Phase relations in the system fayalite–magnetite at high pressures and temperatures

The phase relations in the Fe₂SiO₄–Fe₃O₄ binary system have been determined between 900 and 1200 °C and from 2.0 to 9.0 GPa. At low to moderate pressures magnetite can accommodate significant Si, reaching X_Fe2SiO₄=0.1 and 0.2 at 3.0 and 5.0 GPa respectively, with temperature having only a secondary influence. At pressures below 3.5 GPa at 900 °C and 2.6 GPa at 1100 °C magnetite-rich spinel coexists with pure fayalite. This assemblage becomes unstable at higher pressures with respect to three intermediate phases that are spinelloid polytypes isostructural to spinelloids II, III and V in the Ni-aluminosilicate system. The phase relations between the spinelloid phases are complex. At pressures above ≈8.0 GPa at 1100 °C, the spinelloid phases give way to a complete spinel solid solution between Fe₃O₄ and Fe₂SiO₄. The presence of small amounts of Fe³⁺ stabilises the spinel structure to lower pressures compared to the Fe₂SiO₄ end member. This means that the fayalite–γ-spinel transition is generally unsuitable as a pressure calibration point for experimental apparatuses. The molar volumes of the spinel solid solutions vary nearly linearly with composition, having a small negative deviation from ideal behaviour described by W_v=−0.15(6) cm³. Extrapolation yields V°₍₂₉₈₎ = 41.981(14) cm³ for the Fe₂SiO₄-spinel end member. The cell parameters and molar volumes of the three spinelloid polytypes vary systematically with composition. Cation disorder is an important factor in stabilising the spinelloid polytypes. Each polytype exhibits a particular solid solution range that is directly influenced by the interplay between its structure and the cation distributions that are energetically favourable. In the FeO–FeO_1.5–SiO₂ ternary system Fe₇SiO₁₀ (“iscorite”) coexists with the spinelloid phases at intermediate pressures on the SiO₂-poor, or Fe³⁺-poor side of the Fe₂SiO₄–Fe₃O₄ join. On the SiO₂ and Fe³⁺-rich side of the join, orthopyroxene or high-P clinopyroxene coexists with the spinelloids and spinel solid solutions. The assemblage pyroxene+spinel+SiO₂ is stable over a wide range of bulk composition. The stability of spinelloid III is of particular petrologic interest since this phase has the same structure as (Mg,Fe)₂SiO₄–wadsleyite, indicating that Fe³⁺ can be easily incorporated in this important phase in the Earth's transition zone, in addition to silicate spinel. This has important implications for the redox state of the Earth's transition zone and for the depth at which the olivine to spinel transition occurs in the mantle, potentially leading to a shift in the “410 km” seismic discontinuity to shallower depths depending on the prevailing redox state. In addition, a coupled tetrahedral substitution of Fe³⁺+OH for Si+O could provide a further mechanism for the incorporation of H₂O in wadsleyite. Received: 10 January 2000 / Accepted: 12 May 2000     

Batiferrite, Ba[Ti2Fe10]O19, a new ferrimagnetic magnetoplumbite-type mineral from the Quaternary volcanic rocks of the western Eifel area, Germany

Summary Batiferrite, ideally Ba[Ti₂Fe₁₀]O₁₉, was found in the Quaternary volcanic rocks near üdersdorf, Graulai, and Altburg, western Eifel area, Germany. The new mineral typically occurs as euhedral platy grains in cavities of melilite- and leucite-nephelinite basalts. Associated minerals are hematite, magnetite, titanite, g?tzenite, clinopyroxene, nepheline, and biotite. It exhibits a hexagonal tabular habit flattened on {0001}, diameter 0.5–1 mm, thickness 20–125 μm, and {10&1macr;3}, {10&1macr;0} as observable forms. The mineral is opaque, of black color with submetallic lustre, and shows a ferrimagnetic behavior. VHN₅₀ is 793 with a range of 710–841 from ten indentations. The quantitative reflectance measurements of R_o/R_e on oriented grains in air and oil immersion, respectively, are [%]: for 470 nm 22.1/20.1 and 8.4/7.1, for 546 nm 21.0/19.4 and 7.8/6.6, for 589 nm 20.2/18.8 and 7.4/6.3, and for 650 nm 19.3/18.3 and 6.8/5.9. The bireflectance is distinct (air) to weak (oil), and parallel (0001) a moderate anisotropy with straight extinction can be observed. Typical microprobe analyses give [wt%] K₂O 0.28–0.33, Na₂O 0.17–0.20, SrO 0.46–0.55, BaO 11.80–12.17, MgO 1.27–1.47, Al₂O₃ 0.31–0.33, TiO₂ 13.11–13.63, MnO 2.38–2.57, Fe₂O₃ 61.36–63.12, FeO 5.49–5.86 (Fe³⁺/Fe²⁺ calculated for charge compensation), which is equivalent to (Ba_0.84Na_0.06K_0.06Sr_0.05)_1.01(Fe_8.48 ³⁺Fe_0.86 ²⁺Ti_1.82Mg_0.37Mn_0.37Al_0.06)_11.96O₁₉ as the average composition based on 19 oxygen atoms. Batiferrite is a magnetoplumbite-type mineral with hexagonal symmetry, space group P6 ₃ /mmc (no. 194), a = 5.909(1) ?, c = 23.369(4) ?, V = 706.6(2) ?³, Z = 2, and a calculated density of 5.016 gcm⁻³. The structure was refined to R1 = 0.031 for 278 unique reflections with F_o ² > 4σ (F_o ²) and R1 = 0.079 for all 452 unique observations using single crystal X-ray data. The strongest reflections of the X-ray powder diffraction pattern are [d _obs, I/I_o, (hkl)]: 2.631, 100, (114); 2.799, 80, (107); 1.478, 70, (220); 2.429, 60, (203); 1.672, 50, (217). The new mineral is comparable to the other Ba containing magnetoplumbite-type minerals haggertyite and hawthorneite, the iron content, however, is much higher and in the range of magnetoplumbite. The large cation site (A) is dominated by Ba, and four of the five remaining crystallographic cation sites in the structure are dominated by Fe (M1, 2, 3, 5), the octahedrally coordinated M4-site is dominated by Ti. No oxygen vacancy on the O3-site like in plumboferrite can be observed. Batiferrite is named for its main chemical composition and the relationship to the M-type hexaferrites (polytype 5H).

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Zusammenfassung Batiferrit, ein neues ferrimagnetisches Mineral des Magnetoplumbit-Typs aus den quart?ren Vulkaniten der West-Eifel, Deutschland Das neue Mineral Batiferrite, mit der Idealformel Ba[Ti₂Fe₁₀]O₁₉, wurde an drei Fundpunkten in den Quart?ren Vulkangesteinen der westlichen Eifel, Deutschland, in der N?he von üdersdorf, Graulai und Altburg gefunden. Das neue Mineral tritt typischerweise bl?ttchenf?rmig in kleinen Hohlr?umen von Melilith- und Leucit-Nephelininit Basalten auf. Vergesellschaftete Minerale sind H?matit, Magnetit, Titanit, G?tzenit, Klinopyroxen, Nephelin und Biotit. Der Habitus ist hexagonal tafelig nach {0001}, mit einem Durchmesser von 0.5–1 mm und einer Dicke von 20–125 μm, zus?tzlich k?nnen die Formen {10&1macr;3} und {10&1macr;0} beobachtet werden. Das Mineral ist opak, hat eine schwarze Farbe mit einem leicht metallischen Glanz, und ist ferromagnetisch. Die H?rte VHN₅₀ ist 793 mit einem Bereich von 710–841 aus 10 Eindruckbestimmungen. Die quantitativen Reflexionsmessungen von R_o/R_e an orientierten K?rnern in Luft beziehungsweise ?limmersion, ergaben [%]: für 470 nm 22.1/20.1 und 8.4/7.1, für 546 nm 21.0/19.4 und 7.8/6.6, für 589 nm 20.2/18.8 und 7.4/6.3, und für 650 nm 19.3/18.3 und 6.8/5.9. Die Bireflexion ist deutlich (Luft) bis schwach (?l) und parallel (0001) kann eine mittlere Anisotropie mit gerader Ausl?schung beobachtet werden. Eine typische Mikrosondenanalyse ergibt [wt%] K₂O 0.28–0.33, Na₂O 0.17–0.20, SrO 0.46–0.55, BaO 11.80–12.17, MgO 1.27–1.47, Al₂O₃ 0.31–0.33, TiO₂ 13.11–13.63, MnO 2.38–2.57, Fe₂O₃ 61.36–63.12, FeO 5.49–5.86 (Fe³⁺/Fe²⁺ berechnet zum Ladungsausgleich), die mittlere chemische Formel auf der Basis von 19 Sauerstoffatomen lautet (Ba_0.84Na_0.06K_0.06Sr_0.05)_1.01 (Fe_8.48 ³⁺Fe_0.86 ²⁺Ti_1.82Mg_0.37Mn_0.37Al_0.06)_11.96O ₁₉. Batiferrit ist ein Mineral der Magnetoplumbitgruppe, hat hexagonale Symmetrie mit der Raumgruppe P6₃/mmc (Nr. 194), a = 5.909(1) ?, c = 23.369(4) ?, V = 706.6(2) ?³, Z = 2, und einer berechneten Dichte von 5.016 gcm⁻³. Die Struktur wurde aus Einkristall-R?ntgendaten bis zu einem R1-Wert von 0.031 für 278 F_o ² > 4σ(F_o ²), und einem R1-Wert von 0.079 für alle 452 F_o ² verfeinert. Die st?rksten Beugungsreflexe der Pulver-R?ntgendaten sind [d_obs, I/I_o, (hkl)]: 2.631, 100, (114); 2.799, 80, (107); 1.478, 70, (220); 2.429, 60, (203); 1.672, 50, (217). Das neue Mineral weist deutliche ?hnlichkeiten zu den anderen beiden Ba-reichen Mineralen Haggertyit und Hawthorneit der Magnetoplumbit-Gruppe auf, jedoch ist der Eisengehalt wesentlich h?her und im Bereich des Minerals Magnetoplumbit. Der gro?e Kationenplatz (A) ist von Barium dominiert, vier (M1, 2, 3, 5) der restlichen fünf kristallographischen Kationenpl?tze in der Struktur sind fast ausschlie?lich mit Fe, die oktaedrisch koordinierte M4-Position ist überwiegend mit Ti besetzt. An der O3-Position konnte kein Sauerstoffdefizit wie in Plumboferrit festgestellt werden. Batiferrit ist nach seiner chemischen Beschaffenheit und nach seiner Zugeh?hrigkeit zu den M-Typ Hexaferriten (Polytyp 5H) benannt.

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Received December 14, 1999; accepted March 2, 2000     

SPINMELT-2.0: Simulation of spinel–melt equilibrium in basaltic systems under pressures up to 15 kbar: I. model formulation,calibration, and tests

The paper presents results of testing currently used models proposed to describe Cr-spinel–melt equilibrium: models of the MELTS family by M.S. Ghiorso with colleagues, the SPINMELT program by A.A. Ariskin and G.S. Nikolaev, and the “MELT–CHROMITE spinel calculator” by А.А. Pustovetov and R.L. Roeder. The new calibration of the SPINMELT model presented in this publication enables calculating a sixcomponent (Mg, Fe²⁺, Cr, Al, Fe³⁺, and Ti) composition of Cr-spinel and the \(T - {f_{{o_2}}}\) parameters of its stability on the liquidus of basaltic melts under pressures up to 15 kbar. The model is based on results of 392 runs from 43 experimental studies, including systems of normal alkalinity at \({f_{{o_2}}}\) ≤ QFM + 2. The experimental dataset (which was extended compared to that used for the previous calibration) allowed us not only to estimate the pressure effect, but also apply the model to aluminous and hydrous systems. Tests of the SPINMELT-2.0 model show that the errors of the calculated temperature of the spinel–melt equilibrium increase with pressure from 16°C at 1 atm to 50°C at 15 kbar. Experimental spinel compositions are reproduced by the model accurate to < 3 at % Al and Cr, and no worse 1 at % for the other cations.     

Electric conductivity of Fe2SiO4–Fe3O4 spinel solid solutions

 The spinel solid solution was found to exist in the whole range between Fe₃O₄ and γ-Fe₂SiO₄ at over 10 GPa. The resistivity of Fe_{3− x} Si _x O₄ (0.0<x<0.288) was measured in the temperature range of 80∼300 K by the AC impedance method. Electron hopping between Fe³⁺ and Fe²⁺ in the octahedral site of iron-rich phases gives a large electric conductivity at room temperature. The activation energy of the electron hopping becomes larger with increasing γ-Fe₂SiO₄ component. A nonlinear change in electric conductivity is not simply caused by the statistical probability of Fe³⁺–Fe²⁺ electron hopping with increasing the total Si content. This is probably because a large number of Si⁴⁺ ions occupies the octahedral site and the adjacent Fe²⁺ keeping the local electric neutrality around Si⁴⁺ makes a cluster, which generates a local deformation by Si substitution. The temperature dependence of the conductivity of solid solutions indicates the Verwey transition temperature, which decreases from 124(±2) K at x=0 (Fe₃O₄) to 102(±5) K at x=0.288, and the electric conductivity gap at the transition temperature decreases with Si⁴⁺ substitution. Received: 15 March 2000 / Accepted: 4 September 2000     

Mg-Fe partitioning between silicate spinel and magnesiowüstite at high pressure: experimental determination and calculation of phase relations in the system Mg2SiO4-Fe2SiO4

 Mg-Fe partitioning experiments between (Mg,Fe)₂SiO₄ spinel and (Mg,Fe)O magnesiowüstite were carried out at pressures of 17–21.3 GPa at temperatures of 1400 and 1600 °C, using a multi-anvil apparatus, in order to determine interaction parameters of spinel and magnesiowüstite solid solutions and also to constrain the equilibrium boundaries of the postspinel transition in the Fe-rich side in the system Mg₂SiO₄-Fe₂SiO₄. The obtained values of the interaction parameters were 3.4 ± 1.5 and 13.9 ± 1.4 kJ mol⁻¹, respectively, for spinel and magnesiowüstite solid solutions at 19 GPa and 1600 °C. The partitioning data in the system Mg₂SiO₄-Fe₂SiO₄ at 1400 and 1600 °C showed that the transition boundary between spinel and the mixture of magnesiowüstite and stishovite has a negative dP/dT slope. Using the above interaction parameters and available thermodynamic data of the Mg₂SiO₄ and Fe₂SiO₄ end members, the transition boundaries of spinel to the mixture of magnesiowüstite and stishovite were calculated. Within the uncertainties of the data used, the calculated boundaries are in good agreement with the boundaries at 1400 and 1600 °C experimentally determined in this study. The dissociation boundary of Fe₂SiO₄ spinel to wüstite and stishovite, calculated from the thermodynamic data, has a negative slope of −1.5 ± 0.6 MPa K⁻¹. Received: 18 February 1998 / Revised, accepted: 18 October 1999     

An empirical model for the calculation of spinel-melt equilibria in mafic igneous systems at atmospheric pressure: 2. Fe-Ti oxides

In order to develop models simulating the crystallization of Fe-Ti oxides in natural lavas, we have processed published experimental data on magnetite-melt and ilmenite-melt equilibria. These data include 62 Mt-melt and 75 Ilm-melt pairs at temperatures 1040–1150 °C, oxygen fugacities from IW to NNO+2, and bulk compositions ranging from ferrobasalts to andesites and dacites. Five major cations (Fe³⁺, Fe²⁺, Ti⁴⁺, Mg²⁺ and Al³⁺) were considered for the purpose of describing Fe-Ti oxide saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure. The empirically calibrated mineral-melt expression based on multiple linear regressions is: ln D _i  = a/T + blog f _O2 + c + d ₁ X _Na + d ₂ X _K + d ₃ X _P, where D _i represents molar distribution coefficients of the given cations between Mt/Ilm and melt; X _Na, X _K, and X _P are the molar fractions of Na, K, and P in the melt. The empirically calibrated Mt-melt and Ilm-melt equilibria equations allowed us to develop two models for calculating crystallization temperatures of the Fe-Ti oxides in the melts with an accuracy of 10–15 °C, and compositions with an accuracy of 0.5–2 mol%. These models have been integrated into the COMAGMAT-3.5 program, improving our ability to study numerically the effects of temperature and oxygen fugacity on the stability and phase equilibria of Fe-Ti oxides. Application of this approach to the tholeiitic series of Chazhma Sill from Eastern Kamchatka (Russia) indicates oxygen fugacity conditions near NNO + 0.5. Numerical simulation of fractional crystallization of an iron-enriched basaltic andesite parent at these oxidizing conditions accurately reproduces the FeO-SiO₂ relations observed in the Chazhma suite. Received: 3 March 1998 / Accepted: 7 August 1998     

Hydrous peridotites with Ti-rich chromian spinel as a low-temperature forearc mantle facies: evidence from the Happo-O’ne metaperidotites (Japan)

The Happo-O’ne peridotite complex is situated in the northeastern part of the Hida Marginal Tectonic Zone, central Japan, characterized by the high-P/T Renge metamorphism, and is considered as a serpentinite mélange of Paleozoic age. Peridotitic rocks, being massive or foliated, have been subjected to hydration and metamorphism. Their protoliths are mostly lherzolites to harzburgites with subordinate dunites. We found a characteristic mineral assemblage, olivine + orthopyroxene + tremolite + chlorite + chromian spinel, being stable at low-T, from 650 to 750°C, and high-P, from 16 to 20 kbar, tremolite–chlorite peridotites of the tremolite zone. Olivines are Fo₈₈–Fo_91, and orthopyroxenes (Mg# = 0.91) show low and homogenous distributions of Al₂O₃ (up to 0.25 wt%), Cr₂O₃ (up to 0.25 wt%), CaO (up to 0.36 wt%) and TiO₂ (up to 0.06 wt%) due to the low equilibration temperature. Chromian spinels, which are euhedral and enclosed mainly in the orthopyroxenes, have high TiO_2, 3.1 wt% (up to 5.7 wt%) on average, and high Cr# [=Cr/(Cr + Al) atomic ratio], 0.95 on average but low Fe³⁺ [=Fe³⁺/(Cr + Al + Fe³⁺) atomic ratio, <0.3]. The bulk-rock chemistry shows that the Happo-O’ne metaperidotites with this peculiar spinel are low in TiO₂ (0.01–0.02 wt%), indicating no addition of TiO₂ from the outside source during the metamorphism; the high TiO₂ of the peculiar spinel has been accomplished by Ti release from Ti-bearing high-T pyroxenes during the formation of low-T, low-Ti silicates (<0.1 wt% TiO₂) during cooling. Some dunites are intact from hydration: their olivine is Fo₉₂ and spinel shows high Cr#, 0.72. The Happo-O’ne metaperidotites (tremolite–chlorite peridotites), being in the corner of the mantle wedge, are representative of a hydrous low-T, high-P mantle peridotite facies transitional from a higher T anhydrous peridotite facies (spinel peridotites) formed by in situ retrograde metamorphism influenced by fluids from the subducting slab. They have suffered from low-T (<600°C) retrogressive metamorphism to form antigorite and diopside during exhumation of the Renge metamorphic belt.     

Origin of Neoproterozoic ophiolitic peridotites in south Eastern Desert, Egypt, constrained from primary mantle mineral chemistry

The ophiolitic peridotites in the Wadi Arais area, south Eastern Desert of Egypt, represent a part of Neoproterozoic ophiolites of the Arabian-Nubian Shield (ANS). We found relics of fresh dunites enveloped by serpentinites that show abundances of bastite after orthopyroxene, reflecting harzburgite protoliths. The bulk-rock chemistry confirmed the harzburgites as the main protoliths. The primary mantle minerals such as orthopyroxene, olivine and chromian spinel in Arais serpentinites are still preserved. The orthopyroxene has high Mg# [=Mg/(Mg + Fe²⁺)], ~0.923 on average. It shows intra-grain chemical homogeneity and contains, on average, 2.28 wt.% A1₂O₃, 0.88 wt.% Cr₂O₃ and 0.53 wt.% CaO, similar to primary orthopyroxenes in modern forearc peridotites. The olivine in harzburgites has lower Fo (93?94.5) than that in dunites (Fo_94.3?Fo_95.9). The Arais olivine is similar in NiO (0.47 wt.% on average) and MnO (0.08 wt.% on average) contents to the mantle olivine in primary peridotites. This olivine is high in Fo content, similar to Mg-rich olivines in ANS ophiolitic harzburgites, because of its residual origin. The chromian spinel, found in harzburgites, shows wide ranges of Cr#s [=Cr/(Cr + Al)], 0.46?0.81 and Mg#s, 0.34?0.67. The chromian spinel in dunites shows an intra-grain chemical homogeneity with high Cr#s (0.82?0.86). The chromian spinels in Arais peridotites are low in TiO₂, 0.05 wt.% and Y_Fe [= Fe³⁺/(Cr + Al + Fe³⁺)], ~0.06 on average. They are similar in chemistry to spinels in forearc peridotites. Their compositions associated with olivine’s Fo suggest that the harzburgites are refractory residues after high-degree partial melting (mainly ~25?30 % partial melting) and dunites are more depleted, similar to highly refractory peridotites recovered from forearcs. This is in accordance with the partial melting (>20 % melt) obtained by the whole-rock Al₂O₃ composition. The Arais peridotites have been possibly formed in a sub-arc setting (mantle wedge), where high degrees of partial melting were available during subduction and closing of the Mozambique Ocean, and emplaced in a forearc basin. Their equilibrium temperature based on olivine?spinel thermometry ranges from 650 to 780 °C, and their oxygen fugacity is high (Δlog ?O₂?=?2.3 to 2.8), which is characteristic of mantle-wedge peridotites. The Arais peridotites are affected by secondary processes forming microinclusions inside the dunitic olivine, abundances of carbonates and talc flakes in serpentinites. These microinclusions have been formed by reaction between trapped fluids and host olivine in a closed system. Lizardite and chrysotile, based on Raman analyses, are the main serpentine minerals with lesser antigorite, indicating that serpentines were possibly formed under retrograde metamorphism during exhumation and near the surface at low T (<400 °C).     

The crystal structure of arsentsumebite, Pb2Cu[(As, S)O4]2(OH)

Summary The crystal structure of arsentsumebite, ideally, Pb₂Cu[(As, S)O₄]₂(OH), monoclinic, space group P2₁/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?³, Z = 2, d_calc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb₂ Me(XO₄)₂(Z) where Me = Cu²⁺, Mn²⁺, Zn²⁺, Fe²⁺, Fe³⁺; X = S, Cr, V, As, P; Z = OH, H₂O. Members of this group include tsumebite, Pb₂Cu(SO₄)(PO₄)(OH), vauquelinite, Pb₂Cu(CrO₄)(PO₄)(OH), brackebuschite, Pb₂ (Mn, Fe)(VO₄)₂(OH), arsenbracke buschite, Pb₂(Fe, Zn)(AsO₄)₂(OH, H₂O), fornacite, Pb₂Cu(AsO₄)(CrO₄)(OH), and feinglosite, Pb₂(Zn, Fe)[(As, S)O₄]₂(H₂O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO₆ octahedra and M–T represents corner sharing between octahedra and XO₄ tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)₂(AsO₄)₂ (OH, H₂O)₂ and tsumcorite-group minerals Me(1)Me(2)₂(XO₄)₂(OH, H₂O)₂. Received June 24, 2000; revised version accepted February 8, 2001     

Electronic absorption and luminescence spectroscopic studies of kyanite single crystals: differentiation between excitation of FeTi charge transfer and Cr3+ dd transitions

A selected set of five different kyanite samples was analysed by electron microprobe and found to contain chromium between <0.001 and 0.055 per formula unit (pfu). Polarized electronic absorption spectroscopy on oriented single crystals, R₁, R₂-sharp line luminescence and spectra of excitation of λ₃- and λ₄-components of R₁-line of Cr³⁺-emission had the following results: (1) The Fe²⁺–Ti⁴⁺ charge transfer in c-parallel chains of edge connected M(1) and M(2) octahedra shows up in the electronic absorption spectra as an almost exclusively c(||Z′)-polarized, very strong and broad band at 16000 cm⁻¹ if <, in this case the only band in the spectrum, and at an invariably lower energy of 15400 cm⁻¹ in crystals with  ≥ . The energy difference is explained by an expansion of the O_f–O_k, and O_b–O_m edges, by which the M(1) and M(2) octahedra are interconnected (Burnham 1963), when Cr³⁺ substitutes for Al compared to the chromium-free case. (2) The Cr³⁺ is proven in two greatly differing crystal fields a and b, giving rise to two sets of bands, derived from the well known dd transitions of Cr^{3+ 4}A_2g→⁴T_2g(F)(I), →⁴T_1g(F)(II), and →⁴T_1g(P)(III). Band energies in the two sets a and b, as obtained by absorption, A, and excitation, E, agree well: I: 17300(a, A), 17200(a, E), 16000(b, A), 16200(b, E); II: 24800(a, A), 24400(a, E); 22300(b, A), 22200(b, E); III: 28800(b,A) cm⁻¹. Evaluation of crystal field parameters from the bands in the electronic spectra yield Dq(a)=1730 cm⁻¹, Dq(b)=1600 cm⁻¹, B(a)=790 cm⁻¹, B(b)=620 cm⁻¹ (errors ca. ±10 cm⁻¹), again in agreement with values extracted from the λ³, λ⁴ excitation spectra. The CF-values of set a are close to those typical of Cr³⁺ substituting for Al in octahedra of other silicate minerals without constitutional OH⁻ as for sapphirine, mantle garnets or beryl, and are, therefore, interpreted as caused by Cr³⁺ substituting for Al in some or all of the M(1) to M(4) octaheda of the kyanite structure, which are crystallographically different but close in their mean Al–O distances, ranging from 1.896 to 1.919 A (Burnham 1963), and slight degrees of distortion. Hence, band set a originates from substitutive Cr³⁺ in the kyanite structural matrix. The CF-data of Cr³⁺ type b, expecially B, resemble those of Cr³⁺ in oxides, especially of corundum type solid solutions or eskolaite. This may be interpreted by the assumption that a fraction of the total chromium contents might be allocated in a precursor of a corundum type exsolution. Received: 3 January 1997 / Revised, accepted: 2 May 1997     

Point defects and cation tracer diffusion in (Ti<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Fe<Subscript><Emphasis Type="Italic">1−x</Emphasis></Subscript>)<Subscript>3−δ</Subscript>O<Subscript>4</Subscript>. II. Cation tracer diffusion

 Cation tracer diffusion coefficients, D_Me ^*, for Me=Fe, Mn, Co and Ti, were measured using radioactive isotopes in the spinel solid solution (Ti _x Fe _1−x )_3−δO₄ as a function of the oxygen activity. Experiments were performed at different cationic compositions (x=0, 0.1, 0.2 and 0.3) at 1100, 1200, 1300 and 1400 °C. The oxygen activity dependence of all data for D_Me ^* at constant temperature and cationic composition can be described by equations of the type D_Me ^*=D^∘ _Me[V]. C_V·a _O2 ^2/3+D_Me[I] ^∘·a _O2 ^−2/3·D_Me[V] ^∘ and D_Me[I] ^∘ are constants and C_V is a factor of the order of unity which decreases with increasing δ. All log D_Me ^* vs. loga _O2 curves obtained for different values of x and for different temperatures go through a minimum due to a change in the type of point defects dominating the cation diffusion with oxygen activity. Cation vacancies prevail for the cation diffusion at high oxygen activities while cation interstitials become dominant at low oxygen activities. At constant values of x, D_Me[V] ^∘ decreases with increasing temperature while D_Me[I] ^∘ increases.     

Platinum group minerals in podiform chromitites of the Bou Azzer ophiolite, Anti Atlas, Central Morocco

Summary The Neoproterozoic Bou Azzer ophiolite complex hosts numerous, small lenticular bodies of massive and disseminated chromite. Metallurgical-grade high-Mg and high-Cr spinels (cores with 48–62 wt% Cr₂O₃) reveal complex alteration patterns of successive Cr and Mn enrichment and loss of Al towards the rims, while the Mg# ratios [(Mg/(Mg + Fe²⁺)] remain almost constant. Concentration patterns of platinum-group elements are typical for ophiolitic chromitite poor in sulfides, with predominance of the IPGE, variable Rh, and low Pt and Pd. The most abundant platinum-group mineral is Rh-bearing laurite that occurs either included in spinel or in silicate matrix, whereas Os-Ir-Ru alloy is always included in spinel. Laurite inclusions reveal complex intergrowth textures with Rh-Ru-Pt rich alloy, and with Rh-rich sulfide. Most laurites display trends to sulfur-poor compositions leading to local formation of very fine-grained Ru-Os-Ir alloy phases. Ni-Co-Fe sulfides, arsenides and sulfarsenides devoid of PGE are associated with the alteration of chromite. Textural position and chemical composition of the base metal inclusions, as well as comparison of alteration features between chromite and accessory chromian spinel in the Co-Ni-As ores of the Bou Azzer ophiolite indicate a close connection. It is suggested that hydrothermal fluids percolated through the marginal zones of the ophiolite belt during greenschist facies metamorphism and deposited Ni-Co-Fe arsenides, sulfarsenides and minor sulfides as accessories within altered chromitites, and also in structurally favourable zones as Ni-Co-As ores. Author’s address: Dr. Frank Melcher, Federal Institute for Geosciences and Natural Resources, Stilleweg 2, 30655 Hannover, Germany     

Mineralogy and origin of stichtite in chromite-bearing serpentinites

Stichtite, a rare (14 known localities worldwide) hydrated carbonate-hydroxide of Mg and Cr with ideal formula Mg₆Cr₂ (OH)₁₆ CO₃ · 4H₂O, occurs exclusively in Cr-rich serpentinites of ophiolites or greenstone belts. Physical properties (hardness = 1.5–2, specific gravity = 2.16–2.2, perfect basal [0001] cleavage, grain size commonly < 100 μm) resemble talc, but the mineral has an attractive purple to lilac color; chemical analyses demonstrate it to be a non-silicate. Stichtite generally occurs as irregular to rounded masses (< 1 cm – 30 cm across) and as veinlets (< 1 mm – > 2 cm wide) within serpentinite. Macroscopic and microscopic textures, such as crosscutting veinlets and stringers, demonstrate that stichtite formation invariably post-dated serpentinization. In some specimens stichtite surrounds relict grains of Cr-rich spinel; in others stichtite has completely replaced euhedral or subhedral chromites. Chemical analyses of stichtites reveal substantial substitution of Al and Fe³⁺ for Cr in specimens from many localities, reflecting a possible compositional continuum between stichtite and rhombohedral polymorphs hydrotalcite (Mg₆Al₂ (OH)₁₆ CO₃ · 4H₂O) and pyroaurite (Mg₆Fe₂ (OH)₁₆ CO₃ · 4H₂O). We report the first electron microprobe analyses of stichtites from seven localities, and summarize all available published chemical data. Stichtites very likely inherited part of their trivalent cation chemistry from precursor Cr-rich spinels, but stichtite growth apparently post-dated characteristic “ferritchromit” alteration, as demonstrated by the depletion of Al and enrichment in Fe³⁺ in stichtite relative to primary chromite core compositions. Stichtite appears to form by reaction between serpentine and altered chromite, during addition of substantial fluid, either as separate H₂O and CO₂ phases, or as a mixed volatile phase. Such reactions must involve removal of substantial SiO₂, possibly by transport and remote deposition of silica by throughgoing aqueous and carbonic fluid. Received: 4 April 1996 / Accepted: 16 September 1996     

Mode of formation of hibonite (CaAl12O19) within the U-Th skarns from the granulites of S-E Madagascar

 In Madagascar, hibonite occurs as a rather frequent mineral within thorianite-bearing skarns which are widespread in the Pan African granulitic formations constituting the S-E part of the Island (Tranomaro area). In these skarns, leucocratic segregations made up of CO₃-scapolite to meionite (An_equivalent=89–95% which implies T≥850° C), spinel and corundum were formed at stage 1 of metasomatism in a titanite-bearing matrix consisting of scapolite (An_eq=77–88) and aluminous diopside. During stage 2 of metasomatism, scapolite from the lenses were altered to anorthite+calcite while the less calcic scapolite remained stable which indicates T≈800° C. Hibonite crystallized at the expense of corundum and spinel. Expressed as mol% of the CaAl₁₂O₁₉/Ca(Al₁₀TiR²⁺)O₁₉/REE(Al₁₁R²⁺)O₁₉ [+Th (Al₁₀R²⁺ ₂)O₁₉] end-members (R ²⁺=Mg, Fe²⁺, Zn²⁺; Al=Al, Fe³⁺; Ti=Ti, Si), its composition varies from 26/72/2 to 50/23/27. The ideal activity of the CaAl₁₂O₁₉ component is about 0.25. Fluid inclusions in corundum, hibonite and anorthite are composed of nearly pure CO₂. In corundum, the isochores for primary inclusions are in agreement with the P-T estimates for regional metamorphism and stage 1 metasomatism (T≈850° C, P≈5 kbar). Inclusions with the highest density in hibonite and anorthite constrain P to about 3–3.5 kbar for T=800° C. Thermodynamic calculations indicate that, in addition to a low activity of CaAl₁₂O₁₉, stability of hibonite in equilibrium with anorthite and calcite implies an extremely low activity of silica (below the zircon-baddeleyite buffer). By contrast the activity of CO₂ may be high, in agreement with the observed fluid compositions. These results are corroborated by a short comparison with the other granulite occurrences of hibonite in Tanzania and South India. Received: 18 August 1994 / Accepted: 12 October 1995     

Magnetite, ilmenite and ulvite in rocks and ore deposits: petrography, microprobe analyses and genetic implications

Summary ?Detailed petrographic studies and microchemical analyses of titanomagnetite from igneous and metamorphic rocks and ore deposits form the basis of this investigation. Its aim is to compare the data obtained and their interpretations with the experimentally deduced subsolidus oxidation-exsolution model of Buddington and Lindsley (1964). The results are also considered relevant for the interpretation of compositional variations in black sands which are recovered for titanium production. The arrangement of the samples investigated is in accordance with textural stages C1 to C5 caused by subsolidus exsolution with increasing degrees of oxidation (Haggerty, 1991). Stage 1 is represented by two types of optically homogeneous TiO₂-rich magnetite: a. An isotropic type considered to represent solid solutions of magnetite and ulvite containing between 5.2 to 27.5 wt% TiO₂ corresponding to about 14.7 to 77.7 mol% Fe₂TiO₄ in solid solution with magnetite. The general formula of this type is Fe²⁺ _1+x Fe³⁺ _2−2x Ti _x O₄ (x = 0.0–1.0). b. The second type which has not been reported so far is anisotropic and shows complex internal twinning resembling inversion textures. It is thus attributed to inversion of a high-temperature ilmenite modification (with statistical distribution of the cations) which forms solid solutions with magnetite. TiO₂ varies between 9.3 and 24.5 wt% corresponding to about 17.2 to 43.6 mol% ilmenite in solid solution with magnetite. This type is interpreted as a cation-deficient spinel with the general formula Fe²⁺ _{12/12 + 1/4x}Fe³⁺ _{24/12 − 3/2x} □ _{0 + 1/4x} Ti _x O₄ (x = 0.0–16/12). Isotropic and anisotropic homogeneous magnetites occur in volcanic rocks only; the homogeneity of the solid solutions was explained by fast cooling which prevented the development of exsolution textures. Stages 2 and 3 are represented by magnetite with or without ulvite. The magnetite host contains ilmenite lamellae forming trellis and sandwich textures. In contrast to the requirement of the oxidation-exsolution model, the ilmenite lamellae are concentrated exclusively in the cores of the host crystals. The reverse host-guest relationship may also occur. Stages 4 and 5 are identical with thermally generated martite (= martite due to heating). The textures are characterized by very broad lamellae of ferrian ilmenite or titanohematite dominantly concentrated along the margins of the host crystals. Thermally generated martite is restricted to subsolidus-oxidation reactions. The ilmenite lamellae of trellis and sandwich textures contain low Fe₂O₃-concentrations (average 4.8 mol%; to a maximum of 8.3), whereas the Fe₂O₃-content of thermally generated martite is between 32 to 71 mol%. With respect to the Fe₂O₃-concentrations in the ilmenite lamellae, no transition between the two types was observed. The results of this paper show that the widely accepted oxy-exsolution model of Buddington and Lindsley (1964) which is based on experimental results can – with the exception of thermally generated martite – not explain the tremendous variety of magnetite–ilmenite–ulvite relationships in natural rocks and ore deposits. Received October 16, 2001; accepted May 2, 2002     

TEM evidence of perovskite–brownmillerite coexistence in the Ca(AlxFe1−x)O2.5 system with minor amounts of titanium and silicon

Observations by transmission electron microscopy (TEM) of the submicrometer phases present in calcium aluminate cements have shown that Ca-Al-Fe oxides coexist in two forms with brownmillerite (b) and perovskite (p) structures, respectively. Homogeneous single crystals of both brownmillerite and perovskite have been observed but exsolved lamellae also occur on the scale of tens of nanometers. Perovskite lamellae in brownmillerite exhibit coherent interfaces with an almost perfect [1 0 1]_b = {1 0 0}_p topotactic relationship. Energy-dispersive X-ray spectroscopy (EDXS) measurements show that perovskite lamellae are enriched in Ti and Si relative to the brownmillerite lamellae. The perovskite phase may accommodate up to 0.17 Si atoms per formula unit, but the exsolution process seems mainly to concern the Ti content. It is estimated that the solvus width ranges between concentrations of 0.06 < Ti < 0.13 atoms per formula unit. O K and Fe L _2,3 edges collected by electron energy loss spectrometry (EELS) confirm that both phases are mainly composed of Fe³⁺, requiring that the perovskite is highly oxygen-deficient. Al K and Si K EELS spectra have features comparable with those of fourfold-co-ordinated Al and Si sites, suggesting that they are probably located close to oxygen-vacant sites. Received: 23 June 1999 / Accepted: 18 February 2000     

Chemical mass transfer in magmatic processes IV. A revised and internally consistent thermodynamic model for the interpolation and extrapolation of liquid-solid equilibria in magmatic systems at elevated temperatures and pressures

A revised regular solution-type thermodynamic model for twelve-component silicate liquids in the system SiO₂-TiO₂-Al₂O₃-Fe₂O₃-Cr₂O₃-FeO-MgO-CaO-Na₂O-K₂O-P₂O₅-H₂O is calibrated. The model is referenced to previously published standard state thermodynamic properties and is derived from a set of internally consistent thermodynamic models for solid solutions of the igneous rock forming minerals, including: (Mg,Fe²⁺,Ca)-olivines, (Na,Mg,Fe²⁺,Ca)^M2 (Mg,Fe²⁺, Ti, Fe³⁺, Al)^M1 (Fe³⁺, Al,Si)₂ ^TETO₆-pyroxenes, (Na,Ca,K)-feldspars, (Mg,Fe²⁺) (Fe³⁺, Al, Cr)₂O₄-(Mg,Fe²⁺)₂ TiO₄ spinels and (Fe²⁺, Mg, Mn²⁺)TiO₃-Fe₂O₃ rhombohedral oxides. The calibration utilizes over 2,500 experimentally determined compositions of silicate liquids coexisting at known temperatures, pressures and oxygen fugacities with apatite ±feldspar ±leucite ±olivine ±pyroxene ±quartz ±rhombohedral oxides ±spinel ±whitlockite ±water. The model is applicable to natural magmatic compositions (both hydrous and anhydrous), ranging from potash ankaratrites to rhyolites, over the temperature (T) range 900°–1700°C and pressures (P) up to 4 GPa. The model is implemented as a software package (MELTS) which may be used to simulate igneous processes such as (1) equilibrium or fractional crystallization, (2) isothermal, isenthalpic or isochoric assimilation, and (3) degassing of volatiles. Phase equilibria are predicted using the MELTS package by specifying bulk composition of the system and either (1) T and P, (2) enthalpy (H) and P, (3) entropy (S) and P, or (4) T and volume (V). Phase relations in systems open to oxygen are determined by directly specifying the f _{o 2} or the T-P-f _{o 2} (or equivalently H-P-f _{o 2}, S-P-f _{o 2}, T-V-f _{o 2}) evolution path. Calculations are performed by constrained minimization of the appropriate thermodynamic potential. Compositions and proportions of solids and liquids in the equilibrium assemblage are computed.     

Variation of the oxygen content and point defects in olivines, (Fe x Mg 1−x )2SiO4, 0.2 ≤ x ≤ 1.0

 The variation of the oxygen content in olivines, (Fe _x Mg_{1− x} )₂SiO₄, with 0.2 ≤ x ≤ 1.0, was investigated by thermogravimetric measurements. Mass changes occurring upon oxygen activity changes were measured as a function of oxygen activity and cationic composition at 1130 and 1200 °C. During the measurements the samples were in direct contact with gases containing CO, CO₂ and N₂ and, at a few spots at the bottom of the sample stack, also with SiO₂. By fitting experimental data of mass changes to equations derived using point defect thermodynamics, it was shown for olivines with 0.2 ≤ x ≤ 1.0 at 1130 °C and 0.2 ≤ x ≤ 0.7 at 1200 °C within the oxygen activity ranges investigated that the observed variations in the oxygen contents are compatible with cation vacancies and Fe³⁺ ions on M sites and Fe³⁺ ions on silicon sites as majority defects if it is assumed that only three types of point defects occur as majority defects. Different cases were considered, closed systems, taking into account that ξ=[Si]/([Si]+[Fe]+[Mg]) is not necessarily equal to 1/3, and olivines in equilibrium with SiO₂ or pyroxenes. The oxygen content variations observed in this study are significantly smaller than those reported previously in the literature. It is proposed that these differences are related to the dissolution of Fe into noble metal containers used as sample holders in earlier studies and/or to the presence of secondary phases. Received: 1 November 1995 / Accepted: 15 September 2002 Acknowledgements This work was supported by the Cornell Center for Materials Research (CCMR), a Materials Research Science and Engineering Center of the National Science Foundation (DMR-0079992). The authors thank Mr. Daniel M. DiPasquo and Mr. Jason A. Schick for helping in experimental work.     

Synthetic MgGa2O4-Mg2GeO4 spinel solid solution and β-Mg3Ga2GeO8: chemistry, crystal structures, cation ordering, and comparison to Mg2GeO4 olivine

 Structural parameters and cation ordering are determined for four compositions in the synthetic MgGa₂O₄-Mg₂GeO₄ spinel solid solution (0, 8, 15 and 23 mol% Mg₂GeO₄; 1400 °C, 1 bar) and for spinelloid β-Mg₃Ga₂GeO₈ (1350 °C, 1 bar), by Rietveld refinement of room-temperature neutron diffraction data. Sample chemistry is determined by XRF and EPMA. Addition of Mg₂GeO₄ causes the cation distribution of the MgGa₂O₄ component to change from a disordered inverse distribution in end member MgGa₂O₄, ^[4]Ga = x = 0.88(3), through the random distribution, toward a normal cation distribution, x = 0.37(3), at 23 mol% Mg₂GeO₄. An increase in a_o with increasing Mg₂GeO₄ component is correlated with an increase in the amount of Mg on the tetrahedral site, through substitution of 2 Ga³⁺⇄ Mg²⁺+Ge⁴⁺. The spinel exhibits high configurational entropy, reaching 20.2 J mol⁻¹ (four oxygen basis) near the compositional upper limit of the solid solution. This stabilizes the spinel in spite of positive enthalpy of disordering over the solid solution, where ΔH _D  = αx + βx ², α = 22(3), β = −21(3) kJ mol⁻¹. This model for the cation distribution across the join suggests that the empirically determined limit of the spinel solid solution is correlated with the limit of tetrahedral ordering of Mg, after which local charge-balanced substitution is no longer maintained. Spinelloid β-Mg₃Ga₂GeO₈ has cation distribution ^M1[Mg_0.50(2)Ga_0.50(2)] ^M2[Mg_0.96(2)Ga_0.04(2)] ^M3[Mg_0.77(2) Ga_0.23(2)]₂ (Ge_0.5Ga_0.5)₂O₈ (tetrahedral site occupancies are assumed). Octahedral site size is correlated to Mg distribution, where site volume, site distortion, and Mg content follow the relation M1<M3<M2. The disordered cation distribution provides local electrical neutrality in the structure, and stabilization through increased configurational entropy (27.6 J mol⁻¹; eight oxygen basis). Comparison of the crystal structures of Mg_{1+ N} Ga_{2−2 N} Ge _N O₄ spinel, β-Mg₃Ga₂GeO₈, and Mg₂GeO₄ olivine reveals β-Mg₃Ga₂GeO₈ to be a true structural intermediate. Phase transitions across the pseudobinary are necessary to accommodate an increasing divergence of cation size and valence, with addition of Mg₂GeO₄ component. Octahedral volume increases while tetrahedral volume decreases from spinel to β-Mg₃Ga₂GeO₈ to olivine, with addition of Mg and Ge, respectively. Furthermore, M-M distances increase regularly across the join, suggesting that changes in topology reduce cation-cation repulsion. Received: 9 November 1998 / Revised, accepted: 3 August 1999     

Microanalysis of Fe3+/ΣFe in oxide and silicate minerals by investigation of electron energy-loss near-edge structures (ELNES) at the Fe M 2,3 edge

The Fe M _2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe₃(Al_1–xFe_x)₂[SiO₄]₃ and andradite-skiagite (Fe_1–xCa_x)₃Fe₂[SiO₄]₃), pyroxenes (acmite-hedenbergite (Ca_1–xNa_x)(Fe²⁺ _1−xFe³⁺ _x)Si₂O₆), and spinels (magnetite-hercynite Fe(Al_1–xFe_x)₂O₄) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission electron microscope (TEM). The Fe M _2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge feature varies depending on Fe³⁺/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship between Fe³⁺/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M _2,3 edge is observed. Since the partial cross sections of the Fe M _2,3 edges are some orders of magnitude higher than those of the Fe L _2,3 edges, the Fe M _2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated by Fe M _2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that shows different edge shapes consistent with variations in the Fe³⁺/ΣFe ratio over distances on the order of 100 nm. Received: 14 April 1998 / Revised, accepted: 8 March 1999