Economic

Geology
Vol, 87, 1992, pp. 1253-1264

Contrasting
Mineralogical-Geochemical
Signatures
of Manganese
Oxides'
Guidesto Metallogenesis
KEITH NICHOLSON

School
ofApplied
Sciences,
TheRobert
Gordon
University,
Aberdeen
AB11HG,Scotland,
UnitedKingdom

Abstract

Manganese oxideshavea strong sorption

capacity
forcationicspecies
inthedepositional
fluid.Thissorptioncapacity
isreflectedinthechemistryoftheoxides,whichisdifferent
from
thatfortheoxides precipitatedfromfreshwater,seawater,andhydrothermalfluids.
Charac-
teristic
mineralogical-geochemicalenrichment andgeochemicalassociation
(definedstatisti-
cally)signatures,
inconjunction withseveraldiagnostic
plots,
canbeemployed todistinguish
between thefollowingdifferentgenetictypesofmanganese deposits:
supergene hydrother-
mal;supergene marine terrestrial;
supergene dubhite;
andsupergene marinehydrothermal
sedimentary exhalative
(sedex). "Dubhites"aremanganese oxidesderived
fromtheweather-
ingofa mineralized sequence (i.e.,baseandprecious
oreminerals andgangue).Hydrother-
maldeposits characteristically
showgeochemical enrichmentsin theassemblageAs-Ba-Cu-
Li-Mo-Pb-Sb-Sr-V-Zn
andan Mn-Asgeochemicalassociation.
Supergene
marinedeposits
showNa-K-Ca-Mg-Sr andCo-Cu-Nigeochemicalenrichments,
whereassupergene
terres-
trialdeposits
tendtohaveveryhighBacontents
andanMn-Baassociation.
Dubhirescontain
highlevels
ofPbandZn,show anMn-Pb-base metalassociation,
andarecomposed ofsignifi-
cantquantities
of basemetal-bearingmanganese oxides.
Bixbyite,braunitc,
hausmannite,
htibnerite,
jacobsite,
andpyrochroite occurpredominantlyonlyin hydrothermal deposits,
whereaschalcophanite,
coronadite,crednerite,
&MnO2,groutitc,hollanditc,
lithiophorite,
manganite,nsutite,
quenselite,
ramsdellite,
romanechite,
todorokite,andwoodruffitc are
generally
of supergeneorigin.In addition
to established
plotspresentlyusedto identify
marinesedimentaryexhalative
deposits,thefollowing
diagnostic
graphsweredevised: Navs.
Mgdistinguishes
deposits
ofmarine andfresh
waterorigin,
Co+ Ni vs.As+ Cu+ Mo+ Pb+
V + Zndiscriminates
between hydrothermalandsupergeneoxides,andPbvs.Zncanbeused
to recognizedubhitesandthereforeprospective
sequences.

Introduction whichdepositthe manganeseoxides.Freshwater,

seawater,andhydrothermal
fluidseachhavea dis-
MANGANESE oxidesare depositedin a varietyof ter- tinctiveand contrasting chemistry.The concentra-
restrialandmarineenvironments asa consequence of tionandrangeof dissolved speciesavailable forreac-
supergeneand hydrothermalprocesses. Regardless tion will determine which cationsare adsorbedby
of depositionalprocesses, the oxidescontaina net the manganese oxides.In thismanner,the adsorbed
surfacechargewhich playsa significantrole in the species willimpartachemical signaturetotheoxides,
mineralogyand geochemistry of manganese oxides. whichisrepresentative ofthedepositional fluidcom-
The pH of the isoelectricpoint (i.e., the positionof position. Thissignature will be differentfor oxides
zero net surfacecharge)varieswith the mineralin precipitated fromfreshwater,seawater, or hydro-
questionand the degreeof crystallinitybut for the thermalfluidandshouldthereforeprovidea diagnos-
amorphous oxidesusuallyoccursat aboutpH 2 (Cal- tic toolto metallogenesis. If, onagingandcrystalliza-
vert and Price, 1977; Murray and Brewer, 1977; tionof the amorphous precipitate,the adsorbed and
YarivandCross,1979).At thehigherpH valuestypi- coprecipitated species
areincorporated intothe ox-
cal of most depositionalenvironments,the oxides ide structure,then a suiteof distinctivemineralsmay
thereforepossess a strongnegativesurfacecharge alsoform.It istowardthe definitionof suchgeochem-
anda commensurately strongadsorption capacityfor ical andmineralogical metallogenic signatures that
cationicspecies.This adsorptioncapacitywill in- thispaperis directed.
creasewith increasingpH (Crerar et al., 1980). It The broadcategories of manganese mineralization
should,therefore,be possibleto usethispropertyto whichthisstudyseeksto characterize are foundin
advantage in devisingdiagnostic metallogenic crite- Table 1. Discriminationbetweensupergene andhy-
ria for manganese deposits.The basisfor this ap- drothermal depositsandbetweendifferenttypesof
proachlies in the differentchemistryof the fluids supergene mineralizationare the principalobjec-

o3ol-o128/92/13o2/1253-12/$3.oo 1253
1254 KEITH NICHOLSON

TABLV.1. Classification
of the DifferentGeneticTypes 1978, 1980; Potter and Rossman,1979a, b; Sozanski
of ManganeseOxideDepositson the Basis and Cronan, 1979; Carlson and Schwertmann,1987;
of FormationProcessandDepositional Environment
Nicholson,1988a, b, c, 1989b.)
Supergene Hydrothermal Weatheringdeposits(Sw):Surfacecrustsandcoat-
ings formed by weathering,dendrites,desert var-
Terrestrial Marine Terrestrial Marine nish, laterites. (Data sources:Hewett and Fleischer,
1960; Boyle, 1965; Roy, 1968; Potter andRossman,
Bogsandsoils Crusts Hot spring Sedimentary
Freshwater Coatings Vein exhalative
1979a, b; Nahon et al., 1983; Nicholson, 1987a;
Weathering Nodules Hawker andThompson,1988.)
Dubhites Sediments Dubbites(Sa):Oxidesformedby the weatheringof
a mineralizedsequence(from the Gaelic dubhithir,
"black earth," cf. gossan,"ferruginousearth"), i.e.,
the manganeseoxide equivalentof a gossan.(Data
tives.Within thislatter category,the recognitionof sources:Hewett and Fleischer,1960; Heyl and Bo-
oxidesassociated with baseandpreciousmetalminer- zion, 1962; Boyle, 1965; Hewett, 1971; Blain and
alization is also considered. Andrew, 1977; Ashley,1980; Butt andSmith,1980;
Siderov et al., 1980; van Moort and Swensson,1982,
Environmentsof Formationof Manganese 1984; Taylor and Appleyard,1983; Nickel, 1984;
Oxide Minerals
Nicholson, 1986, 1987a, 1989a; Scott, 1986; Scott
For the purposesof this paper, manganese oxide andTaylor, 1987; MosserandZeegers,1988; Nimfo-
depositsare classifiedfirst by the mineral-forming pouloset al., 1988;Nimfopoulos
andPattrick,1991.)
processandthenonthe basisof the depositional envi-
ronment(Table1); oxidesformedby supergene and Supergene: marine(S•Aa)
hydrothermalprocessesare therefore each subdi- Manganesenodules,crusts,and coatingsprecipi-
videdinto thosedepositedin the terrestrialandma- tated directlyfrom seawater(hydrogenic-hydrogen-
rine environments. The term "supergene"is usedto ousdeposits)and beddedmanganiferous sediments
refer to oxides formed under ambient conditions at
the earth's surface in both terrestrial and marine envi-
deposited in the marineenvironment with the manga-
nesesuppliedfrom sourcesotherthanhydrothermal
ronmentsandnotin the morerestrictivesenseofRoy (i.e.,continental run-off,hydrogenic, diagenetic,hal-
(1981), whichincludesonly oxidesformedby pro- myrolytic). In some studies, manganeseoxides
cesses of secondary enrichment.Brief descriptions of formed in the continental shelf-shallow-sea environ-
the typesof depositsincludedin eachcategoryare ment are termed "shallow-marine"depositsand
givenbelow.In addition,to avoidrepeatedmultiple have been differentiated from "oceanic," "deep-
references, the data sourcesused to create the tables
sea," or "marine" oxides(e.g., Calvert and Price,
andfiguresin thisworkarelistedfollowingeachcate- 1977). Where relevant,thisdistinctionhasbeenre-
goryof deposit.Metamorphosed depositsarenotcon- tainedsinceit mayfurtheraid reconstructions of an-
sideredbecausethis additionalprocesswill distort cient depositionalenvironments.(Data sources:He-
the primarymineralogicalsignature;the distinctive wett, 1966; Horn, 1972; Mart and Saas,1972; Cal-
geochemistry of the depositmay, however,be pre- lender and Bowser,1976; Glasbyand Read, 1976;
servedfollowingmetamorphism and the diagnostic Burns and Burns, 1977, 1979; Calvert and Price,
signatures derivedin thiswork maythereforebe ap- 1977; Jenkyns,1977; MargaritzandBrenner,1979;
plicableto suchdeposits. Cronan, 1980; Ostwald, 1980, 1981; Craig et al.,
Supergene: Terrestrial(ST) 1982; Moorby and Cronan, 1983; Baturin, 1988;
Bolton et al., 1988; Pattan, 1988; Bernat et al., 1989;
Bogsandsoils(Ssoid:All accumulations of manga- Jauhari,1989, 1990; Le Suaveet al., 1989; Usui et
neseoxidesfoundin soilprofiles,includingswampor al., 1989; Ajmal, 1990; E1 Sharkawlet al., 1990;
bogdeposits,regardlessof morphology, i.e., crusts, Manginiet al., 1990; Roy et al., 1990.)
coatings,nodules,etc. (Data sources:Jonesand
Milne, 1956; Taylor et al., 1964; Taylor, 1968; Hydrothermal:
Terrestrial(HT)
Chew, 1978; McKenzie, 1980; Chukhrov and Gorsh-
kov, 1981; Nicholson,1987a.) Hot spring(Hh/s):
Oxidesdeposited directlyfrom
Freshwater(Sfw)deposits: andcoatingsgeothermalwaters around hot springsand pools.
Cements
on stream or lacustrine sediments, lacustrine nod- (Datasources:
CallaghanandThomas,1939; Hewett
ules,lacustrinesediments, oxidecoatings,andveins andFleischer,1960; Hariya, 1961, 1980; Hewett et
depositedfromgroundwater. (Datasources: Hewett al., 1963; Hewett, 1966; Roy, 1968, 1981; Ossa,
and Fleischer, 1960; Vasari et al., 1972; Callender 1970; Sillitoe, 1975; Usui et al., 1989; Nicholson,un-
and Bowser,1976; Calvert and Price, 1977; Ghosh, pub. data.)
 MANGANESEMINERALIZATION: MINERALOGICAL-GEOCHEMICAL SIGNATURES 19.55

Vein (Hvein):
This categoryonly includesthe pri- foundin hydrothermaldeposits.Within the super-
•naryprecipitatesandnot the mineralsin the upper genedeposits,
nomineralscanbeemployed todiffer-
oxidizedsequence.Theselatter oxidesare secondary entiate between oxides formed in marine or terres-
in originandare thereforeclassified
eitherassuper- trial environments.However, it is notable that chal-
gene-weathered depositsor as dubhitesif derived cophanite, coronadite,
hetaerolite,i.e., the common
from mineralization.(Data sources:Burbank, 1933; Zn-Pb-bearingoxides,and possiblycredneriteand
Hewett and Fleischer, 1960; Hewett, 1966; Casade- woodruffiteareinvariablyassociated with basemetal
vail and Ohmoto, 1977; Roy, 1981; Tindle and mineralization. Recognitionoftheseminerals isthere-
Webb, 1989.) fore of value in mineral explorationprogramsbe-
causethey enabledubhitesto be distinguished from
Hydrothermal:Marine (H•vO barrensupergene oxidedeposits.It isinterestingthat
Sedimentary exhalative(Hsedex):
Beddedmangani- although base metal depositscommonlydevelop
feroussedimentsof exhalativeorigin. (Data sources: dubhitescontainingZn-Pb-(Cu?)manganese oxides
Bonatti et al., 1972; Cronan, 1972, 1980; Rona, (e.g.,BrokenHill, New SouthWales,Australia;van
1978, 1984; Zantop, 1978, 1981; BurnsandBurns, Moort and Swensson,1982, 1984), the manganese
1979; Bostrom,1980; Rossiet al., 1980; Grill et al., oxidecapswhich commonlyform over epithermal
1981;Meylanet al., 1981;Roy, 1981;Cronanet al., Au-Ag mineralization (e.g., Wau, Papua New
1982; Moorby and Cronan, 1983; Taylor, 1983; Guinea;Webster and Mann, 1984) are invariably
Moorby et al., 1984; Alt, 1988; Boltonet al., 1988; composed of amorphous wadwith no crystalline ox-
Varnavaset al., 1988; Nicholson, 1989a, 1992; Usui idespresent.The exceptionto thisis the occurrence
et al., 1989.) of cryptomelanefrom the oxidizedprofile of the
Marthagoldmine,Waihi, New Zealand(Nicholson,
MineralogicalSignatures unpub.data)andthe presence of todorokitein black
Mineralogyasa tool in characterizing the genetic calcitefromAu-Agveins(HewettandRadtke,1967).
originof manganese depositshasbeenusedoccasion-
GeochemicalEnrichment Signatures
ally,but diagnostic mineralogical signatureshavenot
beenrigorouslydefined.Roy (1968; 1981, table 18) Althoughthe identificationof chemicalenrich-
hassummarizedthe occurrenceof commonmanga- ments is well establishedas a method in lithogeo-
nese minerals but does not discriminate oxides chemicalexplorationfor mineraldeposits(e.g., Go-
formedby the weatheringof ore deposits.Cronanet vett, 1983), the applicationof thistechniqueto man-
al. (1982) noted that b-MnO2commonlyoccursin ganesedepositsis not asstraightforward asthat for
submarinesupergenemanganese deposits,whereas silicatelithologies.The reasonfor this lies in the
birnessiteand todorokitepredominatein exhalative strongadsorption capacityof manganese oxidesfor
mineralization(Rona,1978, 1984). cations. Because these oxides are the dominant com-
A review of the literature (Table 2) revealsthat ponentin the deposits, thispropertymeansthat the
manyof the Mn+4 oxidesoccurin a wide rangeof traceelementsignatureis stronglydependenton the
environments. In orderto clarifythe distributionpat- concentrationof manganese oxidesin the deposit,a
tern, mineralswhich consistentlyappearonly as an situationwhichis notparalleledin the interpretation
accessory mineral,or whicharerecordedin lessthan of silicaterockgeochemical enrichments.Thisprop-
10 percentof the depositsreviewed,are designated erty canlead to misleadingresultswhen comparing
asrare (r) in thatparticularenvironment. Theserare the chemistry of depositswith verydifferentconcen-
occurrences are regardedas not typicalof mineral trationsof manganese oxides.This situationcanbe
genesisandare thereforenot consideredin deriving readily overcomeby normalizingthe resultsagainst
the following mineralogicalsignatures.Similarly, the manganese contentof the deposit;failureto doso
mineralswhichare foundin a wide rangeof environ- canresultin the productionof apparentenrichments
mentsare not considered further,asthey are clearly or in obscuringreal enrichments(e.g., Nicholson,
of little diagnosticvalue,e.g., birnessiteis particu- 1992).
larly common,occurringasa primarycomponentin a The mineralogyof silicatelithologiescanbe an im-
variety of both supergeneand hydrothermalde- portantfactorin the creationandevaluation of geo-
posits. chemicalanomaliesin mineral exploration,and it
Bixbyite, braunitc, hausmannite,huebnerite, ja- may, therefore, be similarlyconsideredthat the
cobsite,andpyrochroitearedominantlyofhydrother- chemistryof manganese oxidesisdeterminedlargely
malorigin;whereaschalcophanite, coronadite,cred- by the mineralogy of the deposits.However,suchan
heritc, b-MnO2, groutitc, hollanditc,lithiophorite, assumption couldbe mistakensincethe manganese
manganite, nsutite, quenselite, ramsdellite, and mineralswhichcomposea depositarenotnecessarily
woodruffitcare supergene in nature.Romanechite is the primaryprecipitatesbecausethe mineralogyof
alsopredominantlysupergenein origin and rarely manganese oxidedepositsis commonlydetermined
12 5 6 KEITH NICHOLSON

T•.BI•2. Occurrence
of Manganese
Oxidesin Supergene
(S)andHydrothermal
(H) Depositional
Environments

Birnessite Cryptomelane Hiibnerite

(Ca,Na)(Mn+gMn+4)7014ß3HgO Kl_•(Mn+g,Mn+4)8016.
xH•O MnWO4
St/w:
common [16c,17, 21, 24, 25, 39, Sf/w Svw
50c, 62] Sm•:known[9, 18r, 19] Sm•r
Sm•r:common[18c, 19, 20, 21, 22, Ssoi•:
rare [4] Ssoi•
23c, 53, 60] S•,:common[48, 49, 50] S•,
S•oi•:
common[2c, 3c, 4, 26, 32c] Sa:common[7, 31, 35, 38, 51] Sa
Sw:common
[30,50c,57c] Hh/s:
known[12,33, 48] Hh/s
Sa:rare [7] H•a• Hs•a•
H•/,:known
[34] H•i. H•i.: known
[41,42]
H,•a•: common[13, 22c, 28c, 55, 56c,
58c,60,63] •5-MnOz Jacobsite
H•i. (Vernadite) MnFe•O4
Sr/.•:
common
[16c,17c] Sr/w
Bixbyite Smar:
common[13, 20, 21, 22c, 23c, Sm•r
a-(Mn+a,Fe+•)•Oa 53c, 54, 59, 60, 61, 64] S,oi•
Sf/w Ssoil:
common
[4c] Sw
Smar Sw Sd
S,oii Sa:rare[6r] H•/•:rare[30?]
Sw Hh/s Hsede•
Sd:rare[6r, 45r] Hsedex:
known[56, 60] H•i.: known[48]
Hh/• H.•n
H.•d• Lithiophorite
H•,.:known
[49] Groutitc
a-Mn+aOOH
(AI,Li)(Mn+•,Mn+4)O•(OH)•
St/w:
known[24]
Braunitc Sf/w:
rare[28r] Smut:
rare[9r,19]
Mn+e,Mn•aOs(SiO4) Sm•r:
rare[18r1 S•oa:
common [2c,3c,32c1
Sw, S,oi• Sw:
known
[31]
Sm•:rare[9r] Sw Sa:known[38]
S,oi• Sd:rare [28r] H•/•
Sw Hh/s Hsedex
Sd Hsedex Hvein
H•/•:known[30] H•.
Hs•d•:
known
[11] Manganite
H•: common
[48c,
49] Hausmannite •,-MnOOH
Mn+•Mn•aO4
Chalcophanite Svw Smar;
rare[9r,1Or,19]
ZnMn•407ß3H•O Sm•r:
rare[10r,19] S,oa:
known[27, 32r]
Svw S•oa:
rare[4r] Sw:
known
[1,40]
Sm•r:
rare[9r, 19r] Sw Sa:rare[40]
S•o• Sd Hh/s
Sw Hh/s H•edex:
rare[58]
Sd:common[5, 7, 31, 35, 37, 38, 48c] Hsede
x Hvein
Hh/.• H•i•: common
[48c,49]
H•d• Manganosite
H•. Hetaerolite Mn•_•O
ZnMn•O4 Sf/w
Coronadite Svw Smar:
rare[23r]
Pbl_•(Mn+e,Mn+4)sO16
ßxH•O Sma
r Ssoil
S•/,• S•o• Sw
Smar Sw Sd
S•o• Sa:known[35, 48] H•/•
S•,:rare[50r] Hh/s Hs•d•
Sd:common [29,38, 43, 45c,46c,48] H•d• H•: rare[48r]
H•/, H•ein:
known
[48] Nsutite
Hsedex Hollanditc 3,-MnO•
H•,,• (Ba,
K),_=(Mn+Z,Mn+4)sO,6-
xHzO SVw
Crednerite Sf/w:
known
[28,50] Smar;
rare[9r,18r,21r,22r]
CuMnOe Sm• S•o•
Se/w S,oi•:
rare[32] Sw:
known
[57c]
Sma
r Sw:known[50] Sa:rare[7]
S•oa Sd:known[29, 38, 48r] Hh/s
Sw Hh/•:rare[12] H•d•
Sd:rare [44?] Hsede
Hh/s Hvein
Hsede•
avein
 MANGANESE MINEtlALIZATION: MINEtlALOGICAL-GEOCHEMICAL SIGNATURES 1257

TABLE
.2. (Cont,)

Pyrochroite Quenselite Romanechite

Mn(OH)z Pb(Mn+Z,Mn+4)Oz(OH) (Ba,K,Mn+Z,Co)zM%Olo
ßxHzO
St/w St/w:
rare[.24] St/w:
common
[16r,17,21,28,50]
Smarl
rare[10r] Stoa
r Smar;
known[9r,10, 18,19r,21,22r]
Ssoi• Ssoi• Ssoi•:
rare[27r,32r]
S,, S,, S,,:known[40, 49, 50]
So So So:common [6, 29, 35, 38, 40]
Hh/• Hh/s Hh/s:
known[33r,49c]
H•eaex:
rare[52] Hsea•x Hs•a•x
Hvein:
known[48] Hvein H•ei
n
Pyrolusite Ramsdellite Todorokite
(/•-MnO2) MnOz (Na,Ca,K)(Mn+Z,Mg)Mn+40•2
ßxH•O
St/,•:
known
[28] St/,, St/,•:
known
[16,17,21]
Sm•r:common [9, 10, 15, 18, 19c,22r, Sm•:rare[18r,22r] Sm•r:
common [9r, 13r, 17, 18c,19c,
36] S.•oi• 20, 21, 22c,23c,53c,54c,59,
S•oi•:
rare[.27r,3.2r] S,,:rare[31r,48] 60, 61, 64]
S,•:known[40,49] Sa S•oi•:
rare[4r,3.2]
Sd'known[6,7,35,40] Hh/s Sw:rare[50r,57]
Hh/•:
known[33,34] Hseaex Sa:known [6r,8r,38,47r,48]
Hsedex:
known[11,14] Hvein Hh/s
H.•. Rancieite H•aex:common
58c, 60, 63]
[13r,
28r,55,56,
Pyrophanite (Ca,Mn+•)Mn4Oo
ß3HzO H,•i•
MnTiOa St/,,:
rare[48]
St/,, Sm•:rare[18r, .21r,'2.2r] WoodruffRe
Sm• S•oi• (Zn,Mn+•)•Mn+4Ol•
ß4H•O
S•o• S,• St/,•
Sw Sd Smar:rare[18r,21r]
Sa Hh/•:rare[33r,48r] S•oi•
Hh/.• H•ea•x S,•:
Hs•a• H•ein Sa:known[28,31]
Hvein Hh/s
Hvein

c = common;
r = rare;(referto relativeabundances
in deposits
described
in references
cited)
References:1 = Nahonetal.(1983);'2= Taylor(1968);3 = Taylor etal.(1964);4 = ChukhrovandGorshkov (1981);5 = Blainand
Andrew (1977);6 = Siderov
et al.(1980);7 = Nimfopouloset al.(1988);8 = Nimfopoulos andPattrick (1991);9 = Ostwald(1980,
1981);10 = MartandSass(1972);11 = Zantop (1978);12 = Ossa (1970);13 = Craiget al.(1982);14 = Bonattiet al.(1972);15 =
MargaritzandBrenner (1979);16= DeanandGhosh (1980);17= Calvert andPrice(1977);18= Burns andBurns (1977);19= Jenkyns
(1977);20 = Glasby andRead(1976);21 = Callender andBowset (1976);22 = BurnsandBurns (1979);23 = Baturin(1988);24 =
Nicholson(1988c);25= Nicholson (1988a);
26= Jones andMilne(1956);27= Chew(1978);28= Nicholson (1989b); 29= Nicholson
(1986);30 = Nicholson (1990);31 = Nicholson(1987a); 3.2= McKenzie (1980);33 = Hewettetal.(1963);34 = Haryia(1961);35 =
HeylandBozion (196.2);36= ButtandSmith (1980);37= Ashley (1980);38= Scott (1986);39= Carlson andSchwertmann (1987);40
= Boyle(1965);41 = CasadevallandOhmoto (1977);41 = Burbank (1933);42= TindieandWebb(1989);43 = TaylorandAppleyard
(1983);44 = Mosser andZeegers (1988);45 = Scott
andTaylor(1987);46 = vanMoort andSwensson (1984);47 = Nickel(1984);48 =
HewettandFleischer (1960);49 = Roy(1968);50 = PotterandRossman (1979a,b);51 = Nicholson (unpub.data);5.2= Taylor(1983);
53 = Goddard etal.(1987);54 = Pattan(1988);55 = Corliss etal.(1978);56 = Alt(1988);57 = Hawker andThompson (1988);58 =
Rona(1984);59 = Royet al.(1990);60 = Bolton et al.(1988);61 = Le Suave et al.(1989);6.2= SozanskiandCronan (1979);63 =
Moorbyet al. (1984);64 = Bernatet al. (1989)

by the agingandrecrystalizationof initiallyamor- al. (1963). Theseauthorsnotedthat hydrothermal

phousoxides andtheirassociated
species. It isthere- manganese
depositsshowenrichmentsin As, B, Ba,
forethechemistry oftheamorphous oxides (and,indi- Be,Ge,Pb,Sb,Sr,TI, andW. Subsequent workcon-
rectly,that of the depositional
fluid) whichinflu- firmedthatat leastsomeof theseelements, together
encesthefinalmineralogyof thedepositandnotthe withLi, Cd,Mo,V, andZn, areconsistentlyenriched
mineralogywhichexercisesa primarycontrolonthe in oxidesdepositedfromhydrothermal fluidsin both
depositchemistry. terrestrialand marineenvironments (Bostromand
The useof geochemistry
to aidtheidentification
of Valdes, 1969; Ossa, 1970; Cronan, 1972; Sillitoe,
hydrothermal
manganese mineralization
was pio- 1975; Zantop,1978, 1981; Moorbyet al., 1984;Var-
neeredbyHewettandFleisher(1960)andHewettet navaset al., 1988), andthe elementalassociation
As-
12 5 8 KEITH NICHOLSON

Ba-Cu-Li-Mo-Pb-Sb-Sr-V-Zn can be considered to be TABLE

3. AverageCompositionof ManganeseOxides
the diagnostichydrothermalsignature.This geo- fromFreshWater andMarineDepositional
Environments
chemicalsignatureis, asdiscussed
above,a function Shallow Marine
of the chemistryof the depositional fluid and it is Freshwater marine (Oceanic)
thereforenot surprising
to learnthat theseelements
are alsoenrichedin geothermalfluids(e.g.,Hewerr (wt %)
Si 6.53 6.98 8.62
et al., 1963; Sillitoe, 1975; Ellis and Mahon, 1977;
A1 1.19 1.69 2.82
Edmondet al., 1979). Fe 24.40 23.05 15.55
Severalauthorshave integrateddata on marine Mn 13.51 18.69 16.02
manganesenodulesand exhalativemanganiferous Mg 0.53 0.95 1.82
sediments to show that certain elemental enrich- Ca 1.29 3.42 2.47
Na 0.26 0.57 1.94
mentsarecharacteristic of depositsof a givengenetic K 0.40 0.87 0.64
type. In sedimentaryexhalativedeposits,iron and P 0.2P• 0.84 0.22
manganese are characteristicallyfraetionated,pro-
(ppm)
dueinghigh or low Fe/Mn ratios.In general,the Ba 7,157 2,816 2,013
range0.1 > Fe/Mn > 10 holds;whereasin hydrogen- Co 170 117 2,840
ousdeposits thisratiois closerto unity(Rona,1978). Cr 28 29 35
Bonattiet al. (1972)producedanearlyversionofthe Cu 147 29 2,595
Mo 32 93 412
nowwell-established Fe-Mn-10(Co+ Cu + Ni) ter-
Ni 209 229 4,800
naryplotwhichdifferentiates betweenoceanichy- Pb 44 29 900
drogenous andhydrothermal exhalative
manganifer- Sr 167 770 825
oussediments. It hasbeenrecognized thathydrother- V 43 112 558
maloxidesaredepletedin Co,Cu, Ni, andZn relative Y 34 14 310

to hydrogenous deposits,and Moorby and Cronan Zn Zr

687
69
82
49
780
648
(1983) effectivelydemonstrated that metalCo ratios
couldbe usedas a measureof hydrothermal metal
input.Creraret al. (1982)recognizedhydrothermal
depositsusingan Si-A1plot, whereasMeylanet al. sedimentcoatingsasa samplingmediumin mineral
(1981) additionally illustratethe useof an Fe/Ti - exploration.This makesthe characterization of a
A1/(A1+ Mn + Fe) graphto distinguish exhalative diagnostic
freshwater signaturedifficult.Only Ba is
depositsfromterrigenous sediments.Thesediagrams enriched in the fresh water oxides relative to the ma-
arewellestablished, havebeenwidelyusedto recog- rine deposits.However, becauseBa is also often
nize exhalative sediments,and need no further dis- enrichedin hydrothermalmineralization, it cannot
cussion. Sedimentarymanganiferous horizons,which be regardedasa reliableguideto genesis on its own.
are not of hydrothermalorigin,are differentiatedin Althoughmanystudiesonlyreportpartialanalyses
thesefiguresandarealsorecognized by theabsence of the manganese oxides,publisheddatahavebeen
of the aboveelementalenrichments(e.g., Ajmal, employedwith the hydrothermal andmarinesigna-
turesdevelopedabove,in the developmentof two
Comparedwith their marine equivalents,rela- diagnostic scatterplotsto discriminatebetweenfresh
tively little attentionhasbeen paid to freshwater water andmarineoxidesandhydrothermaldeposits
manganese deposits.Within this group,lacustrine (Figs. 1 and 2). Figure 1 clearly discriminates be-
nodulesand crusts,togetherwith streamsediment tween oxidesdepositedin the freshwater, shallow-
coatings havereceivedthe greateststudy(e.g.,Cal- marine,and marineenvironments.Figure 2 distin-
lender andBowser,1976; CalvertandPrice, 1977; guishesbetweensupergeneand hydrothermalox-
Roy, 1981, p. 143-146 andreferences therein),al- ides,andwith furtherdevelopment it may alsobe
thoughQuaternary oxidecements havealsobeencon- possible to usethissinglediagramto distinguishma-
sidered(Vasariet al., 1972;Nicholson, 1988e).The rine from fresh water oxides,becausethese tend to
chemistryof marineandfreshwateroxidesissumma- plot in distinct(if overlapping)areas.It shouldbe
rizedin Table3. Evenin a qualitative comparison,noted,however,that in Figure2, supergene oxides
thesedatashowthatthemarineoxides display
enrich- derivedfromthe weatheringof mineralization(dub-
mentsin Na-K-Ca-Mg-Sr (i.e., all majorcomponentshites)alsoplotin the hydrothermal fielddueto their
of seawater);
whereas thoseformedin the deepoce- high metal content,and it is the discriminationof
anic environmentare additionallyenrichedin Co- thesesignificant depositswhichwill nowbe consid-
Cu-Ni. The chemistryof the freshwaterdeposits is ered.
verysusceptibletolocalchanges inthegeologic envi- The abilityto distinguish
dubbitesfrom other su-
ronment,a factwhichisexploitedin the useof stream pergeneor hydrothermalmanganese oxidedeposits
 MANGANESEMINERALIZA TION: MINERALOGICAL-GEOCHEMICAL SIGNATURES 1259

Na * marino • ß ß Pb
ß shallow marino ß ß
(wt% ß freshwater ß ß
A ß
A ß 10wt%.
2.0
ß ß AAA

ow 1000 ppm

øo•4i•ti•"
• "•:o 2'.0 '
Mg (wt%)
100 ppm-

FIG. 1. Diagnosticplot to differentiatesupergenemarineand VV m ß ß ß

freshwater(f/w) deposits.
10 ppm-
ß marine
¸ ¸ ß shallow marine
ß freshwater

is clearlyimportantin mineralexploration.
Although ß weathered
ß dubhite
dataon the chemistryof manganese oxidesderived 1 pprn.
o hot-spring
0 sedex
frommineralization arefew (analysesareusuallyre-
portedforheterogeneous mixturesofironandmanga-
neseoxides),thoseavailablehavebeenemployedto
derivea Pb-Znplot (Fig.3). Thissuccessfully sepa- 100'ppm 100'0
ppm 1•/o Zn
ratesthe dubhiteswhichplotin the highPb andZn
fields;in generaldubhitescontainmore than i wt FIG.3. Diagnosticplotto differentiatedubhitesfromothersu-
percentZn and/ori wt percentPb. Thiscut-•off may pergeneandhydrothermal oxides.
be reducedto a Pb concentration of 1,000 ppm(at
1% Zn), providedthe criteria describedaboveare
employedto eliminatethe marineoxideswhichover- the overlapof the freshwater, shallow-marine, and
lap this lower sectionof the dubhitefield. Interest- sedimentary
exhalativeoxidesprecludesthe useof
ingly,marine,freshwater,soil,weathering,andhot Figure 3 to recognizesuchdeposits.
springoxidesalsoplot in discreteareas.However,
GeochemicalAssociation
Signatures
Co+Ni
Normalization of the oxidechemistryagainstman-
(wt%)
ganesecontentcanproducea more clearlydefined
elementpattern;however,suchpatterns canbemore
0.1-
rigorouslyquantifiedby the useof statisticaltech-
niquesto producea geochemical association
signa-
ture. Correlationcoefficientsor factoranalysis are
two methodscommonly employed.The majorityof
quantitative
correlation analyses
reportedin theliter-
0.01- ature have been conducted on marine and fresh
wateroxides(Table4). Althoughcorrelations vary
betweendeposits,the followingsignificant
associa-
tionsare shownin the majorityof analyses:
super-
genefreshwater= Mn-Ba-Co-Cu-Ni-[Sr]-Zn, super-
genemarine = Mn-Co-Cu-Ni-[Zn],supergenedub-
FIG. 2. Diagnostic
plot to differentiatesupergene andhydro- Mn-As.
hite = Mn-Co-[Cu]-Ni-Pb-Zn,and hydrothermal=
thermalmanganese oxides.Notethatbecause of their highmetal
content,dubhitesplot in the hydrothermal field;however,these Bracketsindicatea possibleregularassociation but
canbe recognizedusingthePb-Znplotin Figure3. one whichis not reportedin all analyses.
This high-
1260 KEITH NICHOLSON

T•,BLV.
4. PositiveCorrelations
of Elementswith Manganese
in DifferentGeneticTypesof Deposit

Type Corelation Reference

St/,, Mn-Ba-Ca-Co-Cu-K~Mg-Na-Ni-Sr-Zn DeanandGhosh(1980)

Mn-Ba-Co-Cu-Ni-Sr-Zn CallenderandBowser(1976)
Mn-Ag-Ba-Ce-Co-Cu-K-La-Li-Mo-Nb-P-Zn Nicholson(1992)
Mn-Cd-Co-Cu-Fe-Ni-Zn Whitney (1981)
Mn-Ca-Co-Cu-K-Mg-Ni SozanskiandCronan(1979)
Smar Mn-Ba-Co-Cu-Mo-Ni~Zn Baturin(1988)
Mn-Cu-Cr-Mo-Ni-V-Zn Baturin(1988)
Mn-Co-Cu-Ni-Zn Baturin(1988)
Mn-Cu-Ni CallenderandBowser(1976)
Mn-Co-Cu-Ni Craig et al. (1982)
Mn-Co-Ni Cronan(1977)
Mn-Co-Cu-Ni Cronan(1977)
Mn-Co-Cu-Ni Cronan(1977)
Mn-Co-Cu-Ni Cronan(1977)
Mn-Cu-Ni Cronan(1977)
Mn-Ca-Co-Cu-K-Mg-Ni-Zn DeanandGhosh(1980)
Mn-Cu-Ni-Zn Bernatet al. (1989)
Mn-Cu-Ni Jauhari(1989)
Mn-Cu-Ni-Zn Pattan(1988)
Sa Mn-Co-Ni-Pb-Zn Andrew(1984)
Mn-Ag-Ba-Ce-Co-Cr-Cu-La-Mo-Ni-Pb-Sb-Sr-V-Y-Zn Nicholson(1992)
S•, Mn-Ag-Ba-Ca-Ce-Co-Cr-Cu-K-La-Mo-Na-Nb-Sr-V-Zn-Zr Nicholson(1992)
H,eaex Mn-As-Ba-Sr Nicholson(1992)
Mn-Cu-V Zantop( 1981)
Mn-Mo Moorbyet al. (1984)
Hh/5 Mn-Ag-As-Cr-La-Mo-Ni-Zn Nicholso•l
(1992)

lightsa problemin summarizing reportedcorrela- As is presentasthe unchargedH3AsO3species(Bal-

tions, becausethe associationsare a function of the lantyneandMoore, 1988; Webster,1989). Clearly,
elements determined andmanystudies, particularly this association
is not readily explainedby invoking
on marinemanganese nodules,only analyzefor Mn, simpleadsorption processes and maybe due to the
Fe, Co, Cu, and Ni. A better approachwouldbe to presenceof a coprecipitated As-bearingphase,ashas
performa singlecorrelationanalysis on a largedata beensuggested to explainAsenrichments in epither-
setcomposed of the raw analyses;collationof datafor mal sinters(NicholsonandParker, 1990; Parkerand
suchan analysisis currentlyunderway.Despitethis Nicholson,1990).
recognizedlimitation,it isclearthatfew Mn element Conclusions
associations are exclusiveto a given deposittype.
Nonetheless,three correlations can be identified as Diagnosticcriteriawhichidentifythe genesisof a
potentiallydiagnostic, namely,Mn-Bafor freshwater manganese depositare relevantin the searchfor po-
oxides;Mn-Pbfor dubhites,andMn-Asforhydrother- tential manganese ore horizons,both in evaluating
mal deposits.Note that althoughBa enrichmentsoc- the prospectfor manganese-related base-precious
cur in bothsupergene freshwaterandhydrothermal metalmineralization and,of wider interest,in paleo-
deposits,the Mn-Ba statisticalassociation is only de- geographic-depositional environment reconstruc-
fined in fresh water oxides and is therefore discrimi- tions.The mineralogy andgeochemistry oftheoxides
natory.The immobilityof Pb in the secondaryenvi- shouldenablemanganese depositsof the following
ronment creates the Mn-Pb association,enabling geneticoriginsto be differentiated(Table 5): super-
dubhitesto be discriminated fromotherweathering genehydrothermal(S-H); supergenemarine-terres-
deposits. The lattercorrelationisinterestingbecause trial (SMAR-ST); supergenedubhite(S-Sa);supergene
in supergene deposits Asisinvariablyassociated with marine-hydrothermal sedimentaryexhalative(SM•-
the iron oxide fraction(e.g., Nicholson,1987a). As Hsedex). The depositunder investigationshouldfirst
statedabove,manganese oxideshavea strongnega- be characterizedas hydrothermalor supergene;if
tive surfacechargeandthereforeadsorbcations,im- the latter, then the depositionalenvironmentcanbe
plying,therefore,that in hydrothermaldepositsAs further characterized as marine or terrestrial. Multi-
occurredas a cationicspecies.This seemsunlikely elementanalyses coupledwith a statistical
analysis of
andcontrasts with investigationson the speciation of the dataoffer a reliableandincreasingly affordable
Asin geothermalfluids,wheremostof the dissolved approachto depositevaluation.The useof statistics
 MANGANESE MINERALIZA TION: MINERALOGICAL-GEOCHEMICAL SIGNATURES 1261

T^BLE
5. Diagnostic
Mineralogical
andGeochemical
Signatures comemorewidelyavailable,thistechniquedeserves
to DiscriminateManganeseOxide Depositsof Different
Metallogenesis
considerationin the evaluationof oxidegenesis.
In mineralexploration,manganese oxidesareoften
Supergene-hydrothermal
(S-H) regardedasubiquitous weatheringproductsof little
Mineralogy consequence. However, extensive,well-developed
Supergene:chalcophanite,
coronadire,crednerite,&MnO•, outcropsof manganese oxidescanbe derivedfrom
groutite,hollandite,
lithiophorite,
manganite, the oxidationof bothAu-Ag-andPb-Zn-bearing min-
nsutite,quenselite,ramsdellite,woodruffite,
(romanechite) eralizedsequences, andassuchtheydeservegreater
Hydrothermal:bixbyite,braunite,hausmannite, hiibnerite, attentionin an explorationprogram.It is important,
jacobsite,pyrochroite however, if misleadinginterpretationsare to be
Geochemical enrichments
avoided,that the significanceof manganeseoxide
Supergene: Co-Ni
Hydrothermal: As-Ba-Cu-Li-Mo-Pb-Sb-Sr-V-Zn outcropsisnotassessed usingchemicalcriteriadevel-
Geochemical associations opedon silicateor ironstonelithologies.The adsorp-
Supergene: Mn-Co-Cu-Ni-Zn tion propertiesof the oxidesraisethe thresholdof
Hydrothermal:Mn-As significanceof manyelements,relativeto that used
Diagnosticplot on conventional samples,suchthatwhatwouldbe an
(Co+ Ni) vs.(As+ Cu + Mo + Pb + V + Zn) [Fig.2]
anomalous concentration ofatargetorpathfinderele-
Supergenemarine-terrestrial(SM•-ST) ment in a silicate rock or ironstone is within the back-
Mineralogy groundrangefor a manganiferous lithology.Thispar-
No diagnostic
mineralassemblage
Geochemical enrichments ticularlyapplieswhenevaluatingmanganiferous gos-
Marine: Na-K-Ca-Mg-Sr;Co-Cu-Ni sans;the presenceof manganese oxideswill distort
Terrestrial: Ba anomalous signaturesdevelopedon, and designed
Geochemical associations
for, conventionalgossans.In suchcircumstances, ap-
Marine: No reliablediagnostic
association
Terrestrial: Mn-Ba plicationof the dubhiterecognitioncriteria(Table3)
Diagnosticplot to a mineralogicaland geochemicalanalysisof the
Navs. Mg [Fig. 1] separatedmanganese oxideswill be more revealing
Supergene-dubhite
(S-Sa) thanattemptsto interpretbulk analyses of an iron-
Mineralogy manganese oxidemixture.
Dubbite: chalcophanite,
coronadite,
hetaerolite,andother
Zn-Pb-(Cu?)-bearingoxides(e.g., crednerite, Acknowledgments
woodruffite)
in dubbites
overbasemetaldeposits
Geochemical enrichments I am gratefulto two EconomicGeologyreviewers
Dubhite: Pb-Zn for helpful,criticalcomments
on the originalmanu-
Geochemical associations
script.
Dubbite:Mn-Pb-(base
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Diagnosticplot REFERENCES
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