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Estimates of the oxidation states of magmas are important to current investigations of the geochemical characteristics of their source regions and of evolved magmatic series created during differentiation. One means of achieving such estimates is to capitalize on compositions of coexisting cubic and rhombohedral Fe-Ti oxides determined by electron microprobe. A combination of experimental calibration points and thermodynamic modeling provides a basis for translating such compositions into T-ƒO2 values. This has been done until recently by estimating Fe3+/ΣFe on the basis of charge balance and stoichiometry by the method of Droop (1987), after matrix corrections of X-ray intensity data have been performed, as EPMA cannot be used routinely to distinguish different elemental valence states, much less accurately quantify abundances of Fe3+ and Fe2+. The traditional approach of undertaking post-data-reduction calculations falls short of attaining the best possible quantitative results. The tactical choice of not accounting for light elements that have not been explicitly analyzed prior to matrix corrections of X-ray intensity data leads to systematic errors in reported oxide abundances for measured elements. This article addresses one such issue, the oxygen associated with Fe3+ (hereafter "excess oxygen"), on the basis of coexisting Fe-Ti oxides from Andean lavas. A new software routine in probe for EPMA (PFE) uses an iterative calculation scheme to calculate amounts of excess oxygen that would not be considered if all iron were assumed to be ferrous and then applies this excess oxygen during matrix corrections. The PFE approach reveals that Fe-concentrations have been underestimated, universally, in these minerals because O atoms absorb FeKα radiation: discrepancies increase as total Fe and Fe3+/Fe2+, hence excess oxygen, increase. Analyses of the most Fe-rich cubic oxide compositions in this data set have ~6 wt% excess oxygen and ~1 wt% more FeO+Fe2O3 than would be reported without incorporating the impact of excess oxygen in matrix corrections. Minor to negligible differences in other elements are also observed. These effects are not because excess oxygen is directly attributed to these elements, although some may be present in multiple valence states, as matrix corrections are undertaken on the basis of the conventional assumptions that they occur as Cr3+, V3+, Mn2+, Mg2+, Ca2+, and Si4+. Rather, variably small increases in total Fe propagate through the matrix corrections for other elements, and these differences may be recorded as minor increases or decreases in some concentrations, depending on the particular element and the amount of change in Fe-concentration. Fe3+/ΣFe in analyses produced with the PFE routine are essentially identical to those determined in the traditional mode, as cation proportions calculated on the basis of charge balance and stoichiometry, with the method of Droop (1987), is a necessary step. The new method: (1) provides more accurate concentrations, mainly for Fe and Ti; (2) is applicable to any mineral containing ferric iron (subject to stoichiometric constraints); (3) provides more accurate analytical totals, which can be advantageous for evaluating analytical quality; and (4) does not impact estimates of oxidation state. Oxygen fugacities and temperatures determined with the model of Ghiorso and Evans (2008) are essentially unchanged. [ABSTRACT FROM AUTHOR]

Heamanite-(Ce) (IMA 2020-001), ideally (K0.5Ce0.5)TiO3, is a new perovskite-group mineral found as an inclusion in a diamond from the Gahcho Kué mine in the Northwest Territories, Canada. It occurs as brown, translucent single crystals with an average maximum dimension of ~80 μm, associated with rutile and calcite. The luster is adamantine, and the fracture conchoidal. Heamanite-(Ce) is the K-analog of loparite-(Ce), ideally (NaCe)Ti2O6. The Mohs hardness is estimated to be 5½ by comparison to loparite-(Ce), and the calculated density is 4.73(1) g/cm3. Electron microprobe wavelength-dispersive spectrometric analysis (average of 34 points) yielded: CaO 10.70, K2O 7.38, Na2O 0.16, Ce2O3 13.77, La2O3 8.22, Pr2O3 0.84, Nd2O3 1.59, SrO 6.69, BaO 2.96, ThO2 0.36, PbO 0.15, TiO2 45.77, Cr2O3 0.32, Al2O3 0.10, Fe2O3 0.09, Nb2O5 0.87, UO3 0.01, total 99.98 wt%. The empirical formula, based on 3 O atoms, is: [(K0.268Na0.009)Σ0.277(Ce0.143La0.086Pr0.009Nd0.016)Σ0.254(Ca0.326Sr0.110Ba0.033Pb0.001)Σ0.470Th0.002]Σ1.003 (Ti0.979Nb0.011Cr0.007Al0.003Fe0.002)Σ1.002O3. The Goldschmidt tolerance factor for this formula is 1.003. Heamanite-(Ce) is cubic, space group Pm3m, with unit-cell parameter a = 3.9129(9) Å, and volume V = 59.91(4) Å3 (Z = 1). The crystal structure was solved using single-crystal X‑ray diffraction data and refined to R1(F) = 2.61%. Heamanite-(Ce) has the aristotypic perovskite structure and adopts the same structure as isolueshite and tausonite. The six strongest diffraction lines are [dobs in angstroms (I in percentages) (hkl)]: 2.764 (100) (110), 1.954 (41) (200), 1.596 (36) (211), 1.045 (16) (321), 1.236 (13) (310), and 1.382 (10) (220). The Raman spectrum of heamanite-(Ce) shows two broad bands at 560 and 787 cm−1, with no bands observed above 1000 cm−1. Heamanite-(Ce) is named after Larry Heaman, a renowned scientist in the field of radiometric dating applied to diamond-bearing kimberlites, mantle-derived eclogites, and lamprophyre dikes. The dominant REE should appear as a Levinson suffix, hence heamanite-(Ce). [ABSTRACT FROM AUTHOR]

Nixonite (IMA 2018-133), ideally Na2Ti6O13, is a new mineral found within a heavily metasomatized pyroxenite xenolith from the Darby kimberlite field, beneath the west-central Rae Craton, Canada. It occurs as microcrystalline aggregates, 15 to 40 mm in length. Nixonite is isostructural with jeppeite, K2Ti6O13, with a structure consisting of edge- and corner-shared titanium-centered octahedra that enclose alkali-metal ions. The Mohs hardness is estimated to be between 5 and 6 by comparison to jeppeite, and the calculated density is 3.51(1) g/cm3. Electron microprobe wavelength-dispersive spectroscopic analysis (average of 6 points) yielded: Na2O 6.87, K2O 5.67, CaO 0.57, TiO2 84.99, V2O3 0.31, Cr2O3 0.04, MnO 0.01, Fe2O3 0.26, SrO 0.07, total 98.79 wt%. The empirical formula, based on 13 O atoms, is: (Na1.24K0.67Ca0.06)S1.97(Ti5.96V0.023Fe0.018)S6.00O13 with minor amounts of Cr and Mn. Nixonite is monoclinic, space group C2/m, with unit-cell parameters a = 15.3632(26) Å, b = 3.7782(7) Å, c = 9.1266(15) Å, b = 99.35(15)°, and V = 522.72(1) Å3, Z = 2. Based on the average of seven integrated multi-grain diffraction images, the strongest diffraction lines are [dobs in Å (I in %) (hkl)]: 3.02 (100) (310), 3.66 (75) (110), 7.57 (73) (200), 6.31 (68) (201), 2.96 (63) (311), 2.96 (63) (203), and 2.71 (62) (402). The five main Raman peaks of nixonite, in order of decreasing intensity, are at 863, 280, 664, 135, and 113 cm–1. Nixonite is named after Peter H. Nixon, a renowned scientist in the field of kimberlites and mantle xenoliths. Nixonite occurs within a pyroxenite xenolith in a kimberlite, in association with rutile, priderite, perovskite, freudenbergite, and ilmenite. This complex Na-K-Ti-rich metasomatic mineral assemblage may have been produced by a fractionated Na-rich kimberlitic melt that infiltrated a mantle-derived garnet pyroxenite and reacted with rutile during kimberlite crystallization. [ABSTRACT FROM AUTHOR]

Goldschmidtite is a new perovskite-group mineral (IMA No. 2018-034) with the ideal formula (K,REE,Sr)(Nb,Cr)O3. A single grain of goldschmidtite with a maximum dimension of ∼100 μm was found as an inclusion in a diamond from the Koffiefontein pipe in South Africa. In addition to the dark green and opaque goldschmidtite, the diamond contained a Cr-rich augite (websteritic paragenesis) and an intergrowth of chromite, Mg-silicate, and unidentified K-Sr-REE-Nb-oxide. Geothermobarometry of the augite indicates that the depth of formation was ∼170 km. The chemical composition of gold-schmidtite determined by electron microprobe analysis (n = 11, WDS, wt%) is: Nb2O5 44.82, TiO2 0.44, ThO2 0.10, Al2O3 0.35, Cr2O3 7.07, La2O3 11.85, Ce2O3 6.18, Fe2O3 1.96, MgO 0.70, CaO 0.04, SrO 6.67, BaO 6.82, K2O 11.53, total 98.53. The empirical formula (expressed to two decimal places) is (K0.50La0.15Sr0.13Ba0.09Ce0.08)Σ0.95(Nb0.70Cr0.19Fe0.05Al0.01Mg0.04Ti0.01)Σ1.00O3. Goldschmidtite is cubic, space group Pm3m, with unit-cell parameters: a = 3.9876(1) Å, V = 63.404(6) Å3, Z = 1, resulting in a calculated density of 5.32(3) g/cm3. Goldschmidtite is the K-analog of isolueshite, (Na,La)NbO3. Raman spectra of goldschmidtite exhibit many second-order broad bands at 100 to 700 cm–1 as well as a pronounced peak at 815 cm–1, which is possibly a result of local ordering of Nb and Cr at the B site. The name goldschmidtite is in honor of the eminent geochemist Victor Moritz Goldschmidt (1888–1947), who formalized perovskite crystal chemistry and identified KNbO3 as a perovskite-structured compound. [ABSTRACT FROM AUTHOR]

Perovskite mineral oxides commonly exhibit extensive solid-solution, and are therefore classified on the basis of the proportions of their ideal end-members. A uniform sequence of calculation of the end-members is required if comparisons are to be made between different sets of analytical data. A Microsoft Excel spreadsheet has been programmed to assist with the classification and depiction of the minerals of the perovskite- and vapnikite-subgroups following the 2017 nomenclature of the perovskite supergroup recommended by the International Mineralogical Association (IMA). Compositional data for up to 36 elements are input into the spreadsheet as oxides in weight percent. For each analysis, the output includes the formula, the normalized proportions of 15 end-members, and the percentage of cations which cannot be assigned to those end-members. The data are automatically plotted onto the ternary and quaternary diagrams recommended by the IMA for depiction of perovskite compositions. Up to 200 analyses can be entered into the spreadsheet, which is accompanied by data calculated for 140 perovskite compositions compiled from the literature. [ABSTRACT FROM AUTHOR]