Properties of fluids attending variable recrystallization of quartzite during contact metamorphism in the White‐Inyo Range,California

Fluid inclusions in the metamorphic aureole of the Eureka Valley‐Joshua Flat‐Beer Creek (EJB) pluton in the White‐Inyo Range, California, reveal the compositions and origin of fluids that were present during variable recrystallization of quartzite with sedimentary grain shapes to metaquartzite with granoblastic texture. Metamorphosed sedimentary formations, including quartzites, marbles, calcsilicates and schists, became ductile and strongly attenuated in the aureole during growth of the magma chamber. The microstructures of quartzites have an unusual distribution in that within ~250 m from the pluton, where temperatures exceeded 650 °C, they exhibit relict sedimentary grain shapes, only small amount of grain boundary migration (GBM), and crystallographic preferred orientations (CPOs) dominated by <a> slip. At distances >250 m, quartzites were completely recrystallized by GBM and CPOs are indicative of prism [c] slip, characteristics that are typically associated with H₂O‐assisted, high‐T recrystallization. The lack of extensive GBM in the inner aureole can be attributed to rapid replacement of H₂O by CO₂ produced by reaction of quartz grains with calcite cement that also produced interstitial wollastonite. Fluid inclusions in the inner aureole generally occur in margins of quartz grains and are either wholly aqueous (Type 1) or also contain H₂S, CO₂ and CH₄ (Type 2). Type 2 inclusions occur only in some stratigraphic layers. In both inclusion types, NaCl and CaCl₂, in variable proportions, dominate the solutes in the aqueous phase, whereas FeCl₂ and KCl are less abundant solutes. The solutes indicate attainment of a degree of equilibrium with carbonates and schists that are interbedded with the quartzites. Some Types 1 and 2 inclusions in the inner aureole show evidence of decrepitation due to high amounts of strain and/or heating suffered by the host rocks, which suggests that they represent pore fluids that existed in the rocks prior to contact metamorphism. In addition to Type 1 inclusions, outer aureole quartzites also contain inclusions that contain CO₂ vapour bubbles in addition to aqueous phase (Type 3). These inclusions only occur in interiors of granoblastic quartz that was produced by large amounts of GBM. The aqueous phase has identical ranges of first melting and final ice melting temperatures as Type 1 inclusions, suggesting that they have the same solute compositions. These inclusions are thought to represent the interstitial pore H₂O that promoted recrystallization of quartz and reacted with graphite to produce CO₂. Absence of significant amounts of CH₄ in Type 3 inclusions is attributed to elevated fO₂ that was buffered by mineral assemblages in interbedded schists. As opposed to the large amount of CO₂ that was produced by the wollastonite‐forming reaction in the inner aureole to inhibit GBM, the amount of CO₂ produced in the outer aureole by reaction between H₂O and graphite was apparently insufficient to inhibit recrystallization of quartz.     

Carbon isotopic thermometry calibrated by dolomite-calcite solvus temperatures

The temperature dependence of carbon isotopic fractionations between calcite and graphite, and between dolomite and graphite are calibrated by the calcite-dolomite solvus geothermometry using marbles collected from the contact metamorphic aureole in the Kasuga area, central Japan. The carbon isotopic fractionations (Δ¹³C_Cc-Gr and Δ¹³C_DoGr) systematically decrease with increasing metamorphic temperature. The concordant relationships between the fractionations and solvus temperatures are approximately linear with T^?2 over the temperature range. 400° to 680°C: Δ¹³C_CcGr (%.) = 5.6 × 10⁶ × T^?2 (K) ? 2.4 Δ¹³C_DoGr (%.) = 5.9 × 10⁶ × T^?2 (K) ? 1.9 These systematic relationships between fractionation and temperature suggest that carbon isotopic equilibria between carbonates and graphite were attained in many cases. The equation for the calcite-graphite system has a slope steeper than Bottinga's (1969) results. It is, however, in good agreement with that of Valley and O'Neil (1981) in the temperature range from 600° to 800°C.Because of the relatively high sensitivity to temperature, these isotopic geothermometers are useful for determining the temperatures in moderate- to high-grade metamorphosed carbonate rocks.     

Analysis of relationships between geochemical parameters of petroleum potential in related source and carbonaceous materials

A worldwide data set of 1,085 samples containing organic matter of the type II/III kerogen from Carboniferous to Cenozoic was used to analyse the evolution of the hydrogen index (HI), quality index (QI), and bitumen index (BI) with increasing thermal maturity. The HI_max, QI_max and BI_max lines were defined, based on statistical analysis and cross-plots of HI, QI and BI versus the vitrinite reflectance (%Ro) and T _max (°C). The constructed HI, QI and BI bands were broad at low maturities and gradually narrowed with increasing thermal maturity. The petroleum generation potential is completely exhausted at a vitrinite reflectance of 2.0–2.2 % and T _max of 510–520 °C. An increase in HI and QI suggests extra petroleum potential related to changes in the structure of the organic material. A decline in BI signifies the start of the oil window and occurs within the vitrinite reflectance range 0.75–1.05 % and T _max of 440–455 °C. Furthermore, petroleum potential can be divided into four different parts based on the cross-plot of HI versus %Ro. The area with the highest petroleum potential is located in “Samples and methods” with %Ro = 0.6–1.0 %, and HI > 100. Oil generation potential is rapidly exhausted at “Results and discussion” with %Ro > 1.0 %. This result is in accordance with the regression curve of HI and QI with %Ro based on 80 samples with %Ro = 1.02–3.43 %. The exponential equation of regression can thus be achieved: HI = 994.81e^?1.69Ro and QI = 1,646.2e^?2.003Ro (R ² = 0.72). The worldwide organic material data set defines two range of oil window represented by the upper and lower limits of the BI band: %Ro 0.75–1.95 %, T _max 440–525 °C, and %Ro 1.05–1.25 %, T _max 455–465 °C, respectively.     

Mineral reactions and geothermobarometry in a suite of granulite facies rocks from Paderu, Eastern Ghats granulite belt: A reappraisal of the P-T trajectory

High Mg-Al spinel-sapphirine granulites, orthopyroxene-bearing quartzofeldspathic granulites, two pyroxene-bearing mafic granulites and metapelitic gneisses are exposed around Paderu, Eastern Ghats Belt. Geothermobarometry in orthopyroxene-bearing quartzofeldspathic granulites and mafic granulites indicate near isobaric cooling through 90°C from ca. 720°C to 630°C, at 8.0 kbar. However, signatures of ultrahigh temperature metamorphism are recorded from the mineralogy and reaction textures in the high Mg-Al granulites. Mineral reactions deduced in this work, when combined with others described by Lalet al (1987) from the same area and plotted in an appropriate petrogenetic grid in the system FMASO indicate an ACW path comprising a high dT/dP prograde arm reaching P_max − T_max = 9.5 kbar, ∼ 1000°C, followed by near-isobaric cooling down to 9 kbar, 900°C and subsequent decompressive reworking.     

Diffusion-controlled growth of wollastonite rims between quartz and calcite: comparison between nature and experiment

Growth rates of wollastonite reaction rims between quartz and calcite were experimentally determined at 0.1 and 1 GPa and temperatures from 850 to 1200 °C. Rim growth follows a parabolic rate law indicating that this reaction is diffusion‐controlled. From the rate constants, the D′δ‐values of the rate‐limiting species were derived, i.e. the product of grain boundary diffusion coefficient D′ and the effective grain boundary width, δ. In dry runs at 0.1 GPa, wollastonite grew exclusively on quartz surfaces. From volume considerations it is inferred that (D′_CaOδ)/(D′_SiO2δ)≥1.33, and that SiO₂ diffusion controls rim growth. D′_SiO2δ increases from about 10^?25 to 10^?23 m³ s^?1 as temperature increases from 850 to 1000 °C, yielding an apparent activation energy of 330±36 kJ mol^?1. In runs at 1 GPa, performed in a piston‐cylinder apparatus, there were always small amounts of water present. Here, wollastonite rims always overgrew calcite. Rims around calcite grains in quartz matrix are porous and their growth rates are controlled by a complex diffusion‐advection mechanism. Rim growth on matrix calcite around quartz grains is controlled by grain boundary diffusion, but it is not clear whether CaO or SiO₂ diffusion is rate‐limiting. D′δ increases from about 10^?21 to 10^?20 m³ s^?1 as temperature increases from 1100 to 1200 °C. D′_SiO2δ or D′_CaOδ in rims on calcite is c. 10 times larger than D′_SiO2δ in dry rims at the same temperature. Growth structures of the experimentally produced rims are very similar to contact‐metamorphic wollastonite rims between metachert bands and limestone in the Bufa del Diente aureole, Mexico, whereby noninfiltrated metacherts correspond to dry and brine‐infiltrated metacherts to water‐bearing experiments. However, the observed diffusivities were 4 to 5 orders of magnitude larger during contact‐metamorphism as compared to our experimental results.     

Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure

This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO₃ into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A _o ?=?22.69 h^?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10^?14 m²/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.     

Laboratory organic matter maturation at high pressures: heat-up effect on vitrinite reflectance

A laboratory study was conducted to assess the effect of heat-up to high diagenetic to low metamorphic temperatures on vitrinite reflectance (VR) at high pressures using the same heat-up processes, apparatus and starting material as those employed in prior experimental studies on huminite/vitrinite maturation. ??Heat-up?? is the isobaric increase in temperature of an organic matter maturation experiment from room temperature to the desired run temperature T ^ehu (T ^ehu ?=?temperature at the end of heat-up). The experiments were performed on xylite of swamp cypress and used a heating rate of 50?°C/min. These confined system maturation experiments were carried out at 10?kbar and involved temperatures T ^ehu ranging from 175 to 450?°C. Additional experiments were conducted at pressures of 5, 20 and 25?kbar to evaluate the influence of pressure on the effect of heat-up on VR. At 10?kbar, results of this study show that heat-up does not influence VR for T ^ehu ?< ~270?°C. This absence of maturation is viewed as the result of an activation time delaying vitrinite maturation at these diagenetic to very low metamorphic temperatures. For T ^ehu ?> ~270?°C, heat-up has a significant effect on VR at 10?kbar: VR greatly increases with T ^ehu during the short heat-up event. This effect of heat-up on VR points out the rapid kinetics of the initial VR increase. Increasing pressure reduces VR increase gained during heat-up. Obviously, pressure retards the initial VR increase and thus controls organic matter maturation. In addition to temperature, the formulation of VR evolution rate equation must consider pressure, activation time and VR gained during heat-up.     

Petrology of contact metamorphic metapelites from the southern rim of the Permian Brixen Granodiorite (South Tyrol, italy)

The Brixen Granodiorite is part of the Permian calc-alkaline plutonic association (Brixen Granodiorite, Ifinger Granite, Kreuzberg Granite, Cima d’Asta Granitoid) that intruded the Variscan Southalpine metamorphic basement. The Brixen Granodiorite is located to the south of the Periatriatic Lineament in the eastern part of the Southalpine basement complex and comprises a series of tonalitic, granitic and granodioritc intrusions, which were emplaced during the Permian (280?Ma) into the country rocks of the Brixen Quarzphyllites. The depth of these Southalpine granodioritic intrusions was less than 10?km (P?≤?0.3?GPa) and solidus temperatures were 670–720?°C (Visona, Mem Sci Geol 47:111–124, 1995; Acquafredda et al., Miner Petrogr Acta XL:45–53, 1997; Wyhlidal et al., Austr J Earth Sci 102:181–192, 2009). Only a small, about 200?m wide, contact aureole formed at the southern rim of the Brixen Granodiorite near the village Franzensfeste/Fortezza (South-Tyrol, Italy). Within the contact aureole four different zones can be distinguished based upon mineralogical, mineral chemical and textural features. Approximately 200?m from the granite contact zone I occurs. The rocks from this zone are macroscopically still quartzphyllites and are characterized by two texturally and chemically different generations of micas (muscovite, biotite) and the appearance of cordierite. Zone II is characterized by quartzphyllites containing pseudomorphs of cordierite + biotite after garnet. The inner contact aureole (zone III) starts approximately 50?m from the granite contact and shows already typical hornfels textures. This zone is characterized by the first occurrence of andalusite. In the innermost area (zone IV), ca 10?m from the granite contact, spinel and corundum occur. Geothermometry (two-feldspar-, Ti-in-biotite) yielded an increase in temperature from 540?°C in the outermost aureole (zone I) to <740?°C in the innermost aureole (zone IV). Pseudosection modelling of hornfelses from zones III and IV also resulted in similar P-T conditions of <0.28?GPa and <620?°C. This contact aureole represents one of the few well-developed remaining areas of Permian contact metamorphism in the Southalpine domain, which are otherwise mostly obliterated by late-stage hydrothermal alteration in the course of the Alpine tectonic overprint.     

The chemistry of geothermal waters in Iceland. III. Chemical geothermometry in geothermal investigations

New data from geothermal wells in Iceland have permitted empirical calibration of the chalcedony and $\text{Na}\text{K}$ geothermometers in the range of 25–180°C and 25–250°C respectively. The temperature functions are:

$\text{t°C=}\text{1112}\text{4.91?}\text{log SiO}{}_2\text{?273.15}$

$\text{t°C=}\text{933}\text{0.993+}\text{log Na/K}\text{?273.15}$

Concentrations are expressed in ppm. These temperature functions correspond well with the chalcedony solubility data of Fournier (1973) and the thermodynamic data for low-albite/microcline/solution equilibria of Heloeson (1969).A new CO₂ geothermometer is proposed which is considered to be useful in estimating underground temperatures in fumarolic geothermal fields. Its application involves analysis of CO₂ concentrations in the fumarole steam. The temperature function which applies in the range 180?300°C is: logCO₂ = 37.43 + 73192/T- 11829· 10₃/T² + 0.18923T- 86.187·logT where T is in °K and CO₂ in moles per kg of steam.     

An equation correlating the solubility of quartz in water from 25° to 900°C at pressures up to 10,000 bars

The solubility of quartz in water from 25° to 900°C at specific volume of the solvent ranging from about 1 to 10 and from 300° to 600°C at specific volume of the solvent ranging from about 10 to 100 is given by an empirically derived equation of the form: log m = A + B(log V) + C(log V)² where m is the molal silica concentration, V is the specific volume of pure water, and A = ?4.66206 + 0.0034063T + 2179.7T^?1 ? 1.1292 × 10⁶T^?2 + 1.3543 × 10⁸T^?3B = ?0.0014180T— 806.97T^?1C = 3.9465 × 10^?4T T is temperature in kelvins. The experimental data used in formulating the empirical relation ranged in pressure from 1 bar at 25°C to about 10,000 bars at 900°C, and the lowest pressure in the low-density steam region was about 30 bars. According to the above equation, the average difference in molality between 518 measured and calculated solubilities is ?0.016 m with a standard deviation of 0.089.     

The electrical conductivity of calcite between 300 and 1200° C at a CO2 pressure of 40 bars

The electrical conductivity of calcite cleavage fragments was measured using direct current. Five temperature intervals, characterized by different activation energies of conduction, were established — T ₁: (300°)–500° C, T ₂: 500–725° C, T ₃: 725°–800° C, T ₄: 800°–985° C and T ₅: 985°–(1,200)° C. The data above 600° C indicate various intrinsic conduction mechanisms which are likely to be related to disorder in the CO₃-sublattice of calcite. The transitions between the temperature intervals T ₂-T ₃-T ₄ and T ₄-T ₅ are probably correlated with high-temperature transitions of calcite at 800° and 985° C. Measurement of the thermoelectric voltage indicates a conductivity dominated by negatively charged carriers.     

Metamorphism of high‐P metagreywacke from the Eastern Himalayan syntaxis: phase equilibria and P–T path

High‐pressure (HP) metagreywacke from the Namche Barwa Complex, Eastern Himalayan Syntaxis (EHS), consists of garnet, biotite, plagioclase, quartz, rutile and ilmenite with or without K‐feldspar, sillimanite, cordierite, spinel and orthopyroxene. Two types of metagreywacke are recognized: medium‐temperature (MT) and high‐temperature (HT) types. Garnet in the MT metagreywacke shows significant growth zoning and contains lower MgO than the weakly zoned garnet in the HT metagreywacke. Petrographic observations and phase equilibria modelling for four representative samples indicate that both types of metagreywacke experienced clockwise P–T paths subdivided into three stages: stage I is the pre‐peak prograde to pressure peak (P_max) stage characterized by progressive increase in P–T conditions. The P_max conditions are estimated using the garnet composition with maximum CaO, being 12.5–13.5 kbar and 685–725 °C for the MT metagreywacke, and 15–16 kbar and 825–835 °C for the HT one. Stage II is the post‐P_max decompression with heating or near‐isothermal to T_max stage and the T_max conditions, constrained using the garnet compositions with maximum MgO, are 11 kbar and 760 °C for the MT metagreywacke, and ~12 kbar and 830–845 °C for the HT one. The modelled mineral assemblages at T_max are garnet + biotite + K‐feldspar + rutile + plagioclase ± ilmenite in the presence of melt for both types of metagreywacke, consistent with the petrographic observations. Stage III is the post‐T_max retrograde metamorphism, characterized by decompression and cooling. The modelling suggests that the melts with high Na/K ratios (1.7–5.2) have been produced during stages I and II, which could be responsible for the formation of sodium‐rich leucogranites. This study and previous results indicate that the Higher Himalayan Crystallines in the EHS consist of MT–HP and HT–HP metamorphic units separated by a speculated tectonic contact. Petrological and structural discontinuities within the EHS cannot be easily interpreted with ‘tectonic aneurysm’ model.     

Dolomite microstructures between 390° and 700 °C: Indications for deformation mechanisms and grain size evolution

Dolomitic marble on the island of Naxos was deformed at variable temperatures ranging from 390 °C to >700 °C. Microstructural investigations indicate two end-member of deformation mechanisms: (1) Diffusion creep processes associated with small grain sizes and weak or no CPO (crystallographic preferred orientation), whereas (2) dislocation creep processes are related with larger grain sizes and strong CPO. The change between these mechanisms depends on grain size and temperature. Therefore, sample with dislocation and diffusion creep microstructures and CPO occur at intermediate temperatures in relative pure dolomite samples. The measured dolomite grain size ranges from 3 to 940 μm. Grain sizes at T_max >450 °C show an Arrhenius type evolution reflecting the stabilized grain size in deformed and relative pure dolomite. The stabilized grain size is five times smaller than that of calcite at the same temperature and shows the same Arrhenius-type evolution. In addition, the effect of second phase particle influences the grain size evolution, comparable with calcite. Calcite/dolomite mixtures are also characterized by the same difference in grain size, but recrystallization mechanism including chemical recrystallization induced by deformation may contribute to apparent non-temperature equilibrated Mg-content in calcite.     

In situ observation of crystal growth in a basalt melt and the development of crystal size distribution in igneous rocks

The speciation of CO₂ in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO₂ into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO₂ re-appeared. Infrared extinction coefficients of both carbonate and molecular CO₂ decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/t = 0.98) and basaltic andesite (NBO/t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/t = 0.09) and phonolite melts (NBO/t = 0.14), the equilibrium CO₂ + O^2? = CO₃ ^2? in the melt shifts toward CO₂ with increasing temperature, with ln K = ?4.57 (±1.68) + 5.05 (±1.44) 10³ T ^?1 for dacite melt (ΔH = ?42 kJ mol^?1) and ln K = ?6.13 (±2.41) + 7.82 (±2.41) 10³ T ^?1 for phonolite melt (ΔH = ?65 kJ mol^?1), where K is the molar ratio of carbonate over molecular CO₂ and T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that ΔS and ΔH are linear functions of NBO/t. Based on this relationship, a general model for CO₂ speciation in silicate melts is developed, with ln K = a + b/T, where T is temperature in Kelvin and a = ?2.69 ? 21.38 (NBO/t), b = 1,480 + 38,810 (NBO/t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO₂, and therefore, the diffusion coefficient of CO₂ is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO₂ solubility and speciation on melt composition, in accordance with available solubility data.     

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.     

Determination of the first ionization constant of silicic acid from quartz solubility in borate buffer solutions to 350°C

The solubility of quartz has been determined in borax buffer solutions having total boron concentrations of 0.10, 0.20, 0.40 and 0.60 mol kg^?1 and over the temperature range 130–350°C at the saturated vapour pressure of the system. The first ionization constant of silicic acid was calculated from the solubility data and varied from ?logK₁ = 8.88 (± 0.15) at 130°C to ?logK₁ = 10.06 (± 0.20) at 350°C. The solubility of quartz in these solutions was due to the presence of the three species, H₄SiO₄, H₃SiO₄^? and NaH₃SiO₄°. The equilibrium constant for the reaction, Na⁺ + H₃SiO₄^? = NaH₃SiO₄° extended from log K_as = 1.18?1.40 (± 0.20) over the temperature interval 135–301°C. The formation of NaH₃SiO₄° ion pairs was concluded to contribute significantly to the solubility of quartz in alkaline hydrothermal solutions when pH > 8 and sodium concentration exceeds 0.10 mol kg^?1.     

Un « point chaud » sous le système du Rift syrien : données pétrologiques complémentaires sur les enclaves du volcanisme récent

Ultrabasic xenoliths (pyroxenites, lherzolites, harzburgites) in recent (Neogene–Quaternary) volcanoes have been studied in three localities within Syria: Jubates (North), Mhailbeh (Center), Tel Thannoun (South). P–T conditions of mineral equilibration have been estimated by pyroxene thermometry (temperature) and maximum CO₂ density in primary inclusions (minimum pressure). Pyroxenites equilibrate at significantly higher conditions (T about 1200 °C, P>15 kbar) than lherzolites and harzburgites (900<T<1100 °C, P between 10 and 15 kbar). All are within the spinel lherzolite field, whereas Cretaceous xenoliths originate within the garnet lherzolite field. To cite this article: A. Bilal, F. Sheleh, C. R. Geoscience 336 (2004).     

Structure of mineral glasses—III. NaAlSi3O8 supercooled liquid at 805°C and the effects of thermal history

The distribution of interatomic distances in amorphous NaAlSi₃O₈ has been determined at 805°C by X-ray radial distribution analysis to investigate structural differences between the glass (T < 763°C) and the supercooled liquid (763°C < T < 1118°C). Except for slight differences attributable to thermal expansion, no significant changes were observed. The sample crystallized during the course of the experiment, but at least one crystal-free data set was obtained. The transition from the inferred six-membered ring structure of the supercooled liquid to the four-membered ring structure of the crystal was clearly visible in radial distribution function (RDF's) determined before and after crystallization.RDF's were also determined at 25°C for two NaAlSi₃O₈ glasses with different histories. The first was derived from a melt that had been cooled slowly from 1600 to 32°C above the melting point (T_f = 1118°C) to detect possible repolymerization to a more ‘crystal-like’ structure as the melt approached T_f. The second glass was prepared by holding a single crystal of Amelia albite at 50°C above T_f to see if the crystalline four-membered ring structure was preserved in melts at temperatures just above the liquidus. No significant differences were observed between these two RDF's and one obtained from a glass quenched from 1800°C. These results suggest that in addition to the destruction of formation of a periodic structure, melting and crystallization in NaAlSi₃O₈ also involves a repolymerization of tetrahedra. This would explain the observed kinetic barrier to melting and crystallization in the anhydrous system and the catalytic effect of small amounts of water or alkali oxide.     

The formation of lead(II) chloride complexes to 300°C: A spectrophotometric study

The spectra of chlorolead(II) complexes in the ultraviolet region have been measured in acid chloride solutions from 0.0012 to 3.223 m and at temperatures from 25 to 300°C. The thermodynamic cumulative and stepwise formation constants as well as the spectra of the individual chlorolead(II) species have been calculated from the spectrophotometric data. At 25°C, the five species PbCl^2?n_n (0 ≤ n ≤ 4) occur, however, at 300°C the predominant species were PbCl⁺, PbCl⁰₂ and PbCl^?₃. Pb²⁺ occurs as a minor species in dilute solutions where total chloride is <0.003 m at 300°C and the presence of PbCl^2?₄ in concentrated solutions was not detected above 150°C. With increasing temperature, chlorolead(II) complex stability is characterised by large endothermic enthalpies and large positive entropies of formation. Lead(II) chloride complexes are important in the transport and deposition of lead by hydrothermal ore solutions of moderate to high salinity.