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Stannite from the Otoge Kaolin-Pyrophyllite Deposits, Yamagata Prefecture, NE Japan and Its Genetical Significance As Well As Ca

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Stannite from the Otoge Kaolin-Pyrophyllite Deposits, Yamagata Prefecture, NE Japan and Its Genetical Significance As Well As Ca RESOURCE GEOLOGY, 44(6), 439•`444, 1994 Stannite from the Otoge Kaolin-Pyrophyllite Deposits, Yamagata Prefecture, NE Japan and Its Genetical Significance Makoto WATANABE*, Ken-ichi HOSHINO*, KO KO MYINT*, Kazunori MIYAZAKI* and Hirotugu NISHIDO** Abstract: Stannite was found in the Otoge kaolin-pyrophyllite deposits of ca. 4Ma(K-Ar), which are localized in rhyolitic pyroclastic rocks of middle Miocene time. Stannite occurs exclusively in pyrite-rich silicified portion within the sericite zone. Under the microscope, stannite, strongly anisotropic, shows a close association with sphalerite and pyrite. Microprobe analysis of stannite reveal that it is of Zn-rich variety with Fe/Fe+Zn atomic ratios of 0.49 to 0.71. It is noted that the atomic contents of the (Fe+Zn) site exceed 1.000 by up to 30% for stannite which contains more than 6 wt. % of Zn, suggesting a possibility of non-stoichiometry. The temperatures estimated based on the Fe and Zn partition are 300•‹to 340•‹C with Log fs2 of ca. -10 to -8, approximately corresponding to the corrected filling temperatures of fluid inclusions in quartz nearby stan- nite. the Yatani and Otoge deposits. The resultant ages Introduction are: 3.25•}0.26 to 3.6•}0.27 Ma on adularia; As well as cassiterite, stannite, Cu2(Fe, 5.16•}1.95 Ma on sericitized rock, respectively. Zn)SnS4 , is a mineral of rather ubiquitous occur- During the course of our investigation of the rence especially in skarn deposits and plutonic kaolin-pyrophyllite deposits at the Otoge mine, veins, which are genetically related to granitic we have found stannite. As far as we know, stan- intrusives of ilmenite series(e.g., SOEDA and nite has never been known from ore deposits of. WATANABE, 1982; SHIMIZU and SHIKAZONO, this type. We will report its mineralogical charac- 1985; SOEDAet at., 1988; WATANABEet al., 1988; teristics and discuss the genesis. WATANABEand HOSHINO, 1991). Geologic Setting Stannite occurs also in polymetallic veins of subvolcanic affinity such as those of the Ikuno and The Otoge mine area (Fig. 1), located near the Akenobe deposits, Japan and the Oruro deposits, boundary between Yamagata and Fukushima Pre- Bolivia. In the paper dealing with the geochemical envi- ronments of the Neogene epithermal Au-Ag-Pb- Zn veins at the Yatani mine, located about 3 km northeast of the Otoge mine, HATTORI(1975) de- scribed only briefly an occurrence of stannite in the Kanizawa Au-Ag vein. This is likely a rare case in such epithermal environments without an associated granitic stock. SHIKAZONO(1985) measured the K-Ar ages for Received on December 10, 1993, accepted on March 17, 1994 *Department of Earth and Planetary Sciences , Hiroshima University, Higashi-Hiroshima 724, Japan **Hiruzen Research Institute, Okayama University of Science, Okayama 682-02, Japan Keywords: Otoge kaolin-pyrophyllite deposit, 4Ma(K-Ar age), Zn-rich stannite, Genesis, NE Japan Fig. 1 Location map showing the Otoge mine. 439 440 M. WATANABE, K HOSHINO•¬ KO KO MYINT, K. MIYALAKI and H. NISHIDO RESOURCE GEOLOGY: Fig. 2 Ore minerals from the Otoge mine. a) Microphotograph showing a mode of occurrence of stannite. Reflected light. Scale bar indicates 100 ƒÊm in length. b) Same as a), partially crossed nicols. c) Microphotograph showing a mode of occurrence of stannite. Reflected light. Scale bar indicates 100 ƒÊm in length. d) EPMA compositional image of arsenopyrite showing a zonal structure. Mineral abbreviation are: Stn=stannite; Sph=sphalerite; Py=pyrite; Cp=chalcopyrite; Apy=arsenopyrite. fectures in northeast Japan, and forming part of prep.). Stannite occurs exclusively in the pyrite- the Green Tuff region, a major tectonic division rich silicified part of the sericite zone. and a metallogenic province of the Neogene Ter- K-Ar age determination has been made on the tiary in Inner Zone of Japan, consists mainly of sericite-rich fraction in the sericite zone, using a rhyolitic pyroclastic rocks, named the Otoge For- 30 cm radius sector-type mass spectrometer with a mation (TANIGUCHI,1969). This formation, being single collector system installed at the Okayama correlatable with the Yatani formation hosting the University of Science. The age obtained is nearby Yatani Au-Ag-Pb-Zn veins (e.g., 3.96•}0.10 Ma, which is considerably younger and HATTORI,1975; SATOet al., 1978), is divided into more precise than that reported by SHIKAZONO two, the lower and upper formations. The former (1985). Therefore, it is concluded that the kaolin- is mainly composed of acidic tuff breccias, while pyrophyllite mineralization and the nearby Pb-Zn- the latter of slightly altered welded tuffs. The ka- Au-Ag mineralization took place almost simulta- olin-pyrophyllite deposits occur selectively in the neously. uppermost part of the lower formation. Intrusive rocks such as those observed in Yatani mine area Ore Mineralogy are not recognized in the immediate vicinity of the As sulfide minerals, euhedral to subhedral py- Otoge mine. Based on mineral assemblages and rite crystals up to about 5 mm in size are predomi- their relative abundance observed at the Otoge de- nant in the silicified portion of the sericite zone. posits, a zonal distribution of ores is recognized: They occur as aggregates to form a veinlet-like pyrophyllite, sericite and kaolinite ones. Their form and as disseminations in the silicate matrix. detailed descriptions and genetical discussions Small amounts of galena and chalcopyrite are in- will be given elsewhere (MIYAZAKIet al., in cluded in the pyrite grains. Subordinate amounts 44(6), 1994 Stannite from the Otoge kaolin-pyrophyllite deposits and its genetical significance 441 Table 1 Microprobe analyses of coexisting stannite and sphalerite from the Otoge mine (wt. %). ( ): sphalerite compositions, n.d. = not determined dicated the miscibility gap between stannite and of sphalerite with or without abundant fine- kesterite and suggested their difference in crystal grained exsolved dots of chalcopyrite are closely structure. The latter conclusion was confirmed by associated with pyrite. Sphalerite is sometimes HALL et al., (1978), who refined the structure of accompanied by a small amount of chalcopyrite stannite and kesterite in space group I42m and I4, and galena. Very fine-grained Ag-bearing min- respectively. However, in some cases, from their eral, 1 to 2 microns in size, is rarely associated chemical compositions alone, the two minerals with stannite, chalcopyrite and galena. It is noted that stannite always occurs as long and narrow are indistinguishable from each other. Recently, strips up to 0.1 mm in width and as fine-grained KISSIN and OWENS (1989) and KISSIN (1989) re- and irregularly-shaped crystals within sphalerite ported two new minerals, ferrokesterite and petru- kite, approximately the same composition as that as shown in Fig. 2(a, b, c). In reflected light, stan- of stannite, but differing crystal structures. Both nite is gray in color with an olive green tint and minerals are very similar shows a strong anisotropism (Fig. 2b). Investigat- ,to kesterite in optical ing the phase relations in the pseudobinary system properties, being weakly anisotropic, while the Cu2FeSnS4-Cu2ZnSnS4, SPRINGER (1972) dis- Otoge material is strongly anisotropic. Although, strictly speaking, its structural refinements are closed that below 680•‹C, there are two different needed, we may conclude that the tin-bearing sul- stannite-kesterite phases separated by a miscibil- fide from the Otoge mine is stannite, mainly based ity gap. Using Gandolfi X-ray camera and micro- on their optical property and chemical composi- probe analyzer, KISSIN and OWENS (1977) also in- 442 M. WATANABE, K HOSHINO•¬ KO KO MYnvT, K. MIYAZAKI and H. NisHmo RESOURCE GEOLOGY: tions, as will be stated later. Small amounts of euhedralarsenopyrite are sometimesobserved as- sociated with pyrite. Pyrrhotite has never been observed. As gangue minerals, quartz, sericite and apatite with an euhedralhabit occur in the si- licifiedportion. EPMA analyses of stannite and associated sphaleriteare listed in Table 1. Althoughstannite from Otoge is compositionallyzoned, exsolution textures such as those describedby HARRISand OWENS(1972), KISSINand OWENS(1977) and SOEDAet al. (1988)are not recognized.Tin an Zn contents(in atomic %) of stanniteare in the range: 10.74 to 12.34 and 3.64 to 8.35, respectively. Therefore,the Otogestannite is of Zn-richvariety, with Fe/Fe+Znratios of 0.49 to 0.71. It is noted that the Zn-poor stanniteshows the atomic con- tents of the (Fe+Zn) site to be almost1.000, while thoseof the Zn-richone deviatefrom the value,by up to about 30 %, suggesting a possibility of non- stoichiometry as found by PETRUK (1973). This will be treated in a separate paper. On the con- Fig. 3 Fe/Zn partition diagram for coexisting stannite trary, the Yatani stannite is of Zn-poor variety and sphalerite (After NAKAMURAand SHIMA,1982). with the ratio of 0.97 (SHIMIZU and SHIKAZONO, 1985). FeS contents (in mol. % FeS) of sphalerite (NAKAMURAand SHIMA, 1982), coexisting with stannite range from 6.0 to 13.7 %. where T is temperature in kelvin. For the com- Usually, arsenopyrite contains As of 30 to 32 parison between the two geothermometers, as atom. %. KRESTCHMARand SCOTT (1976) indi- well as some problems inherent to its application, cated that in S-rich assemblage such as arsenopy- see SHIMIZUand SHIKAZONO(1985) and SOEDA et rite-pyrite, centers of arsenopyrite crystals are S- al. (1988). rich relative to rims. However, arsenopyrite from Using the partition coefficients by NEKRASOV the Otoge mine does not show such a regular zon- et al. (1975) and NAKAMURAand SHIMA (1982) ing (Fig. 2d). These analytical results will be dis- and phase relations for the Fe-Zn-S system cussed later. (BARTON and TOULMIN, 1966; SCOTT and BARNES, 1971), equilibrium temperature and sul- Stannite Genesis fur fugacity conditions can be estimated. The re- Partition of Fe and Zn between coexisting stan- sults are graphically shown in the partition dia- nite and sphalerite solid solutions can be repre- gram (Fig.
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