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The Canadian Mineralogist THE CANADIAN MINERALOGIST Journal of the MineralogicalAssociation of Canada Volume 25 JI.JNE 1987 Pafi 2 Canadian Mineralogist Vol.25, pp. 201-2ll (1987) WOODHOUSEITEAND SVANBERGITEIN HYDROTHERMALORE DEPOSITS: PRODUCTSOF APATITE DESTRUCTIONDURING ADVANCED ARGILLIGALTERATION ROGER E. STOFFREGEN* axo CHARLES N. ALPERS*'{' Departmmt of Geology and Geophysics, University of Colifurnia, Berkeley, California 94720, U.S.A. ABSTRACT SOMMAIRE Woodhouseite and svaubergite,previously documented Woodhous6ite et svanbergite, identifi6es d ce jour dans from roughly two dozen localities, have been found with environ deux douzaines d'endroits, ont 6td trouvdes dans advanced argillic alteration in three hydrothermal ore trois gits min€raux hydrothermaux, caractdrisdspar une deposits. These aluminum phosphate-sllfate (APS) alt6ration argilac€eavanc6e. Ces deux espbces,de compo- minerals are isostructural with alunite (R3m), with the sition sulfate-phogphate d'aluminium (APS), sont isoty- generalized formula RAl3(POdl +r(SO/1-r(OH)6-r. pes de I'alunite (R3n). Elles rdpondent i la formule g6n6- = (HzO)r, where R is Ca or Sr, and x is less than 0.5. At raliseeiRAl3@odr *lsodt-loH)e-r.(llzo)o avecR ca Summitville, Colorado, an epithermal gold*opper deposit, ou Sr et x < 0.5. A Summiwille (Colorado), la svanbergite svanbergiteoccurs with hypogenekaolinite and alunite in setrouve dans un glte cuivre-or €pithermal, of elle sepr6- the upper portions of the deposit, and woodhouseite is setrte, avec kaolinite et alunite hypog0nes, dans la partie observedat deeperlevels, where pyrophyllite is locally abun- supdrieuredu grsement,tandis que la woodhous€itese ren- dant. In the porphyry-copper deposit at La Granja @eru), contre I des niveaux inf6rieurs, oir la pyrophyllite est loca- woodhouseiteoccurs witl pyrophyllite and appearsto have lement abondante. Dans le gite de La Granja (Pdrou), la replacedapatite. The porphyry-copper depositat La Escon- woodhousdite se pr6sente avec de la pyrophyllite dans le dida (Chile) contains woodhouseite-svanbergitesolid solu- porphyre cupriflre, of elle aurail remplac6 I'apatile. Le tions, some hypogene, others supergene,as judged from porphyre cuprifBre de La Escondida (Chili) contient des textual criteria. Alunite specimensfrom Summitville, La solutions solideswoodhous€ite-svanbergite, les uneshypo- Escondida, and severalother localities investigated in this g0nes,les autres supergOnes,i en juger d'aprbs les critbres study contain someAPS component, lvith up to 2.41 wt. q0 texturaux, Des spdcimens d'alunite de Summitville, La P2O5and l.l2wt.tlo SrO, reflectingtie coupledsubstitu- Escondida, et plusieursautres gltes 6tudi€s,contiennent un tion K+ + SO42-= (Ca,Sr)z+ + POo3-io gt. t*t r*"- constituant APS, dont la teneur en P2O5atteint2, lclo en ture. The APS phasesare consideredto form by replace- poids, avec l.l29o en poids de SrO. Ceschiffres reflEtent ment of apatite in the acidic, sulfate-rich environment ttrat la substitution accoupl6e K+ * SOa2-= $12+ 4 pQo3- characterizesadvauccd argillic alteration. Their occurrence dans la structure cristalline de l'alunite. Les phasesAPS probably has been overlooked in loany areasshowing such se seraient form€es par remplacement de l'apatite dans le alteration of apatite-bearing host rocks. milieu acide et riche en sulfate, caract6ristique d'une alt6- ration argilac€eavanc€e. Ces phrases seraient pass6es inap- Keywords: svanbogite, woodhouseite,alteration (advanced perguesdans plusieurs examples d'une telle alteration de argillic), alunite, apatite, ore deposits, roches h6tes porteuses d'apatite. xPresedt address: Depafiment of Geological Sciences, Southern Methodist Urlivssity, Dallas, Texas 75275, (Traduit par la Rddaction) U.S.A. *lPresent adrlress:Departrnent of GeologicalSciences, 1006 C.C. Little Building, University of Michigan, Ann Arbor, Mots-clds: svanbergite,woodhousdite, alt6ration argilac€e Mchigan 48109-1063,U.S.A. avancde, alunite, apatite, gftes mindraux. 201 202 TI{E CANADIAN MINERALOGIST INTRoDUCTIoN and X i-s either sulfur, phosphorus, or arsenic (Botinelly 1970. Perhapsthe most common of these The behavior of phosphate minerals during minerals is alunite KAl3 (SOr2(OH)u, which occurs hydrothermal alteration has receivedlittle attention mainly as a vein mineral or alteration product of feld- in the literature. This is in contrast to numerous spars and micas in sulfur-rich, highly oxidized en- studieson phosphateminerals in the weatheringcycle vironments (Hemley et al. 1969). (e.g., Nriagu 1976,Vieillard et al. 1979,de Lima & Substitution of one mole of POa3-for SO42-in Reymio 1983),and on the complex mineralogy of alunite createsan excessnegative charge, which can phosphate-richpegmatites (e.9., Moore 1973).Apa- be compensatedby substitution of an.equimolar tite is the most common phosphate mineral in igne- amount of a divalent cation on the R position. Our ous rocks, where it generally occrus as an accessory findings suggesta limited degreeof this coupled sub- phase.Apatite also ocbursas a trace phasein the zone stitution of potassic alteration developedin porphyry-copper deposits(e.9., Gustafson & Hunt 1975, Reynolds 1985), and it can occur with sericite in vein miner- SOr2-+ R+ = Pgo:- .u 4z+ (l) alization (e.9., Kelly & Rye 1979).However, apatite has not beenreported in the "advanced argillic" al- teration zone, generallycharacterized by alunite and in samplesof natural alunite formed at temperatures aluminosilicate minerals (Meyer & Hemley 1967). below 300oC, although at higher temperaturesa This suggests that apatite may be dissolved or more extensive solid-solution may exist. replacedby another phosphatemineral in the acid- In the APS minerals woodhouseite aad svanber- ic, sulfur-rich environmentrequired for this type of gite, half of the SOo2-groups in the alunite struc- alteration. ture are replaced by POa3-,and all of the monova- lent cations are replaced by the divalent cations We discuss here the occurrence of such a Ca2+and Sr2*, respectively.This coupledsubstitu- mineral, with the generalized chemical formula tion has little effect on crystal structure, as these RAl3(P04)r+"(S04)r-x(OH)e-".(HzO),, in the minerals have the same symmetry as'alunite (space advanced argillic zones of three hydrothermal ore group R3m) and only slightly modified a and c deposits.Specifically, we considerwoodhouseite and parameters,as noted by Pabst (1947),Kato (197L, svanbergite, the Ca and Sr end-membersfor which 1977)and Kato & Miura (1977). .lr= 0, and solid solutions betweenthese two minerals In addition to variation in ttre amount of Sr and and members of the crandallite-goyazite series,for Ca in the R site, we haveobserved substantial devi- which r= 1. Formulae for theseand other alumi- ation from a 1:l ratio of sulfateto phosphatein the num phosphate-sulfatesare listed in Table l. Xsite. An increasein phosphateabove one mole per Woodhouseite, svanbergite,and the other alumi- formula unit at the expenseof sulfate requires fur- num phosphate-sulfate(APS) minffals listed in ther compensationof charges,which can be achieved Table I belong to an isostructural group of minerals either by the addition of a trivalent cation, such as that have the generalizedformula R 43(XOJz(O}I)0, cerium, or by protonation of someof tlte hydroxyl where R is a monovalent, divalent, or trivalent ca- groups in the structure. Where phosphatecompletely tion, A is a trivalent cation, generally Al3+ or Fd+, replacessulfate, the end membersgoyazite, crandal- lite and florencite are formed (formulae listed in Table l). In this communication we usethe abbrevi- TABLE 1. ALUI{TNUI,IPHOSPHATE (SULFATE) ation "APS" to designatesolid solutions between END-I.If,I'tsER COMPOSITIONS all end-membercompositions listed in Table l. OccunnsNcBs Svanber.glie Sr At3 (P04) (s04) (0H)5 There'are approximately two dozen published tloodhouselte Ca Al3 (P04) (s04) (0H)6 localities for svanbergite and woodhouseite (Table 2). Most of these occurrenc€sare in intermediate- (Po4) (so4) (0H)6 Htn6daLl,te Pb Ar3 grade aluminous metamorphicrocks, in which the Coyazlte sr A13 (P04)2 (0H)5.H20 APS minerals are associatedwith quartz, pyrophyl- lite, andalusite, alunite, and other phosphate CrandaLLtbo ca Al-3 (P04)2 (0H)5.H20 minerals such as lazulite and augelite (e.9., Ygberg Gorcelxlte Ba 413 (P04)2 (0u)5.H20 1945,Switzer 1949,Wise 1975).The APS minerals also occur in bauxite (Shalit 1965,Bulgakova 1973), Florenclte Ce A13 (P04)2(0H)6 sedimentary phosphate deposits (Jiang el al. 1984), kaolinite clay$tone$ (Goldbery 1978) and quartz- WOODHOUSEITE AND SVANBERGITE IN ORE DEPOSITS 203 apatite veins (Morton 1961),though thesesettings generally occur are mineralogically similar to the are geologically unrelated to the hydrothermal advancedargillic assemblage(Meyer & Hemley 1967) environment of interest in our study. well developed in some porphyry-copper deposits The aluminum-rich rocks in which APS minerals @eane& Titley 1981),and also associatedwith some epithermal gold deposits and polymetallic vein sys- tems. This alteration assemblageis characterizedby extensive hydrolytic leaching of alkali cations and may contain alunite, kaolinite and diasporein lower- temperatureoccurrences, or pyrophyllite, andalusite a, mffi-TmEmTmE (mffi) ocfl88ilcBs and, more rarely, corundum from higher-tempera- 1. @pio! ntn€, rd, sv qtr, ed, pf], ala, L@n (1937) (e.9., he 6h!y, rl, n@eto6 pnos- Itso (19?5) ture occurrencs Gustafson & Hunt 195). The phale olnaals mineralogical and chemical similarity between the 2. Clltreut1, !9 qtz, &d, prl,
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