Economic Geology

Vol. 70, 1975, pp. 1190-1201

Lead-Silver,Manganese,and Native Sulfur Mineralization

within a Stratovolcano,
E1 Queva,NorthwestArgentina
•RICHARD I-I. SILLITOE

Abstract

A descriptiveaccountis presentedof the principal characteristicsof, and time-space

interrelationships between,hydrothermalalteration and lead-silversulfide,native sulfur,
and manganeseoxide mineralization in the E1 Queva area, located on the Puna block
of northwest Argentina. Alteration and mineralization are genetically related to the
final stages of activity of a complex Quaternary stratovolcanoof andesitic to rhyo-
dacitic composition. Glacial erosion of the volcanic superstructurehas exposed areas
of argillic and advanced argillic alteration and silicification, containing pyrite-galena-
silver sulfosalt mineralization accompaniedby chalcedonicsilica, dickire, alunite, and
barite, that were formed some400 to 500 m beneaththe original volcanic surface. The
sulfidemineralizationis transitionalupward to an accumulationof native sulfur. Around
the unerodedperiphery of the volcanic edifice, small manganeseoxide and travertine
depositswere subsequently precipitatedat the orificesof thermal springs,one of which
is still weakly active.
This geometricalarray of subvolcanicand volcanic mineralizationtypes, preserved
becauseof unusual erosional circumstancesand well exposedin the E1 Queva area, is
believedto be typical of that to be .expectedin the surficialparts of large hydrothermal
systemsthat may .includethe developmentof porphyry copperdepositsin depth at the
level of a sourcestock. The r.elationships exhibitedat E1 Queva confirmthat "epither-
mal" mineral depositsare not related exclusivelyto caldera development,as in many
.parts of the San Juan Mountainsof Colorado,but also occur within uncollapsedvol-
canic cones.

Preliminary Statement Three additional observationsof significancefor

Ix recentyears muchattentionhas beenfocusedon
understanding
the role of ore deposition
in volcanic
cycleshavealsobeenmade. Theseare:
the relationshipbetweenstratiform, pyritic massive
sulfide deposits and submarine volcanic activity 1. That volcanicgasesand sublimatescarry small
whereas ore deposition associatedwith subaerial quantitiesof the .common
ore metals (White and
volcanismhas received little attention. It has long Waring, 1963);
been accepted,however, that certain "epithermal"• 2. That bicarbonate-richthermal spring waters,
ore depositswere formed during episodesof sub- someof whichhave precipitatedmanganese oxides,
aerial volcanicactivity (Lindgren, 1933; Burbank, are spatiallyassociatedwith several"epithermal"
1933, 1950; Schmitt, 1950a, b; White, 1955) and basemetal and silver deposits(White, 1955), al-
structuraland stratigraphicstudiesindicatethat the thoughit seemsunlikelythat they were directlyre-
loci o{ mineralizationmay be in the interiorso{ vol- sponsiblefor sulfideformation(White, 1967); and
canoes. The silver-bearing,base metal vein and 3. That hypogene manganiferousvein deposits
and
pipe depositsof the San Juan Mountains, southwest manganiferous thermal-springapronsare genetically
Colorado (Burbank and. Luedke, 1968; Steven, related and contain small amounts of the common ore
1968), the silver-goldveins of Nevada (Albers and metals(Hewett and Fleischer,1960; Hewett et al.,
Kleinhampl,1970), the silver and tin-silverveinsof 1963).
the Altiplano and easternCordillera of southernBo-
livia (Ahlfeld and Schneider-Scherbina, 1964), and However,despitethe realizationthat a closelink
the goldtelluride veinsof the Tavua area, Fiji (Den-
existsbetweencertainore depositional processesand
holm, 1967) may be cited as examplesof mid-to-late the subaerialvolcaniccycle,we lack a preciseunder-
Tertiary age that have been subjectedto extensive standingof the temporaland spatialsituationof ore
field study. deposition
in relationto present-day
volcanicland-
forms and activity. This article describesthe re-
• "Epithermal" is used in the senseof Schmitt (1950a) to sults of a reconnaissanceexamination of hydrother-
signify magmatic-hydrothermalmineralization at shallow mal alteration and sulfide and oxide mineraliz'ation of
depth,without the temperatureconnotationimpliedby Lind-
gren (1933). Quaternaryagein the vicinityof the El Quevalead-
1190
 NATIVE SULFUR MINERALIZATION 1191

silvermine in northwestArgentina. Here the inter- I I

relationshipsbetween mineralization,little-eroded
volcaniclandforms,thermal springs,and solfataras 22"-
can be worked out with a minimum of conjecture
and lead to a better appreciationof what is con-
sideredto be one of the most important situations
for ore depositionin the volcaniccycle. It is hoped
that the resulting model will provide a better geo- _...'"'.).
C3 i ,,,,/
metrical basisfor geochemicalstudiesof ore forma-
tion in the "epithermal"environment. I
I

Introduction to the E1 Queva Area

The E1 Queva mine is located in Salta Province,
2.4 ø.

•',•'•"
'FIG.
e/
I S.Antonio
e3ujuy
northwestArgentina,some53 km directlysouthwest
of the regionalcapitolof San Antonio de los Cobres
in an area that, thoughremote,is accessible by both
rail and road (Fig. 1). The mine and zonesof hy-
drothermalalterationin its vicinityare on the flanks
•de
los
Cobres e Salta

of the Nevados de Pastos Grandes, in the eastern

Cafayate
part of the Puna. This range, which attains a maxi- 26 •.
©
mum altitude of 6,130 m above sea level at Cerro
Quevais oneof manyvolcanicmassifsthat havebeen
constructed on the Puna block. The Puna is the
_/
southwardcontinuationof the Bolivian Altiplano
(see Turner, 1970) and is a cold, arid, high-level 6• ø •6ow.
plateau (generallyabout3,800 m abovesea level)
characterizedby internal drainage basins that are Fro. 1. Location map of the Nevados de Pastos Grandes
occupiedby salares(saltpans) in which halite and region, northwesternArgentina, depictedon Figure 2.
borates have accumulated.
Incompleteand rather imprecisefigures suggest Steeply-dippingphyllitesare commonon the western
that the E1 Queva mine has produceda little over sideof the Nevadosde PastosGrandesrange (Fig.
3,000 tonsof ore duringits intermittentoperating 2). The sedimentary basementhas beenprovenby
life from 1968to early 1973,with a maximumoutput fossilevidenceto be of Middle to Upper Ordovician
of 1,270 tons in 1970. Ore gradesare difficultto age (Acefiolazaand Toselli, 1971; Acefiolaza,1973),
estimate but hand-cobbed material seems to have
To the eastof the Nevadosde PastosGrandesrange,
averagedabout8 percentleadand0.2 percentsilver. a graniticbatholith,probablyof Silurianage (Men-
These figures emphasizethat the mine is only a dezetal.,1973),intrudes thesedimentary basement
small-scale.operationworkedin a rudimentaryfash- (Fig. 2). From the Silurianto the presentday, the
ion. However, this does not detract from the use- Punablockis believedto havebeena positiveregion.
fulnessof the E1 Queva mineralizationfor the eluci- The Ordovicianbasementis overlainwith strong
dationof interrelationships betweenvolcanismand unconformityby cross-bedded, red sandstonesand
ore deposition. conglomerates that occupysmall areas peripheral
to the Nevadosde PastosGrandesrange (Fig. 2).
GeologicalSetting
They are referredto as the PastosGrandesGroup
Geologicalmapping of the Nevados de Pastos (Calchaquense of the older terminology),are Mio-
Grandesregion was undertakenby Vilela in 1950 ceneto Pliocene in age,andweredeposited in tec-
(Vilela, 1969) andremapping hasrecentlybeencom- tonic basinscomparableto the present-daysalar-
pleted by geologistsof Plan NOA-1 Geo16gico- filled depressions.
Minero, Salta. This more recent work has resulted In variouspartsof the Puna,the red-bedsequences
in little modification
of the mappeddistributionor are overlainby volcanicrocks,consistingof early
definitionof formationsbut has incorporated a re- dacitesand rhyodacites,andesiteswhich are com-
vision of stratigraphicages. monly quartz-bearing,and late latites of alkaline
The exposedbasementin the Nevadosde Pastos affinity (Vilela, 1953; Turner, 1970; Schwab,1971;
Grandesregion consistsof a low-grade (greenschist H6rmannet al., 1973). Theseare intrudedby sub-
facies) metamorphicflysch succession comprising volcanicstocks. Small-scalecopper, lead, zinc,
mainly lutites intercalated with lesser arenites. silver, antimony, and manganesemineralizationis
1192 RICHARD H. SILLITOE

:::::::::::::::::::::::::::

•OCITOS

67øW.
I0 kin.
i

LEGEND •' Pb-Ag Lead-Silver

•' S Native Sulfur
•-] Evaporites. '• Mn Manganese
• Alluvium. •QUATERNARY
•' P Perlite

i:[•
[•
Andesites
•Less
Dffcites.
[
Dadtes&Rhyodacites.
J
),' Dip and Strike
•, ",,,. Road; Ra'llroad
• Pastos
GraJxles
groupMIOCENE-
red beds. PLIOCENE
• Contour in meters
• Granites SILURIAN
--• Lutites
&Areni•s ORDOVICIAN All--- -4A S[CnO UNœ
 NATIVE SULFUR MINERALIZATION 1193

associatedwith theselate ,Cenozoicmagmaticrocks undergone only minor fault displacement. The

(Angelelli et al., 1970)andmaybeassigned to'the principalidentifiableconesof the Nevadosde Pastos
southernpart of a copper-lead-zinc-silver metallo- Grandesstratovolcanooverlie a particularlypersist-
genicbelt in the centralAndes (Sillitoe, 1975). ent zone of north-trendingfaults as depictedon the
In the region under consideration,the Pastos 1:200,000 geologicalmap preparedby Plan NOA-1
Grandes Group is overlain by a calc-alkalinevol- Geo16gico-Minero,Salta.
canicpile that constitutesthe north-trendingNevados Dissection of the Nevados de Pastos Grandes
de Pastos Grandes range. The range comprisesa stratovolcanois not very far advancedand was
complex stratovolcano,some 44 x 26 km in area, largely accomplishedduring the Pleistoceneglacia-
made up of three main coalescingcones that rise tion When erosion was locally active at altitudes
1,750 to 2,130 m above the surroundingsalaresof greater than about 4,500 m. This observationis in
the Puna. Separate,smaller conesare situated to keepingwith thoseof previousworkers in adjacent
the east and west of the Nevados de Pastos Grandes parts of Chile (Briiggen, 1950; Hollingworth and
range (Fig. 2). Except for thermal-springactivity, Guest, 1967). Large cirquesand U-shapedvalleys
volcanismhas apparentlyceased. were carved on the west and north sides of the sum-
The Nevados de Pastos Grandes stratovolcano is mit regions of Cerros Gordo and Azufre, whereas
constructed almostentirely of lava flowsof andesitic their south and east sides and most of the highest
to dacitic-rhyodaciticcompositionaccompaniedby peak, Cerro Queva, underwent much less erosion
subordinate pyroclasticunits. Vilela (1969) divided and have their original depositionallava slopespre-
the volcanicpile into a daciticlower part, which out- servedover wide areas (Fig. 3). Even on the west
crops on the northern and eastern lower slopes side,the lower slopesof the superstructure possess
(Fig. 2) and an andesiticupper part which con- largely unmodifiedvolcaniclandforms. Loose talus
stitutesmost of the superstructure. A similar divi- and morainicdebriscoverthe upper slopes,and rock
sion of the post-PastosGrandesGroup volcanicsap- glaciers and "stone stripes" demonstratethe con-
plies to most of the Puna region (Vilela, 1953; tinuance of freeze-thaw conditions. The localized
Turner, 1970). While the basaldacitesin the Neva- glacialdissectionon the west and north 'sidesof the
dosde PastosGrandesregionare easily separableon edifice exposedone large zone and several smaller
the basis of their friable nature, pale gray-white patches of hydrothermally altered volcanic rocks
color and higher quartz content, it should be em- (Fig. 2 and 4), that are describedbelow. In spite
phasizedthat the main superstructurealso contains of the localizedglacial erosionof its summit regions,
flowsof dacite-rhyodacite, somecontainingpoikilitic the overall form of the complexvolcanohas under-
sanidine megacrysts,as well as andesires,some gone remarkablylittle modification.
quartz-bearing. Biotite is the commonestmafic min-
eral in the flows. An interbeddedflow of perlitic Zones of Hydrothermal Alteration
rhyolite has been exploitedat a number of localities The exposedpart of the largest zone of hydro-
on the southwestside of Cerro Azufre (Fig. 2). thermal alteration on the west side of the Nevados
Vilela (1969) consideredthe basal dacites to be de PastosGrandesstratovolcano approximates5 x
upper Miocene and the overlying volcanicsto be 10 km and possesses three extensionsdown west-
Pliocene. On the basisof regionalconsiderations and ward-draining,U-shapedvalleys (Fig. 2). In these
the goodstateof preservationof the volcanicedifices, valleys, strong alteration is evident only on their
it is now generallyagreed (e.g., Turner, 1970) that sides and floors, the interveningareas being com-
the volcanicsof the Puna, includingthe Nevadosde posedof fresherlavaswith only patchesof alteration.
Pastos Grandes stratovolcano,are lower Pleistocene In the area of the E1 Queva mine, however,all lavas
in age,althoughthere is a possibilitythat the forma- are believedto predate alteration but elsewherein
tion of the basaldacitesbeganin the Pliocene. the massif,particularly on Cerro Queva, some of
The block-faulted structure of the Puna is char- the uppermostflows may be postalterationin age.
acterizedby north-trending,high-anglereversefaults Although not apparent from the line of sectionon
that were particularly active during uplift in the Figure 2, there is someevidenceto suggestthat the
Miocene and Pliocene (Turner, 1970; Schwab, alteration zone decreasesin diameter in its upper-
1970). Local faulting was active during the Qua- most parts, as schematizedin Figure 6. This gives
ternary (Pratt, 1961) but well-preservedstrato- rise to the westward extensions noted above. The
volcanoes,such as the Nevados de Pastos Grandes, upward narrowing probably heralded the approach
generally postdatemajor block faulting and have to the then-existingsurfaceand confirmsthat up-

Fro. 2. Geologicalmap and sectionof the Nevados de Pastos Grandesregion, northwesternArgentina. Geology taken
from Vilela (1969) with stratigraphic ages modified after Plan NOA-1 Geo16gico-Minero,Salta.
1194 RICHARD H. $ILLITOE

FIG. 3. The little-eroded eastern side of the Nevados de Pastos Grandes stratovolcano viewed from the road
leadingto Santa Rosa de PastosGrandes(Fig. 2). The peak on the left is Cerro Azufre and the native sulfur
depositis located on the col to its right.

ward flaring of the alteration zone is absent. The rhyodaciteflows. In spiteof an examinationof •
alteration zone outcropsover a maximum vertical altered areas, no intrusive stockswere recognize,
interval of about 1,000 m, between 4,500 and 5,500 althoughthe presenceof dikes and sills is local
m above sea level. The effects of alteration render evident.
identificationof originalrocktypesextremelydifficult First impressions
suggestthat a large part of t!
in parts of the area, but they are thoughtto consist alteration zone has undergone argillic alteratio:
largely of quartz-bearingandesite and dacite to However, thin-sectionand X-ray study of select{

FIG. 4. The main alteration zone on the western flank of the Nevados de Pastos Grandes stratovolcano viewed
from the road north of Pocitos (Fig. 2). The peak in the centeris Cerro Gordo.
 NATIVE SULFUR MINERALIZATION 1195

samples of heavilyalteredmaterialindicates
that the The lead-silver mineralization, described more
alterationis partly of the advancedargillic type fully below,is mostwidespread as a llhear belt in
(HemleyandJones,1964),termedsolfataric altera- the vicinity of the E1 Queva mine, not far abovethe
tion by earlierworkers(Burbank•!O50). The hy- lowestaltitudeat whichthealteration zofieoutcrops.
drothermal minerals identified are chiefly dickite, Small podsof similar lead-silve/-mineralizationwere
kaolinite,quartz,alunite,and•pYritewith smaller also encounteredelsewhere in the large alteration
amountsof transparentgypsum(in veinletsup to zone,oneoutcrop being•ear theaccumulation of
20 cm across)and variousclaymineralsof dubious native sulfur on Cerro AzuYre. Stream-sediment
affiliation; pyrophyllitewas searchedfor but not geochemical samples collected:away fromknown
identified. The claysand alunitepreferentiallyre- mineralizationin the large alteration zone gave lead
placeplagioclase phenocrystsbut locallythe whole andzincvaluesashighas2,400and3,900ppm,re-
rock has been completelytransformed. Some of spectively(J. Mancini, unpub. rept.), thereby sub-
these minerals,especiallythe clays and gypsum, stantiatingthe presenceof scattered•ineralization.
locallymay be of supergene origin but, sincethey
commonlyoccurwith unoxidizedpyrite, a hypogene ß Lead-Silver Mineralization'
,

originis generallypreferred. In high-level,subvol- The main'lead-silver sulfidemineraliz•ttionoccurs

canic environments,however,it is particularlydif- as an east-trendi,ng, 3-kin long belt in a.•westward-
ficult to distinguishbetweenthe effectsof hypogene projectingtobe''c•,the principalalterationzone.The
and supergeneprocesses:. belt,.outcrops
onth½' •:0•or
ofa'U,shapedvalleycutting
Lessstronglyalteredareason the marginsof the westward-dipping flo•v•i. The E1 Queva mine is
zoneand as patchesin it exhibitpropyliticaltera- located approximately _halfwayalongthe belt at an
tion containingchlorite and epidote. The most altitudeof 4,600m (the•iPb-Agoccurrence on Fig.
heavily altered areas are veinlike or irregular 2). The mineralized zonehasa variablewidth,up
patcheswithin the zoneof advancedargillic altera- to a maximumof 200 m, and has undergonestrong
tion that haveundergonesilicification.The silicais postmineralfaulting. The sulfidemineralizationnow
creamto gray in color,aphanitic,and locallyporous occursas lensesand irregular pocketsdue, at least
due to leachingof feldsparphenocrysts.The pres- in part, to disruptionby the late faulting. The fault-
enceof pocketsof aluniteand dickitein someof the ing producedbrittle rupture of silicifiedrock but is
silicified rock indicates material transitional to the
representedby complexlybroken,clayey,gouge-rich
nonsilicified advancedargillicfacies. It is this type groundelsewhere. From the dispositionof the min-
of silicified rock that carries the lead-silver mineral- eralizedbelt, it appearsthat a premineralfault zone
ization. The silicified patches form prominent controlledthe locusof deposition.
moundssimilarto the patchesof fine-grainedquartz The nature of the mineralization and its accom-
rockdescribed by Stevenand Ratt• (1960) from the panying alteration has been examined in the E1
Summitville subvolcanicdistrict in the San Juan Quevamineworkings andin numerous pits,trenches,
Mountains, Colorado. and adits scatteredalongthe length of the mineral-
In variouspartsof the alterationzone,particularly ized outcrop. At the immediatesurface,oxidation
in silicifiedpatches,smallroughlycircularbodiesof hasdestroyed mostof the sulfides,but they are ob-
hydrothermalreplacementbreccia were observed. servablein shallowpits and trenches.
Fragmentsare angularto roundedand are cemented The dacite flow rocks in the mineralized belt have
by aphaniticsilicawhichhas formedby replacement undergoneadvancedargillic alteration and silicifica-
of the original rock. Pebble dikes possessing a tion and mostmagmatic minerals,with the excep-
matrix of rockflour alsooccurin parts of the altered tion of quartz phenocrysts, have been destroyed.
zone. Mineralizedhydrothermal replacement brecciaswere
Native sulfuris locallypresentas a dissemination notedlocallyand consistof unrotated,angular,ad-
in the argillic and advancedargillic rock but forms vancedargillicalteredfragments cemented by chal-
irregular concentrations closeto the highestpoint cedony. Patches, pockets, and streaks of inter-
in the alteration zone not far from the summit of grown chalcedonic silica,alunite, dickite,kaolinite,
Cerro Azufre (Fig. 2), where it was once ex- and barite, in intimateassociation with sulfides,
ploited. This nativesulfuris coarselycrystalline, characterize
the mineralized
belt.They wereformed
yellowto brownin colorandaccompanied by chalce- by replacementand,to a lesserextent,by infillingof
donicsilicaand gypsum. Minor manganese oxides, open spacesproducedduring passageof the min-
containingsignificantamountsof todorokite,were eralizing fluids. The chalcedonicsilica is cream to
foundon jointsand fracturesin the higherpartsof grayin colorandnormallyfinelybanded.It may
the main alteration zone and also at lower elevations be interbanded
with sulfidesor coloredblackby
in the neighborhood
of the E1 Quevamine. fine-grained,disseminated
galenaand sulfos•lt.s:A
1196 RICHARD H. SILLITOE

FiG. 5. Talus fragments of perlitic rhyolite coated and cemented by manganese oxides
(black), from the depositon the southwestflank of Cerro Azufre (Fig. 2).

porous,slag-like texture is commonin much of the surface replacementof galena. Postmine gypsur
gray, intensely silicified rock carrying fine-grained chalcanth.
ite, and iron sulfates coat the walls,
sulfides. The silicified rock may be devoid of workingsin the E1 Queva mine.
alumina-bearingmineralsor may containlocal dick-
Manganese Mineralization
ite, in part pseudomorphous after plagioclasepheno-
crysts. A single group of small quartz crystals Six separatesmall depositsof manganeseoxid.
intergrown with barite was found at one locality. are located in the Nevados de Pastos Grandes r
Barite occursas aggregatesof interlocking,white, gion, most of which have been worked in a-sin;
tabularcrystalsin vuggypocketsor as isolatedcrys- way, and other occurrencesprobably exist. All tl
tals embeddedin dickite, alunite, or chalcedony;in- observed manganeseoxide concentrationsare sit•
dividual crystalsattain 4 cm in length. The white ated around the peripheryof the stratovolcano ar
dickiteand cream,white, or yellow alunite commonly are not spatiallycoincidentwith the zonesof hydr•
infilledvuggyopenspace. thermal alteration (Fig. 2).
Pyrite and galenaare the principal sulfides. They Three distinct modes of occurrenceof mangane;
are typically fine grained and commonlyoccur as oxidesare apparent: 1. The manganeseoxides.
disseminationsin silicified rock. Microscopicex- four localitiescement talus, float material, or terra•
aminationof polishedsectionsof ore also revealsthe gravels that overlie volcanic.rock and in whk
presenceof complexintergrowthsof silver sulfosalts, Ordovicianphyllite,Quaternaryandesiteand daci
includingstephaniteand pyrargyrite,and minor chal- or perlitic rhyolite are the dominant fragrn/m!
copyrite and sphalerite,the latter as inclusionsin Manganeseoxides are colloformand coat and o
galena. mentfragmentsin the alluvialandcolluvialmateria
Postglacial supergeneoxidation, in an acid en- (Fig. 5). 2. In the occurrence near Olacapatotl
vironmentabove the presentwater table, reachesa manganese oxidesoccuras veinletsand dissemin:
maximumdepth of about 30 m and has resultedin tions in a dacite flow; and 3. In the deposit ;
widespreadtransportedgoethiteand jarositederived Boratera Antuco the manganese oxides occur •
from pyrite, and anglesiteafter galena. Crusts of friable beds and lenses admixed with subordina
anglesiteenvelopmassesof galena in the surface goethitein a travertinehorizonthat constitutesa
zone. One sampleof beudantiteof probablesuper- old thermal-springapron. Both manganese oxid•
gene origin was also identified and minor amounts and travertine havebeenexploited. The manganes,
of covellite were visible in polished sectionsas a bearingtravertineis overlainby a mudflowdeposi
 NATIVE SULFUR MINERALIZATION 1197

a secondtravertinehorizonwith tracesof manganese, TABLE 2. Partial Analysis of Water from Boratera Antuco
Spring (in ppm)
and finally a thin tuff at the presentsurface,the
wholesectionapproximately 20 m in thickness. Ca 14.2 HCOa 374.7
A selection
of manganeseoxidesfromthedeposits Mg 6.6 SO4 185.8
Na 646.0 C1 950.0
wasX-rayedand the resultsconfirmed
that crypto- K 84.0 NOa 9.0
melanewas the principalmineral and that some Cu 0.2
amorphousmaterial was also present. In all de- As 1.0 pH 6.9
posits,transparent,
botryoidalchalcedony
is present,
as a surfacecoatingto manganese
oxides. Goethite
is alsolocallypresent,particularlyat BorateraAn- borateswith the Boratera Antuco springand spring
tuco, and gypsum and yellowish-greenmontmoril- apron corroboratesa volcanic source for borates in
lonite occur in the depositnear Olacapato. At the salaresof the Puna, where they are exploitedat
Boratera Antuco, pale-green,fibrous calcite and a several localities. A partial analysisof the spring
borate,ulexite, fill vugs in the manganese oxides. water (Table 2) shows that it is not bicarbonate-
Samplesof travertinegave an X-ray patternfor rich as might be expected(White, 1967) but rela-
calcite. tively enrichedin Na and C1.
Five samplesof manganeseoxides from the Althoughtravertineaccompanies manganeseoxides
manganeseshowswere analyzedto determinetheir only at Boratera Antuco and at the Antuco show
copper,zinc, lead, silver, and arseniccontentswhich to the south, it is consideredthat all the manganese
are listedin Table 1. Althoughcopper,lead, and oxide deposits around the Nevados de Pastos
silverare consistently low, the zinc contentreaches Grandesstratovolcano are the productsof once-active
over0.6 percentin two samples from the depositon thermalsprings. At severallocalitiesthe manganese
the southwestside of Cerro Azufre, and arsenic oxide concentrations are now situated a few meters
exceeds1 percentin two samplesfrom Boratera abovethe presentvalleybottomsbut they outcropat
Antuco. Comparableheavy metal contentshave the ground surface,their original site of deposition.
beendescribedin manganeseoxidesassociated with They must thereforehave been depositedin post-
thermal-springapronsin the westernUnited States glacial times and after all volcanicactivity (except
(Hewett et al., 1963) andare probablyattributable for the depositionof the thin tuff at, and in the im-
to adsorbtionby the manganese oxidesof elements mediatevicinityof, BorateraAntuco) in the general
from solution. The highestzinc contentnotedby region had ceased. The main period of manganese
theseauthorsis, however,only0.3 percent.Hewett depositionhas been followedby only minor stream
et al. (1963) also recorded0.07 percentboron in incision. Consequently, a relativelyrecentperiod of
thermal-springaprons,which clearly correspondsmanganesedepositionis favored, which at Boratera
to the borates identified at Boratera Antuco. Antuco is still continuing,apparentlyat a reduced
At BorateraAntuco,a sluggishspringwith a rate.
wintertemperature of 7øC issuesonly severaltens The manganesedepositsare clearly similar to
of metersupslopefrom the old manganese-bearing others on the Puna of Argentina (Angelelli'et al.,
thermal-spring
apron. This apronclearlyrepresents 1970) and in northernmostChile (Ruiz et al., 1965;
previousactivityfrom the samespringsystem,at Cruzat Ossa, 1970). In the Chilean occurrences,
a slightlyhigherlevel prior to streamentrenchment. manganeseoxides occuras superficialaccumulations
Borates,recoveredcommercially, and minor manga- depositedfrom thermalspringssurroundingQuater-
neseandiron oxidesare, in fact,precipitated by the nary volcanoes. Hewett and Fleischer (1960) and
watersfrom the presentspring. The association of Hewett et al. (1963) have also describedmanganese
oxide deposits,commonlyaccompanied by travertine,
TABLE1. Partial Analysesof Mn Oxides,E1 QuevaArea at activeand inactivethermal springsin the western
(in ppm, exceptwherestated) United States.

32,749• 32,750• 32,7513 32,7525 32,753a Synthesis and Interpretation

Cu 38 35 30 4 10 The spatialinterrelationships
of lead-silversulfide,
Pb 10 6 5 6 11 manganeseoxide, and native sulfur mineralization
Zn 1,330 1,420 292 6,620 6,450 present within and upon the Nevados de Pastos
Ag 1 1 0.5 n.d. n.d.
As 10,000 10,000 3,000 460 480 Grandes stratovolcano can be understood with a
Mn(%) 26.8 35.4 49.4 n.d. n.d. minimum of stratigraphicand structuralreconstruc-
tion. An idealizedrepresentationof their interrela-
From Boratera Antuco.
From Antuco. tionshipsis given in Figure 6. Sulfide mineraliza-
From SW side of Cerro Azufre. tion in the main east-trendingbelt outcropson the
1198 RICHARD H. SILLITOE

1 { l Fumaroles

0
Solar with halite '"• '<:'"'
:--:_•__-_
-:•:_-_-•_-_-_-r•:
Subvolcanicbasement--'
.... ------• + + . ----•----•--:--•--••--•_--:
......
-z .... zz l•_+++
-F +4- i---------
..... -
1 z s K•. ?_/•orphyry
.... ' copper
stock

.:.;-;.:;:..'.:.
Advanced
argillicalteration
andsilic/h•ation.• Nativesulfurdeposit.
III Precious and base metal veins and pipes.
e Thermal springs, manganese deposits and travertine aprons.
Ft. 6. Diagram showingthe interrelationshipsbetween hydrothermal alteration and precious and
base-metal,manganeseoxide and native sulfur mineralization associatedwith a calc-alkaline stratavol~
cano,as interpretedfrom the Nevadosde Pastas Grandesregion, northwesternArgentina. The subjac-
ent porphyry copper-bearingstock may completethis scenario (Sillitoe, 1973).

floor of a U-shapedvalley cut 400 to 500 m below had largely ceasedprior to alteration-mineralization
the surroundingdeposittonalslope of the volcanic and only the thin bed of tuff at Antuco and possibly
edifice. Therefore .sulfide depositiontook place someandesitcflowscappingthe highestgroundout-
beneatha cover of only 400 to 500 m of volcanic sidethe alterationzonesseemto postdatealteration.
rocks, and subordinate sulfide mineralization oc- Sincealterationand sulfidemineralizationare largely
curred even closer to the surface. The sulfide min- preglacialand the peripheralmanganeseoxide ac-
eralizationis an integral part of the main hydro- cumulations are demonstrably postglacial,a time lag
thermal alterationzone, as evidencedby the presence of perhaps1 or 2 m.y. musthaveexistedbetweenthe
of dickitc and alunite in both altered volcanics and, two events,the secondof which is still weakly con-
intergrownwith lead-silversulfides. The alteration tinuing.
and mineralizationappear to have been emplaced It is believedthat the mineralizingfluidsresponsi-
beneathand marginal to the vent regionsof the vol- ble for generation of lead-silver ore and advanced
canic conesat a level beneaththat characterizedby argillic alteration precipitatednative sulfur as they
native sulfur deposition. The Cerro Azufre sulfur approachedthe volcanicvent regions,where they
depositwas probablyformedcloseto a vent on the were presumablyrepresentedby fumarolesand sol-
Cerro Azufre cone. The sulfide mineralization is fataras. A gaseousphasewas apparentlygenerated
evidentlytransitionalupward to native sulfur min- in the surficial zone and presumablycarried traces
eralization,sinceminor native sulfur accompanies
the of metals (White and Waring, 1963). Judging.by
main lead-silver ore and minor lead-silver mineraliza- the presenceof advancedargillic alteration,min-
tion occurs near .the native sulfur deposit and eralizingfluidsat the levelsobservedpossessed a low
both native sulfur and lead-silverdepositsare en- pH and were capableof extremehydrolyticleaching
velopedby the samealterationtype. of bases(Hemley and Jones,1964; Hemley et al.,
The manganeseoxide accumulationsare located 1969). The silicifiednodes,characterizedby almost
peripherallywith respectto alterationand sulfide total leachingof both basesand alumina, could be
mineralization in the center of the edifice, were consideredas the conduits through which most of
precipitatedby thermal-springwaters from which the fluids ascended. Sulfideswere precipitateddur-
they scavenged metals,and are accompanied at An- ing this base-leaching
process. The fine grain size
tuco by travertineaprons. The minor manganese of the sulfidesand the aphaniticnature of the silica
oxide crusts in the alteration zone provide a link suggesta rapid dumpingof materialfrom the trans-
betweenthe centralsulfideand peripheraloxidemin- portingfluidsprobablydue to an abruptdecreasein
eralization. temperatureas the surfacewas approached,a mecha-
These mineralizationevents represent the final nism that would also accountfor barite deposition
phasesin the activity of the Nevadosde Pastas (Holland, 1967). Althoughthe mineralizingfluids
Grandes stratavolcano,correspondingto what is probablyderivedat leasta part of their metalsand
generallyassignedto the fumarolicstage. Lava sulfur from a magmaticsource,they were likely to
emissionleadingto construction cones have beencomposed
of the volcanic largely of heated,low-salinity
 NA TI VE SULFUR MINER.4LIZ.4 TION 1199

meteoricwaters (cf., Schmitt, 1950a, b; White, Fleischer(1960) and Hewett et al. (1963). Hence
1955). Stable isotopestudiesof Miocene,"epi- it is temptingto considerthat porphyrydepositsare
thermal",preciousmetaldepositsof volcanicaffilia- commonlyfringed and cappedby zones of "epi-
tion in Nevada have recently confirmedthe pre- thermal" preciousand base metal veins (Sillitoe,
ponderance waterin the orefluid (Tay- 1973), whichin somecasesincludeor passoutward
of meteoric
lor, 1973). In the caseof the similarCaudalosa to manganese veinsin depthandmanganiferousther-
Peru, however,mag- mal-springapronsat surface.
silverdepositin south-central
matic water has been shown to be an important Bicarbonate-type springs,associatedwith traver-
process(Sawkinsand Rye, tine aprons,commonlyissuein closeproximity to
factorin the metallization
1974). "epithermal"basemetal vein depositsas at Creede,
The marginalmanganese mineralizationwas ap- Colorado,althoughthey are not directly responsible
parentlyproducedduring the debouchment at sur- for ore deposition(White, 1967). This may be due
face of somewhatdifferent fluids. Thermal-spring to displacement of the springorificesduringerosion,
waters,of the sort believedto have formed manga- so that their originalmarginalpositions,exemplified
neseoxide deposits,are normallyof the Na-Ca- at E1 Queva and in northernmostChile (Cruzat
HCOa type accordingto White (1967). He has Ossa, 1970), are lost.
also suggested that separationof a more fugitive, The observationthat E1 Queva sulfide ore was
CO2-richvaporphasefrom higherdensity,metal- formed 400 to 500 m beneath surface and that minor
bearingbrinesand its subsequent admixturewith mineralization occurred at even shallower depths
the meteoriccircul'ation
couldexplainsuchbicarbon- confirmsthe suggestionsof earlier workers that the
atespringwaters.In theNevadosde PastosGrandes "epithermal"mineralizingenvironmentcan be as
region,however,the presentBorateraAntucospring shallowas 300 (Lindgren, 1933; Burbank,1950) to
water is more a dilute Na-C1 type, but this water 1,000 m (Hewett, 1964).
may well be distinctfrom that whichprecipitated the It is now widely acceptedthat important "epi-
maintravertine-manganese oxideaccumulation; it is thermal" mineral depositsdevelopbeneathvolcanic
probablylittle more than meteoricwater that has calderaswith ores emplacedduring final phasesof
percolatedthroughthe volcanicpile. the caldera cycle in ring and radial fracturesgen-
erated during cauldroncollapse(Smith and Bailey,
Overview 1968; Albers and Kleinhampl, 1970; Lipman and
Steven,1970; Stevenet al., 1974). It is clear from
It was recentlysuggested (Sillitoe, 1973) that
the evidenceat E1 Queva, however,that the "epi-
high-level,advancedargillic alterationand sulfide
thermal" environmentcan also exist in the upper-
deposition like that in the E1 Quevaarea can take
most parts of a stratovolcanoat which a calderahas
placein volcanic superstructures aboveconsolidating,
cogeneticmagmabodiesin which porphyrycopper not formed. The rarity of suchdepositsin uncol-
deposits are generated(Fig. 6). If this is so, then lapsededificesis readily explicablein terms of their
the hydrothermalphenomenarepresentedat E1 susceptibilityto erosion. As in the caseof mineral-
Quevaare probablyproducedby fluidsderivedfrom ized calderas,however,ore depositionconcludesthe
the grossdilutionof high-density magmaticbrines volcanicactivity and is localizedby zonesof struc-
of thetypethatgiveriseto potassium silicatealtera- tural weakness. It would seemthereforethat "epi-
thermal"ore depositionin the upperparts of a vol-
tion, with suprajacent, convectively-circulating
groundwaters(Sheppardet al., 1971). The possi- canicedificeis dependenton processes accompanying
the consolidationof residualmagmachambersin the
bilitytherefore existsthattheE1 Quevaalterationis
transitional downward to sericitic alteration in the roots of the edifice or in the underlying basement
upper parts of a porphyrycopper-bearing stock (Fig. 6) and is not controlledexclusivelyby the
peculiaritiesof calderadevelopment. It is interest-
(Sillitoe, 1973; fig. 1).
In this regardit is instructivethat on the propyli- ing to notethat few examplesof Quaternarycalderas
tic or little-alteredfringes of certain porphyry cop- in the central Andes have been recognized.
per-typedeposits,
withinand beyondthe lead-zinc- Acknowledgments
silverzone (Jerome,1966), as at Bisbee,Arizona,
and Butte, Montana (Meyer et al., 1968), veins I am most grateful to St. J. Mancini, then of Plan
carryingmanganese carbonatesand silicatesoccur NOA-1 Geo16gico-Minero,Salta, Argentina for an
that couldbe considered
as deeperequivalentsof the introductionto the geology of the E1 Queva area
peripheralmanganese oxide accumulations in the and to other geologists,especiallyDr. C. Lurgo, of
Nevadosde PastosGrandesregion. As notedabove, the sameorganizationfor usefuldiscussions.Chemi-
a geneticconnection betweenmanganiferous veins cal analyseswere carried out in the laboratoryof
andhot-spring apronswasadvanced by Hewettand Plan NOA-1, Salta under the supervisionof Ing.
1200 RICHARD H. SILLITOE

A. Rosales. Thanks are due to Mr. R. Curtis and Dr.

Hewett, D. F., Fleischer, M., and Conklin, N., 196,3,De-
C. Halls for valuableadviceon the X-ray diffraction positsof the manganeseoxides,supplement:Ecoa. GEot..,
v. 58, p. 1-51.
and ore microscopicalwork, respectively. Review of Holland, H. D., 1967,Gansuemineralsin hydrothermalde-
the manuscriptwas kindly undertakenby Dr. F. J. posits,in Barnes,H. L., ed., Geochemistryof hydrothermal
Sawkins. ore deposits: New York, Holt, Rinehart and Winston,
Inc., p. 382-436.
Most of the field work was carried out in 1972 as Hollingworth, S. E., and Guest, J. E., 1967, Pleistocene
part of a researchproject financedby the Royal glaciation in the Atacama Desert, northern Chile: Jour.
Glaciology,v. 6, p. 749-751.
Society,London,and additionalvisits were made in H6rmann, P. K., Pichler, H., and Z'eil, W., 1973, New data
1971, 1973, and 1974 during engagements with the on the young volcanism in the Puna of NW-Argentina:
Geol. Rundschau,v. 62, p. 397418.
United Nations, New York. Logistic support was Jerome, S. E., 1966, Some pertinent features in exploration
providedby Plan NOA-1 Geo16gico-Minero, Salta. of porphyry copper deposits,in Titley, S. R., and Hicks,
Someof the laboratorywork was completedduring C. L., Geology of the porphyry copper deposits,southwest-
ern North America: Tucson, Univ. of Arizona Press, p.
tenure of a Shell postdoctoralResearchFellowship 75-85.
at the Royal Schoolof Mines, London. Lindgren, W., 1933, Mineral deposits: New York, McGraw-
Hill, 930 p.
DEPARTMENT OF MINING GEOLOGY Lipman, P. W., and Steven, T. A., 1970, Reconnaissance
geology and economicsignificanceof the Platoro caldera,
ROYAL SCHOOL Or MINES southeasternSan Juan Mountains, Colorado: U.S. Geol.
IMPERIAL COLLEGE OF SCIENCE AND TECHNOLOGY Survey Prof. Paper 700-C, p. C19-C29.
PRINCE CONSORT ROAD Mendez, V., Navarini, A., Plaza, D., and Viera, V., 1973,
LONDONSW7 2BP, ENGLAND Faja eruptira de la Puna Oriental: Quinto Cons. Geol.
Argentino Actas, v. 4, p. 89-100.
October25,197,4;January16, 1975 Meyer, C., Shea, E. P., Goddard, Jr., C. C., and Staff,
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