AN OCCURRENCE of the ASSEMBLAOE, NATIVE SULFTIR- COVELLITE-"Cu5 6,Fe,S6.S"", AUCANQUILCHA, CHILE Aran H. Cr-Etr&L

THE AMERICAN MINERALOGIST, VOL. 55, MAY_JUNE, 1970

AN OCCURRENCE OF THE ASSEMBLAOE, NATIVE SULFTIR- COVELLITE-"Cu5 6,Fe,S6.s"",AUCANQUILCHA, CHILE AraN H. Cr-etr<, Deportmentof GeologicalSciences, Queen's U niaersity, Kingston, Ontario. AssrnA.cr A mineral with composition near to CusFeSo has been found associated with nzrtive sulfur and covellite in the volcanic sulfur deposit at Aucanquilcha. Microprobe, optical and X-ray powder diffraction data match closell'a previously reported occurrence at Nu- kundamu, Fiji. Comparison with equilibrium synthesis by Kullerud and others indir:ates formation in the temperature range 434-482"C.

INrnonucrroN Electron probe microanalysis(L6vy, 1967; Sillitoe and Clark, lt69) of naturally-occurring,supergene idaite has cast considerabledoub1. on the equation (Frenzel, 1959) of this not uncommon sulfi.de with the phaseof generalformula Cur r,Fe,Se.s,1 (Yund, 1963), which has h,een synthesizedby Merwin and Lombard (1937), Roseboomand Kullerud (1958),and Yund and Kullerud (1966).Idaite has been shown to have the compositionCurFeSa, or Cu3FeS4-,1orrd there is as yet no evidence of solid solution in nature between this and more copper-rich comF,osi- tions.The well-establishedX-ray powder data"(a:3.772 A; c:11.1U A; Yund, 1963) for hexagonal Cus.s,Fe"Se.r, are only with difficulty recon- ciled with thoseof natural idaite (Frenzel,1959, 1963), and L6vy (I\167) has suggestedthat Frenzel'soriginal powder data may be adequately fitted to a stannite-type,tetragonal cell. A differencein crystal struclure between thesephases is supported by the dissimilar reflectivity disper- sion profi.lesof natural idaite (L6vy, 1967; Sillitoe and Clark, 1969) and the synthetic "Cu5FeS6"of Merwin and l-ombard (1937; inLlvy, 1967). Frenzel and Ottemann (1967) have, on the other hand, presented microprobe data for a hypogene,idaite-like mineral from Nukundamu, Fiji, indicating a compositionclose to CusFeSo.Hexagonal cell param- etersof o:3.780*0.001A and c:11.182F0.003 A *e.e determinedfor this sulfide, clearly allying it to the synthetic Cus.s,Fe,So.r,phase. In order to avoid confusion,Sillitoe and Clark (1969) have recommended that the name idaite be retained for the probably tetragonal, and still imperfectly cha.racterizednatural sulfide occurring, as originally de- scribedby Frenzel (1959),in zonesof supergeneoxidation, with the im- plication that the more copper-richphase reported by Frenzeland Ottte-

l This formula, while not entirely satisfactory, rvill be used hereinafter to avoid confusion in reference to published data.

913 9T4 A. II . CLARK

mann is in fact a new mineral. A phase with the CusFeS+composition has yet to be synthesizedunder dry conditionsin the systemCu-Fe-S, although Frenzel (1959) probably formed this mineral in low temperature, hydrothermal experiments approximately simulating the supergene oxidation environment. Conversely,the "idaite" he synthesized(1960) at 400oCin an alkali halide medium may correspondto Cus.s,Fe"So.r,. A secondoccurrence of a mineral with a compositionclose to CusFeSo, and clearly comparable to that synthesizedby Yund and Kullerud (1966) and earlier workers,is reported in this note.

Sur-r'rocsIN THE AucaNqurrcHA SULFURDoposrr The Aucanquilcha sulfur deposit (Lat. 2lol4'5.; Long. 69"24'W.), lying at 6,000-6,100 m a short distancewest of the Chile-Boliviafrontier in AntofagastaProvince, Chile, has long beenknown for the presencein the ore of small amounts of copper sulfides,dominantly covellite (e.g', Ruiz, 1965).The covellite forms small (generally(50 cm), irregularly- shaped massesassociated with native sulfur cementing andesitic tuff- aceous material in a volcanic vent. Volcanism and mineralization are generallyconsidered to be of Quaternary age, but may be appreciably older. The unusual association,covellite*native sulfur, is here undoubtedl,v of hypogeneorigin, and supergeneoxidate minerals are absent. Micro- scopic examination of covellite-rich aggregateshas shown that this sulfide is representedby the optically normal variety, albeit with a rather pale bluish colorationin plane-polarizedIight, assuminga strongpurplish hue under oil immersion.No areasexhibiting "blue-remaining" properties are observed.The covellite yields a normal X-ray powder pattern, including the several weak lines which are absent in patterns of the higher-symmetry blaubleibendermodification (Moh, 1964; Sillitoe and Clark, 1969). The covelliteforms irregular,anastomosing networks of veinlets,fringes and patches, rimming and cementing angular fragments of strongly bleachedandesitic lavas and tuffs. The native sulfur has a generally similar textural role, and exhibits relatively smooth contacts with the covellite. Neither mineral extensivelyveins the other, although locally sulfur has apparently overgrown nodules of covellite; such sulfur is, however, intimately intergrown with further covellite. These minerals appear to have formed over essentiallythe sameperiod in the courseof post-volcanic hydrothermal activity, but the smoothly curving grain boundariesexhibited by the sulfur when in contact with the covellite may indicate that the sulfide in part crystallized in equilibrium with liquid sulfur. A second opaque mineral occurs in associationwith the covellite, TIIE ASSEMBLAGEST]1,F1,'IT-COVELLITE 915 forming occasionalminute to moderate-sized.,highlyelongate laths, u'ith lengthsof up to 1,200pm. This mineral displaysextreme bireflectanc,: in air from brownish-pink, through yellowish pink, to pale gray, and a 'llhe similarly egregious anisotropism, from pale green to gray-green. Iaths exhibit straight extinction,and both bireflectanceand anisotropism are slightly enhancedunder oil immersion,but with no appreciablecolor changes. These striking optical properties are, at. least superficially, similar to to those of supergeneidaite, but the Aucanquilcha mineral lacks, in plane-polarizedlight, the reddish-orangecolors, and, under crossed nicols, the bright, yellowish greenswhich have been found to be chLar- acteristic of idaite from the Copiap6 region of northern Chile (Sillitoe and Clark, 1969). The laths of this mineral are interlaminatedwith covelliteplates where that sulfide forms fringes or combs around andesiticfragments, andlin many zonesthe two minerals extinguish simultaneously.A very small proportion (-5 vol. percent) of the grains of the pinkish-gray mineral have been partially or wholly pseudomorphosedby mesh-like int-er- growths of normal covellite and minute equigranular grains of an iiso- tropic, pyrite-like phase. This alteration is not, however, shown by grainscompletely enclosed by covellite.Examples of grain contact of the covellite, native sulfur, and the idaite-like mineral are quite commorLin the specimensexamined. X-ray powder studies, using a Nonius Guinier-de Wolff quadruple- focussingcamera, and Co-Ka radiation and, as an external standa,rd, silicon,were carried out on a fairly pure aggregateof grainsof the pinkish- gray mineral, removed by drilling from a polished surface. A small amount (probably lessthan 10 vol. percent) of covellite was present.in the sample,but the strongerlines due to this contaminant could be

ANervrrcal De'ra Electron probe microanalysis of this mineral lends further support to its identification as the hexagonalCu5.5,Iie"56.sc phase of Yund and others. The anall'siswas carried out on an A.R.L. AMX microprobe,in co-opera- 916 A. H. CLARK tion with the late Merle Crozierof this department.An optically normal, hypogenebornite (o:10.950+0.001 A) from Mina Manto Esperanza, Copiap6, Chile, and the associatednormal covellite were used as stan- dards. The bornite was found to be compositionallyhomogeneous on a microscopicscale, and was taken to have the stoichiometric composition, Cu5FeSa,a not unreasonableassumption made in earlier analytical studies of copper-ironsulfides (Sillitoe and Clark, 1969),and supported by previous microprobe analyses of hypogene bornites from this area (ibid.). The Aucanquilcha covellite, unlike much normal, supergene covellitein northern Chile, is free from iron (i.e.(0.01 weight percent), and its optical propertiesand unzonednature were acceptedas evidence for stoichiometry(Kullerud, 1965). During the analysis of the Aucanquilcha sulfide, a coarse-grained, supergeneidaite, formed through the oxidation of the Manto Esperanza bornite, was also analyzed, to ensure comparability with the earlier studies cited above. No additional elements (e'g.Se) were detectedin either sulfide or in the native sulfur. The rather small corrections for absorption, "atomic number effect" and characteristic fluorescencewere calculated according to the schemes of Duncomb and Shields(1966), Duncomb and Reed (1967),and Reed (1965), respectively.The results of the microprobe analysis are presented in Table 1, together with comparative data for compositionally contiguous minerals. It will be seenfrom these data that the Aucanquilcha sulfide has a composition falling very close to that of the synthetic ternary phase prepared by Roseboom and Kullerud (1953) and Yund and Kullerud (1966),but differing appreciablyfrom that of supergeneidaite from the Copiap6 region. The calculated composition, which may be expressedas

Tasm 1. Er,ncrnow Pnosr MTcRoaNALYSEsol tna Auc,qxQurlcrrA Sutrror .tNo CoNrrcuous Prresns rw rnn Cus.aFnSo.s-CusFrSr RncroN or' rrln Svsteu Cu-Fn-S

"idaite" idaite Aucanquilcha Cur.sFaSe.s Nukun- CusFeSe Mina Manto CurFeSr suifide damu' Esperanza

Cu 56.94 56.7+0.4 JO. J 56.14 51.1+0.5 50.87 Fe 9.11 9.5+ 0.6 9.8 9.87 15.6+0.6 14.90 s 33.95 33.9+0.5 JJ. / 33.99 33.3+ 0.5 34.23 Total 100.00 100.1 99.8 r00.00 100.0 100.00

s Frenzel and Ottemann (1967) THE ASSEMBLAGI]SI]LFL.R-COVELLITE 917

Cus.zaFeSo.zr,is slightly more iron-rich than Cur.rFeSo.s,but has a Cu: F'e atomic ratio exceedingthe 5: 1 found {or the similar mineral from Nu- kundamu by Frenzeland Ottemann (1967).Quantitative analysisof the fi.ne-grained,intergrown phases apparently resulting from the break- down of this sulfide was not possible,but their identification as covellite and pyrite was confirmed.

Drscussrox The very similar compositions and X-ray powder patterns of the sulfides from Aucanquilcha and Nukun

natural assemblagesb)' Kajiwara (1969) and synlhs5izedat 225"C by Shimazaki (1969), is not representedin the ores r.rnderdiscussion. The stability relations of the disulfidephase are still undefined,and there is as yet no evidencethat soiid solution extendsas far as the Cu-S join under geologicallyreasonable pressures.

AcKNowLEDGEMENTS Field and laboratory studies are financed by the National Research Council ot Canada.

RrlrrcNcns

DuNcorun, P., euo S. J. B. Rnro (1967) The calculation of stopping power and back- scatter effects in electron probe microanalysis. Tube Investments Research Lab., Cantbri.dgeEng., Teclt.Rep.,22lr 24 p. [freely available from Company or authors]. P. K. Snrrros (1966) Efiect of critical excitation potential on the absorption. InT.D McKinley, K.F.J.Heinrich, and D. B. Wittry, The ElectronMicrofrobe. Wiley, New York, 1035 p FruNzrr., G. (1959) Idait und "blaubleibenclerCovellin." NeuesJoltrb. M,ineral. Abh.,93, 87-r32. --- (1960) Uber die Darstellung von CurFeSo Schwaiz Minerat Petrogr Mitt.40,243- 25r. - (1963) On crystal data for idaite Amer. Minerol.48,676-678. J. OrmueNN (1967) Eine Sulfidparagenese mit kuplerhaltigem Zonarpyrit von Nukundamr/Fijt Miner. De.posita,l, 307-316. K.t;r'"vana, Y. (1969) Fukuchilite, Cu:FeSs,a nev'mineral from the Hanawa mine, Akita Prefecture, Japan. Mi,neral. J. lTohyol, S, 399-416. Kurtrnuo, G. (1965) Covellite stability relations in the Cu-S system. Freibug. Forschungst. c186, 145-160. Lavv, C. (1967) Contribution d la min6ralogia des sulfures du cuivre du type Cu:XSr. Pr. Rep. Mem. Bur Rech.Geol. Minieres Bull.54, 178 p. Mnnwrw, H. E. eNo R. H. LoMsenn (1937)The system, Cu-Fe-9. Econ. Geo|.32,203-284. Mor, G. H. (1964) Phase relations at low temperatures: blaubleibender covellite. Carnegie Inst. Wash. Year 800k,63,208-209. Rnro, S. J. B. (1965) Characteristic fluorescencecorrections in electron probe microanalysis. Brit. J. Appl. Phys. 16,913-926. Rosreoou, E. H., Jr , aNo G. Kulr,nnuo (1958) The solidus in the system Cu Fe-S between 400'C and 800'C. Carnegie I nst W osh. Y earB ook,57, 222-227. Rurz, C. Furr,Bn (1965) Geol,oglay Yaci,m'ientosMetohJeros deChile.Instituto de Invest. Geol., Santiago de Chile, 305 p. Sxruezlrt, H. (1969) Synthesis of a copper-iron disulfide phase (abstr.) Can.Mi,nual. lO, pt. t,146 Stllrron, R. H., eNo N. H. Cr.enr (1969) Copper- and copper-iron sulfides as the initial products of supergene oxidation, Copiap6 mining district, Northern Chile. Amer. Mineral.54, 168+1710. YuNo, R. A (1963) Crystal data for synthetic Cuss,Fe,So;, (idaite). Amer. Mineral.48, 6?2-676. - AND G. Kurrnnuo (1966) Thermal stability of assemblagesin the Cu-Fe-S system J. P etrol.ogy,7, 45+-488.

Manuscr'ipt receir.:ed.,December 7,1969; acceptd. Jor publ,i.cation,January 5, 1970.