Kinetics of leaching of oxidized and reduced ilmenite in dilute hydrochloric acid solutions

Ilmenite separated from beach sands of Bangladesh was oxidized for 1 h at 950 °C and then reduced in charcoal for 4 h at 1050 °C. This was followed by leaching in 5% to 15% hydrochloric acid solution in temperature range of 30 to 75 °C for periods of up to 2 h. The results were compared with those obtained by leaching of ilmenite reduced without oxidizing. Oxidation prior to reduction of the ilmenite was found to increase both the extent and the rate of leaching. The residual iron contents after leaching were also found to be lower than that obtained for non-oxidized samples. The kinetic data of leaching of ilmenite reduced after oxidation was found to follow first order reaction model, i.e., G(α) = − ln(1 − α) up to an α value of 0.5 (i.e. up to 50% reduction) and then changed to spherical model, i.e., G(α) = [1 − (1 − α)]³. On the other hand, leaching of ilmenite reduced without oxidizing was found to follow the Ginstling-Brounshtein reaction, i.e., G(α) = 1 − (2/3)α − (1 − α)^2/3 throughout the leaching process. Oxidation of ilmenite prior to reduction was also found to have decreased the activation energy of leaching from 43 kJ/mol, found for samples leached after reduction without oxidizing, to 30 kJ/mol.     

Order-disorder kinetics in orthopyroxenes of ophiolite origin

The kinetics of the Fe–Mg order-disorder reaction in four low-Fe orthopyroxenes (Fs_7–14) has been studied by use of Mössbauer spectroscopy, to determine cooling rates for the host rocks. The obtained Fe²⁺ distribution data were corrected for the thickness effect. The sample set was selected from rocks expected to have distinctly different cooling histories. Equilibrium data for the exchange reaction were determined for the temperature range 600–800°C, and kinetic data at 650°C. The results indicate that the degree of ordering in low-Fe orthopyroxene is substantially lower than estimated by thermodynamic models. The cooling rates obtained seem realistic for most samples, ranging from 19°C/min at 760°C for a boninite pillow lava to 2°C/million years at 267°C for a regionally metamorphosed olivinite. The errors in obtained cooling rates are estimated to be near one order of magnitude. An Fe³⁺ containing sample yields an unreasonably slow cooling rate which may be due to oxidation of Fe²⁺, occurring after the quenching point of the order-disorder reaction was reached.     

Titanium solubility in olivine in the system TiO<Subscript>2</Subscript>–MgO–SiO<Subscript>2</Subscript>: no evidence for an ultra-deep origin of Ti-bearing olivine

The finding of ilmenite rods in olivine from orogenic peridotites has sparked a discussion about the processes of incorporation and exsolution of titanium in olivine. We have experimentally investigated the solubility of Ti in olivine as a function of composition, temperature and pressure in the synthetic TiO₂–MgO–SiO₂ system. Experiments at atmospheric pressure in the temperature range 1,200–1,500°C showed that the highest concentration of TiO₂ is obtained when olivine coexists with spinel (Mg₂TiO₄). The amount of TiO₂ in olivine in the assemblages olivine + spinel + periclase and olivine + spinel + ilmenite at 1,500°C was 1.25 wt.%. Changes in the coexisting phases and decreasing temperature result in a significant reduction of the Ti solubility. Olivine coexisting with pseudobrookite (MgTi₂O₅) and a Ti–Si-rich melt at 1,500°C displays a fourfold lower TiO₂ content than when buffered with spinel. A similar decrease in solubility is obtained by a decrease in temperature to 1,200°C. There is a negative correlation between Ti and Si and no correlation between Ti and Mg in Ti-bearing olivine. Together with the established phase relations this suggests that there is a direct substitution of Ti for Si at these temperatures, such that the substituting component has the stoichiometry Mg₂TiO₄. The unit cell volume of olivine increases systematically with increasing TiO₂ content demonstrating that the measured TiO₂ contents in olivine are not caused by micro-inclusions but by incorporation of Ti in the olivine structure. Least squares fitting of 20 olivine unit cell volumes against the Ti content yield the relation: V (ų)=290.12(1) + 23.67(85) N_Ti. The partial molar volume of end-member Mg₂TiO₄ olivine (N_Ti=1) is thus 47.24±0.13 cm³. The change of the Ti solubilty in olivine coexistent with rutile and orthopyroxene with pressure was investigated by piston cylinder experiments at 1,400°C from 15 to 55 kbar. There is no increase in TiO₂ contents with pressure and in all the experiments olivine contains ~0.2 wt.% TiO₂. Moreover, a thermodynamic analysis indicates that Ti contents of olivine coexisting with rutile and orthopyroxene should decrease rather than increase with increasing pressure. These data indicate that the ilmenite exsolution observed in some natural olivine does not signify an ultra-deep origin of peridotite massifs.     

Iron titanium oxides in equilibrium with metallic iron

The iron titanium oxide phases ulvite, ilmenite and ferropseudobrookite were synthesized in equilibrium with metallic iron at 1000 ° C, 1130 ° C and 1300 ° C in CO₂/H₂ gas mixtures.The composition of the phases were determined by wet chemical and electron microprobe analyses and by direct oxygen determination.The chemical composition of the Fe-Ti oxide phases in equilibrium with metallic iron is sensitively influenced by temperature and by bulk composition.Ulvite in equilibrium with wüstite does not contrivalent titanium in the whole temperature range up to the eutectic temperature at 1312 °C.Ulvite+ilmenite phase assemblages contain trivalent titanium only at temperatures above 1200 ° C.A ferropseudobrookite phase is stable under the given conditions at temperatures above 1068 °C (Ender and Woermann, 1977).Ferropseudobrookite in equilibrium with metallic iron always contains trivalent titanium.Deviations from stoichiometric compositions of the solid solution phases are generally small. Thus recalculation of microprobe data to stoichiometric solid solutions does not involve a major error.From: Bruno Simons, Diplomarbeit Aachen, October 1974     

Effect of hydrogen limitation and temperature on the fractionation of sulfur isotopes by a deep-sea hydrothermal vent sulfate-reducing bacterium

The fractionation of sulfur isotopes by the thermophilic chemolithoautotrophic Thermodesulfatator indicus was explored during sulfate reduction under excess and reduced hydrogen supply, and the full temperature range of growth (40-80 °C). Fractionation of sulfur isotopes measured under reduced H₂ conditions in a fed-batch culture revealed high fractionations (24-37‰) compared to fractionations produced under excess H₂ supply (1-6‰). Higher fractionations correlated with lower sulfate reduction rates. Such high fractionations have never been reported for growth on H₂. For temperature-dependant fractionation experiments cell-specific rates of sulfate reduction increased with increasing temperatures to 70 °C after which sulfate-reduction rates rapidly decreased. Fractionations were relatively high at 40 °C and decreased with increasing temperature from 40-60 °C. Above 60 °C, fractionation trends switched and increased again with increasing temperatures. These temperature-dependant fractionation trends have not previously been reported for growth on H₂ and are not predicted by a generally accepted fractionation model for sulfate reduction, where fractionations are controlled as a function of temperature, by the balance of the exchange of sulfate across the cell membrane, and enzymatic reduction rates of sulfate. Our results are reproduced with a model where fractionation is controlled by differences in the temperature response of enzyme reaction rates and the exchange of sulfate in and out of the cell.     

Time-dependent changes of the electrical conductivity of basaltic melts with redox state

The electrical conductivity of basaltic melts has been measured in real-time after fO₂ step-changes in order to investigate redox kinetics. Experimental investigations were performed at 1 atm in a vertical furnace between 1200 and 1400 °C using air, pure CO₂ or CO/CO₂ gas mixtures to buffer oxygen fugacity in the range 10⁻⁸ to 0.2 bars. Ferric/ferrous ratios were determined by wet chemical titrations. A small but detectable effect of fO₂ on the electrical conductivity is observed. The more reduced the melt, the higher the conductivity. A modified Arrhenian equation accounts for both T and fO₂ effects on the electrical conductivity. We show that time-dependent changes in electrical conductivity following fO₂ step-changes monitor the rate of Fe²⁺/Fe³⁺ changes. The conductivity change with time corresponds to a diffusion-limited process in the case of reduction in CO-CO₂ gas mixtures and oxidation in air. However, a reaction at the gas-melt interface probably rate limits oxidation of the melt under pure CO₂. Reduction and oxidation rates are similar and both increase with temperature. Those rates range from 10⁻⁹ to 10⁻⁸ m²/s for the temperature interval 1200-1400 °C and show activation energy of about 200 kJ/mol. The redox mechanism that best explains our results involves a cooperative motion of cations and oxygen, allowing such fast oxidation-reduction rates.     

Stability of ilmenite and titanomagnetite in the presence of carbon dioxide — A thermodynamic evaluation

The stability of ilmenite and titanomagnetite in the presence of CO₂ gas was evaluated thermodynamically. Ilmenite with a composition Ilm₉₀Hm₁₀ breaks down to the assemblage siderite-hematite-anatase below 270° C at 1,000 bars and below 300° C at 2,000 bars. Titanomagnetite with a composition Usp₅₀Mt₅₀ breaks down to the same assemblage below 345° C at 1,000 bars and below 385° C at 2,000 bars. During the low-grade metamorphism of basaltic rocks, a CO₂ partial pressure of only a few hundreds bars is sufficient to alter ilmenite and titanomagnetite to the assemblage siderite-hematite-anatase.     

Volatilization kinetics of silicon carbide in reducing gases: an experimental study with applications to the survival of presolar grains in the solar nebula

The volatilization kinetics of single crystal α-SiC, polycrystalline β-SiC, and SiO₂ (cristobalite or glass) were determined in H₂-CO₂, CO-CO₂, and H₂-CO-CO₂ gas mixtures at oxygen fugacities between 1 log unit above and 10 log units below the iron-wüstite (IW) buffer and temperatures in the range 1151 to 1501°C. Detailed sets of experiments on SiC were conducted at 2.8 and 6.0 log units below IW (IW-2.8 and IW-6.0) at a variety of temperatures, and at 1300°C at a variety of oxygen fugacities. Transmission electron microscopic and Rutherford backscattering spectroscopic characterization of run products shows that the surface of SiC exposed to IW-2.8 is characterized by a thin (<1 μm thick), continuous layer of cristobalite. SiC exposed to IW-6.0 lacks such a layer (or its thickness is <0.01 μm), although some SiO₂ was found within pits and along incised grain boundaries.In H₂-CO₂ gas mixtures above ∼IW-3, the similarity of the SiC volatilization rate and of its dependence on temperature and fO₂ to that for SiO₂ suggests that SiC volatilization is controlled by volatilization of a SiO₂ layer that forms on the surface of the SiC. With decreasing log fO₂ from ∼IW-3 to ∼IW-6, the SiC volatilization rate is constant at constant temperature, whereas that for SiO₂ increases. The independence of the SiC volatilization rate from the gas composition under these conditions suggests that the rate-controlling step is a solid-solid reaction at the internal SiC/SiO₂ interface. For gas compositions more reducing than ∼IW-6, the SiC volatilization rate increases with decreasing fO₂, with both bare SiC surfaces and perhaps silica residing in pits and along incised grain boundaries contributing to the overall reaction rate.If the volatilization mechanism and reaction rate in the solar nebula were the same as in our H₂-CO₂ experiments at IW-6.0, then estimated lifetimes of 1-μm-diameter presolar SiC grains range from several thousand years at ∼900°C, to ∼1 yr at 1100°C, ∼1 d at 1300°C, and ∼1 h at 1400°C. The corresponding lifetimes for 10-μm SiC grains would be an order of magnitude longer. If the supply of oxidants to surfaces of presolar SiC grains were rate limiting—for example, at T > 1100°C for P^tot= 10⁻⁶ atm and sticking coefficient = 0.01, then the calculated lifetimes would be about 10 yr for 10-μm-diameter grains, essentially independent of temperature. The results thus imply that presolar SiC grains would survive short heating events associated with formation of chondrules (minutes) and calcium-, aluminum-rich inclusions (days), but would have been destroyed by exposure to hot (≥900°C) nebular gases in less than several thousand years unless they were coated with minerals inert to reaction with a nebular gas.     

Weathering of ilmenite from Chavara deposit and its comparison with Manavalakurichi placer ilmenite,southwestern India

The magnetic fractions of ilmenite from the beach placer deposit of Chavara, southwest India have been studied for mineralogical and chemical composition to assess the range of their physical and chemical variations with weathering. Chavara deposit represents a highly weathered and relatively homogenous concentration. Significant variation in composition has been documented with alteration. The most magnetic of the fractions of ilmenite, separated at 0.15 Å, and with a susceptibility of 3.2 × 10^?6 m³ kg^?1, indicates the presence of haematite–ilmenite intergrowth. An iron-poor, titanium-rich component of the ilmenite ore has been identified from among the magnetic fractions of the Chavara ilmenite albeit with an undesirably high Nb₂O₅ (0.28%), Cr₂O₃ (0.23%) and Th (149 ppm) contents. The ilmenite from Chavara is compared with that from the nearby Manavalakurichi deposit of similar geological setting and provenance. The lower ferrous iron oxide (2.32–14.22%) and higher TiO₂ (56.31–66.45%) contents highlight the advanced state of alteration of Chavara. This is also evidenced by the relatively higher Fe³⁺/Fe²⁺ ratio compared to Manavalakurichi ilmenite. In fact, the ilmenite has significantly been converted to pseudorutile/leucoxene.     

The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

The yields and stable C and H isotopic composition of gaseous products from the reactions of pure n-C₂₄ with (1) MgSO₄; and (2) elemental S in sealed Au-tubes at a series of temperatures over the range 220–600 °C were monitored to better resolve the reaction mechanisms. Hydrogen sulfide formation from thermochemical sulfate reduction (TSR) of n-C₂₄ with MgSO₄ was initiated at 431 °C, coincident with the evolution of C₂–C₅ hydrocarbons. Whereas the yields of H₂S increased progressively with pyrolysis temperature, the hydrocarbon yields decreased sharply above 490 °C due to subsequent S consumption. Ethane and propane were initially very ¹³C depleted, but became progressively heavier with pyrolysis temperature and were more ¹³C enriched than the values of a control treatment conducted on just n-C₂₄ above 475 °C. TSR of MgSO₄ also led to progressively higher concentrations of CO₂ showing relatively low δ¹³C values, possibly due to input of isotopically light CO₂ derived from gaseous hydrocarbon oxidation (e.g., more depleted CH₄).     

The coprecipitation of Sr into calcite precipitates induced by bacterial ureolysis in artificial groundwater: Temperature and kinetic dependence

A suite of experiments was performed to investigate the partitioning of Sr²⁺ (to mimic the radionuclide ⁹⁰Sr) between calcite and artificial groundwater in response to the hydrolysis of urea (ureolysis) by Bacillus pasteurii under simulated in situ aquifer conditions. Experiments were performed at 10, 15, and 20°C over 7 days in microcosms inoculated with B. pasteurii ATCC 11859, containing an artificial groundwater and urea (AGW) or an AGW including a Sr contaminant treatment. During the experiments, the concentration of ammonium generated by bacterial ureolysis increased asymptotically, and derived rate constants (k_urea) that were between 13 and 10 times greater at 20°C than at 15 and 10°C. Calcite precipitation was initiated after similar amounts of urea had been hydrolyzed (∼ 4.0 mmol L^-1) and a similar critical saturation state (mean S_critical = 53, variation = 20%) had been reached, independent of temperature and Sr treatment. Because of the positive relationship between the rate of ureolysis and temperature, precipitation began by the end of day 1 at 20°C, and between days 1 and 2 at 15 and 10°C. The rate of calcite precipitation increased with, and was fundamentally controlled by calcite saturation state (S), irrespective of temperature. The presence of Sr slightly slowed calcite precipitation rates at equivalent values of S, which may reflect the screening of active nucleation and crystal growth sites by Sr. Homogeneous partitioning coefficients (D_Sr) exhibited a positive association with calcite precipitation rates, but were greater at higher experimental temperatures at equivalent precipitation rates (20°C mean = 0.46; 15°C mean = 0.24; 10°C mean = 0.29).     

Geochemistry and iron isotope systematics of coexisting Fe-bearing minerals in magmatic FeTi deposits: A case study of the Damiao titanomagnetite ore deposit,North China Craton

Geochemical and iron isotopic compositions of magnetite, ilmenite and pyrite separates from the FeTi oxide ores hosted in the Damiao anorthosite-type FeTi ore deposit were analyzed to investigate sub-solidus cooling history of the titanomagnetite. The FeTi oxides form two series of solid solutions, namely, ulvöspinel-magnetite (Usp-Mt_ss) and hematite-ilmenite (Hem-Ilm_ss) solid solutions. The magnetite separates have 14–27 mol% ulvöspinel, while the ilmenite separates have 5–8 mol% hematite. Major element compositions of the mineral separates suggest that the ilmenites were mainly exsolved from the Usp-Mt_ss by oxidation of ulvöspinel in the temperature range of ~820–600 °C and experienced inter-oxide re-equilibration with the magnetites. Associated with the exsolution is the substantial inter-mineral iron isotope fractionation. The magnetite separates are characterized by high δ⁵⁷Fe (+0.27 − +0.65‰), whereas the ilmenite separates have lower δ⁵⁷Fe (−0.65 to −0.28‰). Two types of pyrite are petrographically observed, each of which has a distinctive iron isotope fingerprint. Type I pyrite (pyrite_I) with higher δ⁵⁷Fe (δ⁵⁷Fe = +0.63 − +0.95‰) is consistent with magmatic origin, and type II pyrite (pyrite_II) with lower δ⁵⁷Fe (δ⁵⁷Fe = −0.90 to −0.11‰) was likely to have precipitated from fluids. Iron isotopic fingerprints of the pyrite_I probably indicate variations of oxygen fugacity, whereas those of the pyrite_II may result from fluid activities. The iron isotopic fractionation between the magnetite and ilmenite is the net result of sub-solidus processes (including ulvöspinel oxidation and inter-oxide re-equilibration) without needing varying oxygen fugacity albeit its presence. Although varying composition of magnetite-ilmenite pairs reflects variations of oxygen fugacity, inter-oxide iron isotopic fractionation does not.     

Hydrosulfide/sulfide complexes of copper(I): Experimental confirmation of the stoichiometry and stability of Cu(HS)2− to elevated temperatures

The solubility of chalcocite has been measured over the temperature range 35-95°C at pH 6.5-7.5 in aqueous hydrosulfide solutions in order to determine the stability constants of the Cu(HS)₂⁻ complex. A heated flow-through system was used in which solutions are collected at temperature to avoid the problem of copper precipitation due to quenching. The quality of the data was sufficient to resolve a 0.1 log unit increase of the dissolution/complexation equilibrium constant with each 10°C increase in temperature. The equilibrium constants were fit using previously published methods to obtain the values of thermodynamic parameters for the Cu(HS)₂⁻ complexation reaction. To compare results with predictive techniques, one-term and two-term isocoulombic extrapolation methods were applied to the stability constants measured below 100°C. The two-term extrapolation to 350°C showed excellent agreement with the derived constants proving its applicability to soft metal-soft ligand interactions. The one-term method gave a reasonable agreement but deviated about one logarithmic unit at 350°C. This is attributed to differences in energetic, volumetric, and structural properties of the reactants and products. Speciation calculations show that at low temperatures (<150°C), the hydrosulfide complexes of copper will dominate over chloride complexes at low salinites (<0.1 mol kg⁻¹) while at higher temperatures, chloride complexes will be dominant under most geological conditions. Only in solutions with high reduced sulfur content and alkaline pH values will hydrosulfide complexes predominate and may play a role in the generation of economic copper mineralization.     

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

Optimization and modeling of boric acid extraction from colemanite in water saturated with carbon dioxide and sulphur dioxide gases

In this study, the boric acid extraction from colemanite ore in aqueous media saturated by CO₂ and SO₂ gases was studied and the effects of relevant parameters, namely; reaction temperature, solid-to-liquid ratio, mean particle size, stirring speed and reaction time have been investigated on the boric acid extraction from colemanite ore by using the fractional factorial design and central composite design methods. The chosen experimental parameter levels were as follows: reaction temperature, 11.4–58.6 °C; solid-to-liquid ratio, 0.0685–0.1315 g/mL; mean particle size, 0.2835–3 mm; stirring speed, 107–893 rpm; reaction time, 7.125–22.875 min. A model has been developed between the boric acid extraction efficiency from colemanite ore and relevant parameters by means of variance analysis by using the matlab computer software and the obtained model was used to determine optimum conditions. The optimum conditions were found to be as follows: reaction temperature, 41 °C; solid-to-liquid ratio, 0.0685 g/mL; mean particle size, 0.2835 mm; stirring speed, 266 rpm; reaction time, 7 min. The calculated boric acid extraction efficiency from colemanite ore was approximately 99.9% under the optimum conditions.     

The low-pressure partial-melting behaviour of natural boron-bearing metapelites from the Mt. Stafford area,central Australia

This study has examined the ~300 MPa partial melting behaviour of four metapelites collected from the highest grade rocks occurring below the anatectic zone of the Mt. Stafford area, Arunta Inlier, central Australia. In this area, metasediments are interpreted to have undergone partial melting within the andalusite stability field; possibly as a result of a lowering of the metapelite solidus by the presence of boron in the rocks. Two of the samples were two mica metapelites (MTS70 and MTS71). These both contained significant quantities of tourmaline and were thus boron enriched. The other two samples are biotite metapelites. One of these rocks contains only a trace of tourmaline (MTS8) and the other is tourmaline free (MTS7). Despite expectations that muscovite in the two mica samples would break down via a subsolidus reaction, muscovite was stable to above 750°C due to the incorporation of Ti, phengitic and possibly F components into its structure. Between 750 and 800°C, muscovite melted out completely via a coupled muscovite + biotite fluid-absent incongruent reaction. Tourmaline was partially consumed in this reaction, with the elbaitic component being preferentially consumed. In the most mica-rich sample this reaction produced ~60% melt at 800°C. In the biotite metapelites, biotite melting began at a temperature below 800°C and was accompanied by very modest melt production at this low temperature. In contrast to the two mica metapelites, the main pulse of melt production in these samples occurred at a temperature between 850 and 950°C. In both these samples biotite + melt coexisted over a temperature range in excess of 150°C, and in MTS8, biotite was still in the run products at 950°C. The very refractory nature of these evolved biotite compositions is most likely a consequence of both the presence of a Ti buffering phase in the assemblage (ilmenite) and the essentially plagioclase-free nature of the starting compositions. Under the fluid-absent conditions of this study, tourmaline is clearly a reactant in the partial melting process, but does not appear to shift the fluid-absent incongruent melting reactions markedly. In the tourmaline-rich two mica metapelites, tourmaline only disappears from the run products at a temperature above 850°C, where it coexisted with a substantial melt proportion. This appears to coincide with the point of maximum boron concentration in the melts.

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Crystallization conditions of Los Angeles, a basaltic Martian meteorite

The texture of Los Angeles (stone 1) is dominated by relatively large (0.5−2.0 mm) anhedral to subhedral grains of pyroxene, and generally subhedral to euhedral shocked plagioclase feldspar (maskelynite). Minor phases include subhedral titanomagnetite and ilmenite, Fe-rich olivine, olivine+augite-dominated symplectites [some of which include a Si-rich phase and some which do not], pyrrhotite, phosphate(s), and an impact shock-related alkali- and silica-rich glass closely associated with anhedral to euhedral silica grains. Observations and model calculations indicate that the initial crystallization of Mg-rich pigeonitic pyroxenes at ≤1150 °C, probably concomitantly with plagioclase, was followed by pigeonitic and augitic compositions between 1100 and 1050 °C whereas between 1050 and 920 to 905 °C pyroxene of single composition crystallized. Below 920 to 905 °C, single composition Fe-rich clinopyroxene exsolved to augite and pigeonite. Initial appearance of titanomagnetite probably occurred near 990 °C and FMQ-1.5 whereas at and below 990 °C and ≥FMQ-1.5 titanomagnetite and single composition Fe-rich clinopyroxene may have started to react, producing ilmenite and olivine. However, judging from the most common titanomagnetite compositions, we infer that most of this reaction likely occurred between 950 and 900 °C at FMQ-1.0±0.2 and nearly simultaneously with pyroxene exsolution, thus producing assemblages of pigeonite, titanomagnetite, olivine, ilmenite, and augite. We deem this reaction as the most plausible explanation for the formation of the olivine+augite-dominated symplectites in Los Angeles. But we cannot preclude possible contributions to the symplectites from the shock-related alkali- and silica-rich glass or shocked plagioclase, and the breakdown of Fe-rich pigeonite compositions to olivine+augite+silica below 900 °C. Reactions between Fe-Ti oxides and silicate minerals in Los Angeles and other similar basaltic Martian meteorites can control the T-fO₂ equilibration path during cooling, which may better explain the relative differences in fO₂ among the basaltic Martian meteorites.     

Experimental reduction of aqueous sulphate by hydrogen under hydrothermal conditions: Implication for the nuclear waste storage

Sulphate reduction by hydrogen, likely to occur in deep geological nuclear waste storage sites, was studied experimentally in a two-phase system (water + gas) at 250-300 °C and under 4-16 bars H₂ partial pressure in hydrothermal-vessels. The calculated activation energy is 131 kJ/mol and the half-life of aqueous sulphate in the presence of hydrogen and elemental sulphur ranges from 210,000 to 2.7 × 10⁹ years at respective temperatures of 90 °C, the thermal peak in the site and 25 °C, the ambient temperature far from the site. The features and rate of the sulphate reduction by H₂ are close to those established for TSR in oil fields. The experiments also show that the rate of sulphate reduction is not significantly affected in the H₂ pressure range of 4-16 bars and in the pH range of 2-5, whereas a strong increase is measured at pH below 2. We suggest that the condition for the reaction to occur is the speciation of sulphate dominated by non symmetric species ( at low pH), and we propose a three steps reaction, one for each intermediate-valence sulphur species, the first one requiring H₂S as electron donor rather than H₂. We distinguish two possible reaction pathways for the first step, depending on pH: reduction of sulphate into sulphur dioxide below pH 2 or into thiosulphate or sulphite + elemental sulphur in the pH range 2-5.     

UHT metamorphism on Seram,eastern Indonesia: reaction microstructures and P–T evolution of spinel‐bearing garnet–sillimanite granulites from the Kobipoto Complex

The island of Seram, part of the northern limb of the Banda Arc in eastern Indonesia, exposes an extensive Mio‐Pliocene granulite facies migmatite complex (the Kobipoto Complex) comprising voluminous leucosome‐rich diatexites and scarcer Al–Fe‐rich residual granulites. The migmatites are intimately associated with ultramafic rocks of predominantly lherzolitic composition that were exhumed by substantial lithospheric extension beneath low‐angle detachment faults; heat supplied by the lherzolites was evidently a major driver for the granulite facies metamorphism and accompanying anatexis. Residual garnet–sillimanite granulites sampled from the Kobipoto Mountains, central Seram, contain scarce garnet‐hosted inclusions of hercynite spinel (~1.5 wt% ZnO) + quartz (± ilmenite) in direct grain‐boundary contact – an assemblage potentially indicative of metamorphism under ultrahigh‐temperature (UHT) conditions. thermocalc ‘Average P–T’ reactions and melanosome‐specific thermocalc , T–M_O, and P–T pseudosections in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (NCKFMASHTO) chemical system, supported by Ti‐in‐garnet thermobarometry, are permissive of the rock having experienced a clockwise P–T path peaking at 925 °C and 9 kbar – thus narrowly reaching UHT conditions – before undergoing near‐isothermal decompression to ~750 °C and ~4 kbar. Spinel + quartz assemblages are interpreted to have formed at or just after the metamorphic peak from localized reactions between sillimanite, ilmenite and surrounding garnet. Further decompression of the rock resulted in the formation of complex reaction microstructures comprising cordierite ± plagioclase coronae around garnet, and symplectic intergrowths of cordierite + spinel + ilmenite around sillimanite. Small grains of sapphirine + corundum developed subsequently within spinel by localized quartz‐absent reactions. The post‐peak evolution of the granulites may be related to previously published U–Pb zircon and ⁴⁰Ar/³⁹Ar ages of c. 16 Ma, further substantiating the claim for the Kobipoto Complex granulites having recorded Earth's youngest‐identified episode of UHT metamorphism, albeit at slightly lower temperature and higher pressure than previously inferred. The Kobipoto Complex granulites demonstrate how UHT conditions may be achieved in the ‘modern’ Earth by extreme lithospheric extension, which, in this instance, was driven by slab rollback of the Banda Arc.     

Crystallization of titaniferous chromite,magnesian ilmenite and armalcolite in tholeiitic suites in the Karoo Igneous Province

Titaniferous chromite (up to 8 wt% TiO₂) and magnesian ilmenite (up to 10 wt% MgO) coexist at the base of the differentiated tholeiitic Mount Ayliff Intrusion in the Karoo Province of southern Africa, suggesting that the original magma was TiO₂-rich. Picritic lavas with 3% TiO₂ from the Lebombo monocline of the Karoo Province also contain microphenocrysts of magnesian ilmenite (up to 6 wt% mgO) and armalcolite (up to 7 wt% MgO). These oxide mineral associations and compositions are atypical of tholeiitic magmas, in which chromite usually has less than 1 wt% TiO₂, ilmenite less than 3 wt% MgO and armalcolite is rarely a primary mineral. Experiments have been conducted at one atmosphere pressure on a range of compositions to determine the effect of TiO₂ on the crystallization and composition of chromite, ilmenite and armalcolite. The results indicate that increasing the TiO₂ content of picritic magmas increases the TiO₂ content of the spinel, mainly at the expense of Al₂O₃, whereas Cr₂O₃ is not affected. Spinel compositions in the Mount Ayliff Intrusion (with over 45 wt% Cr₂O₃, less than 10 wt% Al₂O₃ and 8 wt% TiO₂) were duplicated in experiments on a picrite at temperatures of about 1,200°C at the Ni/NiO buffer. Increasing fO₂ from fayalite-magnetite-quartz to Ni/NiO buffer is shown to increase the crystallization temperature of armalcolite and to decrease that of ilmenite. The total FeO content of the liquid has little influence on the crystallization temperature of these phases. The TiO₂ content of the liquid, when either ilmenite or armalcolite crystallizes, varies inversely with SiO₂ content. The MgO content of the liquid at which ilmenite or armalcolite crystallizes depends upon the TiO₂ content of the starting composition, with naturally occurring and experimetally determined saturation being demonstrated for liquids with 5 wt% MgO and 5.5 wt% TiO₂. The partition coefficent for MgO between armalcolite or ilmenite and liquid is about 1.5. Observed magnesian armalcolite and ilmenite compositions in picrite lavas (both minerals) and in the Mount Ayliff Intrusion (ilmenite only) are consistent with crystallization from a TiO₂-rich magma with approximately 5 wt% MgO. The Fe ₂ ³⁺ TiO₅ component of armalcolite in the picrite lavas matches those formed experimentally at temperatures of 1,150–1,110°C and fO₂ of the Ni/NiO to Ni/NiO+1 log unit. Similarities also exist between the compositions of chromite, ilmenite and armalcolite and liquid fraction-ation trends of some Hawaiian high-TiO₂ lavas and the experimental studies presented here.