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Walthierite, Ba".Rno.Sal3(SO4)2(OH)U, and Huangite, Ca"

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Walthierite, Ba American Mineralogist, Volume 77, pages 1275-1284, 1992 Walthierite, Ba".rno.sAl3(SO4)2(OH)u,and huangite,Ca".rn0.sAl3(SO4)r(OH)u, two new minerals of the alunite group from the Coquimboregion, Chile Gn.rrNcLr, DoN.ll,o R. Pr.q,con,Enrc J. Essrnn Department of Geological Sciences,University of Michigan, Ann Arbor, Michigan 48109-1063, U.S.A. Dlvro R. BnosN,c.HA.I.{ LAC Minerals (USA), Inc., 8925 EastNichols Avenue,Englewood, Colorado 80112-3410, U.S.A. Rrcnano E. BuNn l76l EastDeer Hollow Loop, Oro Valley,Arizona 85737,U.S.A. Arsrru.cr Walthierite and huangite, two new members of the alunite group, were found in the Tambo mining district and the El Indio gold, silver, and copper deposit, Coquimbo region, Chile, respectively.Walthierite, Bao,!o ,Al3(SOo)r(OH)u,is associatedwith alunite,jarosite, baite, quartz, and pyrite in veins. Huangite, Caortro rAlr(SOo)r(OH)6, coexists with kaolin- ite, pyrite, and woodhouseitein altered wall rocks. The new alunite group minerals have spacegroup R3m, Z: 6, with lattice parameters4 : 6.992(4)A,, c : 34.443(8)A, D*. : 3.02 g/cm3for walthierite, and a: 6.983(5)A, c : 33.517(9)A, D-,.: 2.80 g/cm3 for huangite.The strongestlines in the X-ray powder diffraction patterns are (d, I, hkl): 5.73, (50),(006);3.49,(55),(l l0); 2.98,(100),(ll6); 2.283,(80),(1,0,14);1.909,(70),(0,0,18) for walthierite,and 4.91,(75),(014);2.97,(100),(116); 2.231,(51),(l,0,la); 1.899,(a3),(306); 1.375,(40),(3,1,14)for huangite.Both mineralsshow superlatticereflections with c that is double that of alunite, resulting from the ordering of cations and vacancieson l2-fold coordinated M sites. Both minerals are transparent,white to liglt yellowish in color, and have perfect {00 I } cleavage.Optically, they are uniaxial positive with negativeelongation. The indicesof refractionare @: 1.588(2),e : 1.604(2)for walthierite.Minamiite is now consideredto be a Na-dominant and Ca-bearingmember, rather than a Ca-dominant end- member of the alunite group; huangite is now consideredto be the Ca end-member. Wide miscibility gapsmay exist betweenwalthierite and natroalunite and betweenhuangite and alunite. Extensive solid solution probably occursbetween walthierite and alunite, huangite and natroalunite, and huangite and woodhouseite.The nature ofoccurrence and stability relations for walthierite and huangite indicate that they, like other alunite group minerals, are stable only under acid sulfate hydrothermal conditions. IxrnonucrroN er hand, compounds Mo5tro5A13(SO,)r(OH)6with M : Ca'?*(Ossaka et al., 1987),Pb'*, Srz*,or Ba2*(Okada et The general formula for minerals of the alunite group al., I 987) synthesizedunder hydrothermal conditions have is MRr(SO)r(OH)u, where the l2-fold-coordinared M site M2*-vacancyordering, although powder X-ray diffraction may be occupiedby one- or two-valent ions such as Na*, (XRD) data of synthetic Sro,tro,Al.(SOo),(OH)uand K*, H3O*, NH/, Ca2*,Sr2*, Pb2+, or Ba2*,and the octa- BaortrorAlr(SOo)r(OH)6were not obtained.Although syn- hedrally coordinated R site is usually occupied princi- theses of many compounds with the formula pally by Al3* or Fe3*. The alunite group consists of ap- M0 5tr05AI3(SOJr(OH)6 have been reported, no naturally proximately 20 trigonal minerals with spacegroup R3m, occurring Ba or Ca end-members have been described. having approximate lattice parameters4 : 7 A and c : In this study, Ba and Ca end-membersof the serieswith 17 A. However, minerals in the alunite group with di- t6lAl3+are characterized.The Ba end-member has been valent cations on M sites, such as plumbojarosite (Szy- named walthierite in recognition of the late Thomas N. mariski, 1985)and minamiite (Ossakaet al., 1982),have Walthier, who played a significant role in the exploration a superlattice with c that is double that of alunite. Dou- of the El Indio deposit and the Tambo mining district, bling is causedby ordering of Pb2* and vacanciesin M Coquimbo region, Chile. The Ca end-member has been sites in plumbojarosite and by partial ordering of vacan- named huangite in honor of Yunhui Huang, in part for cies and some Ca2* substituting for Na* in minamiite, recognition of her contributions to the mineralogical and Nao.uCaorrKo rolo 27A13(SO4)r(OH)., where E represents petrological studies of a contact metamorphic Be-deposit vacancieson the l2-fold-coordinated M site. On the oth- in Hsianghualing,south-central China. Becausethe name 0003404X/ 92 / | | | 2-r 275SO2.O0 t27 5 1276 LI ET AL.: WALTHIERITE AND HUANGITE Fig. l. Walthierite(Wa) associated with alunite(Al), barite Fig.2. Subhedraland euhedralwalthierite enclosed within (Ba),jarosite (Ja), and pyrite (Py),with the walthieritepartially alunite.There are elongated walthierite and alunite grains in the replacedby alunite.SEM BSE image. lower portion of the figure,with somenarrow wavy strips of walthieritewithin alunite.BSE image. minamiite has been used for a Ca-bearing alunite group mineral, it has also been necessaryto determine that the in wall rocks contemporaneouslywith the deposition of name doesnot representend-member material. Both new vein barite and that alunite formation utilized original K minerals. their names. and the status of minamiite have and Al with introduced sulfates.Walthierite is intimately been approved by the Commission on New Minerals and associatedwith alunite, barite, quartz, pyrite, and jarosite Mineral Names (CNMMN), International Mineralogical within the vein (Fig. l). The alunite + barite + quaftz Association flMA). Type materials for walthierite and assemblagein this district is considered to be related to huangite are depositedin the Smithsonian Institution un- Au mineralization(Walthier et al., 1985). der cataloguenumbers NMNH 170208 and NMNH In thin section,walthierite is colorless,granular, or tab- 170209,respectively. ular in habit. It occurs as subhedral to anhedral crystals ranging from 5 to 100 pm in length in individual grains and as aggregates.As revealed by backscatteredelectron OccunnnNcns images (BSE),irregular and angular walthierite is usually Walthierite was found in the Reina vein in the Tambo surrounded and replaced by alunite, whereas euhedral mining district, which is approximately 7 km southeast walthierite is occasionallyobserved overgrown by alunite of the El Indio gold, silver, and copper deposit, Coquim- (Figs. 1, 2). Zonesof intermediate composition occur be- bo region, Chile. Two major hydrothermal assemblages tween walthierite and alunite, as observed by SEM. In fill open spacesin a fault at Reina. The earlier consists some areas,elongated walthierite and alunite grains occur dominantly of barite, with subordinate pyrite, galena, in parallel groups, with some narrow wavy strips of wal- electrum, and tennantite, whereas the latter comprises thierite within alunite (Fig. 2). Crackedgrains of walthier- mostly alunite, with minor amounts of hematite,jarosite, ite are common, with the spacebetween displaced frag- scorodite, quartz, and Au. Fluid inclusion analysesindi- ments having been filled by alunite. cate that barite and alunite formed from solutions with Some walthierite aggregatesare observedclosely asso- salinities of less than I l,laNaCl equivalent at tempera- ciated with and replacing barite. The size of barite grains tures of 175-27 5 'C (B. Ahler, personalcommunication, varies from micrometers to millimeters. Most barite crys- 1988).Wall rocks cut by the fault are pyroclasticrhyolites tals have a rounded or irregular shape,and some are hon- and a quartz monzonite porphyry that have undergone eycomblike, showing a relict texture produced by replace- intense leaching, with preservation only of quartz phe- ment by walthierite or alunite. Some barite grains also nocrysts. Textural relations indicate that alunite formed show internal fractures. Textural relations suggestthat LI ET AL.: WALTHIERITE AND HUANGITE 1277 Fig. 3. A largehuangite crystal (Hu) with a euhedralcore Fig. 4. Subhedralhuangite crystal with a core of woodhouse- consistingofwoodhouseite, svanbergite, and hinsdalite solid so- ite (Wo).The very brightcrystals are pyrite (Py). BSE image. lutions.The fine-grainedmatrix is huangiteand kaolinite(Ka). BSEimage. are also observed,but without exception they show a tur- barite formed earliest; the reaction of barite with fluids bid core, with the clear huangite rims being only 3-8 pm gave rise to walthierite, which was then fragmented and thick. The turbid cores and rims of huangite grains vary deformed. Finally, a K-rich hydrothermal fluid was in- in shape from euhedral to anhedral (Figs. 3, 4). In some troduced, resulting in the formation of alunite, in part instances, the turbid core materials have been cracked through the replacementof walthierite. and individual fragments displaced. They have been Huangite was found in the El Indio deposit in the Cam- overgrown or partially replaced by huangite, with resul- pana B vein. This area has been affectedby complex hy- tant well-defined zoning. The turbid materials were de- drothermal solutions in the late stagesof development of termined by qualitative energy dispersive spectrometry an acid volcanic caldera during the Tertiary. The Cam- analyses (EDS) and quantitative wavelength dispersive pana vein cuts rhyolitic tuffs and is filled with coarse spectrometryanalyses (WDS) to be solid solutions of the euhedralenargite, pyrite, and alunite. The sulfidesare not woodhouseitesubgroup. The turbid coresmay be divided contemporaneouswith the alunite nor are they in isotopic into four compositional zonesby contrast in BSE images equilibrium (Jannaset
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