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Panguite, (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3, a New Ultra-Refractory Titania Mineral from the Allende Meteorite: Synchrotron Micro-Diffraction and EBSD

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Panguite, (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3, a New Ultra-Refractory Titania Mineral from the Allende Meteorite: Synchrotron Micro-Diffraction and EBSD American Mineralogist, Volume 97, pages 1219–1225, 2012 4+ Panguite, (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3, a new ultra-refractory titania mineral from the Allende meteorite: Synchrotron micro-diffraction and EBSD CHI MA,1,* OLIVER TSCHAUNER,1,2 JOHN R. BECKETT,1 GEORGE R. ROSSMAN,1 AND WENJUN LIU3 1Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, California 91125, U.S.A. 2High Pressure Science and Engineering Center and Department of Geoscience, University of Nevada, Las Vegas, Nevada 89154, U.S.A. 3Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, U.S.A. ABSTRACT 4+ Panguite (IMA 2010-057), (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3, is a new titania, occurring as fine-grained crystals with Ti-rich davisite in an ultra-refractory inclusion within an amoeboid olivine inclusion from the Allende CV3 carbonaceous chondrite. The phase was characterized by SEM, EBSD, synchrotron micro-diffraction, micro-Raman spectroscopy, and EPMA. The mean chemical composition of the type panguite is (wt%) TiO2 47.97, ZrO2 14.61, Sc2O3 10.67, Al2O3 7.58, MgO 5.54, Y2O3 5.38, CaO 3.34, SiO2 1.89, FeO 1.81, V2O3 0.95, Cr2O3 0.54, HfO2 0.28, sum 100.56 with a corresponding empirical 4+ 3+ formula calculated on the basis of 3 O atoms of [(Ti0.79Zr0.16Si0.04)Σ0.99(Sc0.20Al0.20Y0.06V0.02Cr0.01)Σ0.49 2+ (Mg0.18Ca0.08Fe0.03)Σ0.29]Σ1.77O3. Synchrotron micro-Laue diffraction (i.e., an energy scan by a high-flux X-ray monochromatic beam and white beam diffraction) on one type domain at sub-micrometer resolution revealed that panguite is an orthorhombic mineral in space group Pbca. The structure is a subgroup of the Ia3 bixbyite-type. The cell parameters are a = 9.781(1), b = 9.778(2), and c = 9.815(1) Å, yielding V = 938.7(1) Å3, Z = 16, and a calculated density of 3.746 g/cm3. Panguite is not only a new mineral, but also a new titania material, likely formed by condensation. It is one of the oldest minerals in the solar system. 4+ Keywords: Panguite, (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3, new ultra-refractory mineral, new titania, Allende meteorite, CV3 carbonaceous chondrite, synchrotron micro-diffraction, EBSD INTRODUctION the first solid materials in the solar system. Holotype material During a nano-mineralogy investigation of the Allende mete- (Section MC2Q of Caltech specimen Allende12A) is deposited 4+ under catalog USNM 7602 in the Smithsonian Institution’s Na- orite at Caltech, a new titania mineral (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3, named “panguite,” was identified in an ultra-refractory inclusion tional Museum of Natural History, Washington, D.C., U.S.A. within an amoeboid olivine inclusion (AOI). Electron probe OccURRENCE microanalysis (EPMA), high-resolution scanning electron micro- scope (SEM), electron backscatter diffraction (EBSD), synchro- The Allende meteorite fell in and near Pueblito de Allende, tron micro-Laue diffraction with subsequent energy scans, and Chihuahua, Mexico, on February 8, 1969 (Clarke et al. 1971). It micro-Raman spectroscopic analyses were used to determine its is a CV3 carbonaceous chondrite and the study of objects in this composition, physical properties, and structure and to character- meteorite has had a tremendous influence on current thinking about 4+ processes, timing, and chemistry in the primitive solar nebula and ize associated phases. Synthetic (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3 is not known. Thus, panguite is not only a new mineral and a new small planetary bodies. The mineral panguite was found within one phase to meteoritics, but it is also a new material. In this work, irregular ultra-refractory inclusion in one polished section (USNM we describe the first occurrence of panguite in nature, as a new 7602), prepared from a ∼1 cm diameter Allende fragment (Caltech ultra-refractory oxide among the oldest solid materials in the Meteorite Collection No. Allende12A). The host refractory inclu- solar system. Preliminary results are given in Ma et al. (2011a). sion is about 30 × 20 µm in size in the section plane and resides within an AOI, surrounded by a matrix of mostly fine-grained MINERAL NAME AND TYPE MATERIAL olivine and troilite. Panguite occurs with Ti-rich davisite and The mineral and the mineral name (panguite) have been minor Sc-Ti-bearing diopside in the refractory inclusion (Figs. approved by the Commission on New Minerals, Nomenclature 1–2). Davisite appears to be the common thread for panguite. We and Classification (CNMNC) of the International Mineralogical have observed this phase in two additional inclusions, one from Association (IMA 2010-057). The name panguite is for Pan Gu, Allende and the other from the CM chondrite Murchison (Ma et the giant in ancient Chinese mythology, who created the world by al. 2011b). In both cases, panguite is invariably in contact with separating the heaven and earth from chaos in the beginning, in davisite. Moreover, Zhang and Hsu (2009) described a phase from allusion to the mineral with an ultra-refractory origin being among the CH chondrite SaU 290, which we have confirmed by EBSD and EPMA at Caltech to be another example of panguite (see their * E-mail: [email protected] Fig. 6c) and their grains are also in contact with davisite. Given 0003-004X/12/0007–1219$05.00/DOI: http://dx.doi.org/10.2138/am.2012.4027 1219 1220 MA ET AL.: PANGUITE, A NEW ULTRA-REFRACTORY MINERAL FIGURE 1. Backscatter electron image of the ultra-refractory FIGURE 2. Enlarged backscatter image showing the area where inclusion within an Allende AOI in section USNM 7602. panguite crystals (type material) occur with smaller Zr-rich panguite in davisite (Fig. 1). The cross marks where the EBSD pattern (shown in Fig. 3) and the synchrotron micro-diffraction data were collected. the occurrence in multiple meteorites of variable type (CH, CM, The mottled appearance of the davisite mostly reflects differences in CV), we conclude that panguite is a rare but widespread constituent Sc concentrations. of carbonaceous chondrites and, given the consistent association with davisite, we conclude that the origin of panguite is intimately 3+ 2+ connected to the origin and evolution of davisite. V0.02Cr0.01)Σ0.49(Mg0.18Ca0.08Fe0.03)Σ0.29]Σ1.77O3, where the oxidation states of Ti and Fe are assumed to be 4+ and 2+, respectively. 4+ APPEARANCE, PHYSICAL AND OPTICAL PROPERTIES The general formula is (Ti ,Sc,Al,Mg,Zr,Ca)1.8O3, expressed as 4+ 4+ Panguite occurs as irregular to subhedral grains, 500 nm to (Ti ,Sc,Al,Mg,Zr,Ca,o)2O3 or (Ti ,Sc,Al,Mg,Zr,Ca)3O5. 1.8 µm in size. In section, panguite is opaque. Color, streak, lus- Associated Zr-rich panguite has an empirical formula 4+ 3+ ter, hardness, tenacity, cleavage, fracture, density, and refractive [(Ti0.56 Zr0.31Si0.12) Σ0.99(Al0.17Sc0.13Y0.13V0.01) Σ0.44(Ca0.23Mg0.07 2+ index were not determined because of the small grain size. The Fe0.05) Σ0.35]Σ1.78O3 and coexisting davisite has a mean com- 3+ density, calculated from the empirical formula, is 3.746 g/cm3. It position of (Ca0.99Mg0.01)Σ1.00[(Sc0.35Ti0.25V0.01Y0.01Al0.01) Σ0.63 2+ 4+ is non-fluorescent under the electron beam of a scanning electron (Mg0.19Fe0.04)Σ0.23(Ti0.12Zr0.03)Σ0.15]Σ1.01(Si1.07Al0.93)Σ2.00O6, with par- 3+ 4+ microscope, and we observed no crystal forms or twinning. Two titioning of Ti and Ti based on a stoichiometric formula unit distinct chemistries are observed for panguite, and this is readily containing 4.00 cations and 6 O atoms. Note that about two thirds appreciated through atomic number (Z) contrast in BSE images. of the Ti is inferred to be trivalent in davisite that coexists with 3+ The larger panguite grains shown in Figure 2 (lighter gray), which panguite containing little if any Ti . Minor isolated Sc-Ti-rich constitute the type material, are much lower in the high-Z elements diopside (Table 1) occurs in the inclusion. Fine-grained (∼250 Zr and Y than are some of the smaller grains (white in Fig. 2). TABLE 1. The mean electron microprobe analytical result for type pan- HEMICAL comPOSITION C guite, Zr-rich panguite, davisite, diopside, and surrounding Chemical analyses of panguite (on the larger grains in Fig. olivine 2) and associated minerals were carried out using a JEOL 8200 Constituent Type Zr-rich Davisite Diopside Olivine electron microprobe (WDS mode, 10 kV, 5 nA beam in focused panguite panguite wt% n = 5* n = 4 n = 4 n = 3 n = 4 mode). Standards for the analysis were TiO2 (TiKα, OKα), zircon TiO2 47.97(1.09)† 30.68(31) 12.74(39) 7.04(95) 0.12(5) (ZrLα), ScPO4 (ScKα), synthetic anorthite (CaKα, AlKα, SiKα), ZrO2 14.61(86) 25.92(22) 1.53(27) 0.79(45) b.d. forsterite (MgKα), YPO4 (YLα), fayalite (FeKα), V2O3 (VKα), Sc2O3 10.67(25) 5.97(20) 10.16(97) 3.90(1.37) b.d. Al2O3 7.58(22) 5.94(38) 20.29(1.56) 11.53(1.74) 0.12(7) Cr2O3 (CrKα), and Hf metal (HfLα). Quantitative elemental mi- MgO 5.54(55) 1.98(7) 3.43(84) 11.15(1.74) 35.47(1.71) croanalyses were processed with the CITZAF correction procedure Y2O3 5.38(37) 10.16(28) 0.41(10) 0.50(23) b.d. (Armstrong 1995) and analytical results are given in Table 1. CaO 3.34(40) 8.73(47) 23.54(8) 24.72(49) 0.17(3) SiO2 1.89(18) 5.04(31) 27.34(1.49) 40.75(2.94) 37.99(21) Repeated electron probe analysis of panguite with and without O FeO 1.81(25) 2.21(29) 1.07(15) 1.25(4) 26.84(1.35) being explicitly measured gave similar results, implying that Ti V2O3 0.95(14) 0.27(6) 0.47(2) 0.18(8) b.d.
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