EconomicGeology

Vol. 79, 1984, pp. 565-572

POTASSIUMAND RUBIDIUM METASOMATISM AT THE ]ULCANI DISTRICT, PERU

DARYL A. SCHERKENBACH

NorandaExploration, Inc., 139 East51stAvenue, Anchorage, Alaska99503

AND DONALD C. NOBLE

Department of Geological Sciences, MackaySchool of Mines,University of Nevada-Reno, Reno,Nevada89557

area was sampledextensivelyto evaluatequantitatively the intensityof alteration, but veinswere purThe Julcani district,centralPeru, is a majorsilverposely avoided during the collection of surfacesamproducing districthostingzoned polymeta]lic vein systems that containtetrahedrite and enargiteasthe pies.This was done to evaluatethe pattern of pervasive metasomatism rather than the more intense principle economicminerals.Resultsof numerous studies at Julcani have addedto our understanding alteration near veins. Samples,composedof four to six selected rock of this depositandthe reader is referred to Petersen weighinga total of 250 to 400 g, were et al. (1977), GoodellandPetersen (1974), andNoble fragments andSilberman (in press) for moredetailed discussionscrushedin a smalljaw crusher,and abouttwo-thirds of this materialwasgroundsuccesof the geology,geochronology, and hydrothermal to three-fourths sively in a disc-type rockpulverizeranda rotarymorevolution of the center.The purpose of the present powderpelletsof this materialwere anstudy isto determine whether base andprecious metal tar. Pressed methods. Potassium was mineralization in altered dacitesand rhyodacites at alyzedby X-ray fluorescence determined using Cr radiation in a helium atmoJulcani isassociated withregular patterns ofpotassium sphere. Rubidium and strontium were determined and rubidium metasomatism on both a district-wide scale andat close proximity to veins andveinsystems. usingMo radiation.The intensity of the Compton In addition, it isimportant to evaluate the application scatteredprimary peak was used to correct for mass effectsandinstrument drift in the Rb and of such patterns asguides to the exploration andde- absorption Sr analyses (Powell et al., 1969). Correctionswere velopmentof additionalareasof mineralization. curvatureandpeak overlap. This communication presents the resultsof a de- appliedfor background studies were pertailedstudyof the changes in concentrations of po- X-ray diffractionand petrographic formed on many samples. tassium,rubidium, and strontium in dacites from the Julcanidistrictduring hydrothermal alterationand mineralization(Scherkenbach, 1978). The Julcani Mineralogy and Chemical Changes districtis well suitedto a studyof potassium metaof the Altered Rocks somatism related to baseand preciousmetal minerUnaltereddacites containabundant phenocrysts of alizationbecause: (1) the dacitesthat hostthe minquartz, and biotite accompanied by minor eralizationhave similaroriginaltexturesand com- andesine, positions, (2) the presence of unaltereddacites outside apatite, Fe-Ti oxides,and, in somecases,pyroxene the area of alteration and mineralization facilitates and/or hornblendeset in a fine-grainedor glassy Most of the altered rocksin the district thedetermination of accurate background values, and groundmass. in(3) extensive underground workings permitsystem- exhibit typical propylitic mineral assemblages, atic sampling in areasof majormineralization normal cludingepidote, chlorite, calcite, pyrite, smectite, quartz, sericite,albite, and/or K-feldspar.X-ray difto selected veinsand vein systems. fractionandpetrographic studies revealthat in most Methods of Study of the rocks near veins the added K and Rb is conOver 500 rock samples were collected,abouthalf tained in adularia(disorderedsecondary potassium fromthesurface andhalffromunderground locations, feldspar)and to a lesserextent in muscovite,illite, to providea systematic coverage of altered and un- or mixedlayer illite-smectite phases (Scherkenbach, altered areas. The subsurface samples werecollected 1978; Wilson, 1979). Adularia in somecasesis acat measured intervalsalongselectedtraverses ori- companied by, or partially altered to, sericiteor kaentedapproximately perpendicular to veins.Mostof olinite. A small number of specimens found in the thesetraverses are in the activelyminedareaof Her- Tentadora area on the surface, or in some casesocminia; three traverses are in the Tentadora area. Sur- curring directly adjacentto veins and vein systems facesamples were collected to obtaina comprehen- underground,are composed primarily of kaolinite, sive coverageof about 20 km2 of the altered and quartz, and pyrite, and in somecases containalunite unaltered dacites. Thecentral, hydrothermally altered or pyrophillite.
0361-0128/84/297/565-8 $2.50 565

Introduction

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The validity of any geochemicalalteration study is dependenton establishing the composition of the rocksprior to alteration.At Julcanithis was accomplishedby analyzing rocksfrom outsidethe area of mineralization and alteration whichdisplay no signs of alteration. A totalof 21 rocksamples werecollected beyondthe boundaries of the alteration map(Fig. 1), includingnine to the north and northwest,eight to
the south, two to the east, and two to the west. All

The range of concentrations determined for these

rocks are 3.1 to 3.8 wt percentK20, 100 to 180 ppm Rb, and650 to 1,600 ppmSr.The original Sr contents show a larger range of values than do K20 or Rb. This variation, found in many igneousrock suites, reflectsthe geochemical complexity of Sr. Unaltered rocks fromthe southwest cornerof the Julcani district

have higher Sr contents, 800 to more than 1,500 ppm, than do unaltered rocks from the south and these rocks and some additionalunaltered samples northwestparts of the district (700-935 ppm). This were used to establishbackgroundvalues and the variation reducesthe usefulness of Sr in evaluating alteration. original K/Rb ratio.

74'/*5'

12'55'

FIG. 1. Map of the Julcani districtshowing surface veinpatterns andboundary of alteration study. Irregular boundaryindicatesarea of dacite lava outcrop (after Petersenet al., 1977).

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I I I I I

567

Surface

samples

Subsurface

samples

&

&

;::'

KO (wt%)
FIC. 2. Plot ofRb vs.K20 for altereddacites fromthe surface andunderground traverses. Outlined area corresponds to the rangeof composition from unalteredrocks(not plotted).

Most of the intenselyaltered daciteshave undergonesignificant chemicalchange,with the K and Rb contentsof these rockshavingbeen increasedsubstantially;somecontainas much as 9.0 wt percent

K20 and 600 ppm Rb. More Rb hasbeen addedrelative to the original rock concentrationthan K, resuitingin a K/Rb enrichmentratio in the addedmaterial of about 110. Thus, altered dacites have lower

surface samples subsurface samples unaltered samples

'

oo

200
K20 values.

400

600 Sr (ppm)

800

tOO0

t200

t400

1600

FIG. 3. Plot of K20 vs. Sr for surfaceand subsurface dacitesshowingthe marked depletion of Sr and accompanying increasein K20. Note the wide variation in original Sr contentbut nearly constant

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SCIENTIFIC COMMUNICATIONS

K/Rb ratios(K/Rb ratio rangingfrom 210-130) than thoseof the unalteredrocks(about215; Fig. 2). Significantamounts of Sr have been lost from many of the dacitesthat have gainedlarge amounts of K and Rb (Fig. 3). Rocks composedof kaolin + quartz _+ alunite_+ pyrophylliteare leachedof K andRb and commonlyenriched in Sr. Spatial and paragenetic relationships relate leachingof thesesamples to mineralization. Suchleaching mayindicateareas of high fluid flow or strongly acidsolutions, andresults from hydrolysis of hostrocksthat may accompany or predate ore deposition.
Surfacepatternsof K and Rb
To facilitate visual evaluation of the variation in

and contoured usingthe SYMAPprogram(Fig. 4). The boundary separating alteredandunaltered rocks
is well definedon the south,southeast, and northwest edgesof the district. Most of the rocksin the central, altered part of the district show an increasein KO

and Rb and a decrease in Sr. Strongenrichmentof K20 andRb isfoundprimarilyin threeareas: Mimosa, Herminia,andeastof Acchilla(Fig. 4A andB). These
areas include most of the surface rocks that contain

morethan5.0 wt percent K20 and250 ppmRb.They are separated from each other by rocksthat contain
markedlylower amountsof KO and Rb. Highly altered rocksoccur throughoutHerminia
and extend to the southwest and north. The area un-

derlain by moderatelyto highly altered rockscorthe patternsof K andRb metasomatism, the analyses responds well with the area of productiveveinsand havebeen groupedinto a few compositional intervals intensefluid movement(GoodellandPetersen,1974;

KO (wt.%)
o

5.6
5.05.6

4.4 - 5.0

5.8 - 4.4
5.1 -5.8

N 10500-

N 9500-

o METERS

500

N 8500-

EIOlOO0 x

EI700

E12000

E 13000
i

FIO. 4. Maps A and B show the distributionof K20 and Rb contents,respectively,in surface samples of altered and unaltereddacite. Note strongenrichmentin the productiveHermina and Mimosaareas. Rocks are depletedin the Tentadoraregion,an areaof verticalfluid movement. Contours are at 4.4., 5.0, and 5.6 wt percentK20 and 200, 250, and 300 ppm Rb. Note similarpatterns of bothA and B. Smallright angles outliningrectangle nearTentadora and Herminiain part A indicate the locationof the underground traverses shownin Figure 5.

SCIENTIFIC

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569

of the alteredrocks;mostcontain Fig. 1). Furthermore, the termination of metaso- in the mineralogy matism east of Herminia correlates well with the teralbite andsomevariablepercentages of alunite. Another area of strongK and Rb enrichmentis minationof mineralization underground. Mimosa and the area between Mimosa and Tenlocatedeastof Achilla.This arealackssignificant vein on the surface,and many of the rocksof tadora,where economicmineralizationhasrecently structures been proven, has undergonestrongenrichmentof the area are not as pervasivelyaltered, as seen in K20 and Rb. Here, the alteration pattern is similar hand specimens and thin sections, as rocksof the to that of Herminia,coinciding with underlyingareas Mimosa and Herminia areas. Furthermore, there are workings to allowevaluation of posof economicallyimportant mineralization.The di- no underground
rection of fluid movement in Mimosa, and in Herminia, shows a correlationwith the locationof altered
sible hidden vein structures or to determine fluid

areas on the surface, notablytowardthe westandthe

southeast.

movement from metal ratio data. In addition, rocks collected from the southern, eastern, and northern

margins of the areaare characterized by highK and

Rb contents but are from localities outside of areas

In contrastto Herminia and Mimosa, the Tentadora

area, which hostsPb-Zn mineralization(Goodelland Petersen,1974) aswell asveinscontainingtungsten and gold, shows a differentchemicalpattern. Here, the rocksare moderately to strongly hydrothermally altered but have K and Rb contentsthat are largely at or belowbackground. The low values are reflected

containing knownmineralization and/or vein structures.

The two areasof major mineralization,pervasive wall-rock alteration,and strongK and Rb metasomatism are separated by areasof lower K20 andRb
contents. This corroborates the conclusion reached

1
x

Rb (ppm)
o

< >

I00 300

250-300
200 - 250

180 - 200 :, IOO - 180

i
I

0(

'
N I0 500-

N 9500-

x x x

x x

N 8500

TERS
x

x
x x

,%ooo

FIG. 4. (Continued).

E :,000

J: vein
6

K20 ( wt % )

o-I000

-o --...o

,',,,

o_o.OoXO '-*-'-*.
_2

..... ...... i...

I000
_

2 Rb (ppmx 10 -2)
IOOO

o.-

500_

......

,
,

,,,/' 500
o ,-o 0

Level 50Or. 1"- ' '--

%'' ....... -

Sr(ppm)

Level 540 Cr 2_08 '

--/i

/o
X /

/o, o-
/ ",,

SCALE (Sections DD' + E-E' only ) t , J

Oo o

meters /-

2900ppm

'

..-' .....

'"

............................

-' .....................

",V ........

..
ooo

0
o - '

o... . ..o

, ,

- -o ........

____. ___o_ __ ___o_ _-o_ _....

Level 580 Cr 67

- o--

_.o. __

pm ,,

- - .... _.

o-.o-o

500_
O_

0 I000
o- - - o_ . _

Y,
500

- - ...... Level420 Cr 233E

......

o-- -o. __-. _o. . - .o. -- ___.o-

-. o-- -

- ..... /

oO.

Lo
2

/ / .....

''"* .... / .'

,/./,,..,'

/ ....
'',

-,,

,,.,, ......... -" %.

/

%o
''''-.

......

I I.... *........ ,................................

o....

* _2

I0

' '' . -. ' ' ''8' o

,,,.., oO _. o ', _,_

meters
6

0 '

4,;/;i

o o Oo
..

frectured
--
.-

4 .,

-.,-II ....

p-.

.... ............... -0
._

_Level 0 Cr 201 E

_ _ _o /

, -o.. o .

'o-. _ _-o - - -o'] F' -. ,

/,o.. -o .... -_._ I

o 5o ioo

-o-.
I

KO wt%) o

Rb(ppmx I0-2)............

Sr(Dpm) .........

meters

FIG. 5. DiagramofKO, Rb, andSr contents of rocksamples plottedvs.distance alongunderground traverses. Vein locations are represented by verticalarrows; vein systems are represented by arrows connected with a line. Rocksfrom traverses showdefinite, yet in many cases irregular, enrichment asveinsare approached. Level 540: Cr (crosscut) 217 and 208 provide goodexamples of enrichment trends next to veins. Cr 208 showssubstantial pervasivepotassium metasomatism at its termination

57O

SCIENTIFIC COMMUNICATIONS

571

by GoodellandPetersen (1974) frommetalratiodata, movement in geothermalfields (Browne and Ellis, that mineralization at Julcani wasproduced by several 1970). distincthydrothermalsystems. It also supportsthe Discussion interpretation that the greatestamountof chemical Rubidium and potassium can be useful indicators changeis associated with abundant fluid movement and or fracturing,which is discontinuous within the of mineralizationbecausethey are commonlycondistrict. centrated in rocks near orebodies. These two elements

are geochemicallysimilar, having the same charge and comparable atomicradii, so that Rb substitutes The chemical changesassociated with selected for K insteadof formingits own mineral.In addition, veinsin underground mineworkingshavebeen stud- hydrothermalfluidsbecomeenriched in Rb relative ied in detailandarepresented in Figure5. Subsurface to K, resultingin a loweredK/Rb ratio (O'Neil et al., samples were collected asclose to the vein aspossible 1973; Goguel, 1983). Strontium, an element that behaves in a manner without actuallysampling the mineralizedportionof the vein, at 5-m intervals from the vein and at ad- similar to calcium (Turekian and Kulp, 1956), is a ditional 10- to 25-m intervals.In somecases sampling less reliable indicator of alteration than Rb or K. intervalsof greaterthan 25 m were usedbecause of StrontiumandCa are depletedin areasof potassium becausemineralsthat do not readily rockhomogeneity. This controlallowsoneto observe metasomatism enrichmentpatternsandto comparethe relationship accept Ca and Sr are stable, which is the case for of K and Rb metasomatism on the surface to minrocksin whichplagioclase is replacedby K-feldspar. eralization.Nearly all of the undergroundsamples At Julcanithis is shown by the plotsof underground are enrichedin K and Rb, except a few samples that traverses,which show Sr depletion with increasing are remote from the activelymined area and outside Rb and KzO (Fig. 5). Many fresh calc-alkalicvolcanic rocks of contiof the area of alterationrecognizedon the surface (Fig. 5). Along sometraverses nearly all the samples nental regionscommonlyhave K/Rb ratios of from are substantially abovebackgroundin K20 and Rb. 200 to 400 (Volkov and Savinova,1961). Studiesof Rb and K20 are enriched and depleted in a sym- K, Rb, and Sr as guidesto ore (Oyarzun, 1975; Armpathetic manner and Sr follows an inverserelation- brust et al., 1977) have shownthat both the Rb conship. As a vein or vein systemis approached,KeO tent andthe Rb/K ratioof rocks increase in the altered and Rb increasemarkedly, even if rocks along the rocksrelated to ore. Even though enrichment in K entire traverse have KeO and Rb contents above and Rb is a common feature of wall rocksfrom epibackground. The highestKeO andRb contentsalong thermalprecious metaldeposits (O'Neil et al., 1973; any traverseare typically found within 10 or 15 m Bonhamand Garside,1979), suchrelationships are of a vein. This increase is in somecases regular if the commonlycomplex.This metasomatism is not only host rocks are not highly fractured and altered and associated with potassium silicate alteration but also very irregularin areasof intensefracturing,highvein accompanies propylitic alteration. At Wairakei and Broadlands, an increase in K and Rb results from the density,and intensehydrothermalalteration. Subsurface K and Rb changes
The termination of metasomatism in the southeast

formation of adularia and illitc. In addition, these

cornerof the districtis well definedand abruptboth mineralscan equilibrate with solutionsfrom depth of heavy alkaliesand on the surfaceand undergroundin the 420 and 580 that have high concentrations levels. However, in the easternportion of the 580 low K/Rb ratios, resulting in decreasedK/Rb ratios level, the last occurrence of K and Rb metasomatism in the altered rocks (Goguel, 1983). However, in is located 100 m farther east than in the 420 level, generalnot all alterationtypes or eventsthat affect suggesting greaterlateral fluid movementat depth. alkali concentrations are associated with mineralizawheremorethanoneperiodof strong Metal ratio data at Julcani (Goodell and Petersen, tion.In districts suchasthis mayhave 1974) supportthis suggestion, as do data on fluid alterationhasoccurred,studies
on the right toward the center of the district. Level 580: Cr 67 located under the central Tentadora regionshows a high background alongthe traverseand addedenrichmentnear the veinson the left but leachingof K and Rb at the vein on the right. Level 420: Cr 233E showsa similar pattern of increasing K20 and Rb enrichmenttoward the left. The first area of K-Rb enrichmentmarksthe beginning of the alteredrocksin Cr 233E andis correlativewith the abruptsurface boundaryon the eastsideof Herminia (Fig. 4A andB). K andRb contents in rocksalongCr 233E decrease to background values beyond the initialareaof alteration but increase towardthe veinsystem encountered at Herminia. Beyondthe vein system, KzO andRb contents return to background values.Level 580: Cr 201 shows a gradualincreasein K20 and Rb to the left away from the unaltered zone. The traversein Cr 201 intersectstwo mineralized veins, one showingK=O-Rb enrichment and the other total leaching of these elementsbut an increasein Sr. Locationof the traverses is given by Scherkenbach (1978).

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limitedusefulness exceptto delineateunalteredareas Acknowledgments or callattention to areas thatrequire closer inspection. The authors gratefullyacknowledge financial and Unaltered dacites fromthe Julcani districthaveK/ logistic support for thisresearch from Compafiia de Rbratios of about215, whereas slightly alteredrocks Minas Buenaventura,S. A., a DomesticMining and average210 and strongly K- andRb-enriched rocks MineralFuel Conservation Fellowship, anda National average about130. TheseratiosreflectRb enrichment ScienceFoundationGrant. Special thanks are exin the mineralizing solutions fromdepthwhichresult tendedto AlbertoBenavides andJ. O. Kalliokoski for in a significant reductionin the K/Rb ratio of the enthusiastic support throughout the study.Thanks altered rocks.Lack of noticeable changefrom dif- are alsoextended to JakeDann,GeorgeBennett,and ferentpartsof the district indicates that the altering Marc Wilson for help in acquiringX-ray diffraction fluids partitioned Rb andK intowall rocks at the same data,andto members of the staffof Mina Julcani for ratio(about110). At Julcani mostareas underlain by assistance duringthe field portionof thisstudy.Fisignificant mineralization, andparticularly those areas nally,we are indebted to H. A. Wollenberg, whose nearveinsasshown by underground traverses, exhibit reconnaissance gamma spectrometry measurements marked enrichment of K and Rb. Here, addition of originally suggested majorarealvariations in potasK and Rb may havetaken place not only before the siumcontentwithin the Julcanidistrict. deposition of ore (NobleandSilberman, in press) but also afterward, during thefinalstages ofhydrothermalJuly 2, November28, 1983
activity.Furthermore,acidandalunite-andkaoliniteREFERENCES

stable solutions responsible for alkalileaching near

vein structures were presentprior to, or during,ore GEOL., v. 72, p. 1086-1100. deposition. Similarrelationships are foundat Butte (Brimhall and Ghiorso, 1983). Absenceof these Bonham,H. F., Jr., and Garside,L. J., 1979, Geologyof the Tonopah, Lone Mountain, Klondike, and Northern Mud Lake chemicalchangessuggests a lack of alteration and quadrangles, Nevada: Nevada Bur. Mines Geology Bull. 92, associated economic mineralization. This relationship 142 p. can be of importanceon two scales.On a district- Brimhall,G. H, Jr., and Ghiorso,M. S., 1983, Origin and oreconsequences of the advanced argillicalteration process widescale, the intensity anddistribution of alteration forming in hypogeneenvironments by magmatic gascontamination of may be evaluated. On a smallerscale,the intensity meteoric fluids:ECON.GEOL.,v. 78, p. 73-90. of the K and Rb enrichment may help to locatein- Browne, P. R. L., and Ellis, A. J., 1970, The Ohaki-Broadlands
dividual veins, since the alteration halo about veins
hydrothermal area,New Zealand: Mineralogy andrelatedgeochemistry:Am. Jour. Sci., v. 269, p. 97-131. Goguel, R., 1983, The rare alkaliesin hydrothermalalteration at Wairakei andBroadlands, geothermal fields,N.Z.: Geochim. et Cosmochim.Acta, v. 47, p. 429-437. Goodell,P. C., and Petersen,U., 1974, Julcaniminingdistrict, Peru: A study of metal ratios:ECON. GEOL.,v. 69, p. 347361.

Armbrust,G. A., Oyarz6n, J., and Arias,J., 1977, Rubidiumas a guide to ore in Chilean porphyry copper deposits:ECON.

andvein systems presents a muchlargertargetthan the veinitself.Thisrelationship couldbe usefulboth when exploring new areasand when attempting to locate displacedveins or continuations of locally
pinched-outveins.
Conclusions

Dacite lavasin the centralportionof the Julcani ECON. GEOL., in press. district were altereddifferentially by hydrothermal O'Neil, J. R., Silberman,M.
fluids;mostbecameenrichedin K20 and Rb and de-

Noble, D. C., and Silberman, M. L., Volcanicandhydrothermal evolution and K-Ar chronologyof the Julcanidistrict, Peru:

pletedin Sr.Resurgence of magma at depthproduced fractures whichchanneled solutions throughmuch of the rock. Strongenrichment of K20 andRb is related to fracturesand mineralization,and rockscontainingthe highestamounts of KO and Rb (asmuch as 8.0 wt % and 700 ppm, respectively) are found
within 10 to 15 m of veins or on the surface, near
the areas that contain substantial mineralization. The

L., Fabbi, B. P., and Chesterman, C. W., 1973, Stableisotopeandchemicalrelationsduringmineralization in the Bodie mining district, Mono County, California:ECON.GEOL.,v. 68, p. 765-784. Oyarzun,J. M., 1975, Rubidiumandstrontium asguides to copper mineralizationemplacedin someChilean andesitic rocks:Devel. Econ. Geology, v. 1, p. 333-338. Petersen, U., Noble, D.C., Arenas, M. J., and Goodell, P. C., 1977, Geology of the Julcani miningdistrict,Peru:ECON. GEOL.,
v. 72, p. 931-949.

altered rocks havelowerK/Rbratios (about 130)than the unalteredrocksfrom the district (about 215), whichindicates enrichment of Rbin the mineralizing
solutions.

Powell, J. L., Skinner,W. R., and Walker, D., 1969, Whole-rock Rb-Srageof metasedimentary rocksbelow the StillwaterComplex, Montana: Geol. Soc. America Bull., v. 80, p. 1605-1612.
Scherkenbach, D. A., 1978, Potassium and rubidium metasomatism related to mineralization at the Julcani district, Peru: Unpub. M.S. thesis, Michigan Tech. Univ., 68 p.

Using K andRb asguides to ore, it maybe possible

to determine favorable sites for mineralization both

on a regionalbasisand on a smallerscalenear productiveveins.In addition,by definingthe limits of

chemical change, unproductive exploration maybe

reduced.

Turekian,K. L., andKulp, J. L., 1956, The geochemistry of strontium: Geochim. et Cosmochim.Acta, v. 10, p. 245-296. Volkov, V. P., and Savinova,E. N., 1961, Variation in the potassium-rubidium ratio during the evolution of calc-alkalicand alkalicmagmas: Geochemistry Internat., v. 12, p. 1227-1236. Wilson, M. L., 1979, Some mineralogical relations in hydrothermally altered dacites,Julcani Peru: Unpub. M. S. thesis, MichiganTech. Univ., 60 p.