Experimental study of chloritoid stability at high pressure and various fO2 conditions

The reaction chloritoid (ctd)=almandine (alm)+diaspore+H₂O (CAD) has been reversed using Fe³⁺-free synthetic chloritoid and almandine, under fO₂ conditions of the solid oxygen buffer Fe/FeO (CADWI), and using partially oxidized synthetic minerals under fO₂ conditions of the solid oxygen buffer Ni/NiO (CADNNO). Experiments have been conducted between 550 and 700°C, 25 and 45 kbar. The equilibrium pressure and temperature conditions are strongly dependent on the fO₂ conditions (CADNNO lies some-what 50°C higher than CADWI). This can be explained by a decrease in aH₂O for experiments conducted on the Fe/FeO buffer, and a decrease in actd and aalm (through incorporation of ferric iron preferentially in chloritoid) for experiments conducted on the Ni/NiO buffer. The H₂O activity has been calculated using the MRK equation of state, and the values obtained checked against the shift of the equilibrium diaspore=corundum+H₂O bracketed on the Fe/FeO buffer and under unbuffered fO₂ conditions. For fO₂ buffered by the assemblage Fe/FeO, aH₂O increases with pressure from about 0.85 at 600°C, 12 kbar to about 0.9 at 605°C, 25 kbar and 1 above 28 kbar. For fO₂ buffered by the assemblage Ni/NiO, aH₂O=1. The aH₂O decrease from Ni/NiO to Fe/FeO is, however, too small to be entirely responsible for the temperature shift between CADNNO and CADWI. In consequence, the amount of ferric iron in almandine and chloritoid growing in the CADNNO experiments must be significant and change along the CADNNO, precluding calculation of the thermodynamic properties of chloritoid from this reaction. Our experimental data obtained on the Fe/FeO buffer are combined, using a thermodynamic analysis, with Ganguly's (1969) reversal of the reaction chloritoid=almandine+corundum +H₂O (CAC) on the same oxygen buffer. Experimental brackets are mutually consistent and allow extraction of the thermodynamic parameters H ^o f,ctd and S ^octd. Our thermodynamic data are compared with others, generally calculated using Ganguly's bracketing of CACNNO. The agreement between the different data sets is relatively good at low pressure, but becomes rapidly very poor toward high pressure conditions. Using our thermodynamic data for chloritoid and K_D=(Fe³⁺/Al)ctd/(Fe³⁺/Al)alm estimated from natural assemblages, we have calculated the composition of chloritoid and almandine growing from CADNNO and CACNNO. The Fe³⁺ content in chloritoid and almandine increases with pressure, from less than 0.038 per FeAl₂SiO₅(OH)₂ formula unit at 10 kbar to at least 0.2 per formula unit above 30 kbar. This implies that chloritoid and almandine do contain Fe³⁺ in most natural assemblages. The reliability of our results compared to natural systems and thermodynamic data for Mg-chloritoid is tested by comparing the equilibrium conditions for the reaction chloritoid+quartz=garnet (gt)+kyanite+H₂O (CQGK), calculated for intermediate Fe–Mg chloritoid and garnet compositions, from the system FASH and from the system MASH. For 0.65<(XFe)gt<0.8, CQKG calculated from FASH and MASH overlap for K_D=(Mg/Fe)ctd/(Mg/Fe)gt=2. This is in good agreement with the K_D values reported from chloritoid+garnet+quartz+kyanite natural assemblages.     

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     

Compositions and phase relations of calcic amphiboles in epidote- and clinopyroxene-bearing rocks of the amphibolite and lower granulite facies,central Massachusetts,USA

Calcic amphiboles coexisting with epidotegroup minerals (zoisite, clinozoisite, epidote) and/or clinopyroxene±plagioclase±quartz±garnet occur in amphibolites and calc-silicate rocks that underwent amphibolite to lower granulite-facies metamorphism in the Acadian metamorphic high of central Massachusetts, USA. Across the region, peak metamorphic conditions range from about 580° C and 6.2 kbar to 730° C and 6.3 kbar. The coexistence of most Ca-amphiboles with Fe³⁺-rich epidote-group minerals suggests the presence of Fe³⁺ in most of these amphiboles. An empirical Fe³⁺ estimation for the microprobe analyses is based on two constraints: the Na?Ca content of the M4 sites of Ca-saturated, gravimetrically analyzed hornblendes gives the relation: Ca(M4) ^c =-1.479 Na(M4) ^c +2 (c=corrected). The second constraint is the stoichiometric equation Ca(M4)+Na(M4)+FM=15, where FM is the sum of all cations exclusive of Ca, Na, and K. Solving the two equations simultaneously gives: 20.185=0.479 Ca(M4)+1.479 ΣFM. Starting with the uncorrected values of Ca(M4) ^u and ΣFM(M4) ^u (u = uncorrected) of the all ferrous formula, the normalization factor NF for calculating the corrected cations of the ferric formulas is: 20.185/(0.478 Ca(M4) ^u +1.479 ΣFM ^u ). From the deficient oxygen the Fe³⁺ content which is equal to 2(23-ΣOX) can be calculated. Determinations of Fe³⁺ contents of four hornblende separates by Mössbauer spectroscopy are in agreement with the calculated values. The Ca-amphiboles show systematic changes in composition with increasing grade of metamorphism within the amphibolite and lower granulite-facies zones: increasing edenite and tschermakite substitution, increasing Ti content, and increasing Fe²⁺/(Fe²⁺+Mg) ratio. In addition, the coexisting clinopyroxenes are also characterized by an increase in Fe²⁺/(Fe²⁺+Mg) ratio. In quartz-free rocks with coexisting Ca-amphibole and plagioclase there is an increase in the ratio X _Ab/X _Ed, where X _Ab=Na/(Na+Ca) in plagioclase and X _Ed=Na in the amphibole A-site. These chemical changes in mineral composition together with the disappearance of epidote at the transition to granulite-facies metamorphic conditions are attributed to the continuous reaction: albite+epidote+Fe-Mg hornblende→Fe?Mg clinopyroxene+anorthite+(NaAlSi_-1)^Hbl+H₂O.     

Geochemistry of coexisting hornblende and biotite from the Ambalavayal granite,Kerala

Major and trace element geochemistry of coexisting hornblendes and biotites from the Ambalavayal granite, northern Kerala, are presented. The hornblendes correspond to edenitic composition, whereas the biotites correspond to annite. The hornblendes typically show high Al₂O₃ contents (9·69–11·89%) comparable with those from anorogenic granites. The biotites are characteristically low Mg-type, similar to those reported from alkaline rocks. The distribution coefficients calculated for all the major and trace elements are presented and an evaluation of the nature of variation indicate near-chemical equilibrium conditions during the crystallization of the two minerals. The hornblende-biotite tie lines in the Fe³⁺?Fe²⁺?Mg compositional triangle, lie parallel to those of buffered biotites, indicating crystallization in an environment closed to oxygen and well above the Ni?NiO buffer. It is inferred that thefH₂O increased towards the residual stage andfO₂ values were high, in the range of 10^?15 bars.     

Biotite and garnet compositional variation and mineral equilibria in Grenville gneisses of the Otter Lake area, Quebec

Garnet-biotite gneisses, some of which contain sillimanite or hornblende, are widespread within the Otter Lake terrain, a portion of the Grenville Province of the Canadian Shield. The metamorphic grade is upper amphibolite to, locally, lower granulite facies. The atomic ratio Fe²⁺/(Fe²⁺+ Fe³⁺) in biotite ranges from 0.79 to 0.89 (ferrous iron determinations in 10 highly pure separates), with a mean of 0.86. Mg and Fe²⁺ atoms occupy 67–78% of the octahedral sites, the remainder are occupied by Fe³⁺, Ti, and Al, and some are vacant. Mg/(Mg + Fe²⁺), denoted X, in the analysed samples ranges from 0.32 to 0.65. Garnet contains 1–24% grossular, 1–12% spessartine and X ranges from 0.07 to 0.34. Compositional variation in biotite and garnet is examined in relation to three mineral equilibria: (I) biotite + sillimanite + quartz = garnet + K-feldspar + H₂O; (II) pyrope + annite = almandine + phlogopite; (III) anorthite = grossular + sillimanite + quartz. Measurements of X (biotite) and X (garnet) are used to construct an illustrative model for equilibrium (I) which relates the observed variation in X to a temperature range of 70°C or a range in H₂O activity of 0.6; the latter interpretation is preferred. In sillimanite-free gneisses, the distribution of Mg and Fe²⁺ between garnet (low in Ca and Mn) and biotite is adequately described by a distribution coefficient (KD) of 4.1 (equilibrium II). The observed increase in the distribution coefficient with increasing Ca in garnet is ln K_D= 1.3 + 2.5 × 10^?2 [Ca] where [Ca] = 100 Ca/(Mg + Fe²⁺+ Mn + Ca). The distribution coefficient is apparently unaffected by the presence of up to 12% spessartine in garnet. In several specimens of garnet-sillimanite-plagioclase gneiss, the Ca contents of garnet and of plagioclase increase in unison, as required by equilibrium (III). The mean pressure calculated from these data (n= 17) is 5.9 kbar, and the 95% confidence limits are ±0.5 kbar.     

Quantitative P–T–X constraints on orthopyroxene-bearing high-pressure granulites in felsic–metapelitic rocks: evidence from the Huangtuling granulite, Dabieshan Orogen

High‐pressure granulites are generally characterized by the absence of orthopyroxene. However, orthopyroxene is reported in a few high‐pressure, felsic–metapelitic granulites, such as the Huangtuling felsic high‐pressure granulite in the North Dabie metamorphic core complex in east‐central China, which rarely preserves the high‐pressure granulite facies assemblage of garnet + orthopyroxene + biotite + plagioclase + K‐feldspar + quartz. To investigate the effects of bulk‐rock composition on the stability of orthopyroxene‐bearing, high‐pressure granulite facies assemblages in the NCKFMASHTO (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃) system, a series of P–T–X pseudosections based on the melt‐reintegrated composition of the Huangtuling felsic high‐pressure granulite were constructed. Calculations demonstrate that the orthopyroxene‐bearing, high‐pressure granulite facies assemblages are restricted to low X_Al [Al₂O₃/(Na₂O + CaO + K₂O + FeO + MgO + Al₂O₃) < 0.35, mole proportion] or high X_Mg [MgO/(MgO + FeO) > 0.85] felsic–metapelitic rock types. This study also reveals that the X_Al values in the residual felsic–metapelitic, high‐pressure granulites could be significantly reduced by a high proportion of melt loss. We suggest that orthopyroxene‐bearing, high‐pressure granulites occur in residual overthickened crustal basement under continental subduction–collision zones and arc–continent collision belts.     

Crystal chemistry of amphiboles: implications for oxygen fugacity and water activity in lithospheric mantle beneath Victoria Land,Antarctica

Amphibole is the hydrous metasomatic phase in spinel-bearing mantle xenoliths from Baker Rocks, Northern Victoria Land, Antarctica. It occurs in veins or in disseminated form in spinel lherzolites. Both types derive from reaction between metasomatic melts and the pristine paragenesis of the continental lithospheric mantle beneath Northern Victoria Land. To determine the effective role of water circulation during the metasomatic process and amphibole formation, six amphibole samples were fully characterized. Accurate determination of the site population and the state of dehydrogenation in each of these amphiboles was carried out using single-crystal X-ray diffraction, electron microprobe and secondary ion mass spectroscopy on the same single crystal. The Fe³⁺/ΣFe ratio was determined by X-ray absorption near edge spectroscopy on amphibole powder. The degree of dehydrogenation determined by SIMS is 0.870–0.994 O3(O^2?) a.p.f.u., primary and ascribed to the Ti-oxy component of the amphibole, as indicated by atom site populations; post-crystallization H loss is negligible. Estimates of aH₂O (0.014–0.054) were determined from the dehydration equilibrium among end-member components assuming that amphiboles are in equilibrium with the anhydrous peridotitic phases. A difference up to 58 % in determination of aH₂O can be introduced if the chemical formula of the amphiboles is calculated based on 23 O a.p.f.u. without knowing the effective amount of dehydrogenation. The oxygen fugacity of the Baker Rocks amphibole-bearing mantle xenoliths calculated based upon the dissociation constant of water (by oxy-amphibole equilibrium) is between ?2.52 and ?1.32 log units below the fayalite–magnetite–quartz (FMQ) buffer. These results are systematically lower and in a narrow range of values relative to those obtained from anhydrous olivine–orthopyroxene–spinel equilibria (fO₂ between ?1.98 and ?0.30 log units). A comparative evaluation of the two methods suggests that when amphibole is present in mantle peridotites, the application of oxy-amphibole equilibrium is preferred, because ol–opx–sp oxy-calibrations are not “sensitive” enough in recording the effects (if any) of amphibole in the peridotite matrix. Amphibole acts as the main H acceptor among the peridotite minerals and may prevent fluid circulation and buffer oxygen fugacity. The important conclusion of this study is that amphibole within the lithospheric mantle does not always means high water activity and oxidizing conditions.     

The application of P–T–X(CO2) modelling in constraining metamorphism and hydrothermal alteration at the Damang gold deposit,Ghana

Orogenic gold mineralization at the Damang deposit, Ghana, is associated with hydrothermal alteration haloes around gold‐bearing quartz veins, produced by the infiltration of a H₂O–CO₂–K₂O–H₂S fluid following regional metamorphism. Alteration assemblages are controlled by the protoliths with sedimentary rocks developing a typical assemblage of muscovite, ankerite and pyrite, while intrusive dolerite bodies contain biotite, ankerite and pyrrhotite, accompanied by the destruction of hornblende. Mineral equilibria modelling was undertaken with the computer program thermocalc , in subsets of the model system MnO–Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–CO₂–H₂O–TiO₂–Fe₂O₃, to constrain conditions of regional metamorphism and the subsequent gold mineralization event. Metapelites with well‐developed amphibolite facies assemblages reliably constrain peak regional metamorphism at ~595 °C and 5.5 kbar. Observed hydrothermal alteration assemblages associated with gold mineralization in a wide compositional range of lithologies are typically calculated to be stable within P–T–X(CO₂) arrays that trend towards lower temperatures and pressures with increasing equilibrium fluid X(CO₂). These independent P–T–X(CO₂) arrays converge and the region of overlap at ~375–425 °C and 1–2 kbar is taken to represent the conditions of alteration approaching equilibrium with a common infiltrating fluid with an X(CO₂) of ~0.7. Fluid‐rock interaction calculations with M–X(CO₂) diagrams indicate that the observed alteration assemblages are consistent with the addition of a single fluid phase requiring minimum fluid/rock ratios on the order of 1.     

Sapphirine parageneses from the Caraiba complex, Bahia, Brazil: the influence of Fe2+–Fe3+ distribution on the stability of sapphirine in natural assemblages

Abstract Sapphirine-bearing rocks occur in three conformable, metre-size lenses in intrusive quartzo-feldspathic orthogneisses in the Curaçà valley of the Archaean Caraiba complex of Brazil. In the lenses there are six different sapphirine-bearing rock types, which have the following phases (each containing phlogopite in addition): A: Sapphirine, orthopyroxene; B: Sapphirine, cordierite, orthopyroxene, spinel; C: Sapphirine, cordierite; D: Sapphirine, cordierite, orthopyroxene, quartz; E: Sapphirine, cordierite, orthopyroxene, sillimanite, quartz; F: Sapphirine, cordierite, K-feldspar, quartz. Neither sapphirine and quartz nor orthopyroxene and sillimanite have been found in contact, however. During mylonitization, introduction of silica into the three quartz-free rocks (which represent relict protolith material) gave rise to the three cordierite and quartz-bearing rocks. Stable parageneses in the more magnesian rocks were sapphirine–orthopyroxene and sapphirine–cordierite. In more iron-rich rocks, sapphirine–cordierite, sapphirine-cordierite–sillimanite, cordierite–sillimanite, sapphirine–cordierite–spinel–magnetite and quartz–cordierite–orthopyroxene were stable. The iron oxide content in sapphirine of the six rocks increases from an average of 2.0 to 10.5 wt % (total Fe as FeO) in the order: C,F–A,D–B,E. With increase in Fe there is an increase in recalculated Fe₂O₃ in sapphirine. The four rock types associated with the sapphirine-bearing lenses are: I: Orthopyroxene, cordierite, biotite, quartz, feldspar tonalitic to grandioritic gneiss; II: Biotite, quartz, feldspar gneiss; III: Orthopyroxene, clinopyroxene, hornblende, plagioclase meta-norite; IV: Biotite, orthopyroxene, quartz, feldspar, garnet, cordierite, sillimanite granulite gneiss. The stable parageneses in type IV are orthopyroxene–cordierite–quartz, garnet–sillimanite–quartz and garnet–cordierite–sillimanite. Geothermobarometry suggests that the associated host rocks equilibrated at 720–750°C and 5.5–6.5 kbar. Petrogenetic grids for the FMASH and FMAFSH (FeO–MgO–Al₂O₃–Fe₂O₃–SiO₂–H₂O) model systems indicate that sapphirine-bearing assemblages without garnet were stabilized by a high Fe³⁺ content and a high X_Mg= (Mg/ (Mg+Fe²⁺)) under these P–T conditions.     

Stability of sapphirine + quartz in the oxidized rocks of the Wilson Lake terrane,Labrador: calculated equilibria in NCKFMASHTO

The equilibrium coexistence of sapphirine + quartz is inferred to record temperatures in excess of 980 °C, based on the stability of this assemblage in the simplified chemical system FeO–MgO–Al₂O₃–SiO₂ (FMAS) system. However, the potential for sapphirine to contain significant Fe³⁺ suggests that the stability of sapphirine + quartz could extend to lower temperatures than those constrained in this ideal system. The Wilson Lake terrane in the Grenville Province of central Labrador preserves sapphirine + quartz‐bearing assemblages in highly oxidized bulk compositions, and provides an opportunity to explore the stability of sapphirine + quartz in such rock compositions within the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) chemical system. Starting with the phase equilibria in FeO–MgO–Al₂O₃–SiO₂–TiO₂–O (FMASTO), expansion into K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (KFMASHTO) allows the effect of the stability of the additional phases, biotite, K‐feldspar and melt, on the stability of sapphirine + quartz to be assessed. These phase relations are evaluated generally using P–T projections, and the ultimate extension into NCKFMASHTO is done with pseudosections. Conditions of peak metamorphism in the Wilson Lake terrane are constrained using P–T pseudosections, and the appropriate H₂O and O contents to use in the modelled compositions are investigated using T–M_H2O and T–M_O pseudosections. The peak P–T estimates from a sapphirine + quartz‐bearing sample are ～960 to 935 °C at ～10 to 8.6 kbar, similar to estimates from orthopyroxene + sillimanite + quartz ± garnet‐bearing samples. Whereas the sapphirine + quartz‐bearing sample is more Fe‐rich than the orthopyroxene + sillimanite‐bearing sample on an all‐Fe‐as‐FeO basis, once the oxidation state is taken into account, the former is effectively more magnesian than the latter, accounting for the sapphirine occurrence.     

Calculated phase equilibria in K2O-FeO-MgO-Al2O3-SiO2-H2O for sapphirine-quartz-bearing mineral assemblages

Sapphirine, coexisting with quartz, is an indicator mineral for ultrahigh‐temperature metamorphism in aluminous rock compositions. Here a new activity‐composition model for sapphirine is combined with the internally consistent thermodynamic dataset used by THERMOCALC, for calculations primarily in K₂O‐FeO‐MgO‐Al₂O₃‐SiO₂‐H₂O (KFMASH). A discrepancy between published experimentally derived FMAS grids and our calculations is understood with reference to H₂O. Published FMAS grids effectively represent constant a_H2O sections, thereby limiting their detailed use for the interpretation of mineral reaction textures in compositions with differing H₂O. For the calculated KFMASH univariant reaction grid, sapphirine + quartz assemblages occur at P–T in excess of 6–7 kbar and 1005 °C. Sapphirine compositions and composition ranges are consistent with natural examples. However, as many univariant equilibria are typically not ‘seen’ by a specific bulk composition, the univariant reaction grid may reveal little about the detailed topology of multi‐variant equilibria, and therefore is of limited use for interpreting the P–T evolution of mineral assemblages and reaction sequences. Calculated pseudosections, which quantify bulk composition and multi‐variant equilibria, predict experimentally determined KFMASH mineral assemblages with consistent topology, and also indicate that sapphirine stabilizes at increasingly higher pressure and temperature as X_Mg increases. Although coexisting sapphirine and quartz can occur in relatively iron‐rich rocks if the bulk chemistry is sufficiently aluminous, the P–T window of stability shrinks with decreasing X_Mg. An array of mineral assemblages and mineral reaction sequences from natural sapphirine + quartz and other rocks from Enderby Land, Antarctica, are reproducible with calculated pseudosections. That consistent phase diagram calculations involving sapphirine can be performed allows for a more thorough assessment of the metamorphic evolution of high‐temperature granulite facies terranes than was previously possible. The establishment of a a‐x model for sapphirine provides the basis for expansion to larger, more geologically realistic chemical systems (e.g. involving Fe³⁺).     

Dielectric constants of tephroite,fayalite and olivine and the oxide additivity rule

The dielectric constants and dissipation factors of synthetic tephroite (Mn₂SiO₄), fayalite (Fe₃SiO₄) and a forsteritic olivine (Mg_1.80Fe_0.22SiO₄) were measured at 1 MHz using a two-terminal method and empirically determined edge corrections. The results are: tephroite, κ′_a= 8.79 tan δ_a = 0.0006 κ′_b = 10.20 tan δ_b = 0.0006 κ′_c= 8.94 tan δ_c= 0.0008 fayalite, gk′_a = 8.80 tan δ_a = 0.0004 gk′_b= 8.92 tan δ_b = 0.0018 gk′_c = 8.58 tan δ_c = 0.0010 olivine, gk′_a = 7.16 tan δ_a = 0.0006 gk′_b = 7.61 tan δ_b = 0.0008 gk′_c = 7.03 tan δ_c = 0.0006 The low dielectric constant and loss of the fayalite indicate an exceptionally low Fe³⁺ content. An FeO polarizability of 4.18 ų, determined from α_D(FeO) = [α_D (Fe₂SiO₄)-α_D(SiO₂)]/2, is probably a more reliable value for stoichiometric FeO than could be obtained from Fe_xO where x = 0.90–0.95. The agreement between measured dielectric polarizabilities as determined from the Clausius-Mosotti equation and those calculated from the sum of oxide polarizabilities according to α_D(M₂M′X₂) = 2α_D(MX) + α_D(M′X₂) is ～+2.8% for tephroite and +0.2% for olivine. The deviation from additivity in tephroite is discussed.     

Coexisting hornblendes and biotites from Precambrian gneisses of the south coast of Western Australia

The compositions of coexisting hornblendes and biotites from amphibolite and granulite facies gneisses from the south coast of Western Australia were controlled by host rock composition, paragenesis, metamophic grade, pressure, and oxygen fugacity. The Mg/(Mg + Fe²⁺) and Mn/Fe²⁺ ratios in both minerals and possibly the Al^vi contents of the hornblendes are related to host rock compositions. Metamorphic grade appears to influence, perhaps only indirectly, the Ti, Mn, and Fe³⁺ contents of both minerals and possibly the hornblende Ca content. The higher Ti and lower Mn contents of the granulite facies hornblendes and biotites are attributed to their coexistence with pyroxenes, whereas their lower Fe³⁺/(Fe²⁺ + Fe³⁺) ratios are probably due to lower oxygen fugacity in the granulite facies environment. Grade-related colour variations in both minerals were controlled by their Ti/Fe²⁺ and Fe³⁺/(Fe²⁺ + Fe³⁺ ratios. The relatively low Al^vi contents of the hornblendes suggest low- to moderate-pressure metamorphism.Variations in element distribution coefficients are related to variations in mineral compositions rather than metamorphic grade. Thus K_{D(Al^iv ?Si)} is related to the Al^iv andedenite alkali contents of the hornblendes, K_{D(Fe²⁺ ?Mg)} to the distributions of Al^iv ?Si and Al^vi + Ti + Fe³⁺, K_D(Mn) to the Mn contents of both minerals, and K_D(Al^vi) to the Al^vi contents of the biotites.     

Quantitative phase petrology of cordierite–orthoamphibole gneisses and related rocks

Cordierite–orthoamphibole gneisses and rocks of similar composition commonly contain low‐variance mineral assemblages that can provide useful information about the metamorphic evolution of a terrane. New calculated petrogenetic grids and pseudosections are presented in the FeO–MgO–Al₂O₃–SiO₂–H₂O (FMASH), Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCKFMASH) and Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) chemical systems to investigate quantitatively the phase relations in these rocks. Although the bulk compositions of cordierite–orthoamphibole gneisses are close to FMASH, calculations in this system do not adequately account for the observed range of mineral assemblages. Calculations in NCKFMASH and NCKFMASHTO highlight the role of minor constituents such as Ca, Na and Fe³⁺ in the mineral assemblage evolution of such rocks and these systems are more appropriate for interpreting the evolution of natural examples.     

Constraining the P–T path of a MORB-type eclogite using pseudosections, garnet zoning and garnet-clinopyroxene thermometry: an example from the Bohemian Massif

A mid‐ocean ridge basalt (MORB)‐type eclogite from the Moldanubian domain in the Bohemian Massif retains evidence of its prograde path in the form of inclusions of hornblende, plagioclase, clinopyroxene, titanite, ilmenite and rutile preserved in zoned garnet. Prograde zoning involves a flat grossular core followed by a grossular spike and decrease at the rim, whereas Fe/(Fe + Mg) is also flat in the core and then decreases at the rim. In a pseudosection for H₂O‐saturated conditions, garnet with such a zoning grows along an isothermal burial path at c. 750 °C from 10 kbar in the assemblage plagioclase‐hornblende‐diopsidic clinopyroxene‐quartz, then in hornblende‐diopsidic clinopyroxene‐quartz, and ends its growth at 17–18 kbar. From this point, there is no pseudosection‐based information on further increase in pressure or temperature. Then, with garnet‐clinopyroxene thermometry, the focus is on the dependence on, and the uncertainties stemming from the unknown Fe³⁺ content in clinopyroxene. Assuming no Fe³⁺ in the clinopyroxene gives a serious and unwarranted upward bias to calculated temperatures. A Fe³⁺‐contributed uncertainty of ±40 °C combined with a calibration and other uncertainties gives a peak temperature of 760 ± 90 °C at 18 kbar, consistent with no further heating following burial to eclogite facies conditions. Further pseudosection modelling suggests that decompression to c. 12 kbar occurred essentially isothermally from the metamorphic peak under H₂O‐undersaturated conditions (c. 1.3 mol.% H₂O) that allowed the preservation of the majority of garnet with symplectitic as well as relict clinopyroxene. The modelling also shows that a MORB‐type eclogite decompressed to c. 8 kbar ends as an amphibolite if it is H₂O saturated, but if it is H₂O‐undersaturated it contains assemblages with orthopyroxene. Increasing H₂O undersaturation causes an earlier transition to SiO₂ undersaturation on decompression, leading to the appearance of spinel‐bearing assemblages. Granulite facies‐looking overprints of eclogites may develop at amphibolite facies conditions.     

P–T–X controls on phase stability and composition in LTMP metabasite rocks – a thermodynamic evaluation

The stability of pumpellyite + actinolite or riebeckite + epidote + hematite (with chlorite, albite, titanite, quartz and H₂O in excess) mineral assemblages in LTMP metabasite rocks is strongly dependent on bulk composition. By using a thermodynamic approach (THERMOCALC), the importance of CaO and Fe₂O₃ bulk contents on the stability of these phases is illustrated using P–T and P–X phase diagrams. This approach allowed P–T conditions of ～4.0 kbar and ～260 °C to be calculated for the growth of pumpellyite + actinolite or riebeckite + epidote + hematite assemblages in rocks containing variable bulk CaO and Fe₂O₃ contents. These rocks form part of an accretionary wedge that developed along the east Australian margin during the Carboniferous–Triassic New England Orogen. P–T and P–X diagrams show that sodic amphibole, epidote and hematite will grow at these conditions in Fe₂O₃‐saturated (6.16 wt%) metabasic rocks, whereas actinolite and pumpellyite will be stable in CaO‐rich (10.30 wt%) rocks. With intermediate Fe₂O₃ (～3.50 wt%) and CaO (～8.30 wt%) contents, sodic amphibole, actinolite and epidote can coexist at these P–T conditions. For Fe₂O₃‐saturated rocks, compositional isopleths for sodic amphibole (Al³⁺ and Fe³⁺ on the M2 site), epidote (Fe³⁺/Fe³⁺ + Al³⁺) and chlorite (Fe²⁺/Fe²⁺ + Mg) were calculated to evaluate the efficiency of these cation exchanges as thermobarometers in LTMP metabasic rocks. Based on these calculations, it is shown that Al³⁺ in sodic amphibole and epidote is an excellent barometer in chlorite, albite, hematite, quartz and titanite buffered assemblages. The effectiveness of these barometers decreases with the breakdown of albite. In higher‐P stability fields where albite is absent, Fe²⁺‐Mg ratios in chlorite may be dependent on pressure. The Fe³⁺/Al and Fe²⁺/Mg ratios in epidote and chlorite are reliable thermometers in actinolite, epidote, chlorite, albite, quartz, hematite and titanite buffered assemblages.     

Serpentinization at Burro Mountain,California

The Burro Mountain ultramafic complex, Monterey County, California, consists of dunites and peridotites which are partially or wholly serpentinized. Primary minerals in both rock types are olivine, enstatite, diopside, and picotite which upon alteration yield chrysotile, lizardite, brucite, magnetite, talc, tremolite, and carbonate. Electron microprobe analyses show that enstatite, En_85.8 to En_90.8, alters to “bastite” composed only of lizardite (5.0–12.0 weight percent FeO), whereas olivine, Fo_90.8 to Fo_91.6, forms lizardite+chrysotile+brucite with or without magnetite. The chrysotile ranges from 3.0 to 5.0 weight percent FeO, the brucite from 16.0 to 43.0 weight percent FeO. As Serpentinization proceeds, the alteration products are enriched in FeO relative to MgO. Serpentinization probably originates in a changing \(P_{O_2 }\)-T environment by two different reactions:

1. (a)
   Olivine+enstatite+H₂O+O₂?Mg, Fe⁺² chrysotile+Mg, Fe⁺³, Fe⁺² lizardite with or without magnetite.     
   
   

The effect of water activity on the oxidation and structural state of Fe in a ferro-basaltic melt

Experimental investigations have been performed at T = 1200°C, P = 200 MPa and fH₂ corresponding to H₂O-MnO-Mn₃O₄ and H₂O-QFM redox buffers to study the effect of H₂O activity on the oxidation and structural state of Fe in an iron-rich basaltic melt. The analysis of Mössbauer and Fe K-edge X-ray absorption nearedge structure (XANES) spectra of the quenched hydrous ferrobasaltic glasses shows that the Fe³⁺/ΣFe ratio of the glass is directly related to aH₂O in a H₂-buffered system and, consequently, to the prevailing oxygen fugacity (through the reaction of water dissociation H₂O ↔ H₂ + 1/2 O₂). However, water as a chemical component of the silicate melt has an indistinguishable effect on the redox state of iron at studied conditions. The experimentally obtained relationship between fO₂ and Fe³⁺/Fe²⁺ in the hydrous ferrobasaltic melt can be adequately predicted in the investigated range by the existing empiric and thermodynamic models. The ratio of ferric and ferrous Fe is proportional to the oxygen fugacity to the power of ∼0.25 which agrees with the theoretical value from the stoichiometry of the Fe redox reaction (FeO + ¼ O₂ = FeO_1.5). The mean centre shifts for Fe²⁺ and Fe³⁺ absorption doublets in Mössbauer spectra show little change with increasing Fe³⁺/ΣFe, suggesting no significant change in the type of iron coordination. Similarly, XANES preedge spectra indicate a mixed (C3h, Td, and Oh, i.e., 5-, 4-, and sixfold) coordination of Fe in hydrous basaltic glasses.     

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.     

Fivegite K4Ca2[AlSi7O17(O2 ? xOHx)][(H2O)2 ? xOH]Cl: A new mineral species from the Khibiny alkaline pluton of the Kola Peninsula in Russia

A new mineral fivegite has been identified in a high-potassium hyperalkaline pegmatite at Mt. Rasvumchorr in the Khibiny alkaline complex of the Kola Peninsula in Russia. This mineral is a product of the hydrothermal alteration of delhayelite (homoaxial pseudomorphs after its crystals up to 2 × 3 × 10 cm in size). Hydrodelhayelite, pectolite, and kalborsite are products of fivegite alteration. The associated minerals are aegirine, potassic feldspar, nepheline, sodalite, magnesiumastrophyllite, lamprophyllite, lomonosovite, shcherbakovite, natisite, lovozerite, tisinalite, ershovite, megacyclite, shlykovite, cryptophyllite, etc. Areas of pure unaltered fivegite are up to 2 mm in width. The mineral is transparent and colorless; its luster is vitreous to pearly. Its Cleavage is perfect (100) and distinct (010). Its Mohs hardness is 4, D(meas) = 2.42(2), and D(calc) = 2.449 g/cm³. Fivegite is optically biaxial positive: α 1.540(1), β 1.542(2), γ 1.544(2), and 2V(meas) 60(10)°. Its orientation is X = a, y = c, and Z = b. Its IR spectrum is given. Its chemical composition (wt %; electron microprobe, H₂O determined by selective sorption) is as follows: 1.44 Na₂O, 19.56 K₂O, 14.01 CaO, 0.13 SrO, 0.03 MnO, 0.14 Fe₂O₃, 6.12 Al₂O₃, 50.68 SiO₂, 0.15 SO₃, 0.14 F, 3.52 Cl, 4.59 H₂O; −O = −0.85(Cl,F)2; total 99.66. The empirical formula based on (Si + Al + Fe) = 8 is H_4.22K_3.44Na_0.39Ca_2.07Sr_0.01Fe_0.01Al_1.00Si_6.99O_21.15F_0.06Cl_0.82(SO₄)_0.02. The simplified formula is K₄Ca₂[AlSi₇O₁₇(O_{2 − x} OH _x ][(H₂O)_{2 − x} OH _x ]Cl (X = 0−2). Fivegite is orthorhombic: Pm2₁ n, a = 24.335(2), b = 7.0375(5), c = 6.5400(6) ?, V = 1120.0(2) ?³, and Z = 2. The strongest reflections of the X-ray powder pattern are as follows (d, ?, (I, %), [hkl]): 3.517(38) [020], 3.239(28) [102], 3.072(100) [121, 701], 3.040(46) [420, 800, 302], 2.943 (47) [112], 2.983(53) [121], 2.880 (24) [212, 402], 1.759(30) [040, 12.2.0]. The crystal structure was studied using a single crystal: R _hkl = 0.0585. The base of fivegite structure is delhayelite-like two-layer terahedral blocks [(Al,Si)₄Si₁₂O₃₄(O_{4 − x} OH _x )] linked by Ca octahedral chains. K⁺ and Cl⁻ are localized in zeolite-like channels within the terahedral blocks, whereas H₂O and OH occur between the blocks. The mineral is named in memory of the Russian geological and mining engineer Mikhail Pavlovich Fiveg (1899–1986), the pioneering explorer of the Khibiny apatite deposits. The type specimen is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences in Moscow. The series of transformations is discussed: delhayelite K₄Na₂Ca₂[AlSi₇O₁₉]F₂Cl—fivegite K₄Ca₂[AlSi₇O₁₇(O_{2 − x} OH _x ]Cl—hydrodelhayelite KCa₂[AlSi₇O₁₇(OH)₂](H₂O)_{6 − x} .