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Stannoidite-Bearing Tin Ore: Mineralogy, Texture And

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Stannoidite-Bearing Tin Ore: Mineralogy, Texture And Canadion Mineralogist Vol. 25, pp,229-236 (1987) STANNOIDITE-BEARINGTIN ORE: MINERALOGY,TEXTURE AND PHYSICOCHEMICALENVIRONMENT OF FORMATION MASAAKI SHMIZU Department of Petrologt and Mineral Deposits, University Mt6eum, University of Tokyo, Tokyo II3, Japan NAOTATSU SHIKAZONO GeologicalInstitute, Facahyof Science,University of Tokyo, Tokyo 113,Jopan (Ramdohr ABSTRACT had been called hexastannite 194, 19ffi) and yellow stannite [-tvy 1967).The chemical for- mula Cur(Fe,Zn)2SnSg had been originally Stannoidite-bearingtin ores fron Japanesevein-type as- tin (Kato depositshave been studied. The stannoidite commonly co- signed 1969)1 however, the formula existswitl chalcopyrite, bornite and sphalerite; the atomic Cur@e,Zn)rSn2st2 was later proposed (Springer Fe/Zn ratio of the sphalerite is low, in the range 0.@2 - 1972,Boorman&Abbott 1967,Petruk 193). Mdss- 0.015. Basedon iron content of sphalerite and the mineral bauer, chemicalanalysis and crystal-structurestudies assemblage,the probable range in sulfur fugacity and tem- confirm the chemical formula as Cu{Fel*@d+, perature for the stannoidite-bearing tin ore is estimatedto za2+)Snt+So (Yamanaka& Kato 1976,fudoh & be lf - - 1fr16atm. and 2@ 300.C. This estima.tedranee Takeuchi 1976).Some analytical data on stannoidite is different from that for the srannite-bearingtin or" oi- have been obtained (e.g., Petruk 1973, Kissin & mated by Shinizu & Shikazono (1985). Tungsten-free tin ore deposits seemto have formed at a higher fugacity of Owens 1979), but details of the natural ocsurrence sulfur or lowo temperaturethan tungsten-beaxingdeposits of the nrineral and its physicochemicalenvironment of rin. of formation have not been clarified. In this paper, the compositional relations of coex- Keywords: stannoidite, sphalerite, tennantit€, tetrahedrite, isting stannoidite, sphalerite and tennantite- stannite, Japan, vein-typetin deposits,Fe-Zn partition- tetrahedrite-seriesminerals are reported. Based on ing, sqlfur fugacity, temperature. thesedala, the sulfur fugacity of stannoidite-bearing tin ore is estimated. Considering the complementary Sonauarnn work on stannite-bearingtin ores from Japaneseore deposits(Shimizu & Shikazono 1985),a comparison On a 6tudi6le minerai d'6tain A $annoidite desgisements betweenenvironmental conditions of thesetwo tlpes d'&ain en veines du Japon. La stannoidite coexiste cou- of tin sulfides is made. ramment avec chalcopyrite, bornite et sphaldrite, Le rap- port atomique Fe/Zn de la sphaldrite est bas, entre 0.002 et 0.015. Vu la teneur en fer de la sphaldrite et l,associa- Satvrpr.aPnnpenanron enn tion desmin6raux, on propose une fugacitd de soufre pour ANALnTcAL PnocsouRE ce minerai entre 10-6 et 1016 atmosphereset une temp6- rature de formation entre 2@ et 3@oC. Ces valeurs diffb- The samples used for this study belong to the rent desr6sultats obtenus par ghimizu s1ghikazono (1985) UniveirsityMuseum of the University of Tokyo; some pour le minerai d'6tain e stannite. Les gisements d'6tain were collected by the present authors. Locations of danslesquels letung$eue est abs€ntindiqueraielrt une fuga- tle samples studied are shown in Figure 1. citd de soufre plus dlevdeou une temperafire plus basse que les gisements d'&ain i tungstOne. The chemical composition of coexisting stannoi- dite, sphalerite and tennantite-teFahedrite-series (Iraduit par la Rddaction) minerals was determinedusing a JEOL 733 electron- microprobe analyzerat the OceanResearch Institute Mots-clds: stantroidite, sphaldrite, tennantite, tetraedrite, of the University of Tokyo. The acceleratingvoltage stannite, Japon, gisementsd'6tain en veines, r6parti- used was 25 kV, and the following standards were tion de Fe et de Zn, fugacit€ de soufre, temp6rature. usedfor analysis:natural chalcopyrite(Cu), synthetic Zno.oFeo.+S(Zn, Fe, S), synthetic CdS (Cd), syn- thetic MnS (Mn), synthetic SnS (Sn), synthetic INr,nooucloN Ag3As$ (Ag, As) and synthetic Cu1sFe1.sZne., Sb4SE(Sb). The characteristic X-ray intensities for Stannoidite is a common tin-bearing mineral in eachpoint were mea$uredtwice for a fixed interval Japinese tin ore deposits, and was frst described of five seconds.The averagedvalues were corrected from the Konjo deposit by Kato (1969). The mineral for dead time and background. Quantitative correc- 229 Downloaded from http://pubs.geoscienceworld.org/canmin/article-pdf/25/2/229/3445999/229.pdf by guest on 30 September 2021 TIIE CANADIAN MINERALOGIST I f tions for atomic number, absdrption and fluores- i C'- cence effects were also perfopmed based on the lli method proposedby Sweatmah& Long (1969). TEXTURES AND ASSEMBLAGES oF STANNOI TlN Onns Two characteristictextures stannoidite-bearing ores are observedunder the (Figs.2,3). Where relict cassiterite such as observedin the ores from the Konjo and deposits,stau- noidite usually includesstanni and stannite in turn includesaggregates of ercins (Fie.2). This texture, which was pointed out by Kato (1969),sug- geststhe following sequenceof tin minerals: cassiterite (early) stannite-stannoi- dite (late). On the other hand, where occursat the margin of somestannoidite suchas observed in the samplesfrom the Tada, idani. Omodani Fro. l. Map of Japan, showing samplelocations' and Fukoku deposits, showsa replace- ment or reaction texture (Fig. ), as mentionedby Lee et sl. (1974). In this case, is invariably absent. This texture suggests following sequence of precipitation: stannoidite wsonite. The sequence of of tin minerals inferred from the two types textures mentioned aboveis consideredto be e*stannite-stan- noidite-mawsonite. This i a trend of increas- ing of metaVsulfur, Fd* and Cu/Sn ratios in the tin sulfides. The mineral assemblages are presentedin Table l. The common opaque that coexist with stannoiditeare bornite, sphalerite, tennantite-tetrahedrite-series and roquesite. This assembl4gegenerally not include stannite. Stannoidite is rarely with galena, wit- tichenite, arsenopyrite and It is notewor- thy that stannoidite does not coexist with pyrite, except in the tin ores from the deposit. Thes'e ores contain stannite together stannoidite. On the other hand, stannite coexistswith pyrite. From the textures observed, idite, bornite, chalcopyrite, sphalerite and te! seriesminerals seemto have foj nearly contem- poraneously. CHEMICAL CosxsrNc Sr ^q,NnTENNANTTTE- MNERAT.S Scanning patterns and analytical data 0- 100um obtained by analyzerreveal that most stannoidite grains compositionally Frc. 2. Photomicrograph of stannoidite-stannite- cassiterite-bearingsample from the Konjo ore deposit' homogeneous.Reprqentative composruons Okayama Prefecture, Japan (Sd stannoidite' St stan- and atomic proportions of mineral coexisting nite, Cp chalcopyrite, Cas cassiterite). with sphalerite and te-series Downloaded from http://pubs.geoscienceworld.org/canmin/article-pdf/25/2/229/3445999/229.pdf by guest on 30 September 2021 STANNOIDITE-BEARING TIN ORE 231 minerals are given in Table 2. It seemsclear from the analytical data on stannoidite that this mineral is represented by the stoichiometry CqFe!*@d+,Zn)Sn2S12, which is in agreement with the results by Yamanaka & Kato (1976) and Kudoh & Takeuchi (197A. There is a wide range in extent of Fe and Zn sub- stitution in stannoidite (DFe/Zn between 2.03 and 14.4), as summarizedin Table 3. The stannoidite from tlre Tada deposit is the richest in Zn (5,2AwtJ/o Zn,9.09 wt.rlo Fe) and has the approximate formula CurFgZnSn2Sp; that from the Konjo deposit is the richestin Fe (11.90wt.Vo Fe, 1.69fi.90 Zn) and has the.formula CurFq(Fee.rrZns.1e)Sn2Sp.From the FeP*/Znzt ratio of stannoidite,a continuoussolid- solution is inferred to exist betweenCusFqZnSn2Sp and CurFerFeSn2Sl2,as already pointed out by Petruk (1973). Iron and manganesecontents of sphaleritecoex- isting with stannoiditeare in the rangefrom 0.lZ to 1.93wt.9o, and from 0.02to 0.16wt.Vo, respectively (Table 2). The cadmium content of sphalerite, from 0.17 to 0.25 wt,0/0,is generallyhigher than iron and manganese.TheFe/Zn ratio of sphaleritecoexist- ing with stanniteor stannoiditeis listed in Table 4. Note that the iron content of sphalerite is very low, comparedwith that of sphaleritecoexisting with stan- nite (Shiml'u & Shikazono 1985). Chemical analytical data on tennantite- tetrahedrite-seliesminelals indicate that the As con- tent is generallyhigher than the Sb conten! thus they can be called tennantite, but someare rich in Sb and 0 100um Ag, and can be called Ag-bearing tetrahedrite. - Representative chemical compositions of coexist- Frc. 3. Photomicrograph of stannoidite-mawsonite- ing stannoidite and sphalerite (Table 2) and ranges bornite-bearing sample from the Tada ore deposit, in the atomic Fe+ /Zrf+ ratio of coexistingstannoi- Hyogo Prefecture, Japan (Sd stannoidite, Mw dite, sphalerite and tennantite-tetrahedrite-series mawsonite, Bn bornite, Cp chalcopyrite, Gn galena,Ag minerals from Japanesevein-type tin deposits are Ag-mineral, gang. gangue minspal). summarized in Table 5 and Figure 4l The atomic Fe* /h2+ rado of stannoidite was calculated from the EFe/Zn ratio obtained by electron-microprobe in which (FeS).' denotes the FeS component in ana)yzerand is based on the r.1u1ie6hip: (F&* / sphalerite. The equilibrium constant for reaction (1) tA{(EFe/20-2}. Zil2+)stmoraite= The Fe+ /Zn2+ is expressed as ratio of stannoidite is positively correlated q/ith that of sphalerite and tennantite-tetrahedrite-series minerals (Fig. a). K = df,.s./(S) (2) The freeenergy of reaction(1) is expressedas DNcussroN As describedabove, stannoidite commonly coex-
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