Minerals of the beudantite–segnitite series from the oxidation zone of the Berezovskoe gold deposit,middle Urals: Chemical variations,behavior of admixtures,and antimonian varieties

In the oxidation zone of the Berezovskoe gold deposit in the middle Urals, Russia, minerals of the beudantite–segnitite series (idealized formulas PbFe₃ ³⁺ AsO₄)(SO₄)(OH)₆ and PbFe₃ ³⁺ AsO₄)(AsO₃OH)(OH)₆, respectively) form a multicomponent solid solution system with wide variations in the As, S, Fe, Cu, and Sb contents and less variable P, Cr, Zn, Pb, and contents K. The found minerals of this system correspond to series from beudantite with 1.25 S apfu to S-free segnitite, with segnitite lacking between 1.57 and 1.79 As apfu. Segnitite at the Berezovskoe deposit contains presumably pentavalent Sb (up to 15.2 wt % Sb₂O₅ = 0.76 Sb apfu, the highest Sb content in the alunite supergroup minerals), which replaces Fe³⁺. The Sb content increases with increasing As/S value. On the contrary, beudantite is free of or very poor in Sb (0.00–0.03 Sb apfu). Many samples of segnitite are enriched in Cu (up to 8.2 wt% CuO = 0.83 Cu apfu, uncommonly high Cu content for this mineral) and/or in Zn (up to 2.0 wt% ZnO = 0.19 Zn apfu). Both Cu and Zn replace Fe. The generalized formula of a hypothetic end member of the segnitite series with 1 Sb apfu is Pb(Fe³⁺ M ²⁺Sb⁵⁺)(AsO₄)₂(OH)₆, where M = Cu, Zn, Fe²⁺. The chemical evolution of beudantite–segnitite series minerals at the Berezovskoe deposit is characterized by an increase in the S/As value with a decrease in the Sb content from early to late generations.     

OH in zoned amphiboles of eclogite from the western Tianshan,NW-China

Chemically-zoned amphibole porphyroblast grains in an eclogite (sample ws24-7) from the western Tianshan (NW-China) have been analyzed by electron microprobe (EMP), micro Fourier-transform infrared (micro-FTIR) and micro-Raman spectroscopy in the OH-stretching region. The EMP data reveal zoned amphibole compositions clustering around two predominant compositions: a glaucophane end-member ( ^B Na₂ ^C M²⁺ ₃ M³⁺ ₂ ^T Si₈(OH)₂) in the cores, whereas the mantle to rim of the samples has an intermediate amphibole composition ( ^A _0.5 ^B Ca_1.5Na_0.5 ^C M ²⁺ _4.5 M _0.5^{3+ T} Si_7.5Al_0.5(OH)₂) (A = Na and/or K; M ²⁺ = Mg and Fe²⁺; M ³⁺ = Fe³⁺ and/or Al) between winchite (and ferro-winchite) and katophorite (and Mg-katophorite). Furthermore, we observed complicated FTIR and Raman spectra with OH-stretching absorption bands varying systematically from core to rim. The FTIR/Raman spectra of the core amphibole show three lower-frequency components (at 3,633, 3,649–3,651 and 3,660–3,663 cm⁻¹) which can be attributed to a local O(3)-H dipole surrounded by ^{M(1) M(3)}Mg₃, ^{M(1) M(3)}Mg₂Fe²⁺ and ^{M(1) M(3)} Fe²⁺ ₃, respectively, an empty A site and ^T Si₈ environments. On the other hand, bands at higher frequencies (3,672–3,673, 3,691–3,697 and 3,708 cm⁻¹) are observable in the rims of the amphiboles, and they indicate the presence of an occupied A site. The FTIR and Raman data from the OH-stretching region allow us to calculate the site occupancy of the A, M(1)–M(3), T sites with confidence when combined with EPM data. By contrast M(2)- and M(4) site occupancies are more difficult to evaluate. We use these samples to highlight on the opportunities and limitations of FTIR OH-stretching spectroscopy applied to natural high pressure amphibole phases. The much more detailed cation site occupancy of the zoned amphibole from the western Tianshan have been obtained by comparing data from micro-chemical and FTIR and/or Raman in the OH-stretching data. We find the following characteristic substitutions Si(T-site) (Mg, Fe)[M(1)–M(3)-site] → Al(T-site) Al[M(1)–M(3)-site] (tschermakite), Ca(M4-site)□ (A-site) → Na(M4-site) Na + K(A-site) (richterite), and Ca(M4-site) (Mg, Fe) [M(1)–M(3)-site] → Na(M4-site) Al[M(1)–M(3)-site] (glaucophane) from the configurations observed during metamorphism.     

Cation distribution in amphiboles synthesized along the Ga analogue of the tremolite–aluminotschermakite join

 Amphiboles were synthesized from bulk compositions prepared along the join Ca_1.8Mg_5.2Si₈O₂₂(OH)₂–Ca_1.8Mg₃Ga₄Si₆O₂₂(OH)₂ hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca₂Mg₅Si₈O₂₂F₂–Ca₂Mg₃Ga₄Si₆O₂₂F₂, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: ^[6]Ga³⁺+2^[4]Ga³⁺+1/2^[A] Ca²⁺ = ^[6]Mg²⁺+2^[4]Si⁴⁺+1/2^[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001     

Crystal chemistry of volcanic allanites indicative of naturally induced oxidation-dehydrogenation

The crystal chemistry of volcanic allanites from both the Youngest Toba Tuff (YTT), Sumatra, Indonesia and SK100 volcanic ash beds (SK100-VAB), Niigata, Japan has been examined by electron microprobe analysis (EMPA), Fourier-transform infrared spectroscopic analysis (FTIR), and single-crystal structure analysis. In the FTIR study, based on the Diamond ATR accessory, YTT and SK100- VAB allanites were observed to have different OH contents, respectively: the former has 0.64 wt% H₂O (OH: 0.40 apfu.), while the latter has 1.65 wt% H₂O (OH: 1.00 apfu.). The crystal structures of these two allanites have been refined to individual R indices (3.64 and 4.25) based on 1350 observed reflections (|Fo| > 4sig|Fo|) measured using a single-crystal diffractometer with MoKα X-radiation. The OH-poor YTT allanite has a shorter b axis, a longer c axis, and larger β value than the relatively OH-rich SK100-VAB one. The bond valence sums of O4 (accepter oxygen for H atom) and O10 (donor oxygen for H atom) are 1.962 and 1.709 v.u. for YTT allanite (valence sum: 3.671 v.u.) and 1.754 and 1.271 v.u. for SK100-VAB one (valence sum: 3.025 v.u.). The difference from the ideal total bond valence value (4.00 v.u.) of O4 and O10 in YTT allanite (0.33 v.u.) is smaller than that in SK100-VAB (0.98 v.u.). These difference values are also broadly consistent with the corresponding differences in OH content between the YTT (OH: 0.40 apfu.) and SK100-VAB allanites (OH: 1.00 apfu.) determined by FTIR- ATR. Chemical analyses, FTIR-ATR and crystal structure refinement of YTT and SK100-VAB allanites yielded the following crystal chemical formula: YTT: (Ca_0.83Mn²⁺ _0.06Fe²⁺ _0.11)(La_0.24Ce_0.32Pr_0.04Nd_0.11Sm_0.02Th_0.04Ca_0.21)(Al_0.73Fe³⁺ _0.19Ti_0.08)(Al_0.89Fe³⁺ _0.11)(Fe²⁺ _0.22Fe³⁺ _0.62Mg_0.16)(SiO₄)Si₂O₇O_1.6(OH)_0.4, SK100-VAB: (Ca_0.81Fe²⁺ _0.13Mn²⁺ _0.06)(La_0.22Ce_0.34Pr_0.05Nd_0.13Sm_0.02Th_0.02Ca_0.22)(Al_0.76Fe³⁺ _0.19Ti_0.05)Al_1.00(Fe²⁺ _0.73Fe³⁺ _0.17Mg_0.10)(Si_0.96Al_0.04O₄)Si₂O₇O(OH). Therefore, it is concluded that welding of the Youngest Toba Tuff caused the following post-crystallization changes to occur in YTT allanite: oxidation of Fe²⁺ to Fe³⁺, release of H₂, and the concomitant replacement of OH^? by O^2?. These oxidation and dehydrogenation processes advanced during the welding to thereby produce oxyallanite. Oxyallanite had been reported only in laboratory studies where it was produced by heating natural allanite. Our report on natural oxyallanite suggests that it may be present in other welded silicic volcanic rocks as well.     

Ferric-ferrous ratios,H2O contents and D/H ratios of phlogopite and biotite from lavas of different tectonic regimes

 Complete chemical analyses, including ferric and ferrous iron, H₂O contents and δD values for 16 phlogopite and biotite and 2 hornblende separates are presented. Samples were obtained from volcanic rocks from four localities: (1) phlogopite phenocrysts from minette lavas from the western Mexico continental arc, (2) biotite and hornblende phenocrysts from andesite lavas from Mono Basin, California, (3) phlogopite and biotite from clinopyroxenite nodules entrained in potassic lavas from the East African Rift, Uganda, and (4) phlogopite phenocrysts from a wyomingite lava in the Leucite Hills, Wyoming. The Fe₂O₃ contents in the micas range from 0.8 to 10.5 wt%, corresponding to 0.09 to 1.15 Fe³⁺ per formula unit (pfu). Water contents vary from 1.6 to 3.0 wt%, corresponding to 1.58 to 3.04 OH pfu, significantly less than would be expected for a site fully occupied by hydroxyl. Cation- and anion-based normalization procedures provide accurate mineral formulae with respect to most cations and anions, but are unable to generate accurate estimates of Fe³⁺/Fe^T, and overestimate OH at the expense of O on the hydroxyl site. These inaccuracies are present despite acceptable adjusted totals and stoichiometric calculated site occupancies. The phlogopite and biotite phenocrysts in arc-related lavas from western Mexico and eastern California have the highest Fe³⁺/Fe^T ratios (56–87%), reflecting high magmatic oxygen fugacities (ΔNNO = +2 to +5), in contrast to those from Uganda (25–40%) and the Leucite Hills (23%). There is no correlation between the OH content and the Fe³⁺/Fe^T ratio in the micas. Values of KMg/Fe²⁺D (± 2σ errors) were calculated for three phlogopite-olivine pairs (0.12 ± 0.12, 0.26 ± 0.14, 0.09 ± 0.12), two biotite-hornblende pairs (0.73 ± 0.08 and 1.22 ± 0.10) and a single phlogopite-augite pair (1.15 ± 0.12). Values of KF/OHD for two biotite and hornblende pairs could not be determined without significant error because of the extremely low F contents (< 0.2 wt%) of the four phases. The δD values obtained in this study encompass a large range (−137 to −43‰). The phlogopite and biotite separates from Uganda have δD values of −70 to −49‰, which overlap those believed to represent “primary” mantle. There is a larger range in δD values (−137 to −43‰) for phlogopite phenocrysts from western Mexico minette lavas, although their range in δ¹⁸O values (5.2–6.2‰) is consistent with “normal” mantle. It is unlikely, therefore, that the variable δD values reflect heterogeneity in the mantle source region of the minette magmas. Nor can the extremely low δD values reflect degassing of H₂ or H₂O since almost 100% loss of dissolved water in the magma is required, an unrealistic scenario given the stability of the hydrous phenocrysts. The very low δD values of the Mascota minette phlogopites require that the hydrogen be introduced from an external source (e.g., meteoric water). Whatever the process responsible for the observed hydrogen isotope composition, it had no effect on the δ¹⁸O value, f _{O 2}, a _{H 2O} or bulk composition of the host magmas. Received: 5 January 1995 / Accepted: 19 March 1996     

H T -XRD study of synthetic ferrian magnesian spodumene: the effect of site dimension on the P 21/ c → C 2/ c phase transition

 Ferrian magnesian spodumene was synthesized in the MLFSH system at P=0.4 GPa, T=700 °C, fO₂=NNO+2.3. The space group at room T is P2₁/c [a=9.638(3) ?, b=8.709(2) ?, c=5.258(2) ?, β=109.83(3)^∘, V=415.2 ?³]. The structure is topologically equivalent to that of ferrian spodumene, LiFeSi₂O₆, and has two symmetrically independent tetrahedral chains, A and B, and two independent octahedral sites, M1 and M2. The crystal-chemical composition was determined combining EMP, SIMS and single-crystal XRD analysis, yielding ^M2(Li_0.85Mg_0.09Fe²⁺ _0.06) ^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆. Li is ordered at the M2 site and Fe³⁺ is ordered at the M1 site, whereas Mg (and Fe²⁺) distribute over both octahedral sites. Structure refinements done at different temperatures (25, 70, 95, 125, 150 and 200 °C) allowed characterization of a reversible displacive P2₁/c→C2/c transition at 106 °C. Previous HT-XRD studies of Li-clinopyroxenes had shown that the transition temperature is inversely related to the size of the M1 cation. For the crystal of this work, the aggregate ionic radius at M1 is longer than that of ferrian spodumene, for which the transition temperature is −44 °C. The higher transition temperature observed can only be explained on the basis of the shorter aggregate radius at the M2 site (due to the presence of Mg substituting after Li), in keeping with the results obtained for ferromagnesian P2₁/c pyroxenes. The effects of all the chemical substitutions must be considered when modelling transition temperatures and thermodynamic behaviour in clinopyroxenes. Received: 7 May 2002 / Accepted: 23 October 2002     

Variation of infrared absorption spectra in the system Bi2Al4−x Fe x O9 (x = 0–4), structurally related to mullite

The crystal structure of Bi₂Al_4−x Fe _x O₉ compounds (x = 0–4) has striking similarities with the crystal structure of mullite. A complete substitution of Al by Fe³⁺ in both octahedral and tetrahedral sites is a particular structural feature. The infrared (IR) spectra of the Bi₂M₄O₉ compounds (M = Al, Fe³⁺) are characterised by three band groups with band maxima in the 900–800, 800–600 and 600–400 cm⁻¹ region. Based on the spectroscopic results obtained from mullite-type phases, the present study focuses on the composition-dependent analysis of the 900–800 cm⁻¹ band group, which is assigned to Al(Fe³⁺)–O stretching vibrations of the corner-sharing MO₄ tetrahedra. The Bi₂Al₄O₉ and Bi₂Fe₄O₉ endmembers display single bands with maxima centred at 922 and 812 cm⁻¹, respectively. Intermediate Bi₂Al_4−x Fe _x O₉ compounds exhibit a distinct splitting into three relatively sharp bands, which is interpreted in terms of ordering effects within the tetrahedral pairs. Thereby the high-energy component band of the band triplet relates to Al–O–Al conjunctions and the low-energy component band to Fe–O–Fe conjunctions. The intermediate band is assigned to stretching vibrations of Al–O–Fe or Fe–O–Al configurations of the corner-sharing tetrahedral pairs. Bands in the 800–600 cm⁻¹ range are assigned to low-energy stretching vibrations of the MO₄ tetrahedra and to M–O–M bending vibrations of the tetrahedral pairs. Absorptions in the 600–400 cm⁻¹ range are essentially determined by M–O stretching modes of the M cations in octahedral coordination.     

Oxyphlogopite K(Mg,Ti,Fe)3[(Si,Al)4O10](O,F)2: A new mineral species of the mica group

Oxyphlogopite is a new mica-group mineral with the idealized formula K(Mg,Ti,Fe)₃[(Si,Al)₄O₁₀](O,F)₂. The holotype material came from a basalt quarry at Mount Rothenberg near Mendig at the Eifel volcanic complex in Rhineland-Palatinate, Germany. The mineral occurs as crystals up to 4 × 4 × 0.2 mm in size encrusting cavity walls in alkali basalt. The associated minerals are nepheline, plagioclase, sanidine, augite, diopside, and magnetite. Its color is dark brown, its streak is brown, and its luster is vitreous. D _meas = 3.06(1) g/cm³ (flotation in heavy liquids), and D _calc = 3.086 g/cm³. The IR spectrun does not contain bands of OH groups. Oxyphlogopite is biaxial (negative); α = 1.625(3), β = 1.668(1), and γ = 1.669(1); and 2V _meas = 16(2)° and 2V _calc = 17°. The dispersion is strong; r < ν. The pleochroism is medium; X > Y > Z (brown to dark brown). The chemical composition is as follows (electron microprobe, mean of 5 point analyses, wt %; the ranges are given in parentheses; the H₂O was determined using the Alimarin method; the Fe²⁺/Fe³⁺ was determined with X-ray emission spectroscopy): Na₂O 0.99 (0.89–1.12), K₂O 7.52 (7.44–7.58), MgO 14.65 (14.48–14.80), CaO 0.27 ((0.17–0.51), FeO 4.73, Fe₂O₃ 7.25 (the range of the total iron in the form of FeO is 11.09–11.38), Al₂O₃ 14.32 (14.06–14.64), Cr₂O₃ 0.60 (0.45–0.69), SiO₂ 34.41 (34.03–34.66), TiO₂ 12.93 (12.69–13.13), F 3.06 (2.59–3.44), H₂O 0.14; O=F₂ −1.29; 99/58 in total. The empirical formula is (K_0.72Na_0.14Ca_0.02)(Mg_1.64Ti_0.73Fe_0.30²⁺ Fe_0.27³⁺Cr_0.04)_Σ2.98(Si_2.59Al_1.27Fe_0.14³⁺ O₁₀) O_1.20F_0.73(OH)_0.07. The crystal structure was refined on a single crystal. Oxyphlogopite is monoclinic with space group C2/m; the unit-cell parameters are as follows: a = 5.3165(1), b = 9.2000(2), c = 10.0602(2) ?, β = 100.354(2)°. The presence of Ti results in the strong distortion of octahedron M(2). The strongest lines of the X-ray powder diffraction pattern [d, ? (I, %) [hkl]] are as follows: 9.91(32) [001], 4.53(11) 110], 3.300(100) [003], 3.090(12) [112], 1.895(21) [005], 1.659(12) [−135], 1.527(16) [−206, 060]. The type specimens of oxyphlogopite are deposited at the Fersman Mineralogical Museum in Moscow, Russia; the registration numbers are 3884/2 (holotype) and 3884/1 (cotype).     

The influence of crystal field stabilization energy on Fe2+ partitioning in paragenetic minerals

In order to explore possible quantitative relations between crystal field stabilization energy, CFSE, and partitioning behaviour of the 3d ⁶-configured Fe²⁺ ion, a suite of 29 paragenetic rock-forming minerals from 12 high-grade metamorphic rock samples of the Ukrainian shield, including the parageneses garnet/orthopyroxene/clinopyroxene (2x), orthopyroxene/clinopyroxene, garnet/clinopyroxene, garnet/orthopyroxene/biotite, garnet/biotite, garnet/cordierite, garnet/cordierite/biotite, garnet/orthopyroxene/clinopyroxene/Ca-amphibole, Ca-amphibole/biotite (retrograde), was studied by electron microprobe analysis to obtain the respective K _D Fe^{2+ (Ph1/Ph2)} values and by polarized single crystal electronic absorption spectroscopy to evaluate the respective CFSE_Fe2+ values. Other than in the case of Cr³⁺, a clear quantitative relation between K _D ^(Ph1/Ph2) and the ΔCFSE^(Ph1/Ph2) was only observed when geometrical factors, mainly the volume of crystallographic sites and ionic radii of ions competing in the partitioning process, are similar in the respective two paragenetic phases to within 15–20%. In such cases, the ΔCFSE_Fe2+ contribution to K _D ^(Ph1/Ph2) amounts to 0.1 to 0.2 log K _D per 100 cm⁻¹ΔCFSE. The conclusion is that ΔCFSE_Fe2+ plays only a secondary role after geometrical factors, in the partitioning behaviour of Fe²⁺. The reason for this is seen in the facts that, compared to the 3d ³-configured Cr³⁺ ion, CFSE of the 3d ⁶-configured Fe²⁺ amounts only to 20–25%, and that the former ion enters only octahedral sites with similar geometrical properties in the paragenetic mineral phases. Received: 17 November 1998 / Accepted: 28 June 1999     

Solid solutions of (Mg,Fe<Superscript>2+</Superscript>)-cordierite: Synthesis,water content,and magnetic properties

The dependence of water concentration in synthetic (Mg, Fe²⁺)-cordierite on the composition of the solid solution was examined in experiments that lasted for 10 days at = 200–230 MPa, t = 600–700°C, and oxygen fugacity corresponding to the Fe-FeO buffer. Mass spectrometric data indicate that the dependence of water concentration in cordierite on its Fe mole fraction Fe²⁺/(Fe²⁺ + Mg) has maxima at compositions with F = 0.2–0.3. IR diffuse reflectance spectroscopic data and data on the structural setting of H₂O molecules in the structural channels of alkali-free (Mg, Fe²⁺)-cordierite indicate that the H-H vector of some H₂O molecules (H₂O-II) is perpendicular to [001] of the crystal. The dependence of the magnetic properties of synthetic (Mg, Fe²⁺)-cordierite was studied by static magnetization technique at 5–300 K in an external magnetic field up to 20 kOe in strength.     

Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

Tashelgite, CaMgFe2 + Al9O16(OH), a new mineral species from calc-skarnoid in Gorny Shoria

A new mineral species has been discovered at the calc-skarnoid occurrence near the mouth of the Tashelga River, Kuznetsky Alatau, Gorny Shoria, Russia, and named after the locality of its discovery. Associated minerals are calcite, hibonite, grossular, vesuvianite, hercynite, magnetite, corundum, perovskite, scapolite, diopside, and apatite. The new mineral occurs as prismatic or finely fibrous crystals up to 1.5–2.0 mm in length, their parallel intergrowths, and felty aggregates as large as 10 mm across. Tashelgite is bluish green, translucent to transparent, with vitreous luster; D _calc = 3.67 g/cm³. The IR spectrum does not contain bands of OH groups. Tashelgite is biaxial (−), with α = 1.736(2), β = 1.746(2), γ = 1.750(2); 2V _meas = −20(2)°. Dispersion is strong, r < ν. Pleochroism is distinct: X (blue-green) > Y (yellowish green) > Z (almost colorless). Chemical composition (electron microprobe, average of five-point analyses, Fe₂O₃ is estimated from the ratio of intensities I(Fe_Kb5 )/I(Fe_Kb1 )I(Fe_{K\beta _5 } )/I(Fe_{K\beta _1 } ) in the X-ray spectrum, H₂O was determined as a weight loss on heating in vacuum up to 1000°C), wt %: 7.98 CaO, 6.75 MgO, 0.45 MnO, 11.32 FeO, 1.40 Fe₂O₃, 70.70 Al₂O₃, 1.8(2) H₂O, 100.40 in total. The empirical formula calculated on the basis of 17 oxygen atoms is H_1.27Ca_0.90Mg_1.06Mn_0.04 Fe_1.00²⁺Fe_0.11³⁺Al_8.80O_17.00. The idealized formula is CaMgFe²⁺Al₉O₁₆(OH). According to single-crystal X-ray structural data, tashelgite is monoclinic, pseudoorthorhombic, space group Pc; unit cell parameters are: a = 5.6973(1), b = 17.1823(4), c = 23.5718(5)?; β = 90.046(3)°; V = 2307.5(1)?³, Z = 8. The crystal structure of tashelgite is unique and characterized by ordering of all cations; Al occupies sites with octahedral and tetrahedral coordination. The cation ordering has also been confirmed by IR spectroscopy. The strongest lines of the X-ray powder diffraction pattern (d, ?]-I[hkl] are: 11.79–48 [002], 2.845–43 [061], 2.616–100 [108], 2.584–81 [146], 2.437–44 [163], 2.406–61 [057], 2.202–72 [244]. The type specimen of tashlegite has been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, Russia.     

A clinopyroxene geobarometer for basaltic systems based on crystal-structure modeling

 The crystal chemical response of basalt clinopyroxene to increasing pressure was investigated by means of crystal-structure simulation (a procedure that enables modeling of the structural parameters of a clinopyroxene of known chemistry without requiring direct X-ray diffraction analysis) using available experimental chemical data. Pressure proved the main physical variable governing clinopyroxene behavior in a magmatic environment. The general internal consistency of the simulation data permitted construction of an empirical geobarometer based on the relationship of cell volume (Vc) vs M1-site volume (VM1). The straightforward geobarometric formulation in the absence of direct X-ray analysis is: P(kbar)=698.443+4.985⋅Al_T−26.826⋅Fe²⁺ _M1−3.764⋅Fe³⁺ +53.989⋅Al_M1+3.948⋅Ti+14.651⋅Cr −700.431⋅Ca−666.629⋅Na−682.848⋅Mg_M2−691.138⋅Fe²⁺ _M2−688.384⋅Mn−6.267⋅(Mg_M2)²−4.144⋅(Fe²⁺ _M2 where: (Fe²⁺ _M1⋅Mg_M2)/(Fe²⁺ _M2⋅Mg_M1)=e^**(0.238⋅R³⁺+0.289⋅CNM−2.315), CNM=Ca+Na+Mn, and R³⁺=Al_M1+Fe³⁺+Ti+Cr, with cations in atoms per formula unit. The geobarometer reproduces experimental pressures within ±2 kbar (=1σ; max. dev. ≤5 kbar; N=29) in the range 0–24 kbar and is applicable to near-liquidus C2/c clinopyroxenes crystallized from basaltic melts in the absence of garnet (excepting high-Al₂O₃ basalts). It is therefore suitable for many natural clinopyroxenes occurring as mega- or phenocrysts or forming well-preserved cumulate pyroxenites. If the above restrictions are not wholly satisfied, the Vc vs VM1 plot can also be used qualitatively to deduce the relative pressure conditions of clinopyroxenes forming from similar batches of magma. The structural simulation of experimental data also provided insight into the influence of minor chemical changes of the parental magma on the crystal chemistry of clinopyroxene at high pressure. Within the considered compositional space at given P-T, a _CaO and a _SiO2 in the melt have opposite effects on M2- and T-site cation populations. As a result, under similar physical conditions, clinopyroxenes from higher-CaO or more undersaturated basalts have higher VM2, VT and Vc and lower VM1. For basalts with normal contents of Al₂O₃ (<18 wt %), variations of major elements in the melt do not reduce the accuracy of the geobarometer. Received: 3 April 1994 / Accepted: 23 December 1995     

A metallogenic survey of alkalic rocks of Mt. Somma-Vesuvius volcano

Summary Somma-Vesuvius is an alkaline volcano whose products (pumice, scoria and lava) have alkaline (Na₂O + K₂O) contents between 6 and 16 wt%, Mg number <50, SiO₂ 59–47 wt% and MgO 0–7.8 wt% (more than 50% of the samples have a content <2 wt%). Immobile-element ratios (Th/Yb, Ta/Yb, Ce/Yb) indicate a shoshonitic character, while the K₂O content (4–10 wt%) is characteristic of ultrapotassic rocks. The behavior of selected metals is discussed by grouping them on the basis of the stratigraphic sequence and differentiating the volcanic activity between plinian and interplinian (Rolandi et al., 1998; Ayuso et al., 1998). This allows observation of the variation within each formation from 25.000 y. BP to the last historic eruptive cycle (1631–1944 AD). The main processes to explain the wide distribution of the data presented are fractional crystallization of a mantle-derived magma, magma mixing, and contamination with heterogeneous lower and/or upper crust. Variation diagrams distinguish different behavior for groups of metals: Ag (0.01–0.2 ppm), Mo (1–8.8 ppm), W (1.3–13 ppm), Pb (16–250 ppm), Sb (0.2–2.6 ppm), Sc (0.2–61 ppm), Li (15–140 ppm) and Be (1–31 ppm) increase with increasing differentiation and tend to correlate with the incompatible trace elements (Th, Hf, etc). Cu (10–380 ppm), Au (2–143 ppb), Co (0.7–35.1 ppm) and Fe (1.3–6.2 wt%) decrease towards advanced stage of differentiation. Iron also identifies three magmatic groups. The ratio Fe³⁺/Fe²⁺ ranges between 0.2 and 1.8, and Fe₂O₃/(Fe₂O₃ + FeO) ranges between 0.2 and 0.8, giving rise to an oxidized environment; exceptions are in the samples belonging to the interplinian formations: I, II, medieval and 1631–1994 AD. Fluorine ranges between 0.1 and 0.4 wt% for the complete Mt. Somma-Vesuvius activity, except for the Ottaviano and Avellino plinian (0.8 wt%) events. Chlorine has a wider range, from 0.1 wt% to 1.6 wt%. Mt Somma-Vesuvius has some features similar to those of mineralized alkaline magmatic systems which coincide with the transition between subduction-related compression and extension-related to continental rifting. We infer that a prospective time for the formation of mineralization at Mt Somma-Vesuvius was during the 1631–1944 eruptive period. Received March 27, 2000; revised version accepted February 28, 2001     

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     

Iron in monticellite as an oxygen barometer for kimberlite magmas

Monticellite is a common magmatic mineral in the groundmass of kimberlites. A new oxygen barometer for kimberlite magmas is calibrated based on the Fe content of monticellite, CaMgSiO₄, in equilibrium with kimberlite liquids in experiments at 100 kPa from 1,230 to 1,350°C and at logfO₂ from NNO-4.1 to NNO+5.3 (where NNO is the nickel–nickel oxide buffer). The XFe_Mtc/XFe_liq was found to decrease with increasing fO₂, consistent with only Fe²⁺ entering the monticellite structure. Although the XFe-in-monticellite varies with temperature and composition, these dependencies are small compared to that with fO₂. The experimental data were fitted by weighted least square regression to the following relationship: \Updelta \textNNO = \frac{ log[ 0.858( ±0.021)\fracX_\textFe^\textLiq X_\textFe^\textMtc ] - 0.139( ±0.022) }0.193( ±0.004) \Updelta {\text{NNO}} = \frac{{\left\{ {\log \left[ {0.858( \pm 0.021)\frac{{X_{\text{Fe}}^{\text{Liq}} }}{{X_{\text{Fe}}^{\text{Mtc}} }}} \right] - 0.139( \pm 0.022)} \right\}}}{0.193( \pm 0.004)} where ΔNNO is the fO₂ relative to that of the Nickel-bunsenite (NNO) buffer and XFe_liq/XFe_Mtc is the ratio of mole fraction of Fe in liquid and Fe-in-monticellite (uncertainties at 2σ). The application of this oxygen barometer to natural kimberlites from both the literature and our own investigations, assuming the bulk rock FeO is that of their liquid FeO, revealed a range in fO₂ from NNO-3.5 to NNO+1.7. A range of Mg/(Mg + Fe²⁺) (Mg#) for kimberlite melts of 0.46–0.88 was derived from the application of the experimentally determined monticellite-liquid Kd Fe²⁺–Mg to natural monticellites. The range in Mg# is broader and less ultramafic than previous estimates of kimberlites, suggesting an evolution under a wide range of petrologic conditions.     

The stability of primary alluaudites in granitic pegmatites: an experimental investigation of the Na2(Mn2−2x Fe1+2x )(PO4)3 system

In order to assess the geothermometric potential of the Na₂(Mn_2−2x Fe_1+2x )(PO₄)₃ system (x = 0–1), which represents the compositions of natural weakly oxidized alluaudites, we performed hydrothermal experiments between 400 and 800°C, at 1 kbar, under an oxygen fugacity (f(O₂)) controlled by the Ni–NiO (NNO), Fe₂O₃–Fe₃O₄ (HM), Cu₂O–CuO (CT), and Fe–Fe₃O₄ (MI) buffers. When f(O₂) is controlled by NNO, single-phase alluaudites crystallize at 400 and 500°C, whereas the association alluaudite + marićite appears between 500 and 700°C. The limit between these two fields corresponds to the maximum temperature that can be reached by alluaudites in granitic pegmatites, because marićite has never been observed in these geological environments. Because alluaudites are very sensitive to variations of oxygen fugacity, the field of hagendorfite, Na₂MnFe²⁺Fe³⁺(PO₄)₃, has been positioned in the f(O₂)–T diagram, and provides a tool that can be used to estimate the oxygen fugacity conditions that prevailed in granitic pegmatites during the crystallization of this phosphate.     

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     

Paragenesis of unusual Fe-cordierite (sekaninaite)-bearing paralava and clinker from the Kuznetsk coal basin,Siberia, Russia

Sekaninaite (X_Fe > 0.5)-bearing paralava and clinker are the products of ancient combustion metamorphism in the western part of the Kuznetsk coal basin, Siberia. The combustion metamorphic rocks typically occur as clinker beds and breccias consisting of vitrified sandstone–siltstone clinker fragments cemented by paralava, resulting from hanging-wall collapse above burning coal seams and quenching. Sekaninaite–Fe-cordierite (X_Fe = 95–45) is associated with tridymite, fayalite, magnetite, ± clinoferrosilite and ±mullite in paralava and with tridymite and mullite in clinker. Unmelted grains of detrital quartz occur in both rocks (<3 vol% in paralavas and up to 30 vol% in some clinkers). Compositionally variable siliceous, K-rich peraluminous glass is <30% in paralavas and up to 85% in clinkers. The paralavas resulted from extensive fusion of sandstone–siltstone (clinker), and sideritic/Fe-hydroxide material contained within them, with the proportion of clastic sediments ≫ ferruginous component. Calculated dry liquidus temperatures of the paralavas are 1,120–1,050°C and 920–1,050°C for clinkers, with calculated viscosities at liquidus temperatures of 10^1.6–7.0 and 10^7.0–9.8 Pa s, respectively. Dry liquidus temperatures of glass compositions range between 920 and 1,120°C (paralava) and 920–960°C (clinker), and viscosities at these temperatures are 10^9.7–5.5 and 10^8.8–9.7 Pa s, respectively. Compared with worldwide occurrences of cordierite–sekaninaite in pyrometamorphic rocks, sekaninaite occurs in rocks with X_Fe (mol% FeO/(FeO + MgO)) > 0.8; sekaninaite and Fe-cordierite occur in rocks with X_Fe 0.6–0.8, and cordierite (X_Fe < 0.5) is restricted to rocks with X_Fe < 0.6. The crystal-chemical formula of an anhydrous sekaninaite based on the refined structure is | \textK_0.02 |(\textFe_1.54^{2 +} \textMg_0.40 \textMn_0.06 )_{\Upsigma 2.00}^M [(\textAl_1.98 \textFe_0.02^{2 +} \textSi_1.00 )_{\Upsigma 3.00}^T1 (\textSi_3.94 \textAl_2.04 \textFe_0.02^{2 +} )_{\Upsigma 6.00}^T2 \textO₁₈ ]. \left| {{\text{K}}_{0.02} } \right|({\text{Fe}}_{1.54}^{2 + } {\text{Mg}}_{0.40} {\text{Mn}}_{0.06} )_{\Upsigma 2.00}^{M} [({\text{Al}}_{1.98} {\text{Fe}}_{0.02}^{2 + } {\text{Si}}_{1.00} )_{\Upsigma 3.00}^{T1} ({\text{Si}}_{3.94} {\text{Al}}_{2.04} {\text{Fe}}_{0.02}^{2 + } )_{\Upsigma 6.00}^{T2} {\text{O}}_{18} ].     

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