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1.
William Cory Beck Ethan L. Grossman John W. Morse 《Geochimica et cosmochimica acta》2005,69(14):3493-3503
In light of recent studies that show oxygen isotope fractionation in carbonate minerals to be a function of HCO3− and CO32− concentrations, the oxygen isotope fractionation and exchange between water and components of the carbonic acid system (HCO3−, CO32−, and CO2(aq)) were investigated at 15°, 25°, and 40°C. To investigate oxygen isotope exchange between HCO3−, CO32−, and H2O, NaHCO3 solutions were prepared and the pH was adjusted over a range of 2 to 12 by the addition of small amounts of HCl or NaOH. After thermal, chemical, and isotopic equilibrium was attained, BaCl2 was added to the NaHCO3 solutions. This resulted in immediate BaCO3 precipitation; thus, recording the isotopic composition of the dissolved inorganic carbon (DIC). Data from experiments at 15°, 25°, and 40°C (1 atm) show that the oxygen isotope fractionation between HCO3− and H2O as a function of temperature is governed by the equation:
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The rates of Sb(III) oxidation by O2 and H2O2 were determined in homogeneous aqueous solutions. Above pH 10, the oxidation reaction of Sb(III) with O2 was first order with respect to the Sb(III) concentration and inversely proportional to the H+ concentrations at a constant O2 content of 0.22 × 10−3 M. Pseudo-first-order rate coefficients, kobs, ranged from 3.5 × 10−8 s−1 to 2.5 × 10−6 s−1 at pH values between 10.9 and 12.9. The relationship between kobs and pH was:
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Infrared spectroscopic and X-ray diffraction characterization of the nature of adsorbed arsenate on ferrihydrite 总被引：4，自引：0，他引：4
Fourier transformed infrared (FTIR) spectroscopy was used to characterize arsenate-ferrihydrite sorption solids synthesized at pH 3-8. The speciation of sorbed arsenate was determined based on the As-O stretching vibration bands located at 650-950 cm−1 and O-H stretching vibration bands at 3000-3500 cm−1. The positions of the As-O and O-H stretching vibration bands changed with pH indicating that the nature of surface arsenate species on ferrihydrite was strongly pH dependent. Sorption density and synthesis media (sulfate vs. nitrate) had no appreciable effect. At acidic pH (3, 4), ferric arsenate surface precipitate formed on ferrihydrite and constituted the predominant surface arsenate species. X-ray diffraction (XRD) analyses of he sorption solids synthesized at elevated temperature (75 °C), pH 3 clearly showed the development of crystalline ferric arsenate (i.e. scorodite). In neutral and alkaline media (pH 7, 8), arsenate sorbed as a bidentate surface complex (in both protonated FeO2As(O)(OH)− and unprotonated forms). For the sorption systems in slightly acidic media (pH 5, 6), both ferric arsenate and surface complex were probably present on ferrihydrite. It was further determined that the incorporated sulfate in ferrihydrite during synthesis was substituted by arsenate and was more easily exchangeable with increasing pH. 相似文献
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Oxygen and hydrogen isotope studies of contact metamorphism in the Santa Rosa Range,Nevada and other areas 总被引：1，自引：0，他引：1
The O18/O16 and D/H ratios have been determined for rocks and coexisting minerals from several granitic plutons and their contact metamorphic aureoles in the Santa Rosa Range, Nevada, and the Eldora area, Colorado, with emphasis on pelitic rocks. A consistent order of O18/O16 and D/H enrichment in coexisting minerals, and a correlation between isotopic fractionations among coexisting mineral pairs are commonly observed, suggesting that mineral assemblages tend to approach isotopic equilibrium during contact metamorphism. In certain cases, a systematic decrease is observed in the oxygen isotopic fractionations of mineral pairs as one approaches the intrusive contacts. Isotopic temperatures generally show good agreement with heat flow considerations. Based on the experimentally determined quartz-muscovite O18/O16 fractionation calibration curve, temperatures are estimated to be 525 to 625° C at the contacts of the granitic stocks studied.Small-scale oxygen isotope exchange effects between intrusive and country rock are observed over distances of 0.5 to 3 feet on both sides of the contacts; the isotopic gradients are typically 2 to 3 per mil per foot. The degree of oxygen isotopic exchange is essentially identical for different coexisting minerals. This presumably occurred through a diffusion-controlled recrystallization process. The size of the oxygen isotope equilibrium system in the small-scale exchanged zones varies from about 1.5 to 30 cm. A xenolith and a re-entrant of country rock projecting into an intrusive have both undergone much more extensive isotopic exchange (to hundreds of feet); they also show higher isotopic temperatures than the rocks in the aureole. The marginal portions of most plutons have unusually high O18/O16 ratios compared to normal igneous rocks, presumably due to large-scale isotopic exchange with metasedimentary country rocks when the igneous rocks were essentially in a molten state. The isotopic data suggest that outward horizontal movement of H2O into the contact metamorphic aureoles is very minor, but upward movement of H2O is important. Also, direct influx and absorption of H2O from the country rock appears to have occurred in certain intrusive stocks. The D/H ratios of biotites in the contact metamorphic rocks and their associated intrusions show a geographic correlation that is similar to that shown by the D/H ratios of meteoric surface waters, perhaps indicating that meteoric waters were present in the rocks during crystallization of the biotites.Except in the exchanged zones, the O18/O16 ratios of pelitic rocks do not change appreciably during contact metamorphism, even in the cordierite and sillimanite grades; this is in contrast to regional metamorphic rocks which commonly decrease in O18 with increasing grade. Thus, contact metamorphic rocks generally do not exchange with large quantities of igneous H2O, but regional metamorphic rocks appear to have done so.Publications of the Division of Geological Sciences, California Institute of Technology, Contribution No. 1565. 相似文献
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The kinetics of iodide (I−) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (δ-MnO2) was investigated over the pH range 4.5-6.25. I− oxidation to iodate proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I− from solution was first order with respect to I− concentration, pH, and birnessite concentration, such that −d[I−]/dt = k[I−][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ± 0.06 × 107 M−2 h−1. The data are consistent with the formation of an inner sphere I− surface complex as the first step of the reaction, and the adsorption of I− exhibited significant pH dependence. Both I2, and to a lesser extent, sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and , as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds. 相似文献
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Melissa E. Schlegel Jennifer C. McIntosh Matthew F. Kirk Anna M. Martini 《Geochimica et cosmochimica acta》2011,75(7):1903-40
Microbial methane in sedimentary basins comprises approximately 20% of global natural gas resources, yet little is known about the environmental requirements and metabolic rates of these subsurface microbial communities. The Illinois Basin, located in the midcontinent of the United States, is an ideal location to investigate hydrogeochemical factors controlling methanogenesis as microbial methane accumulations occur: (1) in three organic-rich reservoirs of different geologic ages and organic matter types - Upper Devonian New Albany Shale (up to 900 m depth), Pennsylvanian coals (up to 600 m depth), and Quaternary glacial sediments (shallow aquifers); (2) across steep salinity gradients; and (3) with variable concentrations of . For all three organic-rich reservoirs aqueous geochemical conditions are favorable for microbial methanogenesis, with near neutral pH, concentrations <2 mM, and Cl− concentrations <3 M. Also, carbon isotopic fractionation of CH4, CO2, and DIC is consistent with microbial methanogenesis, and increased carbon isotopic fractionation with average reservoir depth corresponds to a decrease of groundwater flushing rates with average depth of reservoir. Plots of stable isotopes of water and Cl− show mixing between a brine endmember and freshwater, suggesting that meteoric groundwater recharge has affected all microbial methanogenic systems. Additionally, similar methanogenic communities are present in all three reservoirs with comparable cell counts (8.69E3-2.58E6 cells/mL). TRFLP results show low numbers of archaea species with only two dominant groups of base pairs in coals, shale, and limestone aquifers. These results compare favorably with other methanogen-containing deep subsurface environments. Individual hydrogeochemical parameters that have a Spearman correlation coefficient greater than 0.3 to variations in methanogenic species include stable isotopes of water (δ18O and δD), type of substrate (i.e. coals versus shale), pH, and Cl− concentration. The matching of variations between methanogenic TRFLP data and conservative tracers suggests that deep circulation of meteoric waters influenced archaeal communities in the Illinois Basin. In addition, coalification and burial estimates suggest that in the study area, coals and shale reservoirs were previously sterilized (>80 °C in nutrient poor environments), necessitating the re-introduction of microbes into the subsurface via groundwater transport. 相似文献
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Polythionates (SxO62−) are important in redox transformations involving many sulfur compounds. Here we investigate the oxidation kinetics and mechanisms of trithionate and tetrathionate oxidation between pH 0.4 and pH 2 in the presence of Fe3+ and/or oxygen. In these solutions, Fe3+ plus oxygen oxidizes tetrathionate and trithionate at least an order of magnitude faster than oxygen alone. Kinetic measurements, coupled with density functional calculations, suggest that the rate-limiting step for tetrathionate oxidation involves Fe3+ attachment, followed by electron density shifts that result in formation of a sulfite radical and S3O30 derivatives. The overall reaction orders for trithionate and tetrathionate are fractional due to rearrangement reactions and side reactions between reactants and intermediate products. The pseudo-first order rate coefficients for tetrathionate range from 10−11 s−1 at 25°C to 10−8 s−1 at 70°C, compared to 2 × 10−7 s−1 at 35 °C for trithionate. The apparent activation energy (EA) for tetrathionate oxidation at pH 1.5 is 104.5 ± 4.13 kJ/mol. A rate law at pH 1.5 and 70°C between 0.5 and 5 millimolar [Fe3+] is of the form:
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The solubility of gold has been measured in the system H2O+H2+HCl+NaCl+NaOH at temperatures from 300 to 600°C and pressures from 500 to 1800 bar in order to determine the stability and stoichiometry of chloride complexes of gold(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave system. This approach permitted the independent determination of the concentrations of all critical aqueous components in solution for the determination of the stability and stoichiometry of gold(I) complexes. The solubilities (i.e. total dissolved gold) were in the range 9.9 × 10−9 to 3.26 × 10−5 mol kg−1 (0.002-6.42 mg kg−1) in solutions of total dissolved chloride between 0.150 and 1.720 mol kg−1, total dissolved sodium between 0.000 and 0.975 mol kg−1 and total dissolved hydrogen between 4.34 × 10−6 and 7.87 × 10−4 mol kg−1. A nonlinear least squares treatment of the data demonstrates that the solubility of gold in chloride solutions is accurately described by the reactions,
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Dissolution and precipitation rates of brucite (Mg(OH)2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10−4 to 3 M), saturation index (−12 < log Ω < 0.4) and aqueous magnesium concentrations (10−6 to 5·10−4 M). Brucite surface charge and isoelectric point (pHIEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pHIEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m2) and lack of dependence on ionic strength predicts the dominance of >MgOH2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO− as pH increases to 10-12. Rates are proportional to the square of >MgOH2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity:
14.
Oxygen isotope partitioning between calcite and tremolite was experimentally calibrated in the presence of small amounts of a supercritical CO2–H2O fluid at temperatures from 520 to 680° C and pressures from 3 to 10 kbar. The experiments were carried out within the stability field of the calcite-tremolite assemblage based on phase equilibrium relationships in the system CaO–MgO–SiO2–CO2–H2O, so that decomposition of calcite and tremolite was avoided under the experimental conditions. Appropriate proportions of carbon dioxide to water were used to meet this requirement. Large weight ratios of mineral to fluid were employed in order to make the isotopic exchange between calcite and tremolite in the presence of a fluid close to that without fluid. The data processing method for isotopic exchange in a three-phase system has been applied to extrapolate partial equilibrium data to equilibrium values. The determined fractionation factors between calcite (Cc) and tremolite (Tr) are expressed as:1031n Cc-Tr=3.80 × 106/T
2-1.67By combining the present data with the experimental calibrations of Clayton et al. (1989) on the calcite-quartz system, we obtain the fractionation for the quartztremolite system: 1031n Qz-Tr=4.18 × 106/T
2-1.67Our experimental calibrations are in good agreement with the theoretical calculations of Hoffbauer et al. (1994) and the empirical estimates of Bottinga and Javoy (1975) based on isotopic data from naturall assemblages. At 700 C good agreement also exists between our experimental data and theoretical values calculated by Zheng (1993b). With decreasing temperature, however, an increasing difference between these data appears.Retrograde isotopic reequilibration by oxygen diffusion may be common for amphibole relative to diopside in metamorphic rocks. However, isotopic equilibrium in amphibole can be preserved in cases of rapid cooling. 相似文献
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Charles W. Mandeville James D. Webster Bruce E. Taylor Akira Sasaki Charles R. Bacon 《Geochimica et cosmochimica acta》2009,73(10):2978-3012
Evaluation of the extent of volatile element recycling in convergent margin volcanism requires delineating likely source(s) of magmatic volatiles through stable isotopic characterization of sulfur, hydrogen and oxygen in erupted tephra with appropriate assessment of modification by degassing. The climactic eruption of Mt. Mazama ejected approximately 50 km3 of rhyodacitic magma into the atmosphere and resulted in formation of a 10-km diameter caldera now occupied by Crater Lake, Oregon (lat. 43°N, long. 122°W). Isotopic compositions of whole-rocks, matrix glasses and minerals from Mt. Mazama climactic, pre-climactic and postcaldera tephra were determined to identify the likely source(s) of H2O and S. Integration of stable isotopic data with petrologic data from melt inclusions has allowed for estimation of pre-eruptive dissolved volatile concentrations and placed constraints on the extent, conditions and style of degassing.Sulfur isotope analyses of climactic rhyodacitic whole rocks yield δ34S values of 2.8-14.8‰ with corresponding matrix glass values of 2.4-13.2‰. δ34S tends to increase with stratigraphic height through climactic eruptive units, consistent with open-system degassing. Dissolved sulfur concentrations in melt inclusions (MIs) from pre-climactic and climactic rhyodacitic pumices varies from 80 to 330 ppm, with highest concentrations in inclusions with 4.8-5.2 wt% H2O (by FTIR). Up to 50% of the initial S may have been lost through pre-eruptive degassing at depths of 4-5 km. Ion microprobe analyses of pyrrhotite in climactic rhyodacitic tephra and andesitic scoria indicate a range in δ34S from −0.4‰ to 5.8‰ and from −0.1‰ to 3.5‰, respectively. Initial δ34S values of rhyodacitic and andesitic magmas were likely near the mantle value of 0‰. Hydrogen isotope (δD) and total H2O analyses of rhyodacitic obsidian (and vitrophyre) from the climactic fall deposit yielded values οf −103 to −53‰ and 0.23-1.74 wt%, respectively. Values of δD and wt% H2O of obsidian decrease towards the top of the fall deposit. Samples with depleted δD, and mantle δ18O values, have elevated δ34S values consistent with open-system degassing. These results imply that more mantle-derived sulfur is degassed to the Earth’s atmosphere/hydrosphere through convergent margin volcanism than previously attributed. Magmatic degassing can modify initial isotopic compositions of sulfur by >14‰ (to δ34S values of 14‰ or more here) and hydrogen isotopic compositions by 90‰ (to δD values of −127‰ in this case). 相似文献
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Hydrogen isotopic fractionation in lipid biosynthesis by H2-consuming Desulfobacterium autotrophicum
We report hydrogen isotopic fractionations between water and fatty acids of the sulfate-reducing bacterium Desulfobacterium autotrophicum. Pure cultures were grown in waters with deuterium (D) contents that were systematically varied near the level of natural abundance (−37‰ ? δD ? 993‰). H2 of constant hydrogen isotope (D/H) ratio was supplied to the cultures. The D/H ratios of water, H2, and specific fatty acids were measured by isotope-ratio mass spectrometry. The results demonstrate that D. autotrophicum catalyzes hydrogen isotopic exchange between water and H2, and this reaction is conclusively shown to approach isotopic equilibrium. In addition, variation in the D/H ratio of growth water accounts for all variation in the hydrogen isotopic composition of fatty acids. The D/H ratios of fatty acids from cultures grown on H2/CO2 are compared with those from a separate set of cultures grown on D-enriched formate, an alternative electron donor. This comparison rules out H2 as a significant source of fatty acid hydrogen. Grown on either H2/CO2 or formate, D. autotrophicum produces fatty acids in which all hydrogen originates from water. For specific fatty acids, biosynthetic fractionation factors are mostly in the range 0.60 ? αFA-water ? 0.70; the 18:0 fatty acid exhibits a lower fractionation factor of 0.52. The data show that αFA-water generally increases with length of the carbon chain from C14 to C17 among both saturated and unsaturated fatty acids. These results indicate a net fractionation associated with fatty acid biosynthesis in D. autotrophicum that is slightly smaller than in another H2-consuming bacterium (Sporomusa sp.), but much greater than in most photoautotrophs. 相似文献
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Caroline L. Peacock 《Geochimica et cosmochimica acta》2005,69(15):3733-3745
We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO4Hn)n−6 and binuclear (Cu2O6Hn)n−8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu2+ on ion exchangeable ≡X--H+ sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH)6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH)2Cu(OH)20, tridentate (≡Al3O(OH)2)Cu2(OH)30 and ≡X--Cu2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions
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Interdiffusion coefficients have been determined for H2O-CO2 mixtures by quantifying the flux of CO2 between two fluid-filled chambers in a specially designed piston-cylinder cell. The two chambers, which are maintained at 1.0 GPa and at temperatures differing by ∼100°C, each contain the XCO2-buffering assemblage calcite + quartz + wollastonite, in H2O. The positive dependence of XCO2 on temperature results in a down-temperature, steady-state flux of CO2 through a capillary tube that connects the two chambers. This flux drives the wollastonite = calcite + quartz equilibrium to the right in the cooler chamber, producing a measurable amount of calcite that is directly related to CO2-H2O interdiffusion rates. Diffusivities calculated from seven experiments range from 1.0 × 10−8 to 6.1 × 10−8 m2/s for mean capillary temperatures between ∼490 and 690°C. The data set can be approximated by an Arrhenius-type relation:
20.
Reports of the high ion content of steam and low-density supercritical fluids date back to the work of Carlon [Carlon H. R. (1980) Ion content of air humidified by boiling water.J. Appl.Phys.51, 171-173], who invoked ion and neutral-water clustering as mechanism to explain why ions partition into the low-density aqueous phase. Mass spectrometric, vibrational spectroscopic measurements and quantum chemical calculations have refined this concept by proposing strongly bound ion-solvent aggregates and water clusters such as Eigen- and Zundel-type proton clusters H3O+·(H2O)m and the more weakly bound water oligomers (H2O)m. The extent to which these clusters affect fluid chemistry is determined by their abundance, however, little is known regarding the stability of such moieties in natural low-density high-temperature fluids. Here we report results from quantum chemical calculations using chemical-accuracy multi-level G3 (Curtiss-Pople) and CBS-Q theory (Peterson) to address this question. In particular, we have investigated the cluster structures and clustering equilibria for the ions and H3S+·(H2O)m(H2S)n, where m ? 6 and n ? 4, at 300-1000 K and 1 bar as well as under vapor-liquid equilibrium conditions between 300 and 646 K. We find that incremental hydration enthalpies and entropies derived from van’t Hoff analyses for the attachment of H2O and H2S onto H3O+, and H3S+ are in excellent agreement with experimental values and that the addition of water to all three ions is energetically more favorable than solvation by H2S. As clusters grow in size, the energetic trends of cluster hydration begin to reflect those for bulk H2O liquids, i.e. calculated hydration enthalpies and entropies approach values characteristic of the condensation of bulk water (ΔHo = −44.0 kJ mol−1, ΔSo = −118.8 J K mol−1). Water and hydrogen sulfide cluster calculations at higher temperatures indicate that a significant fraction of H3O+, and H3S+ ions exists as solvated moieties. 相似文献