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Buseckite, (Fe,Zn,Mn)S, a New Mineral from the Zakłodzie Meteorite

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Buseckite, (Fe,Zn,Mn)S, a New Mineral from the Zakłodzie Meteorite American Mineralogist, Volume 97, pages 1226–1233, 2012 Buseckite, (Fe,Zn,Mn)S, a new mineral from the Zakłodzie meteorite CHI MA,* JOHN R. BECKETT, AND GEORGE R. ROSSMAN Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125, U.S.A. ABSTRACT Buseckite (IMA 2011-070), (Fe,Zn,Mn)S, is the Fe-dominant analog of wurtzite, a new member of the wurtzite group discovered in Zakłodzie, and an ungrouped enstatite-rich achondrite. The type material occurs as single-crystal grains (4–20 µm in size) in contact with two or more of enstatite, plagioclase, troilite, tridymite, quartz, and sinoite. Low-Ni iron, martensitic iron, schreibersite, keilite, cristobalite, and graphite, which are also present in the type sample, are not observed to be in contact with buseckite. Buseckite is black under diffuse illumination and nearly opaque grayish brown in transmitted light. The mean chemical composition of buseckite, as determined by electron micro- probe analysis of the type material, is (wt%) S 35.84, Fe 28.68, Zn 23.54, Mn 10.04, Mg 1.18, sum 99.28, leading to an empirical formula calculated on the basis of 2 atoms of (Fe0.46Zn0.32Mn0.16Mg0.04 )∑0.99S1.01. Electron backscatter diffraction patterns of buseckite are a good match to that of synthetic 3 (Zn0.558Fe0.442)S with the P63mc structure, showing a = 3.8357, c = 6.3002 Å, V = 80.27 Å , and Z = 2. Buseckite is likely derived from the breakdown of high-temperature pyrrhotite to form troilite and buseckite following the solidification of sulfide-rich liquids produced during impact melting of an enstatite-rich rock. Keywords: Buseckite, (Fe,Zn,Mn)S, new mineral, wurtzite group, sinoite, Zakłodzie meteorite, enstatite achondrite INTRODUCTION a mineralogist at the Arizona State University, for his many The Zakłodzie meteorite, which is a moderately weathered contributions to mineralogy, meteorite research, and transmis- find discovered near the village of Zakłodzie, Poland, is an sion electron microscopy. Two Caltech sections, ZAK-TS1 ungrouped enstatite-rich achondrite that has been ascribed to an (purchased) and ZAK-TS2 (made at Caltech), taken from facing impact melt (e.g., Keil 2010) and to internal melting within the slices of the meteorite, contain the type material. ZAK-TS2, parent body (Przylibski et al. 2005). During a nano-mineralogy hereafter referred to as USNM 7607, has been deposited in the investigation of this meteorite, a new Fe-dominant monosulfide Smithsonian Institution’s National Museum of Natural History, Washington, D.C., and cataloged under USNM 7607. mineral, (Fe,Zn,Mn)S with a P63mc wurtzite-type structure, was identified and named “buseckite.” Field-emission scanning APPEARANCE, PHYSICAL AND OPTICAL PROPERTIES electron microscope, electron-backscatter diffraction (EBSD), electron microprobe, and micro-Raman spectroscopic analyses The type material appears to consist of 11 single-crystal grains were used to characterize its composition and structure and those scattered in USNM 7607 and ZAK-TS1 along grain boundar- of associated minerals. All of the minerals in this study were ies between two or more of enstatite, plagioclase, quartz, and identified structurally with EBSD and/or Raman. (Fe,Zn,Mn)S tridymite, absent other sulfides or adjacent to troilite (Figs. 1–3). phases similar in composition to buseckite were previously found One of the type grains contains euhedral sinoite (Si2N2O) crystals through electron microprobe analysis of sulfides in the Yilmia (Fig. 3a). Buseckite (Figs. 1–3) is irregular to subhedral, 4–20 EL6 chondrite (Buseck and Holdsworth 1972), the Grein 002 µm in diameter. No forms or twinning were observed. EL4/5 chondrite (Patzer et al. 2004), and the Zakłodzie achon- The Zakłodzie meteorite is a modestly weathered find but drite (on a different sample; Karwowski et al. 2007). This study each of the 11 buseckite grains that we observed is surrounded by a rim of secondary Fe oxyhydroxides, which also fill frac- reports the first confirmed (Fe,Zn,Mn)S mineral with the P63mc wurtzite-type structure and considers the origin of this phase, tures that cut across the grains. Buseckite is black under diffuse relationships to coexisting minerals, and implications through illumination and nearly opaque grayish brown in transmitted its formation and survival for the evolution of the Zakłodzie light. Luster, streak, hardness, tenacity, cleavage, fracture, and meteorite. Preliminary results are given in Ma et al. (2012). optical properties, none of which were determined for buseckite because of the small grain size, are likely close to those of MINERAL NAME AND TYPE MATERIAL wurtzite (Zn,Fe)S. The density, calculated from the empirical 3 The new mineral and its name have been approved by the formula, is 3.697 g/cm . The crystal is non-fluorescent under Commission on New Minerals, Nomenclature and Classification the electron beam in an SEM. of the International Mineralogical Association (IMA 2011-070) CHEMICAL COMPOSITION (Ma 2011). The name is in honor of Peter R. Buseck (b. 1935), Quantitative elemental microanalyses were conducted with a JEOL 8200 electron microprobe operated at 15 kV and 10 nA * E-mail: [email protected] in a focused beam mode. Standards for the analysis were syn- 0003-004X/12/0007–1226$05.00/DOI: http://dx.doi.org/10.2138/am.2012.4110 1226 MA ET AL.: BUSECKITE, A NEW MINERAL 1227 FIGURE 1. Secondary electron image (by an Everhart-Thornley FIGURE 2. Secondary electron image showing buseckite with troilite, detector) showing a buseckite grain with plagioclase and enstatite. Vein plagioclase, and enstatite. Vein material surrounding and intruding into material surrounding and intruding into the buseckite consists of ferric the buseckite consists of ferric oxy-hydroxides. oxy-hydroxides. a b FIGURE 3. Secondary electron images showing (a) buseckite with sinoite inclusions and (b) buseckite with nearby sinoite. thetic FeS (FeKα, SKα), ZnS (ZnKα), MnS (MnKα), forsterite and are either rudashevskyites (Fe dominant) or sphalerites (Zn (MgKα), Cr2O3 (CrKα), TiO2 (TiKα), and anorthite (CaKα). dominant) depending on Fe/Zn. Buseckite from Zakłodzie has Analyses were processed with the CITZAF correction procedure substantially more Mn than known rudashevskyites and the of Armstrong (1995). The average of 14 individual analyses compositions, therefore, plot in the interior of the ternary shown from six grains of the type buseckite reported in Table 1 were in Figure 4, as do Zn-enriched sulfide compositions from EL4-6 carried out using WDS mode. The empirical formula, based on chondrites. The structures of these EL4-6 phases have not been 2 atoms per formula unit, is: (Fe0.46Zn0.32Mn0.16Mg0.04)∑0.99S1.01, determined but, as discussed below, it is likely that many, if not yielding a simplified formula of (Fe,Zn,Mn)S. We observed no all, have the wurtzite structure and are, therefore, buseckites. We significant grain-to-grain differences in buseckite composition are aware of no reports of Zn-rich monosulfides in enstatite achon- and no evidence for zoning within individual grains. drites (aubrites), presumably reflecting the lower bulk Zn in these In Figure 4, we show the compositions of Zn-enriched mono- meteorites and the presence of daubréelite, which can accommodate sulfides from enstatite-enriched meteorites. Note that most of the considerable Zn (Lin and El Goresy 2002; Keil 2010). plotted analyses are consistent with one of the Fe-dominant phas- es buseckite or rudashevskyite rather than one of the Zn-dominant CRYSTALLOGRAPHY phases, wurtzite or sphalerite. Compositions of rudashevskyite Crystallography by EBSD at a sub-micrometer scale was from the EH4 enstatite chondrite Indarch (Britvin et al. 2008) carried out using methods described in Ma and Rossman (2008, and the compositions of structurally uncharacterized sulfides 2009) with an HKL EBSD system on a ZEISS 1550VP scanning from other EH3-4 chondrites plotted in Figure 4 (open circles electron microscope operated at 20 kV and 6 nA in a focused and diamonds) are similarly Mn-Mg poor. As discussed below, beam with a 70° tilted stage and in a variable pressure mode (25 it seems likely that all of these grains have a sphalerite structure Pa). The structure was determined and cell constants obtained 1228 MA ET AL.: BUSECKITE, A NEW MINERAL TABLE 1. Mean electron microprobe analytical results for the type 2.4 (2000). The strongest X-ray powder diffraction lines are [d buseckite, along with keilite and troilite in Å, (I), hkl] 3.322 (100) (100), 3.150 (62) (002), 2.938 (90) Constituent Buseckite Troilite Keilite Troilite Troilite (101), 2.286 (36) (102), 1.918 (76) (110), 1.775 (76) (103), 1.638 (next to (next to (isolated) buseckite) keilite) (48) (112), 1.078 (28) (213). wt% n = 14* n = 5 n = 6 n = 6 n = 4 S 35.84(21)† 37.65(17) 39.50(22) 37.64(21) 37.44(6) RAMAN SPECTROSCOPY Fe 28.68(26) 56.46(44) 29.90(22) 56.23(14) 56.03(87) Zn 23.54(25) b.d. 0.15(6) b.d. b.d. Raman micro-analysis of buseckite and associated phases was Mn 10.04(12) 1.18(12) 24.03(14) 1.32(14) 1.40(58) carried out using a Renishaw M1000 micro-Raman spectrometer Mg 1.18(4) b.d. 4.86(7) b.d. b.d. Cr b.d.‡ 3.83(3) 1.13(4) 4.31(8) 4.13(10) system and a 514.5 nm laser with the methods described in Ma Ti b.d. 1.06(7) b.d. 0.75(4) 0.76(3) and Rossman (2008, 2009). A Raman spectrum of buseckite was Ca b.d. b.d. 0.88(2) b.d. b.d. obtained from 4000 to 100 cm–1. Because some decomposition Ni b.d.
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