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Petersite–(La), a New Mixite–Group Mineral from Ohgurusu, Kiwa, Kumano City, Mie Prefecture, Japan

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Petersite–(La), a New Mixite–Group Mineral from Ohgurusu, Kiwa, Kumano City, Mie Prefecture, Japan Journal of Mineralogical and Petrological Sciences, Volume 115, page 286–295, 2020 Petersite–(La), a new mixite–group mineral from Ohgurusu, Kiwa, Kumano City, Mie Prefecture, Japan Daisuke NISHIO–HAMANE*, Masayuki OHNISHI**, Norimasa SHIMOBAYASHI***, † † ‡ Koichi MOMMA , Ritsuro MIYAWAKI and Sachio INABA *Institute for Solid State Physics, the University of Tokyo, Kashiwa 277–8581, Japan **Takehana Ougi–cho, Yamashina–ku, Kyoto 607–8082, Japan ***Department of Geology and Mineralogy, Graduate School of Science, Kyoto University, Kyoto 606–8502, Japan †Department of Geology and Palaeontology, the National Museum of Nature and Science, Tsukuba 305–0005, Japan ‡Inaba–Shinju Corporation, Minami Ise, Mie 516–0109, Japan Petersite–(La) is a new mineral of the petersite series in the mixite group with an ideal formula of Cu6La (PO4)3(OH)6·3H2O from Ohgurusu, Kiwa–cho, Kumano City, Mie Prefecture, Japan. The mixite–group min- erals occur in small cavities coated by chrysocolla developed along quartz veins. Four members from different cavities have been identified: petersite–(La), petersite–(Ce), petersite–(Y), and agardite–(La). Petersite–(La) oc- curs as a radial aggregate formed by acicular to hexagonal columnar crystals of yellowish green color. Crystals are elongated along [001] and the prismatic face is probably formed by {001} and {100} or {110}. It is non– fluorescent in UV light. Crystals are brittle, cleavage and parting are non–observed, and fracture is uneven. These characteristics are common in other mixite–group minerals. The calculated density of petersite–(La) is 3.33 g/cm3, based on the empirical formula and powder XRD data. It is optically uniaxial positive with ω = 1.680(3) and ε = 1.767(3) (white light), and pleochroism varies from light green to yellowish green. Based on the WDS analysis, the empirical formula of petersite–(La) calculated on the basis of P + As + Si = 3 is (Cu5.692 Fe0.010)Σ5.702[(La0.148Ce0.122Nd0.117Y0.086Sm0.022)Σ0.495Ca0.372]Σ0.866(P1.890As0.799Si0.311)Σ3O10.320(OH)7.680·3H2O. 3 Petersite–(La) is hexagonal (P63/m) with a = 13.367(2) Å, c = 5.872(2) Å, and V = 908.7(4) Å (Z = 2). The eight strongest lines of petersite–(La) in the powder XRD pattern [d in Å(I/I0)(hkl)] are 11.578(100)(100), 4.377(28) (210 + 120), 3.509(18)(211 + 121), 3.211(10)(310 + 130), 2.898(14)(221, 400), 2.656(10)(320 + 230), 2.526(11) (410 + 140), and 2.438(25)(212 + 122). Petersite–(La) is the third defined member in the petersite series and corresponds to the La–dominant analogue of petersite–(Y) and petersite–(Ce). Keywords: Petersite–(La), Petersite series, Mixite group, New mineral, Mie Prefecture INTRODUCTION and named after Thomas and Joseph Peters, curators of minerals at the Paterson Museum, New Jersey and the The mixite–group minerals have a general formula American Museum of Natural History, New York, respec- 2+ 3+ Cu6 A(TO4,TO3OH)3(OH)6·3H2O in which A = REE tively (Peacor and Dunn, 1982). Since this petersite was (lanthanoids + Y), Bi3+,Al3+,Ca2+,orPb2+, and T = mainly composed of Y, it was later renamed petersite–(Y) As5+ or P5+, and the root name is classified on the basis according to the Levinson rule (Levinson, 1966; Bayliss of the occupancy of the A and T sites. Mixite (A = Bi, T = and Levinson, 1988; Nickel and Grice, 1998). Recently, As) was first found in Jáchymov, Czech Republic in 1880 the Ce–dominant analogue of petersite–(Y) was found in AD (Schrauf, 1880), and eleven species have been found the Cherry Creek district, Arizona, USA and described as to be members of the group so far. Among them, agardite a new mineral, petersite–(Ce) (Morrison et al., 2016). Be- (T = As) and petersite (T = P) are series based on A = REE. fore this work, the only minerals in the petersite series The mineral petersite was first found in Laurel Hill, USA were petersite–(Y) and petersite–(Ce). fi doi:10.2465/jmps.191211b The crystal structure of petersite series was re ned D. Nishio–Hamane, [email protected]–tokyo.ac.jp Corresponding only petersite–(Ce), which is isostructural with agardite se- author ries (Hess, 1983; Aruga and Nakai, 1985; Morrison et al., Petersite–(La), a new mixite–group mineral 287 Figure 1. The structural model for petersite–(REE) (a) and an expanded view (b) based on the structure of Hess (1983) drawn with VESTA 3 (Momma and Izumi, 2011). Color version is available online from https://doi.org/10.2465/jmps.191211b. 2013, 2016). Figure 1 shows a representative structural widely developed, while one of the authors (S.I.) first col- model for petersite–(REE). The structure is based on chains lected mixite–group minerals from Ohgurusu, Kiwa–cho, of edge–shared CuO5 pyramids along the c–axis. These Kumano City, Mie Prefecture. As a result of mineralogical chains are connected with REEO9 polyhedra and PO4 tet- investigation, we succeeded in identifying a new mineral, rahedra in the ab plane. The polyhedra are arranged in a petersite–(La), as the La–dominant analogue of petersite– hexagonal array to form the walls of channels along c–axis (Y) and petersite–(Ce). Both the mineral and its name that are large enough to accommodate free water mole- have been approved by the International Mineralogical cules. The hydroxyls are accompanied by O4 and O5 sites. Association, Commission on New Minerals, Nomencla- O4 is shared by the CuO5 pyramids and the REEO9 poly- ture and Classification (no. 2017–089). A typical speci- hedron, and O5 is shared by the CuO5 pyramids. An extra men was deposited in the collections of the National Mu- hydroxyl in association with the REE3+–Ca2+H+ substitu- seum of Nature and Science, Japan, specimen number tion is thought to occur around the O3 site, according to the NSM–M45621. Here we describe a new mineral, peter- results of structural refinement of Ca–rich agardite–(Y) site–(La), and its related mixite–group minerals. (Aruga and Nakai, 1985), which is located at the tip of the CuO5 pyramid and shared by the REEO9 polyhedron OCCURRENCE AND APPEARANCE and the PO4 tetrahedron. The position of hydroxyl associ- ated with the P(As)5+–Si4+H+ substitution is still unclear. The Miocene sedimentary complex, known as the Kuma- The mixite–group minerals widely occur in the oxi- no Group, and the Middle Miocene igneous complex, dized zone of ore deposits, while the occurrence of the called the Kumano acidic rocks, are widely distributed phosphates such as the petersite series is generally very in the southeast part of the Kii Peninsula (e.g., Tanai rare compared to arsenates. In Japan, agardite–(Y) is the and Mizuno, 1954; Aramaki and Hada, 1965). The Kuma- most abundant mixite–group mineral and is found in the no Group consists mainly of mudstone and sandstone, and oxidized zones of copper deposits from several localities the hydrothermal–vein type copper deposits formed by the (e.g., Ohori and Kobayashi, 1996; Miyawaki et al., 2000). Kinan copper mineralization are widely developed along As a phosphate, only petersite–(Y) is known to occur, the contact area associated with the Kumano acidic rocks from the Haiyama quarry, Shiga Prefecture (Okamoto et (e.g., Saeki and Koto, 1972). These large–scale ore depos- al., 1988). To date, no mixite–group minerals have been its were vigorously mined in the Kishu mine and Myoho found on the Kii Peninsula, where copper deposits are mine, while small–scale mineralization zones also occur 288 D. Nishio–Hamane, M. Ohnishi, N. Shimobayashi, K. Momma, R. Miyawaki and S. Inaba widely in the Kumano Group. We conducted a geological It is optically uniaxial positive with ω = 1.680(3) and ε = survey in the Kumano Group, and then the first sample 1.767(3) (white light), and pleochroism varies from light was obtained as a boulder from the confluence of the De- green to yellowish green. Crystals from the #LaP cavity tani River and its tributaries, Ohgurusu, Kiwa, Kumano exhibited some compositional variations (Table 1), but er- City, Mie Prefecture (33°52′57′′N 135°55′46′′E). The rors in optical parameters were small. The compatibility boulder was composed of highly weathered sandstones, 1−(Kp/Kc) was calculated to be −0.007 (superior) using and chalcopyrite with supergene minerals were also found the oxide k values for CuO (Mandarino, 1981). inside it. During a subsequent geological survey, one of the authors (S.I.) found an outcrop of sandstone with a RAMAN SPECTROSCOPY quartz vein containing chalcopyrite and supergene miner- als upstream of the tributary. Although the minerals re- Raman spectroscopic analysis was performed with a ported in this study were obtained from boulders, those HORIBA HR320 spectrometer using a 514.5 nm argon probably originated their outcrop. laser. Measurement was performed with 500, 900, 1500, Sandstones along quartz veins have many cavities 3000, and 3500 cm−1 as the center wavelength. The sam- and cracks by quartz crystals within which supergene ple was collected from the #LaP cavity as a radial aggre- minerals develop. The cavities vary in size and shape, gate. It was mounted on a glass slide by epoxy and then ranging from less than 1 mm to a maximum of about 1 polished (Fig. 3b). The sample was also analyzed by EDS cm in spherical to irregular shapes. The mixite–group before Raman spectroscopy. Figure 4 shows the Raman minerals also occur in cavities coated by chrysocolla, spectra of petersite–(La). As tentative assignments based and the chemical compositions are different for each cav- on Frost et al.
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