Economic Geology

Vol. 72, 1977, pp. 893-924

Environ.merit
of ()re Depositionat Cerro1)ePasco,Peru
M•mco T. EINAUDI

Abstract

The massivesulfidereplacementbodyin carbonatewall rockseastof the Cerrode

Pascovolcanicneck containsan early associationof pyrrhotite and FeS-rich sphalerite
alteredby late fluidsto pyrite-marcasite
and FeS-poorsphalerite. Rapidsulfidedeposi-
tion from an ore fluid that fluctuated widely in sulfidation-oxidationstate is suggested
by' (1) intricatereversalsand broadrangein X s• v•sß(2) lack of detailed correlationon a
local scalebetweenX•es and iron-sulfideassociation'(3) evidencefrom sulfur isotope
data for disequilibrium
sulfideassociations;
and (4) superposition
and telescoping
of
mineral stages.
The first stageof ore depositionfollowedthe formation of an extensivereplacement
body of pyrite-quartzin limestoneand alterationof adjacentquartz monzoniteand
volcanicagglomerateto sericite-pyrite-quartz. Upward and outward zoning relative
to centrallylocatedpyrrhotitepipesfollowsthe sequence quartz-pyrrhotite-wolframite,
pyrrhotite-stannite-chalcopyrite-sphalerite,
and pyrrhotite (pyrite)-arsenopyrite-sphal-
erite. The latter associationrepresents
the main stageof Pb-Zn ore formationand ex-
tends up to 600 metersfrom the pyrrhotite pipes,where pyrrhotite disappearsand
galenabecomes increasinglyabundant. Polishedthin sectionsand electronmicroprobe
analysesindicate that most sphaleritegrains display intricate growth zoning with
numerous reversalsin FeS content and an overall zoning trend from high FeS cores
(X yes
s• = 0.25-0.35) to lower FeS rims \(X FeS
•l = 0.15). Mean valuesof X reS: s• (1) are
0.21 in the pyrrhotite pipes; (2) 0.23 within 50 m of the pipes,wheresphaleriterarely
containspyrrhotite blebsand occursin pyritic ore containingquartz-siderite-chlorite;
and (3) zone outward from this point to lessthan 0.18 in lesspyritic fringe ore that re-
placed limestone.
The application of sulfide equilibrium data yields broad limits to depositionaltem-
peratures,ranging from a minimum of 254øC for hexagonalpyrrhotite, to maxima of
334øC for pyrrhotite q- chalcopyrite and 500øC for pyrite q- arsenopyrite. These
li•nits are compatible with sulfur isotopic fractionation temperatures for sphalerite-
galena(Austria,1975),whichsuggesta thermaldeclinefrom about 340ø to 230øCwith
distancefrom the central pyrrhotite pipes. The compositional data on sphaleritein-
dicatethat the ore fluid was not generallyin chemicalequilibriumwith bothpyrite and
pyrrhotite,a conclusion supportedby the lack of isotopicequilibriumbetweensphalerite-
pyrite and galena-pyritepairs. The overalltrend in chemicalstate of the ore fluid with
decreasingtemperature may have been buffered by pyrrhotite-siderite-chlorite-quartz
toward increasingoxidation-sulfidationstates, such that eventually equilibrium with
pyrite was reached on the fringes of Pb-Zn ore. Samplesof sphalerite from the pyr-
rhotite pipesthat contain local bandsof 10 to 15 mole percent FeS may signify brief
excursions into the quartz-sideriteor quartz-chloritefieldsdue to influx of oxidized
ground water. The lack of sphaleritecontaininglessthan 10 mole percent FeS on the
fringesof Pb-Zn ore and the presenceof arsenopyritesignifiesthat the sulfidation state
never exceededthe arsenopyrite q- pyrite q- arsenic sulfidation curve.
Enargite-luzonite-pyrite
veinswith advancedargillicalterationenvelopes,
locatednear
the contact of the vent with the pyrite-quartz body, represent a second stage of ore
deposition. Relative to the first stage, the ore fluid of the secondstage had evolvedto
significantlyhigher oxidation-sulfidationstates and lower pH at temperaturesaround
300øC. Reaction of this fluid with mineral assemblagesof the first stage east of the
vent resulted in a sharp increasein pH and depositionof sphalerite containing 0 to 10
and averaging3 mole percentFeS, accompaniedby galena, pyrite, marcasite,and minor
tennantite. Alteration minerals, which formed by oxidation-sulfidationof original
hexagonalpyrrhotite below 254øC, display an increasein S/Fe ratio toward the surface
and can be correlated in a general way with 'the presenceof late, low-FeS sphalerite.
Residual hexagonalpyrrhotite is associatedwith monoclinicpyrrhotite on the deepest
level of the mine below the bottom of Pb-Zn ore. On higher levels hexagonalpyrrhotite
is absentand is replacedby mixturesof monoclinicpyrrhotite and Fe-deficientanomalous
893
894 _/'11.4RCO
T. EIN.4UDI

pyrrhotite, •hich in turn are convertedto mixtures of pyrite and marcasitewith local
siderite.
The firststageof oredeposition sharessomeof the featuresof tin andtungstendeposits
of the easternAndesof Bolivia and thus servesas a metallogeniclink betweenthe Cu-
Zn-Pb-Ag provinceof central Peru and the Sn-W-Ag-Bi provinceof Bolivia. The
secondstageexhibitsmineralassemblages and zonalparageneticfeaturesthat are found
in numerousother cordilleranbasemetal sulfidelode deposits,suchas Yauricochaand
Morococha,Peru; Magma and Bisbee,Arizona; and Butte, Montana. High sulfidation
states, above tbe pyrite-chalcopyrite-bornite buffer, and intense base-leachingof wall
rocksare characteristicfeaturesof the central copperzoneof thesedeposits. Suchan
extremedepartureof the ore fluid from chemicalequilibriumwith freshrocksprobably
reflectsthe involvementof oxygenatedgroundwater. Although somelode deposits
are associatedwith an early stageof porphyrycoppermineralizationrepresentingless
of a departure from equilibrium with wall rocks, this is not a general.case. It is con-
cludedthat the two typesrepresentend membersof the process of hydrothermalorefor-
mation associatedwith subvolcaniccalc-alkaline intrusions. The development of
dominantly one or the other ore type may ultimately dependon the timing and degree
of ground-water involvement.

Introduction tion of the field and laboratory data on mineral

assemblagesand compositionswith recent data on
THE complex and superimposedstages of mineral-
ization at Cerro de Pasco reflect extremes of bulk
mineral stabilities yields few contradictions and
inspiresconsiderableconfidencein the accuracy of
composition and depositional environment which
published experimental and theoretical equilibrium
are rarely found in a single ore deposit. Evidence studies.
is provided by numerous investigators (sum-
marized by Petersen,1965) for a temporal evolution Geological Setting
from: (1) low-sulfursulfideassemblages associated
with quartz-siderite-chlorite in replaced carbonate Cerro de Pasco is located on the Andean plateau
wall rocks; to (2) high-sulfur sulfide vein fillings of central Peru at an elevation of 4,300 m. The
associated with sericitic and advanced argillic district lies east of the continental divide and west
alteration of quartz monzonite wall rocks; followTed of the Cordillera Oriental in an area which consists
by (3) hypogeneleachingand open-spaceredeposi- largely of moderately folded and faulted, mio-
tion of sulfides,sulfosalts,native sulfur, realgar, geosynclinal sedimentary rocks of Mesozoic age.
and alunite. The physiochemicalevolution of the This central Andean Mesozoic belt contains the
ore fluid, in a dynamic, near-surface environment, majority of ore deposits of central Peru (Petersen,
must have been dominated both by drastic changes 1965), many of which are associatedwith Tertiary
in temperature (and perhaps pressure) and also hypabyssal intrusives ranging in composition from
by contrasting wall-rock chemistry. granite to diorite (Lacy, 1953).
The literature on ore deposits contains many The Cerro de Pasco orebody is spatially and
referencesto Cerro de Pasco as a classicexample genetically associatedxvith a Tertiary volcanic vent
of high sulfidation states and advanced argillic that is located in the core of a broad, north-
alteration (e.g., Meyer and Hemley, 1967) or of plunging anticline composed of highly contorted
hypogene leaching (e.g., Barton et al., 1963), shales, phyllites, and quartzites belonging to the
based on the detailed studies of these aspects of Excelsior Group of Devonian age (McLaughlin,
Cerro geology by Graton and Bowditch (1936) 1924; Jenks, 1951). On the surface, continental
and Lacy and Hosmer (1956). The earlier stages red beds of the Permian Mitu Group (Newell et al.,
of ore deposition have not been emphasized in the 1953) unconformably overlie the Excelsior Group
publishedliterature. The present study documents on both limbs of the anticline. The Mitu Group
the structure, paragenesis, and zoning in the is absent or unrecognized in the underground mine
early-stage massive sulfide body that formed in workings, where Triassic-Jurassic Pucar,5limestone
sedimentary rocks. An attempt is made to define appears to overlie the Excelsior shales. The
temperature and various chemical parameters of Pucar/t Group, the main Pb-Zn ore host rock,
the depositional environment and to contrast these consists of thick-bedded, dark-colored limestone
with the environments that characterized later
and dolomite with infrequent cherty shaleinterbeds
events. Becausedeposition of sphalerite occurred (Jenks, 1951).
during most stages, the trends in FeS content of The volcanic vent, 2.5 km in diameter, is filled
sphalerite are of particular significance. Integra- with pyroclasticbrecciaand is intruded by multiple
 M.4RCO T. EIN'.4 UDI 895

TA}•LE 1. Tonnage and Grade of Ore Produced at Cerro de Pasco

Million
Period Location Ore type tons % Cu % Pb % Zn oz Ag/ton

1906-1956 underground copper 18.0 4.03 4.26

1957-1970 open pit copper 3.4 1.80 2.58
1957-1976 open pit copper leaching 16.9 0.94 3.18
1955-1976 ]] - underground lead-zinc 14.0 3.76 10.28 3.07
1960-1976 • open pit lead-zinc 13.6 3.47 8.06 2.42

Source: J. W. Nfifiez, Empresa Minera del Centro del Peril.

Note: Approximately100,000tons of Pb and an unknownlesseramount of Zn were producedin the period 1937-1955.

plugs and dikes of quartz monzonite porphyry.
The porphyry dikes extend into the sedimentary
rocks on the eastern vent contact. K-At ages of
mineral separates frownplugs and dikes that pre-
dated mineralization are in the range 14 to 15 m.y.
(Noble and Silberman, 1977). Although the
majority of igneous activity preceded mineral-
ization, a few late dikes of albitized porphyry cut
enargite veins in the vent (Lacy, 1949). On the
basis of morphology and structures in the pyro-

SECTION 29700E

N------ -% •o.• S
-.•D--.,-'-M McCune
Pit •[ vvvvvvvvvvv.•
-•-*N>q
• •,_,---"W-'v
• v•' • '•,
v v'• • v• • • '••

CN-A
SECTION 29300 E

FIG. 1. Vertical, north-south crosssections,looking east, through the central portions of the
pyrite-quartz body east of the vent. Sectionsillustrate the structural control exerted by bedding
in shale (De) on the limits of the pyrite-quartz body (py) and on the configuration,at depth, of the
pyrrhotite pipes (po) and Pb-Zn ore. De -- Devonian Excelsior shale, JRp = Jurassic-Triassic
Pucara limestone, Tv = Tertiary volcanic breccia. A. Section through Eastern CN-A and San
Alberto pyrrhotite pipes. B. SectionthroughwesternCN-A and J-337 pyrrhotite pipes.
896 MARCO T. EINAUDI

FIG.2. Isometricdiagramillustratingspatialrelationof CN-A pyrrhotite

pipes(black)to
Pb-Znore(dense
stippling).Slightvertical
exaggerationofscale.LegendsameasinFigure1with
additionof Tqmp = Tertiary quartzmonzonite
porphyry.

clasticrocksand felsicplugs,the depth of mineral- mentary wall rocks (Lacy, 1949; Ward, 1961).
izationat the presentlevelof exposure is estimated The outcropof the pyrite-quartzbody is 1.8 km
to be in the rangeseveralhundredmetersto 1,000 long (N-S) and up to 300 m wide. Belowthe 1800
m (Bowditch,1935;Nobleand Silberman,1977). level (levelsaredesignated in feetbelowthesurface)
Hydrothermalsolutionsassociatedwith the the body narrowsto a discontinuous sheathalong
volcanic activity formed a massivereplacement the vent-shale contact and at greater depth it
and fissure-veinsulfidedepositestimatedto have passes into theventandapproaches tangency with
contained a total of 100 million tons of pyrite, 4 an enlargingstockof quartz monzoniteporphyry
million tonsof zinc, 2 million tonsof lead (Petersen, (Lacy, 1949).
1965), in excessof 1 million tons of copper,10 Renewedigneousactivity and fracturing fol-
thousandtonsof silver,and lessergoldand bismuth. lowed the formation of the pyrite-quartz body and
Availableore productiondata are summarized in resultedin theopeningof east-west-striking fissures.
Table 1. Figures1 and 2 illustratethe major The fissures served as the dominant structural
featuresof the orebody. Sulfide depositioncom- controlfor sulfidedepositionin the vent and also
menced with the formation of a steep, funnel- were importantore fluid conduitsin the pyrite-
shaped, massive pyrite-quartzbodyin the sedi- quartz body to the east.
 EN•'IRONMENT OF ORE DEPOSITION AT CERRO DE PASCO 897

Pyrrhotitereplacedpyrite-quartzin steep,tabu- zone, with trace amountsof tennantite,or hypo-

lar and pipelike zones from the 2100 level to the gene covellite and bornite, gives way laterally,
surface(Figs. 1 and 2). Lead-zincore is closely both toward the vent center and toward the center
associatedin spaceand time with pyrrhotite. The of the pyrite-quartz body, to tennantite-pyrite-
major zone of Pb-Zn ore (Cayac-Noruega)forms sphalerite with minor galena. Quartz-sericite-
an irregular funnel-shaped mass which extends pyrite alteration envelopes enclose the veins,
to the surface from just above the 1800 level and except in the central enargite-bearingportions,
whose axis is approximatelydescribedby the where the sericitic envelopesextend further into
pyrrhotite pipes (Fig. 3). Its root zoneis crudely the wall rocks and are replacedat their veinward
oval in plan and increasesin diameter upward side by the advancedargillic assemblagealunite-
from 200 m on the 1600 level to 1,000 m on the dickite-quartz (Graton and Bowditch, 1936).
1200level. Abovethe 1200level,Pb-Zn orespreads The lack of crosscutting relations between
out in a north-south direction and rises as three pyrrhotite and enargite mineralization makes it
separate zones along a total strike length of 1.3 difficult to establishage relations between these
kin. The easternand southernportionsreplaced two stages. However, both stagescontain sphal-
limestone rather than pyrite-quartz. Lead-zinc erite as an associated phase:sphaleritedeposited
ore consists of pyrite, sphalerite, galena, and in the eastern limits of the copper veins in the
quartz, with minor pyrrhotite, arsenopyrite,mar- pyrite-quartz body locally overlaps sphalerite
casite, tennantite, chalcopyrite,chlorite, sericite, deposited in associationwith pyrrhotite. The
siderite, and calcite. low-FeS sphalerite of the enargite stage veins,
Copper (enargite) and copper-silver(enargite- replaces, and overgrows the high-FeS sphalerite
tennantite) ore occurs in steep veins in the vent of the pyrrhotite stage.
and pyrite-quartz body and also in steep pipes The final hydrothermalactivity at Cerro resulted
associated with splaying of the veins in the in local leaching of previously depositedsulfides
northernportionof the pyrite-quartzbody (Graton and the formation of collapsebrecciasand open-
and Bowditch, 1936; Lacy, 1949; Ward, 1961). space deposition of a host of rare minerals. Par-
The veins achieve a maximum east-west strike
ticularly revealing assemblagesinclude: pyrite-
length of 500 m, range in width from a few cm to
2 m, and extend to below the 2300 level, consider- hematite-realgar associatedwith high Ag mineral-
ably deeper than Pb-Zn ore. The vein filling ization, which consists of a complex association
consistsdominantly of pyrite-enargite,with minor including gratonite, baumhauerite, aramayoite,
quartz, barite, and epidote. Zoning along the "waxy" sphalerite,and galena (Lacy and Hosmer,
strike of the veins is symmetricallydeveloped 1956); and alunite-sulfur vug fillings in enargite-
relative to the contact between the vent and pyrite pipes (Geological Staff of Cerro de Pasco
pyrite-quartz body. The central enargite-pyrite Corporation, 1950).

FIG.3. Sketch
of majorPb~Zn
orebodies,
asseenfromthewest,based
onmodelconstructed
by
the Geological
Staffof Cerrode PascoCorporation. Levelsare designated
in feetbelowsurface.
898 MARCO T. E[N•4UD[

[ I at Cerro and is designatedp3rite-1, in a manner

analogous to Lacy (1949). Trace amounts of

,,/ PIPE/
ø
SAN ALBERTO
arsenopyrite and sphalerite, and minute inclusions
of chalcopyriteand pyrrhotite in pyrite-1, repre-
sent contemperaneous phases. Minor amounts of
sphalerite, galena, pyrite, and marcasite occur in
crosscuttingveins.
70½1PIPE Nonsulfidemineralsare dominantly red, black, or
white chert or chalcedonic silica, and quartz.
200 Minor minerals, some of which may have formed
later than the bulk of the pyrite and quartz,
% aoo include siderite, ankerite, sericite, ohiorite, and
epidote. Siderite and chlorite are closelyassociated
with areas of pyrrhotite mineralization. Barite is
common near enargite-tennantite pipes in the
northern portion of the pyrite-quartz body.
Limestone in contact with the pyrite-quartz body
is altered to ankerite or siderite, with no trace of
calc-silicates (Bowditch, 1935), or is leached to a
porousmixture of residualquartz and clay minerals
(Lacy, 1949). Some remnants of sedimentary
rock are silicified and contain epidote-clinozoisite
and diopside; most of these remnants occur in the
southern portion of the pyrite-quartz body where
the country rock consists of Excelsior shale.
Quartz monzonite porphyry and volcanic ag-
glomerate in contact with the pyrite-quartz body
are prevasivelysericitized(Lacy, 1949); all feldspar
is completely altered to fine-grained sericite;
biotite is altered to sericite, rutlie, and pyrite; and
the quartz content is higher than in fresh rock.
WESTERN
Configurationof Pyrrhotite Pipes
CN-A
Pyrrhotite at Cerro de Pascooccursexclusively
in the pyrite-quartz body and in Pb-Zn ore. Four
separatezonesof massivepyrrhotite are present

x
rlLOURDES
SHAFT (Fig. 4): two are near the vent contactin the west-
ern portion of the pyrite-quartz body below the
1000 level (J-337 pipe and western CN-A pipe),
and two are near the eastern edge of the pyrite-
0 5OOFT

0
I • I

I00
I I I

2OOM
t,
FIG. 4. Horizontal projectionof pyrrhotite pipes(stippled)
from the 2300 to the 200 level, superimposedon structure con-
tours of the base of Pucarg limestone from the 1800 to the
800 level. Large arrows indicate overall plunge of pipes and
dashed lines indicate projected trend. The symmetry of the
pipes relative to the Matagente crossfold is notable.
quartz body (San Alberto pipe and easternCN-A
pipe). The eastern and western CN-A pipes,
which constitue the bulk of pyrrhotite at Cerro,
are accessible over much of their known vertical
extent and therefore form the basis for the present
study.
Cayac-Noruegapipes

Pyrite-Quartz Body The easternCN-A pipe, namedafter the Cayac-

Noruega-A Pb-Zn orebody within which it is
Pyrite and quartz, present in subequalporpor- centrally located,is oval in plan, 30 to 70 m in
tions, constitutein generalover 90 percentof the diameter, and plunges80ø north-northwestfrom
body. Both phasesare subhedralto euhedralwith the surface to the 1000 level. Below the 1000 level
an averagegrain sizeof 0.5 to 1.0 mm (Fig. 6A). the plungefiattensabruptlyto 25øN,conformable
The pyrite represents the earliestsulfidedeposited with the dip of bedding(Figs.1A and4). The pipe
 ENVIRONMENT OF ORE DEPOSITION AT CERRO DE PASCO 899

is wholly within the portion of the pyrite-quartz
body which replaced Pucar• limestone. Its exten-
sion below the 1400 level is not known.
The western CN-A pipe consistsof at least four
discontinuous, tabular bodies between the 1200
and 2300 levels (Figs. lB and 4). Continuity
below the 2300 level is not known. The western
pipe is wholly within the portion of the pyrite-
quartz body which replaced Excelsior shale, and its
attitude is controlled by bedding. In plan view
(Fig. $), individual tabular bodies, 10 to .50 m
thick, extend along bedding 70 to 140 m. The dip
flattens with depth from 45ø to 30ø below the 1600
level as the thickness and strike length increases.
Within the pipes, areas of massive pyrrhotite
alternate either with zones of massive pyrrhotite
and pyrite or with shale partially replaced and
veined by pyrite or pyrrhotite. Contacts with the
pyrite-quartz body are usually sharp, with un-
broken continuity of massive sulfides,or they may

tennantite- ; "--
ß , t7 •

o.".'.79.-:
.....
- '7.:•:-: ' :/
.%..-'. ,...'
:.:i:i.::
J• massive
py-qtz20-90%suit
• >90%sulfides ½.•'"bedding ••x----•,
•k,• ;
":':.:•
limit
ofpyrrhotite
•,5•'--"
conformable
contact
:; 0 20406OFT vein or shear zone I • I • I • I

B ß

'"'"'"'"':':;;"=
'<.?
:.:':
'5
\:' .'.'..:.:'..'.
i':'.'...'1 x:.:
\'.'.'.::. ,....... ;.:.'-.::..'.•

•• \"-'.'.
:.'".'.'.'..".'.'.'.
'.'.'-i;.'.'.'.'.-5.\
•

bypy-2and
py-• ,..'i:... '<'•':'""'"'
•• 0-10
Core
IO-50
zone
pyrite-
":.':"'.'.""
....
;'zone":•;'i"[
i:.."
'.'i",.':"-'"":;'
"'-•i','.-
'" '
;'.i..".'i."'i.:.:.i-.':':...!.11;!'..'•...•'•.
•x•50-80
J• }Pyrite-Szone
80-100 0 20 40 60 FT
i'.':'• Pb-Zn ore .Sample locations • • i , I , I

Fzo. 5. Plan maps of western CN-A pyrrhotite bodieson 1400 level, illustrating A, relation
between unreplaced shale and chert beds and the tabular nature of massivepyrrhotite and B,
relation betweenthe Pb-Zn ore and extent of pyrrhotite alteration in the transition zone.
9OO M,4RCO T. EIN.4 UDI

TABLE2. Average Modes of SulfideZones,Pyrrhotite-Pyrite-SphaleriteAssociation

Core Pyrite-2 Pyrite-3 Pb-Zn oreb Pyrite-Qtz

Gangue• 19 9 15 28 37
Pyrrhotite 64 40 8 tr
Pyrite-1 10 17 18 59
Pyrite-2 0.4 25 13 47 (tot py) 0
Pyrite-3 0.2 0.1 24 0
Sphalerite 5 6 14 18 tr
Galena 0.5 0.1 0.9 7 tr
Marcasite tr 4 4 tr
Arsenopyrite 1.2 1.5 0.8 tr
po4-py-24-py-3 0.87
c 0.79
c 0.71
ø
po 4- py•o•
po 0.99d 0.61d 0.18d
po 4- py-2 4- py-3
No. of samples 69 28 36 36

Gangueconsistsdominantlyof quartz and chalcedony,with minorsiderite,ankerite,chlorite,and sericite.

Pb-Zn mineralogy calculated from ore reserve and concentrator head data.
This fractionrepresentsthe primarypo/po 4- py fractionbeforelate alterationof pyrrhotite.
This fractionreflectsthe degreeto whichpyrrhotitesurvivedreplacementby late pyrite.

consist of unreplaced cherty shale separating This remarkable symmetry reflectscommonstruc-

massive pyrrhotite from massive pyrite-quartz. tural controls. The most important control is the
Thin, tabular bodies in the hanging wall of the Matagente cross fold (Fig. 4), a syncline whose
western CN-A pyrrhotite pipe are located on the axis tends east-west. In the deeper levels, the
westernfringe of the CN-A Pb-Zn orebody (Fig. 5). attitude of unreplaced limestone and shale near
These pyrrhotite mantos extend eastward up to the Excelsior-Pucar•t contact determined the atti-
30 m into Pb-Zn ore before terminating along tude of the pyrrhotite mantos. In the upperlevels,
gradational contacts marked by an abundance of where limestone constituted the wall rocks and
fine-grained,friable pyrite. On the west, pyrrhotite wherereplacementby pyrite-1 was morethorough,
does not extend into the vent. the fissure patterns were important structural
controls.
San Alberto and J-337 pipes
Mineralogy, Paragenesis,and Zoning
The pyrrhotite pipes in the northern portion of Pyrrhotite Pipes
of the pyrite-quartz body are mirror imagesof the
eastern and western CN-A pipes. The San Alberto The mineralogyand paragenesis of the pyrrhotite
pipe is exposedat the surfacein the McCune pit, pipes is best presented within the context of
where it forms the core of the San Alberto Pb-Zn mapped mineral zones. These zones, illustrated in
orebody in limestone. It is oval in plan and Figure 5 for the 1400 level, consist of a core zone,
transition zone, and wall-rock zone. The latter
plunges steeply to the south. Its extensionbelow
the 300 level is not known (Figs. 1A and 4). The may consist of pyrite-quartz or Pb-Zn ore. The
J-337 pipe is located on the western edge of the average mineralogical modesof the zonesare listed
J-337 Pb-Zn pipe. It is presently inaccessible,but in Table 2. The following descriptionsare based
its general attitude is shown on early Cerro de on mappingof the accessible pyrrhotite areasfrom
Pasco mine maps. It extends as a tabular body the 1800 to the 600 levels and a study of 160
from the 1200 to the 1800 level with a dip which polished slabs and polished thin sections. A
varies with increasingdepth from 25ø SW to 60ø qualitative measureof the FeS contentof sphalerite
SW (Figs. lB and 4). was gained by studying samples in thin section
and in polished sections stained with ammonium
Summary dichromate (Einaudi, 1970). Electron microprobe
analyses, reported in a later section, revealed that
The pyrrhotite pipes are conformablewith the the color of sphalerite in transmitted light is a
overall symmetry of the Cerro de Pasco orebody. reliable indicator of FeS content (Table 3).
In the northern portion of the orebody, Pb-Zn
Core zone
pipes, pyrrhotite pipes, and enargite-tennantite
pipesand veinsall dip steeplysouth. In the south- In addition to the major phases pyrrhotite,
ern portion,all of theseelementsdip north (Fig. 1). pyrite-1, and quartz, minorsphalerite,arsenopyrite,
 ENVIRONMENT OF ORE DEPO•ClTION AT CERRO DE PAXCO 901

latepyrite,galena,siderite,andchloritearepresent. Up to 0.2 percent stannite may be found on the

Marcasite,chalcopyrite,stannite,tennantite,jame- 1800 level, where it is most abundant. It di-
sonite, wolframite, and ilmenite occur in trace minishes to trace quantities on the 1600 level and
quantities. Magnetiteoccurswith pyrite and was not noted on upper levels. $tannite most
commonlyoccursas blebsin chalcopyriteor sphal-
carbonate in late veins cutting pyrrhotite in the
SanAlbertopipe,but nonewasnotedin the CN-A erite, as rims around sphalerite grains in quartz
pipes. or pyrrhotite,and as part of disseminatedcomposite
Pyrrhotite generallyoccurs in xenomorphicgrains of chalcopyrite-sphalerite-stannitein quartz
grainswhichaverage1.0 to 0.1 mm in diameter. (Fig. 6C). More rarely, stannite occursas veinlets
In comecasespyrrhotiteformstabularcrystalsup in chalcopyrite, blebs in pyrrhotite, and along
well pyrrhotite-quartz grain boundaries. The textural
to 4 mm in length,a habitwhichis especially
developedon the 1400level, wherepyrrhotiteis relations indicate that stannite formed both as a
found intergrownand replacedby tabular pyrite primary mineral and also as a later product of
(Fig. 8A and B). exsolutionfrom sphalerite.
One of the most consistent and striking para- Semiquantitative electron microprobe analysis
genetictexturesin samplesfrom the pyrrhotite of stanniteassociatedwith sphaleritein chalcopyrite
of pyrite-1 and quartz yielded close agreement with the ideal formula,
pipesis the replacement
by pyrrhotite(Fig. 6B). This replacement
results Cu2FeSnS•. Zinc also was detected and was found
in an averagedecreasein quartz contentfrom 35 to increasefrom the core of the grain to the contact
percentto 20 percent,and the amountof pyrite-1 with chalcopyrite. Microprobeanalysesof stannite
is reducedfrom 60 percentto 10 percent(Table 2). associated
with pyrrhotitealsoindicatethe presence
Polishedsectionstudy hasrevealedthree mineral of several percent zinc.
associationsof the pyrrhotite stagewhich define Chalcopyrite is more abundant than stannite
a verticalzoningpattern. Theseare: (1) a deep- and is found in trace quantities throughout the
level wolframite association; (2) a deep- to inter- western CN-A pipe. It is most abundant in the
mediate-levelchalcopyrite-stannite and core zone, diminishes in amount through the
association;
(3) an arsenopyrite-sphalerite whichis transitionzone,and is virtually absentin the pyrite-
association,
presentthroughoutthe vertical extent of the quartz body. It has not been noted in accessible
pyrrhotitepipesand which extendsinto Pb-Zn portions of the eastern CN-A pipe nor in its wall
ore in the pyrite-quartzbody. rocks. Chalcopyrite is present in other areas of
Pyrrhotite-quartz-wolframite:Wolframite was the Cerro orebody,most notably in the Cleopatra
noted in trace quantitiesonly on the 1800 and tennantite veins in Excelsior shale south of the
1600 levels of the western CN-A pipe. It occurs vent. Sixty percentof the chalcopyriteoccurrences
as minute subhedral to anhedral grains in pyr- noted in the western pipe are in associationwith
rhotite and quartz. Ilmenite inclusionsin pyr-pyrrhotite, either along pyrrhotite-quartz grain
boundariesor as small blebs in pyrrhotite. It
rhotite associated with wolframite were identified
in one samplefrom the 1800 level. Qualitative also occursin quartz veins cutting pyrrhotite, as
electronmicroprobeanalysisof severalwolframite blebs or veinlets in pyrite-1, and as the most com-
of smallamountsof mon companionof stannite. Chalcopyriteoccurs
grainsindicatesthe presence
Ti in addition to Fe, Mn, and W. The absence rarely as blebs or veinlets in arsenopyriteand as
of wolframite in the pyrite-quartz body suggests oriented and unoriented inclusionsin sphalerite
that wolframite formed during the pyrrhotite up to the 1200 level.
stage. The absense
of wolframitein directcontact $phalerite directly associatedwith either stannite
with phasesother than pyrrhotiteand quartzalso or chalcopyrite,or both, and often containing
suggests may be what appearto beexsolutionblebsof theseminerals,
that pyrrhotite-quartz-wolframite
a discrete assemblagewhich formed only in the occurs in trace amounts and only below the 1200
deeperportionsof the westernpipe. Equivalent level. It is designatedsphalerite-1. No chemical
elevationsin the eastern pipe are not accessible. data were acquired on sphalerite-1 because the
Lacy (1949)reportedcassiterite from the western density of chalcopyrite or chalcopyrite-stannite
CN-A pipe on the 1600 level, but no cassiterite interfered with both staining and electron micro-
was foundduring the presentstudy. probe analysis. However, local areas of uniform
This dark staining imply a relatively high FeS content,
Pyrrhotite-sphalerite-chalcopyrite-stannite:
assemblage is restrictedto the western CN-A greaterthan approximately17 mole percent.
pipe;it hasnot beennotedin any otherareaof Pyrrhotite-sphalerite-arsenopyrite:
A third mineral
the Cerro orebody. Pyrite does not constitute associationof the pyrrhotite stage is characterized
part of the assemblage. by variouscombinations of themineralspyrrhotite•
902 MARCO T. EINAUDI

E
FIG. 6. Microphotographstaken in reflectedlight illustrating mineralassociations
and textures
of the pyrite-quartzbody and pyrrhotite corezone. Long dimensionof photographsis 330
unlessotherwisespecified.
A. Euhedralpyrite-1 disseminated in quartz (black). Length of photographis 950 ym. Sample
12-7, pyrite-quartz body, 1200 level.
B. Pyrrhotite (gray) replacesand cuts pyrite-1. Sample 6-36, pyrrhotite pipe, 600 level.
C. Zonedgrainof chalcopyrite(cp)-stannite(sn)-sphalerite-1 (sl) in quartz (black)and pyrite-1
(white). Lengthof photographis 120 •m. Sample16:12,pyrrhotitepipe, 1600level.
D. Hexagonalpyrrhotite (h-po)-monoclinicpyrrhotite (m-po) intergrowth. M-po is concen-
trated alongthe bordersof quartz crystals (black) and along a fracture in the lower left corner of
photo. Zwischenprodukt (zw) preferentiallyreplacesh-poalongfracturesand is later than m-po.
Sectionstainedwith ammoniumdichromate. Sample18-24, pyrrhotite pipe, 1800 level.
E. Sphalerite-2(gray)-pyrrhotite(white) intergrowthin quartz (black); FeS contentof sphal-
erite rangesfrom 16 to 21 mole percent,with a meanof 19.6 mole percent. Sample14-23, pyr-
rhotite pipe, 1400 level.
F. Sphalerite-2(patchydark gray to mediumgray)-pyrrhotite (palegray) association; sphalerite-
2 containsareaswith pyrrhotite blebs;ammoniumdichromatestain revealspatchy distributionof
FeS content, with pyrrhotite-free areas tending to be more FeS rich; FeS content outside areas
of pyrrhotiteblebsrangesfrom 15to 27 molepercent,with a meanof 20.8molepercent. Sample
14-47•pyrrhotitepipe, 1400level.
 ENVIRONMENT OF ORE DEPOSITION AT CERRO DE PASCO 903

TABLE 3. Correlation of Sphalerite Composition• with Color in Transmitted Light and in Reflected Light after Staining

wt % Color
Mole %
Fe Zn S Total FeS • Transmitted 3 Reflected, stained4

Core 15.1 51.0 34.1 100.2 25.7 purple

12.3 54.8 33.9 101.0 21.0 dark red-brown dark brown to

11.0 55.7 33.9 100.6 18.8

purple,,

i to
op,,aque
10.8 56.1 34.0 100.9 18.6 "
11.4 55.4 34.0 100.8 19.4 "
14.6 52.1 34.0 100.7 24.8 "
,,
13.7 53.0 34.1 100.8 23.3 "
15.1 51.4 34.1 100.6 25.7 " purple
eq 15.0 51.4 34.1 100.5 25.5 " purple
• 11.0 56.6 33.8 101.4 18.8 red-brown light brown
'• 8.1 59.7 33.8 101.6 14.0 " ,,

,,
m 11.0 56.2 33.8 101.0 18.8 "
• 2.6 64.5 33.5 100.6 4.6 yellowish
gray no stain

7.1 60.4 33.6 101.1 12.2 red-brown v. light brown in

• 6.3
60.5
33.5
100.3
11.0
orange
occasional bands
,,
10.5 56.5 33.8 100.8 18.0 "
9.9 57.4 33.8 101.1 17.0 "
,,
8.5 58.5 33.7 100.7 14.6 "

• ••
'• 0.05 67.3 33.3
0.00 67.4 33.0 100.4
100.7 0.1
0.0 v.light,gray no stain

• • 0.00 67.4 33.2 100.6 0.0 "

Rim 0.26 66.9 33.0 100.2 0.5 "

As determined in a single grain by microprobeanalysis.

Mole % FeS calculated from wt % Fe assuming stoichiometry.
Color in transmitted light with maximum light intensity.
Color in reflected light after staining with ammonium dichromate for 2 min.

arsenopyrite, sphalerite, and pyrite. These may
not everywhere constitute an assemblagein the
formal sense, and the mineral textures imply
considerable variability in depositional sequence,
particularly for pyrite and arsenopyrite. This
association extends beyond the pyrrhotite pipe
areas, where it representsan important stage of
Pb-Zn ore deposition.
Arsenopyriteis far more abundant in the pyr-
rhotite pipes than in the pyrite-quartz body or
Pb-Zn ore. In the eastern CN-A pipe, arsenopyrite
occurs in trace quantities; in the western CN-A
pipe, it rangesin abundancefrom i to 2 percent
up to the 1400level and diminishesto traceamounts
in the upper levels. Most of the arsenopyrite
occursas euhedralcrystalsin quartz or as embayed
or zonally replacedgrains in pyrrhotite. It also
occurs as euhedral grains in sphalerite which is
either contemporaneous with or later than pyr-
rhotite. It is commonlyaltered to marcasitealong
cracks and grain boundaries. Pyrrhotite, chal-
copyrite,pyrite, and sphaleriteare rarely observed
filling fractursin arsenopyrite.The great rangein
textural relations observedfor arsenopyrite suggests
separate stages of deposition; contemporaneity
with quartz and pyrite-1 is clearly implied by
many of the textures, whereas minor amounts were
introduced during sphalerite deposition in the
pyrrhotite pipes and Pb-Zn ore.
Sphalerite associated with arsenopyrite, and
generally accompanied by pyrite, is designated
sphalerite-2. It is more abundant than sphalerite-1
in the pyrrhotite core zones, where it increases
from 1 percent below the 1400 level to 10 percent
in the upper levels but becomesa major phase
(15-20%) only in the transition zone of the pyr-
rhotite pipes and in Pb-Zn orebodies. Age rela-
tions between sphalerite-1 and sphalerite-2 are un-
certain. However, a zonal relation is evident,
in which sphalerite-2 extends to higher levels than
sphalerite-1.
The variation in FeS content of sphalerite-2
is complex. Less than ten percent of the samples
studied contained optically homogeneousgrains
which also revealed no compositional variation on
staining (Fig. 7D). In most samples,all sphalerite-
2 grains exhibit a wide range in FeS content.
Compositionalvariation occursi• two modes: (1)
904 MztRCOT. I$IN,,,4UDI

"'•'":"'
'"•"\' •' •'% F
FIG.7. Microphotographs illustrating
sphalerite-2
andsphalerite-$
associations.
Long dimen-
sionof photographs
is 950•m unless
otherwise
specified.
A. Pyrite-1
cubes (py-1)inanintergrowth ofpyrrhotite
(po),siderite
(sd),andpyrite-marcasite
(py-2).Sideritecontainsminute inclusionsofsphalerite-2
which contains
18to19mole percent
FeS. Reflected light. Sample 18-43,pyrrhotit
e pipetransition
zone,1800level.
B. Pyrite-1(white)enclosed in banded pyrite-$(gray,mottled)which hastotallyreplaced
pyrrhotite.The sample contains no pyrrhotiteandcontains sphalerite-2
withan FeScontent
of20to 28molepercent.Reflected
level.
light. Sample 10-15,pyrrhotite
pipetransition
zone,1000
C. Zoned
sphalerite-2
crystals
in smithsonite
(sin). Thecores(gray)contain
15to 20mole
percent
FeS,whereas
theouterzones(black)contain
20to 35molepercent
FeS. A thinouterrim
(gray
andwhite)
contains
10to 15mole
percent
FeS.Transmitted
rhotite pipe transition zone, 1400 level.
light.Sample
14-22,
pyr-
D. Sphalerite-$
(palegray)veins
andreplacessphalerite-2
(darkgray)along
grainboundaries.
RelativeFeScontentisrevealed
inreflected
lightbyammonium dichromate
stain.Inthissample,
sphalerite-2
containsrarepyrrhotiteblebs;
theFeScontentrangesfrom15to 27molepercent,
witha meanof 22.2molepercent.Sphalerite-$ contains
nopyrrhotiteblebs;theFeScontent
rangesfrom0 to4 mole percent,
witha meanof1.0molepercent.
Sample 8-26,northern
portion
of CN-APb-Znoreb9dy•.
n•a[li•ne.•t0ne,
800level.
 ENVIRONMENT OF ORE DEPOSITION AT CERRO DE PASCO 905

as irregular, patchy intergrowths in grains con-
taining pyrrhotite blebs (Fig. 6F) and (2) as
crystallographic growth zones in grains lacking
pyrrhotite blebs (Fig. 7C and E). Patchy inter-
growths, with their associated pyrrhotite blebs,
are uncommon but occur throughout the pyr-
rhotite pipes and also are found in samples of
Pb-Zn ore which contain no separate pyrrhotite
grains. Staining with ammonium dichromate
failed to reveal any systematic differences in
compositionbetween patches containing pyrrhotite
and patches without pyrrhotite. Most sphalerite-2
grains display intricate growth zoning (Table 3).
Though there may be numerous reversals and
repetitions in FeS content, most of these reversals
occur in areas of relatively high FeS content
(> 17 mole percent) and the overall zoning trend
is from relatively high FeS cores to lower FeS rims.
Staining indicates that the FeS content of the
majority of cores is greater than 20 mole percent
and locally exceeds 25 mole percent. Zoning
within different grains in a single sample tends
to be similar, but no correlation of individual
growth zoneswas found between different samples.
Rare low-FeS coreswere noted in some of the larger
sphalerite-2 grains in Pb-Zn ore (Fig. 7C).
Transition zone
The outer contact of the pyrrhotite pipes is
marked by a transition zone of variable width
in which pyrrhotite is altered to fine-grained mix-
tures of pyrite, marcasite, and locally siderite,
accompaniedby an increasein sphaleriteabundance.
The amount of pyrrhotite alteration increases
toward the surface and is clearly dependent on the
degree of overlap between pyrrhotite and Pb-Zn
ore. The transition zone between pyrrhotite and
pyrite-quartz is weakly developed and varies from
2 to 4 m in width; some pyrrhotite survives to the
original outermost contact of the pyrrhotite pipes.
The transition to Pb-Zn ore, however,is developed
over minimum widths of 6 to 10 m. Locally, the
overlap of Pb-Zn ore onto the pyrrhotite pipes
led to the total destruction of pyrrhotite over
distances of 30 m (Fig. 5). Polished section core zones, but its abundance, like that of sphal-
studies resulted in the subdivision of the transition erite-2 and sphalerite-3, increasesin the periph-
zone into two subzones.
.Pyrite-2 subzone:The initial sharp increase in
pyrite on approaching the wall rocks from the
core zone is due to the alteration of pyrrhotite
along grain boundaries,cracks, and basal partings
to a fine-grained (0.05 ram) anhedral to sub-
hedral pyrite (Fig. 8E). Rarely, replacement of
pyrrhotite along basal partings results in large
tabular crystals of pyrite (Fig. 8A and B). The
late pyrite is often intergrown with marcasite,
in which case it may form aggregate lameliar
pseudomorphsafter pyrrhotite. Late pyrite also
occurs with sphalerite-2 and fills fractures in
pyrite-1. Although it is apparent in polished
section that more than one generation of late
pyrite is present, the relations are not resolvable
into a meaningful sequence. All of the pyrite
which appears later than pyrrhotite, in the manner
describedabove, is designated pyrite-2.
.Pyrite-S subzone:The outermost portion of the
transition zone is characterized by near-complete
alteration of pyrrhotite to a very fine grained,
porouspyrite-marcasite mixture (designatedpyrite-
3, Figs. 7B and 8F) and the presenceof late, low-
FeS sphalerite(designatedsphalerite-3). Orbicular,
zonal growth in pyrite-3 is marked by voids and
grain-size variations. In some samples, no pyr-
rhotite remains,but its former presenceis suggested
by textures of pyrite-2 (Fig. 8C, D, and F). The
original outermost limits of the pyrrhotite pipes
can be located on the basis of the pyrite-3-pyrite-2
texture, which does not appear elsewhere in the
Cerro orebody. Sphalerite-3 was first recognized
in thin section and on stained, polished surfaces
as veins of inclusion-free sphalerite cutting
sphalerite with abundant pyrrhotite blebs. This
late sphalerite generationalso replacessphalerite-2
in irregular patches and along grain boundaries
(Fig. 7D, E, and F). Sphalerite-3 takes no stain
and in transmitted light appears uniformly pale
yellow. It is characterized by: (1) the lack of
included pyrrhotite; (2) a low FeS content; and
(3) its associationwith pyrite, marcasite,galena,
and locally siderite. Sphalerite-3 is rarely present
in the pyrrhotite pipe core zones,but it is ubiqui-
tous and abundant in the pyrite-3 subzoneand in
Pb-Zn ore in pyrite quartz and limestone.
Galena is a rare mineral in the pyrrhotite pipe
eriesof the pipesin the upper levels. Most samples
contain textures which suggest that galena was
introduced during the sphalerite-3 stage.

E and F. Irregularreplacement
of sphalerite-2(gray to black)by sphalerite-3(white)as re-
vealed by ammonium dichromate stain in reflected light. Sphalerite-2 contains no pyrrhotite
blebs;the FeScontentrangesfrom 12to 23 molepercent,with a meanof 19.1molepercent. Sphal-
erite-3 contains0.5 to 4.0 mole percentFeS, with a mean of 1.4 mole percentFeS. Length of
photographF is 120 um. Sample6-5, H-308 Pb-Zn orebody,30 m east of vent in pyrite-quartz
body, 600 level.
906 MARCO T. EINAUDI

FzG.8. Microphotographs taken in reflectedlight illustratingtexturesof pyrite-2 and pyrite-3

in the transitionzoneof the pyrrhotite pipes. Long dimensionof photographsis 950/•m, unless
otherwisespecified.
A and B. Intergrowths of pyrite-2 (py) and pyrrhotite (po); tabular growth of pyrite-2 is
probablycontrolledby pyrrhotitebasalparting. Comparewith Figure6B. Lengthof photos
m 1650/an. Sample 14-16, 1400 level.
C. Tabular pyrite~2 (py-2) with interstitial fine-grainedpyrite-$ (py-$) which has replaced
pyrrhotite(absent);samplecontainsonly a traceof pyrrhotite. Blackareasare pits. Compare
with Figure 8A. Sample I4-33, 1400 level
D. Tabular pyrite-2 (py-2) associatedwith sphalerite-2 (black) and containing interstitial
pyrite-$ (py-$) which has replacedpyrrhotite. The samplecontainsno pyrrhotite. Compare
with Figure8B. FeS contentof sphaleriterangesfrom 15.5 to 30.1 mole percent,with a mean
of 24 mole percent. Sample 14-17, 1400 level.
E. Pyrrhotite (gray) replacedby pyrite-2 (white) alongsideritevein (black). Sample18-12,
1800 level.
F. Pyrite-2 veins (white) surroundedby later pyrite-3 (gray) whichhas totally replacedpyr-
rhotite. Black areasare pits. Faint concentricstructurevisiblein lower portionof photo is
typicalof pyrite-3. Comparewith Figure8E. Sample12-12,1200level.
 ENFIRONMENT OF ORE DEPOSITION ./IT CERRO DE P.4SCO 9O7

TAB•.E4. Summary of Sphalerite Generations

Sphalerite-
1 Sphalerite-2 Sphalerite-3
Stage: pyrrhotite pyrrhotite; early Pb-Zn ore late Pb-Zn ore; fringe
of Cu stage?
Abundance in:
po core zone trace below 1000 I. 1-10% trace
transition zone none 10-15% 1-3%
Pb-Zn ore in py-qtz none 2O% 1-3%
Pb-Zn ore in lime none 15% 5 10%
Inclusions: chalcopyrite, stannite pyrrhotite, or none 11o n e

Associatedminerals: pyrrhotite, chalcopyrite, In pipes: pyrrhotite, py-3, marcasite, pyrite,

stannite arsenopyrite,sometimespy-2, galena, tennantite,
rarely galena siderite, calcite
In Pb-Zn ore: py-2, arsenopyrite,
galena, tennantite (?)
FeS content (Mole %): range: > 17 ? 15-35 0-10
mean: unknown 21 3

Summary to include all major mineral associationsin both

the core and transition zones. The results were
The complex sequence of overlapping mineral
associationsoutlined in the preceding pages is but a interpreted on the basis of investigations by
small part of the story of ore depositionat Cerro de Touhnin and Barton (1964) and Arnold (1966)
which showed that the characteristics of the main
Pasco. Although the two principal events result-
pyrrhotite reflection are an indication of structural
ing in deposition of sphalerite-2 and sphalerite-3
state and composition.
are well established, the details of mineral sequence
within stages are not always clear. A general In order to achieve internal consistencyof re-
summary is presented in Table 4, based on sphal- flection characteristics,all sampleswere prepared
erite types as the diagnostic mineral. under identical conditions. Pyrrhotite was concen-
trated by means of a Carpco magnetic separator
Pyrrhotite Studies after light grinding to -160 q-200 mesh. The
concentrate was then reground to 300 mesh and a
At the start of this investigation, it was thought portion was passed through a Frantz magnetic
that a comprehensivestudy of the composition separator to separate the ferrimagnetic toorio-
of pyrrhotite would yield valuable information clinic pyrrhotite (m-po) from the antiferromagnetic
on alepositional temperatures. At present, it is hexagonal pyrrhotite (h-po). The two fractions
known that pyrrhotite rarely retains its high and the originalwhole samplewere then studiedby
temperature composition, and its general use as a X-ray diffraction using Mn-filtered Fe radiation
geothermometeris invalidated. However, a knowl- and a scanningspeedof •o 20/min. Peak positions
edge of pyrrhotite composition and structure can and peak ratios were calculated as averages of
help to resolve certain aspectsof low-temperature two oscillations over the major peak, with silicon
alteration and equilibration in ores and is essential as an internal standard.
for the correctinterpretation of equilibria involving
Table 5 summarizesthe results of X-ray diffrac-
other phases. For this reason, the extensive data
tion. Only three samples from the 1800 level
collected in 1965 to 1966 (Einaudi, 1968) are yielded a relatively clean h-po fraction on magnetic
reported below. Initial studies were made by separation,as indicated by a peak ratio• of greater
X-ray diffraction, but later emphasis was placed
than 0.8. This indicates that grinding to 300 mesh
on the determination of pyrrhotite composition was not sufficient to unlock the intergrowths or
and structure as a function of assemblage in that the magnetic separation was inefficient. The
polished section by a combination of staining mean of six samples of h-po from the 1800 level,
techniquesand electronmicroprobeanalysis. asdetermined fromthe d(10•2) versuscomposition
curve of Toulmin and Barton (1964), is 47.5
X-ray diffraction 4- 0.3 atomic percent iron.
Twenty-three pyrrhotite-bearing samples from The mean peak ratio for whole samples of pyr-
the 1800, 1400, and 800 levels were chosen for •Peak ratios are defined as [(10-2)+ (408)-]/[(10.2)
X-ray diffractionstudy. The sampleswere chosen q- (408)q- (3.08)-].
908 MARCO T. EINAUDI

TAnkE 5. Resultsof X-ray Diffraction Analysisof Pyrrhotite ment with the X-ray results. The intergrowths
Level and Peak ratios
occur exclusivelyas crystallographicallycontrolled
satnple Hex Hex lamellae, 1 to 20 um in width and 10 to several
no. ws mf nmf d(10.2) at %Fe hundredum in length (Fig. 6D). In the great
8-2 0.497 0.490
majority of cases,m-po is the dominant or only
8-3 0.454 0.490 phasealong grain boundaries,grain contactswith
8-6 0.480 0.492 pyrite and quartz, and late pyrite-2-carbonate
8-7 0.500 0.500
8-9 0.461 0.493
veinlets. In all samplesfrom the 1800level, m-po
constitutes70 to 90 percentof the pyrrhotite, and
14-14 0.492 0.464 its proportion relative to h-po increasestoward the
14-23 0.517 0.488 transition zone.
14-26 0.463 0.537
14-27 0.488 Samples of pyrrhotite from all levels above the
14-35 0.490 0.505
14-37 0.480 0.513
1800exhibitedno lameliarintergrowthson staining
14-40 0.464 0.475 with ammonium dichromateor etching with con-
14-42 0.523 0.471 centrated chromicacid. Becauseboth the degree
14-44 0.480 0.467
14-49 0.487 0.495 of stainingand the degreeof etchingare dependent
14-52 0.447 0.461 on crystallographic orientation, these techniques
are generally insufficient to distinguish granular
18-i 0.573 0.532 0.694 2.0671 47.42
18-5 0.534 0.517 0.670 2.0673 47.43 intergrowths of different pyrrhotite modifications.
18-8 0.569 0.544 0.833 2.0697 47.63 The X-ray data indicateda differencein magnetism
18-11 0.545 0.533 0.695
18-14 0.568 0.559 0.792 2.0672 47.43
between m-po and A-po, suggestingthat the use of
18-25 0.547 0.575 0.831 2.0679 47.48 magnetic colloids (Sterns, 1964) might yield con-
18-29 0.644 0.640 0.850 2.0668 47.40 clusiveresults(A. H. Clark, writ. commun.,1966).
Level Avg. Avg. Avg.
This techniquefailed, however,becauseof complex
fiocculation patterns which appeared to be the
800 0.478 0.493
1400 0.485 0.488
result of parallel magnetic domains in anisotropic
1800 0.569 0.557 0.766 47.47 sectionsof m-po and strong, local magnetic fields
at grain boundaries.
Peak ratio = ]-(10.2) h- 408)-]/•(10.2) h- (408)h- (i08)-].
Abbreviations: ws = whole sample, mf = magnetic frac-
tion, nmf = nonmagnetic fraction. Electron microprobeanalyses

Electron microprobe analyses were designed to

rhotite for each level decreases toward the surface. confirm the X-ray studies and to determine the
Normal asymmetric peak splitting (peak ratio local variations in pyrrhotite composition not
between 1.0 and 0.5), characteristic of mixtures of detected by bulk X-ray analysis but suggestedby
h-po and m-po, is presentonly in samplesfrom the the polished section studies. At the start it was
1800 level. Peak ratios for the 1400 and 800 levels also hoped that the microprobe might detect a
are generally less than 0.5, the characteristic value difference in compositionbetween m-po and A-po,
for m-po. Anomalous pyrrhotite (A-po), with but this was not realized.
1(•08)> 1(408),iS most abundant in samples from The analyses were made with an Applied Re-
the 800 level. The magnetic fractions approach search Laboratories EMX instrument, using stan-
a peak ratio of 0.5 more closely than do the non- dard techniques. Calibration curves were based on
magnetic fractions, a fact which suggeststhat A-po five synthetic standards covering the range from
is lessmagnetic than m-po. 63..53 to 46.55 weight percent iron. The use of
standard curves obviated the need for atomic
Polished section studies number, absorption, and fluorescencecorrections,
and the need for drift corrections was avoided
Several methods were used to differentiate be- by using a beam-current mode, rather than a
tween the various pyrrhotite modifications in fixed-time mode, to monitor peak intensities.
polishedsection. In general, no single technique The maximum standard deviation of the mean of
repeated counts at one spot on a single standard
was sufficient to establish confidently the relations
between the modifications. A combination of was 1.0 percent of the iron present. A further check
staining, etching, and magnetic colloid techniques was made on the precision of the analyses as
was used. affected by the length of an analytical period.
The only samplesfound to contain intergrowths After establishing a calibration curve, the four
of h-po and m-po are from the 1800 level, in agree- standards were reanalyzed three times at intervals
 ENVIRONMENTOF OREDEPOSITIONAT CERRODE PASCO 909

of 1.5 hours. The maximum standard deviation APPROX MISCIBILITY

GAP 25øC
of the three compositionsdetermined for each
standard using the initial calibration curve was
found to be 4-0.17 atomic percentiron. The mean
of the standard deviations for all four samples was 48.0 I h-po m-Pol 47.0 46.0

4- 0.10 atomicpercentiron. Theseresultssuggested

that with proper care and analytical periods of
short duration, a precision could be achieved
which would enable the distinction between h-po
and m-po.
I0

600
w
Level
I
CN-A

Approximately 25 spot analyseswere made on 5O

eachof 85 samplesfrom 7 mine levels. The mineral E CN-A

assemblageand location relative to grain bound- 4O

aries were recorded for each spot analysis.

w
3O
The mean Fe content of pyrrhotite decreases
toward the surface (Table 6). The difference in
20
compositionwithin the hanging-wallzone of the
western CN-A pipe from the 1400 to the 1200
level is less than the first standard deviation of the
analyses. The differencesin composition between
I0
1400
Level
levels within the eastern CN-A pipe and within w

the footwall zone of the western CN-A pipe are 5O

equal to or greater than the first standard devia- '-E CN-A ......
tion of the analyses and may be regarded as FOOT
WALL
4O
real changes. The mean iron content of pyrrhotite
on the 600 level correspondsto Fe7S8, the ideal 30
formula for m-po.
The variation in pyrrhotite composition as a 2O
function of elevation is presented in Figure 9.
The range in compositionof most pyrrhotites de- 10
creases toward the surface from 47.6 to 46.6 atomic
percentiron on the 1800level, to 47.0 to 46.3 atomic
48.0 47.0 46.0
percent iron on the 600 level. The analysesconfirm
ATOMIC 5'0 Fe
the presenceof both h-po and m-po on the 1800
level (maxima on the distribution curve fall at
FIG. 9. Histogramsillustratingthe variation in pyrrhotite
47.35 and 46.75 at. % iron, respectively) and are composition as a function of elevation. Compositionsare
compatible with the experimental studies of Scott based on electron microprobe analyses. Approximate posi-
and Kissin (1973) which indicate a miscibility gap tion of miscibility gap between hexagonal and monoclinic
pyrrhotite at low temperatures is taken from Scott and
at low temperatures from 47.0 to 47.25 atomic Kissin (1973).
percent iron. The distinction between m-po
and A-po in the upper levels remains an unresolved
problem; the lack of two populations in the dis- tribution curve of Figure 9 indicates that if a
TABLE 6. Mean Composition of Pyrrhotite and miscibility gap exists between these two modifica-
Sphalerite-2 in the Pyrrhotite Pipes• tions it is not resolvable with the precision of the
microprobe.
Pyrrhotite Sphalerite
Figure 10 presents the frequency of deviation
No. of At.% No. of Mole% of all analyses from the mean of each individual
Pipe Level samples Fe samples FeS sample. The compositions were treated in this
Eastern CN-A 600 8 46.66 10 22.8
manner to ensure that the data did not reflect
800 3 46.77 8 21.7 machine drift. The histogram shows that the
1000 8 46.82 14 21.3
average composition of pyrrhotite grains some
Western CN-A 1200 2 46.82 5 22,0
distance from other phases or cracks is more iron
(hanging wall) 1400 19 46.86 19 20.7
rich than grain boundariesand confirmsthe striking
Western CN-A 1600 20 46.87 5 20.6
(footwall) 1800 25 46.98 7 19.8
relations seen in Figure 6D, in which quartz is
consistently rimmed by a band of pale-staining
• As determined by electron microprobe analysis. pyrrhotite (m-po). The upper levels also display
 910 MARCOT. EINAUDI

- 1.0 AVF'. + 1.0 The maximumiron contentof h-po (47.63q-0.3

Along
cracks
and J atomicpercent)is toohighto represent
equilibrium
2O _ grains
boundaries with m-po. If equilibrium with pyrite-1 was
other
thanwith __t__••:••i, maintained during formation of the pyrrhotite
pipes,then h-po with a mean compositionof 47.5

pyr'te.i]i•:::::::::::::::::::::::::::::::::
::::::•
10
atomic percent iron is compatiblewith pyrite
from 260 ø to 310øC.
I A further estimateof the temperaturesof sulfide
depositionin the pyrrhotite pipes prior to late
4O
alteration is provided by the assemblagepyr-
With pyrite rhotite-chalcopyrite, which is stable relative to
m 30 cubanite-pyritebelow334øC (Yund and Kullerud,
1966). The possibilitythat chalcopyrite-pyrrhotite
>-
1
20 formedfrom the higher temperatureassemblage
on cooling can probably be ruled out because of
z Io lack of pyrite as an intimatelyassociatedphase
and becausethe texturessuggestthat chalcopyrite
o
is often late relative to pyrrhotite. Only the
unique bulk compositioncubanite9gpyrite7 (mole
proportions)would yield a chalcopyrite-pyrrhotite

D 60
Grain
cente
• assemblage without pyrite, on cooling,assuming
that pyrite was reactive at these temperatures.
Most bulk compositionswouldyieldthe assemblage
5O
chalcopyrite-pyrite-pyrrhotite. The upper limit
':':':'.':':':':':':':
of 334øC, however, can only be applied to the
depositionof chalcopyrite and there is no evidence
40 ...........

basedon the texturesaloneto revealwhetherh-po

also was depositedbelow this temperature. Chal-
3O
copyrite-pyrrhotitemay have formed by sulfidation
of an original cubanite-pyrrhotiteassemblage
2O below 334øC but, again, the textures would seem
to rule this out. If the compositionof pyrrhotite
10 determined by X-ray diffraction is used as a
"slidingscale"indicatorof fsv then the stability
of the assemblagepyrrhotite-• chalcopyrite can
1.0 .8 .6 .4 .2 AVE. .2 .4 .6 .$ 1.0 be narrowed down to the limits imposed by the
+ -- po

DEVIATION IN WT. % Fe FROM MEAN OF

intersection of the X•-es= 0.95 isopleth with the
INDIVIDUAL SAMPLES
pyrrhotite-pyrite and pyrrhotite-chalcopyrite-cu-
banireunivariantcurves(Fig. 13). Basedon X•P.•s
versus fs• relations as presentedby Barton and
FIG. 10. Variation in composition of pyrrhotite within
grains. Histograms are constructed from microprobe data
Skinner (1967) the limits are approximately:
and are based on the deviation of each spot analysis on a
T = 250øC, log fs• =-13.2;
samplefrom the mean of all spot analyseson the samesample. and T = 300øC,
log fs• -- -11.6. However, this result is not as
useful as it would appear becauseof: (1) uncer-
a tendency for grain centers to be more iron rich
than grain margins but to a less striking degree.
tainties that the value of X[}s chosenrepresents
chemical equilibrium with chalcopyrite; (2) the
po
error of 4-0.006 in Xves as determined by X-ray
Interpretation of pyrrhotite data
diffraction;and (3) the error of 4-0.35 log fsz
The data on structure and compositionpresented in the pyrrhotite isopleths. The latter two factors
above may be interpreted on the basis of Fe-S result in a possibleerror in temperature of ap-
phase relations as presented by Scott and Kissin proximately 4-40ø becauseof the shallow angle of
(1973). The textures of h-po and m-po on the intersection of the isopleths with the univariant
1800 level imply that m-po formed during a late pyrrhotite-chalcopyrite-cubanite curve.
stage in an original h-po. Although m-po is stable The later development of m-po on the 1800 level
below 254øC, it is not clear whether h-po was may have resulted either by exsolutionfrom h-po
initially depositedaboveor belowthis temperature. as the temperature dropped below 254øC or by
 EN?IRONMENT OF ORE DEPOSITION .4T CERRO DE P.4SCO 911

oxidation or sulfidation somewhere below 254øC.

The fact that m-po is largely concentrated along
cracksand grain boundaries
and that the ratio
m-po/h-po increasesin the transitionzone, where
pyrrhotite is altered to pyrite-3 and marcasite,
imply that the latter processeswere important.
In the upper levels, where the alteration of
!•sl-py,
replacem
of
limest
400,5
L.
B. sl[po]-py,replacement
of limestone,
500L.
pyrrhotite is more complete,h-po is absentand
pyrrhotite consistsof mixtures of m-po and
A-pa. The peak ratios (Table 4) tend to be lower
on the 800 level than on the 1400 level, suggesting
C. sl[po]-py,replacement
of py-qtz body,
that the ratio A-po/m-poincreases
towardthe
surface. By combiningthis informationwith the
microprobeanalyses,which indicatea decreasein
Fe contenttoward the surface,it can be inferred !. ....
that A-po is iron deficient relative to m-pa. The
latter conclusion is supported by experimental D. sl[po]-py,replacement
of py-qtzbody,600 L.
evidence' Clark (1966) first recognized A-po in
syntheticproductsbelow200øCand indicated
that A-pois iron.deficient
relativeto m-po;and
Taylor (1971)foundthat oxidationof h-poat 250øC
ledtothesuccessive appearance, withmagnetite,
of m-po, then A-po, and finally A-po plus pyrite.
The end stage of the trend toward relative sulfur E. po-sl (py), transition zone 600L,
enrichmentwhich initially convertedh-po to
m-poandthento m-po-A-po mixtures,ledto total
replacement
of pyrrhotiteby pyrite-3,deposition
of Iow-FeSsphalerite(sphalerite-3),
and local
depositionof siderite. A similar pyrrhatire altera-
F. po-(py)-sl, core zone 600L.
tion sequence
hasbeendescribed
by Kelly and
Turneaure(1970)in Sn-¾V
oresof Bolivia. As
pointed out by those authors, the overall process
mustinvolve
some
removal
ofironandnotsimply o 5 •o •5 2o 25 30 •5
addition of sulfur, becauseof constraints imposed
by relative volume changes. Some of the leached Mole % FeS in Sphalerite
iron may have been fixed in siderite and late
Fro. 11. Results of electron microprobe•analysis of
sphalerite-3. sphalerite from the 400, 500, and 600 levels. [-po• signifies
pyrrhatire present only as local blebs in sphalerite; (py)
Sphalerite Studies signifies presenceof paragenetically early pyrite-1 but not
necessarilyconstituting part of the assemblage. •
A and B representsamplesof Pb-Zn ore which formed in
Sphalerite occursat Cerro de Pasco in association limestone and are interpreted as including both low-FeS
sphalerite-2 and sphalerite-3.
with numerous sulfide assemblageswhose stabili- C and D representsamplesof Pb-Zn ore which formed in
ties in terms of temperature and fugacity of sulfur pyrite-quartz and include both high-FeS sphalerite-2 and
sphalerite-3.
are reasonably well known from experiment or E and F represent samples of sphalerite from pyrrhatire
approximated by computation. With a knowledge pipes, with sphalerite-3 absent in most samples.
of sphalerite compositions,it should be possibleto
partially reconstructthe environment of deposition FeS contentof sphalerite
or equilibration, if equilibrium assemblagescan
The FeS content of sphalerite from 117 samples
be properly identified. Conversely, a lack of
from the pyrite-quartz body, pyrrhotite pipes, and
agreement between field data and valid experi-
Pb-Zn ore in pyrite-quartz and limestone was
mental data can be used to suggestthe presenceof determined by electron microprobe analysis. Six
nonequilibrium mineral associations. This section synthetic sphalerites, supplied by P. B. Barton, Jr.,
summarizes some of these arguments on the basis and ranging from 0.0 to 50.0 mole percent FeS,
of electron microprobe analyses of sphalerite and were used as standards. The maximum first
recent data on sulfur isotoperatios (Austria, 1975). standard deviation of the mean of five counts on
912 MZIRCO T. EIN.4UDI

16.9 23.5

19.0 20.7

8.4
22.2
23.1
15.1
22 19.4 CN-A
1 22.1
21
19.9•-•

22

21.2
21.8
21.1

22.0
21.7

20.5
21.2

•o•s 'M-309
18.6

19.1 20.5 ::
3

9.9

ß 400,500 FT 6.0
ß 600
0 800
o 1000
,m 1200
ß 1400
,, 1600
CN-B t
• > 22 Mole %FeS
-14.2
}".'.::•< 18 Mole% FeS

0 200 400 600 800 I000 FT

I, , • , , I

0 I00 200 M

FIG. 12. Horizontalprojectionof Pb-Znorein CN-A, CN-B, and M-309 orebodies, illustrating
variation in meansphalerite-2composition(mole % FeS) outsidethe pyrrhotitepipes,whichare
locatedin areaof diagonalruling. Samplelocationsidentifiedaccordingto minelevelin feet below
the surface.

different grains of each of the six standardswas:
=t=0.22wt % S; =t=0.80wt % Fe; and q- 1.08wt %
Zn. Eighty-eight percent of the summations of
Fe-• Zn-+-S fall in the range 98.8 to 101.3; the
remaining 12 percentof the analyseswere rejected.
Semiquantative analyses were made for minor
elements in 22 samples of sphalerite: 52 percent
of the spot analysesrevealed no detectable minor
elements; the remainder showed copper and man-
ganeseto be present in excessof their detection
limits, estimated to be O.10 wt % Cu and 0.03 wt %
Mn. Combined Cu and Mn rarely exceeded 0.8
 ENVIRONMENT OF ORE DEPOSITION AT CERRO DE PASCO 913

wt %. High-copper content (up to 0.98 wt %)
and high-manganesecontent (up to 1.10 wt %)
were found to be mutually exclusive.
Major element analyses reveal that sphalerite
occurs in two fairly distinct populations, as sug-
gested by the microscopic studies. The most
abundant has an FeS content that ranges from
15 to 30 mole percent, rarely reaches 35 mole
percent, and averages 21 mole percent; this
population correspondsto sphalerite-2. A second,
less abundant population correspondsto sphal-
erite-3 and has an FeS content that ranges from
0 to 10 mole percent and averages3 mole percent.
Most samplesstudiedcontain sphaleriteexhibiting
the complete range of compositionsjust cited. An
example of the range of compositionsencountered
is presented in Figure 11, which illustrates the
results from the 400, 500, and 600 levels, arranged
accordingto zoneand mineral assemblage.
Within the pyrrhotite pipes,sphalerite-2exhibits
a progressive increase in mean FeS content toward
the surface (Table 6). In the western CN-A pipe,
the mean FeS content of sphalerite-2increasesfrom
19.8 mole percent on the 1800 level to 22.0 mole
percent on the 1200 level. In the eastern CN-A
pipe, it increasesfrom 21.3 1hole percent on the
1000 level to 22.8 mole percent on the 600 level.
Sixty-eight samples from the pyrrhotite pipes
yield a mean sphalerite-2 composition of 21.2
mole percent FeS.
Forty-five samplesof sphalerite-2locatedoutside
the massive pyrrhotite areas in the CN-A and
CN-B Pb-Zn orebodies define a distinct trend in
mean FeS content (Fig. 12). Thirteen of these
samplesare locatedwithin two broad,north-south-
trending zones coincident with the horizontal
projection of the eastern and western CN-A pyr-
rhotite pipes (Fig. 5) and within 50 m of the contact
with massive pyrrhotite. Samples from these
zonesyield a range of mean FeS contentsof 22.0
to 24.5 mole percent and a mean FeS content of
23.3 mole percent. These two zones contain the
most FeS rich sphaleritesat Cerro de Pasco. The
FeS content of sphalerite-2 decreasesaway from
thesezonesin a systematic manner. The southern
half of the CN-B orebody, which formed largely
by direct replacement of limestone, contains
sphalerite-2 with the lowest FeS content.
Sphalerite-3 is present in most samples but in
variable proportion depending on location. It
constitutesapproximately 35 percent of the locally
disseminatedsphalerite in the pyrite-quartz body,
25 percent of the sphalerite in Pb-Zn ore mantos
in limestone, 10 percent of the sphalerite in Pb-Zn

TABLE7. Summary of Sulfur Isotope Data and Indicated Fractionation Temperatures• for Pb-Zn Ore

Sample no.
6-18 10-19 12-4 14-28 16-41

Level 600 1000 1200 1400 1600

pyrlte 1.1 2.0 0.0 0.1 1.5

sphalerite 2.6 0.8 2.4 2.9 1.4
galena - 0.2 -1.6 -0.7 -0.6 -0.7
zx•4S (%0)
(•348s
l-•g4Sgn 2.8 2.4 3.1 3.5 2.1
•3451,
y-•x4S•n 1.3 3.6 0.7 0.7 2.2
ba4Spy-•a4SM - 1.5 1.2 --2.4 -2.8 0.1

Temperaturc (øC)z
gn-sl (•20øC) 260 (304) 234 (205) 344
gn-py (• 10øC) ? 280 ? ? (434)
slp-y (•30 øC) ? (227) ? ? ?
Mole % FeS in sl
sphalerite-2 range: 16-27 15-27 18-26 14-27 --
avg: 24.1 20.8 21.3 22.1 20.3
sphalerlte-3 0.5-2.5 0-6 absent absent present?
Mineral assoc. sl, py, gn gn, sl, py, (mc) py, sl, gn py, sl, (gn), (asp) sl, gn, py
Inclusions in sl: (po) mc (po) (po, sn) in sl-1 po
Pb-Zn orebody: M-309 CN-A CN-A CN-A CN-A

Distance from pyrrhotite pipe (m) 500 5 60 1 1

• Based on Austria (1975).

•' Based on Kajiwara and Krouse (1971).
Notes: Underlined temperatures are consideredreliable; parenthetical temperatures are rejected (see text); question marks
indicate lack of isotopicequilibrium. Mineral abbreviations:asp = arsenopyrite,gn = galena, mc= marcasite, po = pyr-
rhotite, py = pyrite, sl = sphalerite, sn = stannite. Parenthetical minerals are present in minor or trace amounts.
914 M.4RCOT. EIN.4UDir
ore in pyrite-quartz, and decreasesto less than 1that approximately40 percent of the sphalerite
percentof the sphaleriteassociated
with pyrrhotite in this sampleconsistsof late sphalerite-3. The
areas.
extreme differencein FeS content betweensphal-
Trends in sphalerite composition,other than erite-2 and sphalerite-3mustreflectlargedifferences
thosereflectedin the meancompositions
of sphal- in temperature and/or chemical state of the ore
erite-2 from different locations and the relative
fluid, which in turn would affect sulfur isotopic
abundance of sphalerite-3, are not discernable. compositions(Ohmoto, 1972).
An expected result was a correlation between FeS Multiple sphalerite generationsare present in
content and iron-sulfidemineral association,but most samples,except 12-4, which should yield the
no suchcorrelationwas found. In fact, samples most reliable sphalerite-galenafractionation tem-
of sphaleritewhichcontainedno pyrrhotiteyielded perature. Late sphalerite-3 constitutes less than
someof the highestFeScontents. And, conversely, 25 percent of the total sphalerite in sample 6-18
sphalerite exhibiting mutual intergrowths with and is present in trace amounts in sample 16-41.
pyrrhotitewasfoundto vary widelyin composition, These two samplesmight yield reliable sphalerite-
ranging from 10 to 20 mole percent FeS. galena fractionation temperatures. Sample 14-28
contains an unknown amount of sphalerite-! with
Sulfur isotoperatios both stannite and pyrrhotite blebs, in addition to
sphalerite-2. Fractionation temperatures based
The resultsof a reconnaissancestudy by Austria on sphalerite from this sample should be viewed
(1975) of the sulfur isotopiccompositionof pyrite, with caution.
sphalerite, and galena in five samplesof Pb-Zn Thoughpyrrhotite blebsare presentin sphalerite
ore are summarized in Table 7, which also includes in four of the samplesstudied, the effect on •34S•
pertinent mineralogicaldata from Einaudi (1968). should be negligiblebecauseof their small volume
Austria concludedthat the isotopic fractionation (< 1%) and becausethe sulfurisotopiccomposition
between sulfide pairs in the five samplesindicated of cogenetic pyrrhotite and sphalerite should be
a depositional temperature range of 205ø to 434ø similar (Rye and Ohmoto, 1974).
+ 20øC. A review of the data indicates that this The arguments cited above result in three
temperature range should be modified becauseof reliable sphalerite-galena temperatures ranging
unreliable samples. Of equal importance, is the from 344ø to 234øCand onegalena-pyritetempera-
evidence for lack of isotopic equilibrium between ture of 280øC. These data, which suggest the
someof the sulfidepairs. presenceof a significant variation in temperature
Values of /x•34Sfor sulfide pairs involving pyrite during deposition of sphalerite-2, are integrated
clearly indicate a lack of equilibrium fractiona- with the geologicaland mineralogical data in the
tion in four of the samples. A considerablepor- following section.
tion of the pyrite in these samples must have Conditionsof ore deposition
precipitated under distinctly different conditions
than the sphalerite and galena. On this basis, the Interpretation of the compositional zoning of
temperature estimated for sample 16-41 from the sphaleritein spaceand time in termsof the environ-
galena-sphaleritepair is preferred over that esti- ment of ore deposition must rely on a correlation
mated from galena-pyrite. However, sample 10-19 of this zoning with the associated sulfide assem-
exhibits clear textural evidence that the majority blages,the sulfur isotopedata, and the possiblerole
of both pyrite and galena were deposited con- of silicate-carbonate buffers. Ore solution chem-
temporaneously as open-space rug fillings; the istry must be compatible with a trend from high-
temperature estimated from this pair may be iron sphalerite, pyrrhotite, and arsenopyrite, to
reliable. low-iron sphaleriteand pyrite. It must alsoaccount
Fine-grained mixtures of different phases or for the intricate growth banding of sphalerite-2.
different generations of a single phase are present The ultimate origin of trends in sulfide assemblage
in many of the samplesstudied by Austria. Mar- and composition must largely be tied to reactions
casite is very abundant as minute inclusions in between the ore fluid and its environment. As
sphalerite from sample 10-19. Since mineral stressedby Barton (1970), the trace of the "main
separateswere prepared by hand picking, tempera- line" environment of ore deposition across a
ture based on /x•34Sg._s• and A•34Ssl-pyin sample temperature-rs0. plot reflectscontrol by any of a
10-19 are probably unreliable. Contamination variety of silicate-oxide-carbonate-sulfide buffers,
by marcasite may explain the anomalously low the specificationof xvhichremains a critical topic
value of 834Ss• in the sample. An alternate inter- for research.
pretation of the low value of •a4q•0-•0is the fact In this sectiona correlationis attempted of
 ENVIRONMENT OF ORE DEPOSITION AT CERRO DE PASCO 915

sulfide assemblagesand alteration or gangue pyrrhotite 4- chalcopyrite in the deep levels of the
mineralogy with possibleenvironmentsspecified pyrrhotite pipeswas discussedin an earlier section.
in terms of temperature and the chemicalvariables The close association of these two phases with
rs2, fo2, and pH. Although the discussionis sphalerite-1 and stannite suggeststhat this thermal
centeredon new data from the pyrrhotite pipesand limit also might be applicable to the latter two
Pb-Zn ore, the environmentof copperoredeposition phases. Although the textures indicate an exsolu-
in the vent is alsodiscussed briefly. The tempera- tion originfor muchof the stanniteand chalcopyrite
ture-fs• grid remains a useful framework for associated with sphalerite-1, and although such
interrelating sulfide equilibria (Fig. 13). It is textures may be suggestive of relatively high
particularly useful with reference to Cerro de Paso temperaturesfor the original depositionof the host
becauseof the wide variety of T-rs2 environments sphalerite, there are no reliable experimental data
illustrated by this deposit. However, the role of on exsolutioninvolving these phaseson which to
oxide, silicate, and carbonate minerals is best base a temperature estimate.
discussed
with referenceto an isothermalfs=-fo= Associationof sphalerite-2with arsenopyrite:No
diagram,contouredfor pH at constanttotal content contradictions appear relative to the composition
of sulfur (Fig. 15). Mineral assemblageswhich of sphaleritein associationwith arsenopyriteand
are diagnostic in terms of temperature are sum- pyrrhotite. The maximum FeS content of about
marizedin Table 8, and someof the restrictedT-rs2 37 mole percent for sphalerite in equlibrium with
fieldsof interest are summarizedin Figure 14. arsenopyrite. based on the work of Scott and
Association of sphalerite-1 with pyrrhotite and Barnes (1971) and Barton (1969), is insensitive
chalcopyrite: A speculative upper temperature to temperature (Fig. 13). This value corresponds
limit of 334øC (Fig. 14) for primary depositionof with the maximum FeS content of sphalerite-2at

TABLE8. Summaryof TemperaturesEstimatedfromSulfideMineral Equilibriaand Sulfur IsotopicFractionation

Temperature

Stage Assemblage Min. Max. Reference

Pyrrhotite pipes
Deep to intermed.
level core zone h-po q- py, X•} s = 0.95 260-310 1
h-po q- py 254 1
h-po + cp 334 2
Intermed. to upper
level peripheral h-po+ asp,X•e8 = 0.3 600 3, 4
h-po+ asp,X•e8 = 0.2 491 3, 4
Pb-Zn orebodies
Sphalerite-2 aspq- sl, X sl
FeS = 0.15 420 3,5
gll q- sl, Aaa4S 234-344 6
gn q- py, Aba4S 280 6
Sphalerite-3 m-po q- A-po 254 1

Cu veins
Central enargite alunite •-•350-400 7
kaol q- qtz, Pa2o= 1Kb •-•300 8
enargite •300 9
luzonite •-•300 9
Peripheral tennantite tn + sl, XFe
slS = 0.05 •370 4, 10
tn + sl,X}!es= 0.01 •'•300 4, 10
Pyritic-Ag pipes realgar 307 11
gratonite 250 12
monoclinic sulfur 115 13

Mineralabbreviations
thesameasin Table7 withadditionof h-po= hexagonal
pyrrhotite,m-po= monoclinic
pyrrhotite,
cp = chalcopyrite, tn = tennantite.
References:
1. ScottandKissin,1973;2. YundandKullerud,1966;3. Clark,1960;Barton,1969;4. Scottand Barnes,1971;
5. Czamanske,1974;6. Austria,1975;7. Hemleyet al., 1969;8. ReedandHemley,1966;9. Skinner,1960;Maskeand Skinner
1971;10. Craigand Barton,1973;11. Hall and Yund, 1964;12. Roland,1968;13. Tuller, 1954.
916 MARCO T. EINAUDI

I I I I I I I I

½o\e
-2

-4

-6

/
/

/
/
/
/
/
-12 /
/

-14
HEMATITE
+PYRITE

-16
T øC
200 250 300 350 400 450 500 550 600

2.2 2.0 1.8 1.6 1.4 I.œ

10Z/T oK
F]c. 13. Univariant sulfidationcurvesapplicableto Cerro de Pascoores. Solidlinesrepresent
experimentally determined equilibria from Barton (1969) and as summarized in Barton and
Skinner(1967). Heavy dashedlinesrepresentcomposition isoplethsfor sphaleritein equilibrium
with either pyrrhotiteor pyrite basedon Czamanske(1974). Light dashedlinesrepresentthermo-
chemicalapproximationsfrom Craig and Barton (1973).

Cerro de Pasco, suggestingthat sphalerite-2 and (Boorman, 1967) clearly indicate that this is not
arsenopyrite were in chemical equilibrium. the case. Only a tendency toward chemical
Depositionof sphalerite-2in the pipe peripheries, equilibrium can be hypothesizedon the basis that
locally in associationwith arsenopyrite,led to the maxima on the distribution curves for sphalerite
appearanceof pyrite and galena. The experimental compositionsin samplescontaining pyrrhotite and
studies of Barton (1969) on arsenopyritestability, pyrite are close to the experimental value of 21
consideredwith referenceto figure 2 of Czamanske mole percent FeS for equilibrium below 550øC.
(1974), indicate that the minimum FeS content This was an unexpectedresult, for it was thought
of sphalerite in equilibrium with arsenopyrite that the vast amounts of pyrite present in the
remains constant at about 10 mole percent below pyrite-quartz body would be an effective buffer
360ø -t- 50øC (Fig. 13). Between 360ø and 491ø for a fluid saturated with respect to pyrrhotite.
-4-12øC, the minimum FeS content increases to It underscores the fact that most sulfide assem-
21 mole percent. The general lower limit of 15 blages in ores are merely indicators, rather than
mole percent FeS for sphalerite-2 in the pyrite- buffers,of rs2 (Barton, 1970), and that the actual
quartz body is consistent with a maximum tem- buffers, if they exist, consistof assemblagesinclud-
perature of deposition of about 420øC. ing silicatesand carbonatespresent in the ores and
Association of sphalerite-2 with pyrrhotite and its wall rocks.
pyrite: By the standard textural criteria applied The use of the iron content of coexistingsphal-
in ore microscopy, most sphalerite-2 occurrences erite-pyrrhotite pairs as invariant indicators of
would be interpreted as equilit)rium assemblages both temperature and rs2 is invalidated by the
with pyrrhotite and pyrite. Nevertheless, the extensive late-stage alteration of pyrrhotite below
compositional data combined •vith experimental 254øC. Furthermore, the frequent reversals of
data on pyrrhotite-pyrite-sphalerite equilibria FeS content in the cores of individual sphalerite
 ENVIRONMENT OF ORE DEPOS[TIO•VAT CERRODE PASCO 917

"4

-6

-12

-16
T øC
•oo 25O 300 350 400 450 500 550 600

2.2 2.0 1.8 1.6 1.4 1.2

10S/T øK
Fro. 14. Stability fields of some sulfide assemblagesfrom the first stage (pyrrhotite pipesand
Pb-Zn ore) and secondstage (Cu veins) of ore deposition,basedon equilibria of Figure 13. Cor-
relation between fringe zone of Cu veins (py-t-tn-t-sl) and sphalerite-3 is questioned. Ag-
pyrite ore, associatedwith hydrothermal leaching,representsfinal stage and includesassemblages
indicative of low temperatures and intermediate to high sulfidation states (hm -t- py d- realgar,
gratonite, alunite d- native sulfur). Vertical solid bars representtemperature and range in log is2
for 3 samplesof Pb-Zn ore, as determined by sulfur isotopefractionation and range in FeS content
of sphalerite, respectively. Abbreviations as in Tables 7 and 8.

grains would make it virtually impossible to assemblage siderite-chlorite-quartz-pyrrhotite (or

specify which of the growth zones represented pyrite). This conclusion is developed in the
equilibrium with adjacent pyrrhotite. These following paragraphs.
growth zones, which clearly represent primary The pyrrhotite pipes represent the main plumb-
depositionalfeatures, suggesthighly variable ing system and hence the thermal high for the ore
and/or fo• during initial depositionof FeS-rich fluid which formed the massivesulfide body east of
sphalerite. Temperature fluctuations would be an the vent. The pipes are centrally located within
unlikely mechanism because variations in excess the Pb-Zn ore; the latter expands out from them
of 100øC would be required. toward the surface. The pipes also represent the
Origin of FeS zoning in spAalerite-2: The decrease focus of metal zoning; the upward and outward
in FeS content from core to rim of individual progressionW-Sn-Cu-Zn-Pb is common to many
sphalerite grains matches the general zoning ores. As the ore fluid traveled outward from the
pattern of sphalerite-2compositionswith increasing central conduits and deposited Pb-Zn ore up to 600
distance from the pyrrhotite pipes. Numerous m from the pipes, it must have lost heat in the
different temperature-is2paths theoreticallycould near-surface, subvolcanic environment. The gen-
yield this trend toward FeS depletion, but an eral space-time trend must have been from the
obvious choice is a decreasein temperature along a pyrrhotite stability field at high temperatures
path similar to Barton's (1970) "main line" toward the pyrite field at lower temperatures
environment but at relatively low sulfidation states (Fig. 14).
(Fig. 14). Such a path might have been the result The main result of application of the phase
of partial buffering of the cooling ore fluid by the equilibrium data turns out to be the placement
918 il:C4RCO T. EIN.4UDI

path doesnot representan instantaneousgradient,

nor does it representa true buffered path, because
. sl ½p % .. \ '.. the presenceof spasmodicchangesin the activities
XFes '",,
B
-8 ßO1 on '(0...." ',: '• of componentsin the ore fluid can be inferred from
__ -.., the oscillatory zoning displayed by the cores of
.o•_..... . '_ ...... _..,,,•',,.
.d •'\%"...
..½- - . ,o., sphalerite-2grains.
kb-
--7."-'-- .." '½" To this point the discussionhas been based on
the assumptionthat the orefluid wassaturatedwith
ß
"'"...
"71,
/ "" ' I ',. Xl"..HEMATITE
respect to pyrrhotite and/or pyrite and no other
....
"=.... •"i• /' ;'..
MAGNETITE ". '\ iron-bearing phases. However, it is conceivable
30 .'.-' /,,3'"
/,'".,'
,1" ,'/'
....'..
,".,. '. . . \,. ':. ".. I "'. ' "'"-
that the widespreadchlorite and siderite, which

-14
c,,_O,,T[
". ': "....
proxied for magnetite throughout the Cn ores,
participatedin reactionsof the followingtype:
,,½,;,,;•,.'?'
•
"1;,,,. ,.' O'b
'...
',.
I"..
'..
".i
'..½
"..
•'
... Fe•2e?SisO•0(O•, OH14)4- 12CO••
,.. . '.. '..• : ': chlorite
" + QUARTZ ".• " " '
I I I I I 12FeCOa + 8SiOn.4- 7H•.O + O• (1)
-36 -34 -32 -30 -28
siderite quartz
log fo• 7Fe•2Fe?SiaO•0(O,,OH,4) 4- 48S2•
FIG. 15. Log fs2-1ogfo2 diagram showing the stability chlorite
fields of minerals which delineate chemical environments at
12Fe,Ss 4- 56SiO• 4- 49H•.O 4- 45.50• (2)
300øC of Pb-Zn ore in carbonate wall rocks (A) and of Cu
veins in quartz monzonite (B). The magnetite field is shown pyrrhotite quartz
as partly preemptedby those of chlorite and siderite, whose
locations are schematic (see text). Quartz is present in all 7FeCOa 4- 4S• • FevSs4- 7CO, 4- 3.50, (3)
assemblages. Sphalerite isopleths (short dashed lines, in siderite pyrrhotite
mole fraction FeS) from Czamanske (1974); pyrrhotite-
pyrite boundary from Scott and Barnes (1971); magnetite- Lacking chemicaldata on the chlorite, this phase
hematite-pyritetriple pointand pH contours(for ES = 0.01 m)
basedon data in Robie and Waldbaum (1968); K-spar-K-mica has beenassigneda hypotheticaliron end-member
and K-mica-kaolinite boundaries (for 2KC1 = 1 m) from compositionwith a high Fe+•/Fe+• ratio in keeping
Montoya and Hemley (1975). with the reduced nature of the assemblage. The
three reactions listed above appear as univariant
of constraintson fs• rather than temperature. phase boundarieson a log fs,-log fo• diagram
Figure 14 illustrates the narrow range of fs2 drawn for constant temperature,constantchlorite
for assemblagescharacteristic of lead-zinc ore: composition, and constantfco• with P½o,4- Pa2o
(1) pyrrhotite 4- sphalerite4- arsenopyrite, with = P•o•t (Fig. 15). The phase boundariesmeet
X}!•s < 0.3; (2) pyrite 4- sphalerite4- arsenopy- at an invariant point which representsthe five-
rite; and (3) pyrrhotite 4- chalcopyrite. The phase assemblage pyrrhotite-siderite-chlorite-
temperature range over which sphalerite-2 was quartz-fluid (point A, Fig. 15). The general
depositedcannot be specifiedon the basisof sulfide locations of the siderite and chlorite stability
phase equilibria; these simply yield a minimum fields in Figure 15 are basedon the natural asso-
temperature of 254øC and a series of maximum ciations and are therefore only schematic. The
temperaturesranging from 334ø to 600øC (Table uncertainties in thermodynamic and experimental
8). Specifictemperaturesof depositionor chemical data on sideritestability (French, 1971), combined
equilibration of individual samplesare obtainable, with the lack of data on Pco, at Cerro, prevent
with the present data, only from the isotope the accurate location of the siderite stability field.
analyses, which yield temperatures compatible The effect on the topology of Figure 15 of
with the limits imposedby phaseequilibria. Indi- changingP½o,or temperaturecan be determined
cated depositional temperatures of the three by inspectionof the stoichiometryof reaction(1).
samples from CN-A Pb-Zn orebody decrease The fact that Inco,[> Ina,oJ indicates that
systematicallyfrom 344ø to 234øCwith increasing chlorite is the high-temperature(or high-entropy)
distancefrom the pyrrhotite pipes (Table 7). If assemblageand that an increasein Pco,, with
the thermal range indicated by isotopic fractiona- Pco•4- Paso= P•o•,•, favors siderite4- quartz.
tion is representative,then the decreasein mean Therefore,an increasein Pco• and/or a decrease
X •FeB, from 0.25 to 0.22 near the pipes to 0.18 on in temperaturewould causethe sideritefield to
the fringes of the Pb-Zn orebodies (Fig. •2), expandrelative to both pyrrhotite and chlorite,
indicatesan overall decreasein log fs• from -9.5 and point A would migrate toward the pyrite-pyr-
at 350øC to -13.0 at 250øC. Presumably, this rhotite-chlorite-quartzequilibrium point. Con-
 EXFIRO•V•I[ENT OF ORE DEPOSITION .4T CERRO DE P.4SCO 919

tintledincreasein Pco2and/or decrease in tempera- tion states of the sphalerite-3 stage. The presence
ture might lead to: (1) reactionof pyrrhotite and of m-po and A-po as intermediate phasesin the
chlorite to yield siderite,quartz, and pyrite; and alteration of pyrrhotite to pyrite, and the associa-
(2) generation of the new equilibrium pyrite- tion of siderite with pyrite, indicate a decreasein
siderite-chlorite-quartz,an environmentsuggested temperaturerelative to at least part of the sphal-
by the fringes of the Pb-Zn orebodiesnear lime- erite-2 stage. There is no evidence, however,
stone. which indicates that there was a time gap between
The relevance of the above discussion with the termination of the sphalerite-2 stage and the
respect to sphalerite is that if the ore fluid locally beginningof the sphalerite-3stage. Nevertheless,
was buffered at point A in Figure 15, or by the other lines of evidence suggest that these two
siderite-pyrrhotite or chlorite-quartz-pyrrhotite environments do not represent end members of a
phase boundaries,then the FeS content of sphal- continuum in the evolution of a single ore fluid.
erite would have recordedany changesin fo.,, These include: (1) the erratic distribution of
leo.,, or temperature. The apparent variations in sphalerite-3; (2) the presenceof sharp, crosscutting
rs2 which led to the development of intricately and replacementtexttires between sphalerite-2 and
growth-banded sphalerite largely in the range sphalerite-3; and (3) a general lack of sphalerites
above 20 mole percent FeS could have been caused with compositionsintermediate betweensphalerite-
by fluctuationsin fo2 due to mixing of oxidized 2 and sphalerite-3. The sphalerite-3 stage may
groundwaterswith an orefluid bufferedby siderite- represent a separate surge of fluids, and it is
pyrrhotite or chlorite-quartz-pyrrhotite. The local tempting to correlate it with the enargite stage.
bands containingless than 20 mole percent FeS, This topic is developedin the next section.
and yet apparentlynot in equilibriumwith pyrite,
might have been formed during brief excursions Speculationson the Enargite-Tennantite Stage
into the chlorite or siderite stability fields. These
The detailed study by Graton and Bowditch
oxidation events must have been of local nature,
(1936) of the mineralogy and genesisof copper-
as implied by the lack of correlationof sphalerite
bearing veins and associated wall-rock alteration
"stratigraphy" between samples,thinnessof the at Cerro de Paso is one of the first clear statements
low-iron bands, and the lack of evidence for wide-
spread replacement of pyrrhotite by chlorite or of the correlation between high sulfidation state
sideriteduring the sphalerite-2stage. in the ore assemblageand advanced hydrolyric
alteration of wall rocks (e.g., Meyer and Hemley,
In summary, the field evidenceand isotopic 1967). No significant advances have been made
data indicatethat the fluid crossed from the pyr- in characterizing the mineralogy of these veins
rhotite fieldinto the pyrite fieldin the neighborhood
since the original study. Nevertheless, the new
of 300ø to 250øC, with subsequentdepositionof
data acquired in recent years on the stabilities of
lead-zinc ore lacking pyrrhotite and containing relevant mineral assemblagesand the possibility
sphalerite-2with less than 20 mole percent FeS.
of a cogeneticrelation with the sphalerite-3 stage
The T-fs2 path, therefore,had a flatter stopethan warrants a brief discussion of this classic occurrence.
the pyrrhotite-pyrite buffer, and the fluid may
have been in equilibrium with both iron sulfide
phases only for short periods, if at all. It is Temperature estimates
hypothesized that local fluctuation in the FeS The mineralogy of the vein fillings and wall-rock
content of sphalerite were due to fluctuation in alteration points to a temperature of formation
fo2 caused by influx of oxidized ground waters; of about 300øC (Table 8) at high sulfidationstates
increasein fs• was an effect, rather than a cause. (Figs. 13 and 14). Unfortunately, there are no
The overall trend in T-fs., may be approximated detailed compositional studies of sphalerite, lu-
by an equilibrium betweenchlorite-siderite-quartz- zonite, enargite, and tennantite-tetrahedrite in
pyrrhotite (or pyrite); the actual trace of such a these associations. Petersen (1965) reports that
path would depend on the compositionsof chlorite coexisting enargite and luzonite from the McCune
and values of P½o.,. Both undoubtedly varied, pit contain 15 and 24 mole percent of the Sb end
as did pyrrhotite compositions, and hence the member, respectively. Although these are non-
path was not strictly univariant on a T-fs• pro- equilibrium compositions and cannot be used to
jection. estimate depositionaltemperatures,they do suggest
Alteration of pyrrhotite and sphalerite-3 stage: primary deposition above about 300ø to 320øC,
With time, the relatively low oxidationand sulfida- the lower stability limit for end-member enargite,
tion state characteristicof the sphalerite-2stage and equilibration to below approximately 350øC,
were replaced by the higher oxidation and sulfida- where the $b-rich phase that coexistswith enargite
920 MARCO T. EINAUDI

is luzonite rather than famatinite (Skinner, 1960; Changes in the chemical environment in the
Maske and Skinner, 1971; Feiss, 1974). However, veins are reflected in the zoning pattern docu-
according to experimental data from Hemlev mented t•v (;raton and Bowditch (1036). l.ateral
(Reed and Hemley, 1966), the asselnblagekao- zoning is well developed. The central portions of
linire-quartz is stable relative to pyrophyllite at the veins, near the contact of the vent and pyrite-
temperatures below about 300øC at 1,000 bars quartz body, are characterized by the presenceof
P•I2O,assuminga fluid saturated with respect to kaolinire + quartz rather than sericite, enargite
quartz. At the lower P•i2o values which un- rather than tennantite, pyrite rather than hematite,
doubtedly prevailed at Cerro de Pasco, the thermal and chalcopyrite+ pyrite is more common than
limit for kaolinire q-quartz is less than 300øC. bornite + pyrite (upper right portion of area B,
Because there is little doubt that the enargite Fig. 15). The eastern and western terminations
q- pyrite vein filling is contemporaneous with the of the veins are characterizedby sericiterather than
kaolinire+ quartz alteration assemblagein the kaolinire, tennantite with common chalcopyrite
wall rocks, it is likely that an error exists in one of rather than enargite, and sphalerite containing 1 to
the two sets of experimental data. This author 2 mole percent FeS (lower right portion of area B,
tends to support the speculation of Feiss (1974) Fig. 15). Zoning in the vertical direction is essen-
that either the published value of 300ø to 320øC tially nonexistent. Graton and Bowditch indicate
for the enargite-luzonitetransition (Skinner, 1960; that advanced argillic alteration and enargite-
Maske and Skinner, 1971) is too high or that pyrite persisted to the deepest level (2100) open
enargite commonly forms metastably in the luzonite in 1936, which was 640 m below the surface. How-
field. ever, Ward (1961) notes that a few veins in the
A rough estimate of the lnaximum thermal limit footwall of number 43 vein were nilned for enargite
for the distal portionsof the copper-bearingveins on their deeper levels and for galena-sphalerite
may be based on two samplesof sphalerite from in their upper portions.
tennantite-pyrite veins in the vent which yielded The above facts are compatible with various
less than 1.7 mole percent FeS by wet chemical aspects of Meyer and Hemley's (1967) model for
assay (Petersen, 1965). Intersection of the 1 mole progressivechangesin a hydrothermal fluid during
percent FeS sphalerite isopleth (Czamanske, 1974) ore deposition. Presumably, a combination of
with the thermochemical approximation for the temperature decrease and oxidation by ground
tennantite-enargite sulfidation curve (Craig and water below the 2100 level was sufficient to lower
Barton, 1973) occursat 300øC (Fig. 13). the pH of the ore fluid to the point where advanced
argillic alteration could occur. Continued genera-
Chemical environmentand relation to sphalerite-3 tion of hydrogen ion by dissociatingacids in the
fluid kept up with the lossof hydrogenionsthrough
The general chemical environment of formation hydrolyric alteration of wall rocks, and the ad-
of the enargite-tennantite veins is illustrated by vanced argillic assemblage moved vertically, at
cross-hatchedarea B in Figure 15 at 300øC. In the least to the present surface,and expandedlaterally
absenceof data on the total sulfur and potassiam from the central portions of the veins.
contents of the ore fluid, the following values are At the western extremities of the veins, dis-
assumed: (1) 0.01 m for sulfur, which lies within equilibrium between the ore fluid and fresh quartz
the general boundar5' values suggested by most monzonite was only a matter of 1 or 1.$ pH units.
workers (e.g., Barnes and Czamanske, 1967; First tennantite, and then nilnor sphalerite and
Ohmoto, 1972); and (2) 1.0 m for KCI, which is galena, were deposited as the ore veins died out in
equivalent to the experimental concentration used barren pyrite stringers encasedin sericitized walls.
by Hemley (1959) in his studies of hydrolysis At the eastern extremities, however, disequilibrium
reactions in the alkali-alumina-silica system. A between the ore fluid and certain portions of the
tenfold decrease in the concentration of KC1 shifts massive sulfide body may have been as much as
the K-mica stability field one pH unit higher than 3 or 4 pH units. Enargite-pyrite-alunite con-
shown in Figure 15, which is insignificant for the tinued to be depositedin areas where the fluid met
purposesof the present discussion. The environ- only pyrite-quartz. But, in areas where it met
ment of the copper zone, based on the above limestone or Pb-Zn ore of the sphalerite-2 stage,
assumptions,spans a relatively narrow range of the ensuing reaction caused the fluid to shift
pH values on the acid side of neutrality and at several units higher in pH; minor amounts of
relatively high oxidation and sulfidation states, sphalerite, galena, pyrite, and barite, accompanied
such that sulfate aqueous specieswere dominant by some tennantite, were deposited on the fringes
over reduced sulfur aqueousspecies. of the enargite pipes. Major sphalerite-galena
 ENVIRONMENT OF ORE DEPOSITION AT CERRO DE PASCO 921

deposition occurred farther out in limestone; the
largest of these orebodiesin limestone, the Mata-
gente Pb-Zn vein system, is on strike with and
has the same attitude as No. 28 enargite vein to
the west. These spatial relationssuggestthat the
Matagente and No. 28 veins representa single
zonedfissure,althoughthe presenceof a through-
going structural connection is not clear. The
geneticcorrelationof these two veins is supported
by the fact that the Matagente and No. 28 veins
contain barite (Petersen, 1965), a mineral which
is characteristicof the enargite stage and, in
general,of relatively high oxidationand sulfidation
states, but which is absent in the sphalerite-2
stage.
If the conclusionis valid that major amountsof
fluid of relatively low and fluctuating oxidation-
sulfidationstate and with a near neutral or slightly
alkaline pH for temperaturesin the range 380ø to
250øC. Partial bufferingof rs,. and fo,. by the
assemblagepyrrhotite-siderite-chlorite-quartz may
have occurred, but anomalously low values of
FeS in sphalerite-2suggestbrief periodsof oxida-
tion during which the fluid was undersaturated
xvith respect to both pyrrhotite and pyrite. The
overall trend with decreasingtemperatureappears
to have been toward increasingsulfidation and
oxidation states, perhaps due to buffering by
silicate-carbonate-sulfideassemblages with rela-
tively flat T-rs,. slopes. This trend may have been
enhanced by local influx of oxygenated ground
waters.

sphaleritewere depositedas a fringe product of Although this first stage produced only Pb-Zn
the enargitestage,then it lendsfurther supportto ore, it has many of the characteristicsof tin and
the speculationmade in the previoussectionthat tungsten deposits of the eastern Andes of Bolivia
sphalerite-3 a part of the enargitestage. (Kelly and Turneaure, 1970) and thus serves
represents
The chemistryof the sphalerite-$stage also is as a metallogenic link between the Sn-W-Ag-Bi
compatible with that of the enargite stage as provinceof Bolivia and the Cu-Zn-Pb-Ag province
modifiedby coolingand reactionof an originally of central Peru. The Bolivian deposits,some of
acidicsolutionwith the mineralassemblages of the which are located within volcanic vents (Sillitoe
sphalerite-2stage. The mineral zoning of the et al., 1975), are associatedwith granitic intrusives,
enargitestagesuggeststhat the pH of the ore fluid and are thought to have formed within a depth
increasedalonga path from B towardA in Figure range of 800 to $,000 m below the surface. In
15, as the solutions moved away from the vent both the Bolivian ores and at Cerro de Pasco,
and acrossthe pyrite-quartz body. Reactionof the the base metal sulfidestage was precededby a
fluid with the pyrrhotite-bearingportionsof the feldspar-destructivestage of quartz-sericitealtera-
Pb-Zn ore resulted in extensive alteration of tion, accompaniedby minor to abundant pyrite.
pyrrhotite to pyrite, marcasite,and siderite, and Kelly and Turneaure have documentedthe para-
deposition of sphalerite-$. The solutions never genesisand depositionaltemperaturesof the tin-
reachedpoint A, however. At temperaturesof tungstenores on the basisof detailed mineralogle
250øCand ES = 0.01m, the pH of a fluid saturated and fluid inclusionstudies. Temperaturesinitially
with respect to pyrite, siderite, and sphalerite increasedfrownabout 300ø to 530øC during an
containing 3 mole precent FeS, is approximately early vein stage consistingof quartz-wolframite
$.$, or essentiallyneutral. (or cassiterite).This stagewas accompanied
by
minor sulfides, including pyrrhotite and arsen-
General Conclusions and Relation opyrite, and appearsanalogous,exceptfor higher
to Other Ore Types wolframite/pyrrhotiteratios,with the deepquartz-
pyrrhotite-wolframite association at Cerro de
The first stage of ore depositionat Cerro de Pasco. The later basemetal sulfidestage of the
Pascofollowedthe formationof an extensivebody Bolivian ores formed as temperaturesdeclined
of pyrite-quartz in limestone and alteration of from about 400ø to 260øC. This stage, char-
adjacent quartz monzonite and volcanic breccia acterizedby the association
pyrrhotite-sphalerite-
to sericite-pyrite-quartz. Upward and outward stannite-chalcopyrite, mimics the intermediate-
zoning relative to centrally located pyrrhotite level sulfideassociation in the pyrrhotite pipes
pipes follows the sequencequartz-pyrrhotite- at Cerro de Pasco. At this point, the historiesof
wolframite,pyrrhotite-stannite-chalcopyrite-sphal-ore depositionin the Bolivian and Peruvian ores
erite, and pyrrhotite (pyrite)-arsenopyrite-sphal-diverge. In the tin-tungsten ores, the solutions
erite and is accompaniedby increasingPb/Zn were spent (or diluted) and the waningstagesof
ratios and Ag values. Compositionaldata on hydrothermal activity below 260øC led to the
sphalerite,combinedwith the presenceof siderite- alterationof pyrrhotite to pyrite, marcasite,and
chlorite-quartz and absenceof magnetite, are siderite, and deposition of minor amounts of
interpreted as signifyingdepositionfrom an ore sphalerite.At Cerrode Pasco,a majorepisode of
922 MARCO T. EINAUDI

lead-zinc and copper ore deposition preceded and Meyer and Hemley (1967) suggestthat increases
accompaniedthe late pyrrhotite-destructive stage. in hydrogen metasomatismand suIfidation state
The enargite veins and pipes in the volcanic vent are due to a combination of steady-state cooling
and pyrite-quartz body at Cerro de Pascorepresent and mixing with oxygenatedgroundwater. The
the major period of copper deposition. The ore latter would have the effect of producing more
fluid had evolved to a relatively high sulfidation- highly ionizedsulfuricacid from the lessionized
oxidation state and low pH at temperaturesaround H2S. The authors conclude that a maximizing
300øC. Reaction of this fluid with the rocks and effectmight be produced"wherehot, low density
mineral assemblageseast of the vent resulted in a fluids, containing significant acidic components
sharp increasein pH, depositionof low-FeS sphal- were only slightly diluted, yet considerablycooled,
erite, tennantite, galena, and pyrite, and destruc- in the lower reaches(severalthousandfeet?) of the
tion of pyrrhotite. A similar zonal pattern, ground water zone" (1967, p. 227). This, pre-
accompaniedby a decreasein base leaching of wall sumably,in the environmentof the cordilleranbase
rocks, is present toward the western extremities of metal lode deposits.
the veins within the quartz monzonite vent rocks. Some copper lode deposits,such as Cerro de .
The zoning of sulfide and alteration assemblages Pasco,Yauricocha,and Magma, bottom at depth
implies that the sulfidation state increasedand pH in low-grade,pyritic, enargite,or enargite-chalco-
decreasedwith time at any given spot in the veins, cite mineralization associated with a negligible
because field relations suggest contemporaneous, decrease in base leaching. However, at some
outward growth of successivemineral zones. The localities,the lodestageappearsto have beensuper-
final expressionof the mineralization processseems imposedon an earlier environmentrepresenting
clear: a fumarolic, hot-spring environment was lessof a departurefrom equilibriumwith original
superimposedon the massive sulfide body. Hydro- wall rocks. Such an environment is evident in
thermal leaching was followed by redepositionof the early pyrrhotite stage at Cerro. Other lode
ore high in bismuth and silver and containing depositscontainlow-gradedisseminated andveinlet
native sulfur and alunite. pyrite-chalcopyrite-molybdenitemineralizationof
The enargite stage at Cerro de Pasco exhibits the porphyrycoppertype. The presence of both
mineral assemblages and zonal-parageneticfeatures lode and disseminated-type mineralization at
that are found in numerous other base metal lode Morococha has been pointed out by Petersen
deposits of the American Cordillera. Analogies (1970), and the relation betweenthesetwo stages
have been drawn by others between Cerro de at Butte has been extensively treated by Meyer
Pasco and such deposits as Yauricocha and Moro- and Hemley (1967) and Meyer et al. (1968).
cocha, Peru (Petersen, 1965, 1970), and Butte, Evidence for a weak porphyry copper stage is
Montana (Meyer and Hemley, 1967). Although alsopresentat Bisbee(Bryant, 1964).
variations in details of mineral assemblages are A generallyacceptedmodelfor the evolutionary
present which generally reflect the presence of trend of hydrothermal systems associatedwith
calcareous versus quartz-feldspathic wall rocks, porphyry copper depositsconsistsof an early,
the chief unifying characteristicsof these deposits dominantly magmatic water stage, characterized
are well documented:(1) coppersulfideassemblages by potassium silicatealteration,followedby a late,
indicative of high sulfidation states, above the dominantly meteoric water stage, characterized
pyrite-chalcopyrite-bornite sulfidation curve, are by sericiticalteration (e.g., Gustafsonand Hunt,
associatedwith intense base leaching (silicification- 1975; Sheppardand Gustafson,1976). In those
sericitization and/or advanced argillic alteration) depositswhere age relationsare evident, sericitic
of igneousrocks or massive sulfide-quartz replace- alterationis later than potassiumsilicatealteration
ment of limestone; and (2) significant lead-zinc- at a givenpointof observation.This impliesthat
silver ores in peripheral igneous or calcareous duringthe later stagesof development,the sericitic
wall rocks reflect a decline in both sulfidation state zone encroached downward and inward onto the
and base leaching relative to the copper zone. potassiczone. In the majority of porphyrycopper
On the basis of these characteristics, and a similar deposits,the sulfide assemblages in both stages
petrotectonic habitat, the ore depositsat Magma, indicate depositionat sulfidationstatesbelow the
Arizona (Hammer and Peterson,1968), and Bisbee, pyrite-chalcopyrite-bornitebuffer; the hte stage
Arizona (Bryant, 1964), also are closely related rarely evolvesto the extremesof high sulfidation
types. and low pH exemplifiedby the lode deposits.
The relationshipbetweenlow pH and high sulfur One of the few examplesof this extremein porphyry
and oxygenfugacitescan be expressed by equations copperdepositsis El Salvador,Chile,whereGustaf-
of the type: SO• + 2H+-• •S• • + •0• a + H•O. sonand Hunt (1975) have documenteda significant
 ENFIRONMENT OF ORE DEPOSITION .4T CERRO DE P.4SCO 923

zone of pyrophyllite-diaspore-alunite alteration activities, due to quenching and oxidation of hot,

that shows a close correlation with the distribution H2S-bearing fluids by cooler ground waters.
of disseminatedpyrite-enargite. The advanced Sulfides would exhibit textures indicative of rela-
argillic zone occursat a high level, surroundedby tively rapid deposition in structural openings.
and replacing the sericite zone, and contains less Fluctuations in the chemical state of the ore fluid,
copper than the earlier and deeperzonesof sericitic due to variable proportions of oxidized ground
and potassicalteration. It is also significantthat water and reducedhydrothermal fluidsin a dynamic
sphalerite appears to be concentrated in veinlets hydrologicsetting, couldlead to the suddenchanges
peripheralto the enargitezone. A similargeometric in mineral assemblages
and compositionsdocu-
relation may exist at the Red Mountain porphyry mented at Cerro de Pasco.
copper deposit, Arizona (Corn, 1975). In both
deposits, the enargite zone and its peripheral Acknowledgments
sphaleritezone may be construedas encroaching
onto the deeperlevelzones,resultingin patternsof Much of the descriptive base for the present
distribution of these minerals that are not coin- study comes from the author's doctoral thesis at
cident with earlier patterns. Harvard University. I am deeply indebted to
The geneticrelation betweenlode depositsand Professor Ulrich Petersen for his support and
porphyry depositsis significantand requiresfurther guidanceduring the early courseof the investiga-
documentation. Cerro de Pasco, ¾auricocha, tion and for his encouragementto publish the
and Magma may be consideredexamplesof one present version. I am also grateful to Cerro
end member of a spectrum of base metal sulfide Corporation for financial support while in Peru
depositswhoseother end memberis representedby and to the geologists at Cerro de Pasco;in particu-
the porphyrycopperdeposits.Intermediatetypes, lar, Richard Petersen, then Chief Division Geolo-
such as Butte, Bisbee,and Morococha,contain an gist,andV. RaoulEyzaguirre,thenMine Geologist,
early porphyry copperstage, but the bulk of the for invaluable discussions
on the geologyof Cerro
copper production has come from lode-stage de Pasco,for permitting the use of private maps,
nIineralization. Other intermediatetypes,suchas and for aid in the logisticsof mappingand sample
El Salvadorand Red Mountain, display an em- collection. Laboratory and travel expenseswere
bryoniclode stage,but the bulk of the ore-grade supported by a grant from the National Aero-
nautics and Space Administration (NSG-282 63
mineralizationis restrictedto the earlierporphyry-
type environment. The dominance of one or the to C. Frondel, Harvard University) and by the
other ore type may be a functionof depth of era- Shaw Fund, Harvard University. Reviews of the
placementand degreeof ground-waterinvolvement, nIanuscript by G. P. Landis and G. K. Czamanske
inIplicit in the cheniicalargumentsof were helpful. Perfecto Mari kindly drafted the
a suggestion
Meyer and Hemley (1967) and also previously illustrations.
made by Gustafsonand Hunt (1975) to explain DEPARTMENTS OF .•PPLIED EARTH SCIENCES AND
the variability in intensityof late-stagealteration- GEOLOGY
mineralizationin porphyrycopperdeposits. STANFORD UNIVERSITY
Eraplacementof a niineralizingporphyrybelow ST•'FO}m, C•I. IFO}½•I,X94305
the maximum depth of abundant ground-water August 24, 1976; March 8, 1977
circulationwouldtendto favor the development of
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