The uptake and solubility of water in quartz at elevated pressure and temperature

The uptake of water in quartz at 1.5 GPa total pressure, 1173 K and high water fugacity, over times up to 24 h, has been investigated using a newly developed assembly to prevent microcracking. It is found that the uptake is small, and below the detectability of the presently used technique of infrared spectroscopy and serial sectioning. This observation reflects either a low value for the diffusivity or the solubility or a combination of both, and is in agreement with the observations of Kronenberg et al. (1986) and Rovetta et al. (1986). It brings into question the interpretation of the early experiments on water weakening by Griggs and Blacic (1964) and the recent estimates of the solubility and diffusivity by Mackwell and Paterson (1985). Rults of a combined T.E.M., light-scattering and infrared-spectroscopy investigation of ‘wet’ synthetic quartz before and after heating at 0.1, 300 and 1500 MPa total pressure and 1173 K, strongly suggest that the water in ‘wet’ quartz is mainly in the form of H₂O in inclusions, consistent with the solubility being low, possibly less than 100 H/10⁶Si. From these observations, water-containing inclusions appear to play a major role in the plasticity of quartz, while any role of water in solid solution remains to be clarified.     

Solid solubility of Al2O3 in enstatite at high temperatures and 1–5 kb water pressure

Solid solubility of Al₂O₃ in orthorhombic enstatite by the substitution AlAl=MgSi is, in the range studied, mainly a function of temperature and not strongly pressure-dependent. Even at 1 kb up to 9 wt.-% Al₂O₃ can be substituted at 1200° C. The thermal stability of the orthorhombic pyroxene phase is strongly increased by the incorporation of Al.In crustal rocks the alumina content of orthopyroxene might be used as a geothermometer but not, as sometimes suggested, as a barometer.     

Pressure dependence of hydroxyl solubility in coesite

 The solubility of hydroxyl in coesite was investigated in multianvil experiments performed at 1200 °C over the nominal pressure range 5–10 GPa, at an f _O2 close to the Ni-NiO buffer. The starting material for each experiment was a cylinder of pure silica glass plus talc, which dehydrates at high P and T to provide a source of water and hydrogen (plus enstatite and excess SiO₂). Fourier-transform infrared (FTIR) spectra of the recovered coesite crystals show five sharp bands at 3606, 3573, 3523, 3459, and 3299 cm⁻¹, indicative of structurally bonded hydrogen (hydroxyl). The concentration of hydrogen increases with pressure from 285 H/10⁶ Si (at 5 GPa) to 1415 H/10⁶ Si (at 10 GPa). Assuming a model of incorporation by (4H)_Si defects, the data are fit well by the equation C _OH=Af ² _H2<\INF>Oexp(−PΔV/RT), with A=4.38 H/10⁶ Si/GPa, and ΔV=20.6 × 10⁻⁶ m³ mol⁻¹. An alternative model entailing association of hydrogen with cation substitution can also be used to fit the data. These results show that the solubility of hydroxyl in coesite is approximately an order of magnitude lower than in olivines and pyroxenes, but comparable to that in pyropic garnet. However, FTIR investigations on a variety of ultrahigh pressure metamorphic rocks have failed in all cases to detect the presence of water or hydrogen in coesite, indicating either that it grew in dry environments or lost its hydrogen during partial transformation to quartz. On the other hand, micro-FTIR investigations of quartz crystals replacing coesite show that they contain varying amounts of H₂O. These results support the hypothesis that preservation of coesite is not necessarily linked to fast exhumation rates but is crucially dependent on limited fluid infiltration during exhumation. Received: 23 August 1999 / Accepted: 10 April 2000     

The unequilibrated enstatite chondrites

The enstatite chondrites formed under highly reducing (and/or sulfidizing) conditions as indicated by their mineral assemblages and compositions, which are sharply different from those of other chondrite groups. Enstatite is the major silicate mineral. Kamacite is Si-bearing and the enstatite chondrites contain a wide variety of monosulfide minerals that are not present in other chondrite groups. The unequilibrated enstatite chondrites are comprised of two groups (EH3 and EL3) and one anomalous member (LEW 87223), which can be distinguished by differences in their mineral assemblages and compositions. EH3 chondrites have >1.8 wt.% Si in their kamacite and contain the monosulfide niningerite (MgS), whereas EL3 chondrites have less than 1.4 wt.% Si in their kamacite and contain the monosulfide alabandite (MnS). The distinct mineralogies, compositions and textures of E3 chondrites make comparisons with ordinary chondrites (OCs) and carbonaceous chondrites (CCs) difficult, however, a range of recrystallization features in the E3s are observed, and some may be as primitive as type 3.1 OCs and CCs. Others, especially the EL3 chondrites, may have been considerably modified by impact processes and their primary textures disturbed. The chondrules in E3 chondrites, although texturally similar to type I pyroxene-rich chondrules, are sharply different from chondrules in other chondrite groups in containing Si-bearing metal, Ca- and Mg–Mn-rich sulfides and silica. This indicates formation in a reduced nebular environment separate from chondrules in other chondrites and possibly different precursor materials. Additionally the oxygen isotope compositions of E3 chondrules indicate formation from a unique oxygen reservoir. Although the abundance, size distribution, and secondary alteration minerals are not always identical, CAIs in E3 chondrites generally have textures, mineral assemblages and compositions similar to those in other groups. These observations indicates that CAIs in O, C and E chondrites all formed in the reservoir under similar conditions, and were redistributed to the different chondrite accretion zones, where the secondary alteration took place. Thus, chondrule formation was a local process for each particular chondrite group, but all CAIs may have formed in the similar nebular environment. Lack of evidence of water (hydrous minerals), and oxygen isotope compositions similar to Earth and Moon suggest formation of the E chondrites in the inner solar system and make them prime candidates as building blocks for the inner planets.     

Oxygen fugacity dependence of Os solubility in haplobasaltic melt

Os equilibrium solubilities were determined at 1350 °C over a wide range of oxygen fugacities (−12 < log fO₂ < −7) applying the mechanically assisted equilibration technique (MAE) at 10⁵ Pa (= 1 bar). Os concentrations in the glass samples were analysed using ID-NTIMS. Additional LA-ICP-MS and SEM analyses were performed to detect, visualize and analyse the nature and chemistry of “nanonuggets.” Os solubilities determined range at a constant temperature of 1350 °C from 0.63 ± 0.04 to 37.4 ± 1.16 ppb depending on oxygen fugacity. At the highest oxygen fugacities, Os³⁺ can be confirmed as the main oxidation state of Os. At low oxygen fugacities (below log fO₂ = −8), samples are contaminated by nanonuggets which, despite the MAE technique, were still not removed entirely from the melt. However, the present results indicate that applying MAE technology does reduce the amount of nanonuggets present significantly, resulting in the lowest Os solubility results reported to date under these experimental conditions, and extending the experimentally accessible range of fO₂ for these studies to lower values. Calculated metal/silicate melt partition coefficients are therefore higher compared to previous studies, making Os more siderophile. Neglecting the as yet unknown temperature dependence of the Os metal/silicate melt partition coefficient, extrapolation of the obtained Os solubilities to conditions for core-mantle equilibrium, results in a , while metallic alloy/silicate melt partition coefficients range from 1.4 × 10⁶ to 8.6 × 10⁷, in agreement with earlier findings. Therefore remains too high by 2-4 orders of magnitude to explain the Os abundance in the Earth’s mantle as result of core-mantle equilibrium during core formation.     

常温高压下石膏在水中的溶解度突变现象及其意义

我们在26℃和0.1~900MPa压力下进行了纯水中石膏的溶解实验。实验结果发现在低于608MPa的压力下石膏一直保持稳定,而在高于该压力下石膏才开始发生溶解。在其后的八次加压过程中,尽管体积在缩小,但压力却并不线性上升,且石膏也不发生进一步的溶解。当加压使体系压力增加,且压力超过668MPa时石膏才突然全部溶解完。这种现象一方面表明压力对矿物在水中的溶解具有某种控制作用,另一方面,也可能说明水在高压下具有完全不同于常压下的性质。这意味着地壳内在约18km深度处可能存在着一种物理化学界面。该界面将对矿物、岩石及其地球物理性质产生重要影响。     

The solubility of noble gases in water and in NaCl brine

A direct-sampling, mass-spectrometric technique has been used to measure simultaneously the solubilities of He, Ne, Ar, Kr, and Xe in fresh water and NaCl brine (0 to 5.2 molar) from 0° to 65 °C, and at 1 atm total pressure of moist air. The argon solubility in the most concentrated brines is 4 to 7 times less than in fresh water at 65 °C and 0°C, respectively. The salt effect is parameterized using the Setschenow equation.

$\text{ln}\text{[}\text{β}{}^{\mathrm{i}}{}_{\mathrm{o}}\text{(T)}\text{β}{}^{\mathrm{i}}\text{(T)}\text{= MK}{}^{\mathrm{i}}{}_{\mathrm{M}}\text{(T)}$

where M is NaCl moiarity, βⁱ_o(T) and βⁱ(T) the Bunsen solubility coefficients for gas i in fresh water and brine, and Kⁱ_M(T) the empirical salting coefficient. Values of Kⁱ_M(T) are calculated using volumetric concentration units for noble gas and NaCl content and are independent of NaCl molarity. Below about 40°C, temperature coefficients of all Kⁱ_M are negative. The value of K^He_M is a minimum at 40°C. K^Ar_M decreases from about 0.40 at 0°C to 0.28 at 65 °C. The absolute magnitudes of the differences in salting coefficients (relative to K^Ar_M) decrease from 0° to 65°C. Over the range of conditions studied, all noble gases are salted out, and K^He_M ? K^Ne_M < K^Ar_M < K^Kr_M < K^Xe_M.From the solubility data, we calculated $\text{Δ}\text{G}{}^0{}_{\mathrm{tr}}$, $\text{Δ}\text{S}{}^0{}_{\mathrm{tr}}$, $\text{Δ}\text{H}{}^0{}_{\mathrm{tr}}$ and $\text{Δ}\text{C}{}^{\mathrm{O}}{}_{\mathrm{p,tr}}$ for the transfer of noble gases from fresh water to 1 molar NaCl solutions. At low temperatures $\text{Δ}\text{S}{}^0{}_{\mathrm{tr}}$, is positive, but decreases and becomes negative at temperatures ranging from about 25°C for He to 45°C for Xe. At low temperatures, the dissolved electrolyte apparently interferes with the formation of a cage of solvent molecules about the noble gas atom. At higher temperatures, the local environment of the gas atom in the brine appears to be slightly more ordered than in pure water, possibly reflecting the longer effective range of the ionic fields at higher temperature.The measured solubilities can be used to model noble gas partitioning in two-phase geothermal systems at low temperatures. The data can also be used to estimate the temperature and concentration dependence of the salt effect for other alkali halides. Extrapolation of the measured data is not possible due to the incompletely-characterized minima in the temperature dependence of the salting coefficients. The regularities in the data observed at low temperatures suggest relatively few high-temperature data will be required to model the behavior of noble gases in high-temperature geothermal brines.     

The solubility of alumina in enstatite and the phase equilibria in the join MgSiO3-MgAl2SiO6 at 10–25 kbar

The solubility of alumina in enstatite was determined in the range of 1100–1500° C and 10–25 kbar. The alumina content in enstatite coexisting with sapphirine and quartz increases with increasing temperature and pressure, while that in enstatite coexisting with sapphirine and sillimanite or with pyrope decreases with increasing pressure and decreasing temperature. Two univariant lines, pyrope = enstatite_ss + sillimanite + sapphirine_ss and enstatite_ss + sillimanite =sapphirine_ss + quartz were confirmed. The invariant point involving these phases is metastable. The alumina content of orthopyroxene can not be used either as a pressure indicator or as a temperature indicator without taking the mineral assemblage into account.     

Temperature dependence of sulfide and sulfate solubility in olivine-saturated basaltic magmas

The sulfur concentration at pyrrhotite- and anhydrite-saturation in primitive hydrous basaltic melt of the 2001-2002 eruption of Mt. Etna was determined at 200 MPa, T = 1050-1250 °C and at log fO₂ from FMQ to FMQ+2.2 (FMQ is Fayalite-Magnetite-Quartz oxygen buffer). At 1050 °C Au sample containers were used. A double-capsule technique, using a single crystal olivine sample container closed with an olivine piston, embedded in a sealed Au₈₀Pd₂₀ capsule, was developed to perform experiments in S-bearing hydrous basaltic systems at T > 1050 °C. Pyrrhotite is found to be a stable phase coexisting with melt at FMQ-FMQ+0.3, whereas anhydrite is stable at FMQ+1.4-FMQ+2.2. The S concentration in the melt increases almost linearly from 0.12 ± 0.01 to 0.39 ± 0.02 wt.% S at FeS-saturation and from 0.74 ± 0.01 to 1.08 ± 0.04 wt.% S at anhydrite-saturation with T ranging from 1050-1250 °C. The relationships between S concentration at pyrrhotite and/or anhydrite saturation, MgO content of the olivine-saturated melt, T, and log fO₂ observed in this study and from previous data are used to develop an empirical model for estimating the magmatic T and fO₂ from the S and MgO concentrations of H₂O-bearing olivine-saturated basaltic melts. The model can also be used to determine maximum S concentrations, if fO₂ and MgO content of the melt are known. The application of the model to compositions of melt inclusions in olivines from Mt. Etna indicates that the most primitive magmas trapped in inclusions might have been stored at log fO₂ slightly higher than FMQ+1 and at T = 1100-1150 °C, whereas more evolved melts could have been trapped at T ? 1100 °C. These values are in a good agreement with the estimates obtained by other independent methods reported in the literature.     

The potential use of OH-defects in enstatite as geobarometer

In this study, single crystals of pure enstatite (Mg₂Si₂O₆) were synthesised under water-saturated conditions at 4 and 8 GPa and 1,150°C with variable silica activity, leading to phase assemblages enstatite + forsterite, enstatite or enstatite + coesite. Run products were investigated using an FTIR spectrometer equipped with a focal plane array detector enabling IR imaging with a lateral pixel resolution of 2.7 μm. IR spectra within the OH-absorption region show two different groups of absorption bands: group 1 (wavenumbers at 3,592 and 3,687 cm^?1) shows strongest absorptions for E||n _β, whereas group 2 (wavenumbers at 3,067 and 3,362 cm^?1) shows strongest absorptions for E||n _γ. The groups are related to different defect types, group 1 to tetrahedral defects (T-site vacancies) and group 2 to octahedral defects (M-site vacancies). The intensity ratio of the bands within one group (i.e. A ₃₀₆₇/A ₃₃₆₂ and A ₃₅₉₂/A ₃₆₈₇) and the intensity ratio of E||n _γ and E||n _α in group 2 bands remain constant within error. In contrast, the intensity ratio of group 2 to group 1 absorption bands [e.g. (A ₃₃₆₂)/(A ₃₆₈₇)] is sensitive to the SiO₂ activity and pressure. On the basis of the results of this and previous studies, a barometer for pure orthoenstatite coexisting with forsterite can be formulated:\( P\,[{\text{GPa}}] = 1.056 + \sqrt {{\frac{{1.025 - A_{{\left( {3362} \right)/\left[ {(3362) + (3687)} \right]}} }}{0.009}}} , \) where A ₍₃₃₆₂₎ and A ₍₃₆₈₇₎ are the integral absorbances of the component E||n _γ of the absorption bands at 3,362 cm^?1 and the component E||n _β of the absorption band at 3,687 cm^?1, respectively.     

Experiments of methane gas solubility in formation water under high temperature and high pressure and their geological significance

The solubility of methane in formation water and water content in the coexisting gas phase were measured under the conditions of high temperature and high pressure, using an ultra-high-pressure fluid PVT system, where the experimental temperature reached up to 453 K and pressure reached up to 130 MPa. Experimental results show the following (1) The two phases of gas and liquid still exhibit an obvious interphase interface even under high temperatures and pressures. (2) When temperatures exceed 353 K, the solubility of methane in formation water increases as the temperature and pressure rise. The growth rate of solubility is faster under a relatively low temperature and pressure, and slower at a relatively high temperature and pressure, but the solubility will not increase without limit. In this experiment, the solubility of methane in formation water reached its peak when the temperature was at 453 K and the pressure at 130 MPa. (3) Water content in the coexisting gas phase increases as temperature rises, with a smaller increase at relatively low temperatures and a much greater increase at relatively high temperatures but decreases with the increasing pressure, more rapidly under low pressure and more slowly under high pressure. The solubility of methane in formation water and the water content in the coexisting gas phase are controlled by both temperature and pressure, but using classic calculation models, these two parameters under high temperatures and pressures are inconsistent with our experimental data. Therefore, the study is significant and highlights other possible effects on solubility and condensate water content. Additionally, an example from the Yinggehai Basin in the South China Sea, where the temperature and the pressure are high, demonstrates the influence of solubility and phase behaviour on natural gas migration, its formation and the distribution of gas reservoirs.     

Pressure dependence ot SrSO4 solubility

The solubilities of SrSO₄ in seawater, 0.65 M NaCl and and distilled water were measured as a function of pressure at 2°C. The thermodynamic solubility product was determined from the distilled water measurements and stoichiometric solubility products were determined from the seawater and Nad measurements. The equilibrium quotient for SrSO₄ dissolution at ionic strength of 0.65 was calculated from the NaCl measurements, using the known NaSO₄^? ionpairing association constant. For each of the solubility products values of $\text{Θ V}$ were determined. These experimental values were all $\text{11.0 ± 0.3}\text{ml}$ mole_? lower than the theoretical values based on anhydrous SrSO₄. This difference may be due to the equilibrating solid phase being a hydrated form of SrSO₄.     

The effect of pressure on the solubility of minerals in water and seawater

The effect of presure on the solubility of minerals in water and seawater can be estimated from In

$\text{(}\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^0{}_{\mathrm{sp}}\text{) +}\text{(?ΔVP + 0.5ΔKP}{}^2\text{)}\text{RT}$

where the volume (ΔV) and compressibility (ΔK) changes at atmospheric pressure (P = 0) are given by

$\text{ΔV =}\text{V}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{V}\text{?}\text{[MX(s)]ΔK =}\text{K}\text{?}\text{(M}{}^{\mathrm{+}}\text{, X}{}^{\mathrm{?}}\text{) ?}\text{K}\text{?}\text{[MX(s)]}$

Values of the partial molal volume ($\text{V}\text{?}$) and compressibilty ($\text{K}\text{?}$) in water and seawater have been tabulated for some ions from 0 to 50°C. The compressibility change is quite large (~10 × 10^?3 cm³ bar^?1 mol^?1) for the solubility of most minerals. This large compressibility change accounts for the large differences observed between values of ΔV obtained from linear plots of In K_sp versus P and molal volume data (Macdonald and North, 1974; North, 1974). Calculated values of $\text{K}{}^{\mathrm{P}}{}_{\mathrm{sp}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{sp}}$ for the solubility of CaCO₃, SrSO₄ and CaF₂ in water were found to be in good agreement with direct measurements (Macdonald and North, 1974). Similar calculations for the solubility of minerals in seawater are also in good agreement with direct measurements (Ingle, 1975) providing that the surface of the solid phase is not appreciably altered.     

Equilibration temperatures in enstatite chondrites

Equilibration temperatures for enstatite chondrites are calculated using a method suggested by Larimer (1968). The temperatures range from 640° to 840°C. The method yields temperatures which, in principle, are correct on a relative scale but the absolute error may be a large as 150°. There is a good correlation between the calculated temperatures and petrologic type as well as other mineralogic characteristics and bulk composition. Partial pressures of sulfur and oxygen at the time of equilibration were: pS₂ ~ 10^?8?10^?12 atm and pO₂ ~ 10^?28?10^?37.     

富铁橄榄石的水溶性实验研究SCIEI北大核心CSCD

地幔的力学性质主要受橄榄石流变性的控制,含水对橄榄石流变性质的影响很大,而橄榄石的水溶性受到温度和铁含量的影响,因此,本文进行了不同铁含量橄榄石在不同温度下的水溶性实验研究。实验使用的样品为天然橄榄石单晶Fa_(17)和Fa_(24.7)(Fe_(No.)=100×molar Fe/(Mg+Fe))以及人工合成的橄榄石单晶Fa_(22);橄榄石单晶的水溶性实验在300MPa围压和1273~1473K的温度条件下进行,每隔50K进行一组实验,氧逸度被控制在Ni NiO水平上。实验结束后,对橄榄石单晶沿b面进行双面研磨抛光,用电子探针分析确定橄榄石单晶成分,采用EBSD精确测量橄榄石的单晶方向,使用红外光谱仪(FTIR)的非偏振光路测试橄榄石单晶在b轴上的吸收光谱。对FTIR吸收光谱进行积分得到富铁橄榄石的水溶性实验结果:当温度由1273K升至1473K时,橄榄石单晶Fa_(17)的水溶性变化为600~1200H/10^(6) Si,橄榄石单晶Fa_(24.7)的水溶性变化为1000~1300H/10^(6) Si,人工合成的橄榄石单晶Fa_(22)的水溶性变化为500~900 H/10^(6) Si。因此,相同铁含量橄榄石单晶的水溶性随温度的增加而增加,相同温度条件下,天然形成的橄榄石的水溶性随着铁含量的增加而增加,百分之一的铁含量的增加,可以导致约百分之十的水溶性的增加。本文所研究的不同铁含量的橄榄石可以为更好地估算上地幔水溶性提供依据。     

Grain boundary diffusion in enstatite

We have investigated grain boundary diffusion rates in enstatite by heating single crystals of quartz packed in powdered San Carlos olivine (Mg_0.90Fe_0.10)₂SiO₄ at controlled oxygen fugacities in the range 10^?5.7 to 10^?8.7?atm and temperatures from 1350° to 1450?°C for times from 5 to 100?h at 1?atm total pressure. Following the experiments, the thickness of the coherent polycrystalline reaction rim of pyroxene that had formed between the quartz and olivine was measured using backscatter scanning imaging in the electron microprobe. Quantitative microprobe analysis indicated that the composition of this reaction phase is (Mg_0.92Fe_0.08)₂Si₂O₆. The rate of growth of the pyroxene increases with increasing temperature, is independent of the oxygen fugacity, and is consistent with a parabolic rate law, indicating that the growth rate is controlled by ionic diffusion through the pyroxene rim. Microstructural observations and platinum marker experiments suggest that the reaction phase is formed at the olivine-pyroxene interface, and is therefore controlled by the diffusion of silicon and oxygen. The parabolic rate constants determined from the experiments were analyzed in terms of the oxide activity gradient across the rim to yield mean effective diffusivities for the rate-limiting ionic species, assuming bulk transport through the pyroxene layer. These effective diffusivities are faster than the lattice diffusivities for the slowest species (silicon) calculated from creep experiments, but slower than measured lattice diffusivities for oxygen in enstatite. Thus, silicon grain boundary diffusion is most likely to be the rate-limiting process in the growth of the pyroxene rims. Also, as oxygen transport through the pyroxene rims must be faster than silicon transport, diffusion of oxygen along the grain boundaries must be faster than through the lattice. The grain boundary diffusivity for silicon in orthopyroxenite is then given by D¯gbSiδ=(3.3±3.0)×10^?9f0.0O₂e^?400±65/RT?m³s^?1, where the activation energy for diffusion is in kJ/mol, and δ is the grain boundary width in m. Calculated growth rates for enstatite under these conditions are significantly slower than predicted by an extrapolation from similar experiments performed at 1000?°C under high pressure (hydrous) conditions by Yund and Tullis (1992), perhaps due to water-enhancement of diffusion in their experiments.     

Diffusion and solubility of hydrogen and water in periclase

Cylinders of synthetic periclase single crystals were annealed at 0.15–0.5 GPa and 900–1200 °C under water-saturated conditions for 45 min to 72 h. Infrared spectra measured on the quenched products show bands at 3,297 and 3,312 cm^?1 indicating V _OH ^? centers (OH-defect stretching vibrations in a half-compensated cation vacancy) in the MgO structure as a result of proton diffusion into the crystal. For completely equilibrated specimens, the OH-defect concentration, expressed as H₂O equivalent, was calculated to 3.5 wt ppm H₂O at 1,200 °C and 0.5 GPa based on the calibration method of Libowitzky and Rossmann (Am Min 82:1111–1115, 1997). This value was confirmed via Raman spectroscopy, which shows OH-defect-related bands at identical wavenumbers and yields an H₂O equivalent concentration of about 9 wt ppm using the quantification scheme of Thomas et al. (Am Min 93:1550–1557, 2008), revised by Mrosko et al. (Am Mineral 96:1748–1759, 2011). Results of both independent methods give an overall OH-defect concentration range of 3.5–9 (+4.5/?2.6) ppm H₂O. Proton diffusion follows an Arrhenius law with an activation energy E _a = 280 ± 64 kJ mol^?1 and the logarithm of the pre-exponential factor logD_o (m² s^?1) = ?2.4 ± 1.9. IR spectra taken close to the rims of MgO crystals that were exposed to water-saturated conditions at 1,200 °C and 0.5 GPa for 24 h show an additional band at 3,697 cm^?1, which is related to brucite precipitates. This may be explained by diffusion of molecular water into the periclase, and its reaction with the host crystal during quenching. Diffusion of molecular water may be described by logD_H2O (m² s^?1) = ?14.1 ± 0.4 (2σ) at 1,200 °C and 0.5 GPa, which is ~ 2 orders of magnitude slower than proton diffusion at identical P-T conditions.     

The stable carbon isotopes in enstatite chondrites and Cumberland Falls

The carbon isotopic composition of the total carbon in the enstatite chondrites Indarch, Abee, St. Marks, Pillistfer, Hvittis and Daniel's Kuil and the enstatite achondrite Cumberland Falls has been measured. The empirical relationhip between carbon isotopic composition and total carbon content is distinct from that of carbonaceous and ordinary chondrites. Within the enstatite chondrite group the average ¹³C content increases with petrographic type: E4 < E5 < E6. Daniel's Kuil shows the largest ¹³C enrichment in the bulk carbon of any meteorite. The carbon isotopic composition is most clearly correlated with the abundance of the elements Zn, Cd and In. Insofar as these elements may hold the key to the understanding of enstatite chondrites, more detailed combined carbon isotope and trace element studies of these meteorites will play an important role in the deciphering of their history.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.