 4Ag+ 4C1-+ O2+ 4H+ --• 4AgCIø+ 2H20. (2)
48 A. W. MANN

Table $ showsthat solidAgC1is readilysolubleasthe reprecipitationof gold in the mottled zone of sucha
AgC1ø complexin the presenceof Fe+2 profileis illustratedin Figure 8.
Precipitationof goldfrom a solutionin which it has Dissolution of gold(andsilver)fromthe veinor lode
been dissolvedand existsasthe AuCI•- complexcould systemoccursby reaction(1) at or closeto the water
take placeasa resultof (1) loweringthe C1- ion con- table where CI-, H +, and O2 are abundant and there
centration (e.g.,by dilution),(2) raisingthe pH, or ($) islittleor noFe+2present. Chloridecomplexes of both
reductionof the AuCI• ion. In a laterite profile the Au and Ag migrate away from the vein system,but
frequentcloseassociation of gold with iron oxidesin the mobilityof Au is restrictedbecauseof the presence
the mottledand pisolitezones(e.g.,asin Fig. 5) can of Fe+2in thelateriticprofile.Reprecipitation of high-
be accountedfor by thislatter mechanism.The reaction purity Au occursin conjunctionwith the precipitation
for precipitationof gold by reductionof AuCI• with of FeOOH in the mottled zone. From this mottled
Fe +2 can be written: zone,wheresuitableclimaticand geomorphologic sit-
uationsexist,a ferruginousduricrustor pisoliticlayer
AuCI•- + $Fe+2+ 6H20
incorporatingsomeof thissecondarygoldmay develop.
-• Auø + $FeOOH+ 4C1-+ 9H+. ($) Low pH in laterite profileshas been shownto be
causedby ferrolysis.Development of extremely low
This reactionimpliesa simultaneous depositionof both pH valuesis morewidespreadover graniticbasement
iron oxideandgold,and it can readilybe demonstrated than over basic rocks because of the lower content of
in the laboratoryby precipitatinggoldfrom aquaregia carbonatein the weatheringprofile.Becauseof their
solutionwith FeSO4.Silverchloridecomplexesare not differentweatheringchemistries, weatheringbasicand
similarlyreducedby Fe+2because the redoxpotential graniticterrainsin the vicinityof golddepositsmight
for Ag-AgCIis belowthat of the Fe+2-Fe
+acouple. (independentof primary zone gold content)reflect
The chemicalcharacteristics of an activeweathering differentdistributionsof gold.The distributionof large
lateriticprofile(Figs.2 and $) are suchthat there is goldnuggetsmight,for similarreasons, be dependent
an increasein Eh and a decreasein pH from the on the chemicalcharacteristics of weatheringprofiles
weatheringbed-rockinterface up to the water table. developedover different rock types.It is well known
Implicit in the chemicalmodelfor sucha profilewhere amonggold prospectors that certaintypesof country,
ferrolysisis activeis that there is diffusionof ferrous despitethe presenceof primary or lode gold deposits,
ion,Fe+2,upwardin theprofile(Mann,1985).A chem- are unfavorablefor nuggetprospecting.For residual
ical model for the dissolutionof primary gold from goldnuggets(i.e.,residualfromthe primarylodema-
(for example)a quartz vein or lode systemand the terial), the size distributionof gold in the primary

io 02 Water table

•4Au O + 16Cl-+ 30• + 12H

+ --4AuCl.-+ 6HoO'• • •• LOWpH
••• ••/// -* •' • • • HighEh
• •• •-/// Reprec,..at,onof Au

/// •Fe
2+ •Fe
2+ Bedrock
interface
vL. +, +, +T+'+'+T+T+' +'
•v•••+++++*+*+*+'+ + + + + + + + + + + + + + + NeutralpH
vvvvvvvvvvvvv•/// + + + + + + + + + + + + + + + + + + + + + Low Eh

VVVVVVVVVVV// 7+ + + + + + + + + + + + + + + + + + + + + +

FlO.8. Chemicalmodelfor the redistribution of goldandsilverfroma quartzveinor lodesysteminto

the weatheringzoneof a lateriticprofile.+ -- granite,v = greenstone.
 MOBILITY OF Au AND Ag 49

(hydrothermal)zone is of undoubtedimportance. in Aeolianlandformsandsediments:

Earth-Sci.Rev.,v. 12, p. 279-
$10.
However suchresidualnuggetswould have a much
Brinkman,R., 1977,Surface-water gleysoilsin Bangladesh: Genesis:
greaterlongevityin a weatheringprofile dominated Geoderma,v. 17, p. lll-144.
by carbonates,whereacidsproducedby ferrolysis dur- Brough-Smyth, R., 1869,The goldfields and mineraldistrictsof Vic-
ing weatheringare neutralized.In the Laverton-Leo- toria:Queensberry Hill Press,644 p. (reprinted,1980,Perth,Hes-
noraarea(location,Fig. 1) themostprospectivecountry perian Press).
for gold nuggetsis in weatheredgabbroicmaterial Brugirard,J., Bargain,R., Dupuy, J. C., Mazille, H., and Monnier,
G., 1975, Studyof the electrochemical behaviourof gold dental
(Hallberg,1985).Water-saturated weatheredgabbroic alloys:Jour.Dental Research,v. 52, p. 828-856.
soilhasa pH near 8, and in suchlocationscarbonate Cloke,P. L., andKelly,W. C., 1964,Solubility of goldunderinorganic
is usuallyevidentin the soil.At Kurnalpi,eastof Kal- supergene conditions: ECON.GEOL.,v. 59, p. 259-270.
goorlie,largegoldnuggetshavebeenfoundcemented de la Hunty, L. E., 1975, Murchisonprovince:WesternAustralia
Geol. SurveyMem. 2, p. 54-64.
into calcrete(calcium-magnesium carbonate)devel- Dimmock,G. M., Bettenay,E., andMulcahy,M. J., 1974,Saltcontent
opedoverweathered basicrocks(W. Watts,pers.com- of lateriticprofilesin the DarlingRange,WesternAustralia:Aus-
mun.).NuggetsfromtheAgnewareausedin the pres- tralianJour.Soil Research, v. 12, p. 65-69.
entstudy(Table1), whichshowedonlya verylocalized Evans,D. L., 1981, Lateritizationas a possible contributionto gold
redistribution
of gold,wereobtainedfroma carbonated placers:Eng. Mining Jour.,v. 182, no. 8, p. 86-91.
Fisher,N.H., 1945, The fineness of gold with specialreferenceto
lateritedevelopedover a basicsedimentaryrock se- the Morobegoldfield,New Guinea:EcoN. GEOL.,v. 40, p. 449-
quence. 495.
Instancesof both gold-silverdissolutionand gold Gibb-Maitland,A., 1919, The gold depositsof WesternAustralia:
precipitation in lateriticweatheringprofileshavebeen AustralianGeol.SurveyMem. 1, p. $.
Hallberg,J. A., 1985,Geologyand mineraldeposits of the Leonora-
citedin thispaper.The evidencefor goldprecipitation Laverton area, northeasternYilgarn Block, Western Australia:
in lateriticprofileshasbeenfor smallcrystals (•2 mm) Western AustraliaGeol.Survey(in press).
of extremelyhighpurity.Whetherlargeaccretednug- Hingston,F., and Gailitis,V., 1976,The geographicvariationof salt
getsare formedin lateriteprofilesis opento question. precipitated overWesternAustralia: AustralianJour.SoilResearch,
v. 14, p. $19-$$5.
Photomicrographs suchas thoseshownin Figure 5
Krauskopf, K. B., 1951,The solubilityof gold:EcoN. GEOL.,v. 46,
indicatethat crystalnucleationand growth do take p. 858-870.
place in lateritic profiles.The limit in size to which Lakin, H. W., Curtin, G. C., Hubert, A. E., Shacklette,H. T., and
suchhigh purity crystalscouldgrow is dependenton Doxtader,G., 1974,Geochemistry of goldin the weatheringcycle:
many factorssuchas the rate of supplyof AuCI•-and U.S. Geol.SurveyBull. 1550, 80 p.
Fe+2,the permeabilityandhardness of the profile,the Liversidge, A., 1895,On the originof goldnuggets:
SouthWalesJour.Proc.,v. 27, p. $05-$45.
RoyalSoc.New
forcesof crystallization, and the energetics of nuclea- Mabbutt,J. A., 1980, Weatheringhistoryand landformdevelopment
tion. Smallcrystals,flakegold,and dendriticand wire in conceptual modelsin explorationgeochemistry:Jour.Geochem.
growthsappearto be the more commoncharacteristic Exploration,v. 12, p. 96-106.
formsof secondarygold precipitationin the mottled Mackay,R. A., 1944, The purity of native gold as a criterionin
secondaryenrichment:EcoN. GEOL.,v. 159,p. 56-68.
zoneof lateritic profiles. McCaughey,W. J., 1909,The solventeffectof ferric and cupricsalt
solutions upongold:Am. Chem.Soc.Jour.,v. $1, p. 1261-1271.
Acknowledgments Mann,A. W., 1985,Hydrogeochemistryand weatheringontheYilgarn
The authorgratefullyacknowledges the help and Block,WesternAustralia--ferrolysis
andheavymetalsin continental
assistance
of manycompanygeologistsandprospectors brines:Geochim.et Cosmochim.Acta,v. 47, p. 181-190.
Pitul'ko,V. M., 1976,The behaviorof goldin the oxidationzonesof
whoprovidedsamples and informationfor thisstudy. deposits in the far north:Geochemistry
Internat.,v. 15, no. 2, p.
In particular,
theassistance
of RodElvish(Texasgulf), 157-165.
N. Archibald(Aurex),and W. Wattsis appreciated. Potter,R., 1961,Electrochemistry:
London,Cleaver-HumePressLtd.,
Thanksare alsodue to M. Willing and D. Wright, 418 p.
who performedthe analyses and checkedthe manu- Sarkar, N. K., Fuys,R. A., and Stanford,J. W., 1979, The chloride
corrosionof low-goldcastingalloys:Jour.Dental Research, v. 58,
script,to A. Lawfordand C. Steelfor draftingthe p. 568-575.
diagrams, andto I. Piercyfor typingthe manuscript. Sillen,L. G., and Martell,A. E., 1964,Stabilityconstants
of metal
W. E. Ewersis thankedfor his encouragement and ion complexes: London,Chem. Soc.Spec.Pub. 17, 754 p.
interestin the early daysof this project. Simpson,E. S., 1902,Notesfrom the departmentallaboratory:Geol.
SurveyWesternAustraliaBull., v. 67, p. 8-26.
January 5, June 16, 1983 Smith, F. G., 1943, The alkali sulphidetheoryof gold deposition:
ECON.GEOL.,v. 38, p. 561-590.
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