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1.
Variations in the carbon isotope composition in gases and waters of mud volcanoes in the Taman Peninsula are studied. The δ13C values in CH4 and CO2 vary from ?59.5 to ?44.0‰ (δ13Cav = ?52.4 ± 5.4‰) and from ?17.8 to +22.8‰ (δ13Cav = +6.9 ± 9.3‰), respectively. In waters from most mud volcanoes of the peninsula, this parameter ranges from +3.3 to +33.1‰, although locally lower values are also recorded (up to ?12‰. Fractionation of carbon isotopes in the CO2-HCO3 system corresponds to the isotope equilibrium under Earth’s surface temperatures. The growth of carbon dioxide concentration in the gaseous phase and increase in the HCO3 ion concentration in their water phase is accompanied by the enrichment of the latter with the heavy 13C isotope. The δ13CTDIC value in the water-soluble carbon depends on the occurrence time of water on the Earth’s surface (exchange with atmospheric CO2, methane oxidation, precipitation of carbonates, and other processes), in addition to its primary composition. In this connection, fluctuations in δ13CTDIC values in mud volcanoes with stagnant waters may amount to 10–20‰. In the clayey pulp, concentrations of carbonate matter recalculated to CaCO3 varies from 1–4 to 36–50 wt %. The δ13C value in the latter ranges from ?3.6 to +8.4‰. Carbonate matter of the clayey pulp represents a mixture of sedimentogenic and authigenic carbonates. Therefore, it is usually unbalanced in terms of the carbon isotope composition with the water-soluble CO2 forms.  相似文献   

2.
Stable carbon isotope fractionation by seventeen species of marine phytoplankton, representing the classes of Bacillariophyceae, Chlorophyceae, Prasinophyceae, Chrysophyceae, Haptophyceae and Dinophyceae have been determined in laboratory culture experiments using bicarbonate enriched artificial sea water. The ΔHCO3? values (ΔHCO3? = δ13C of algae vs HCO3?) range from ?22.1 to ?35.5%. Nitzschia closterium shows the smallest fractionation of ? 22.1% and Isochrysis galbana, the greatest of ?35.5%,. Since these algae were cultured under identical laboratory conditions, the wide range of ΔHCO3? values is seemingly due to the presence of different metabolic pathways within these organisms.A temperature dependent fractionation of 0.36% per °C with decreasing temperatures was measured for Skeletonema costatum whereas, smaller temperature dependencies of ?0.13, +0.15 and ?0.07%. per °C were observed for Dunaliella sp., Monochrysis lutheri and Glenodinium foliaceum, respectively.The consistency of ΔHCO3? values of Skeletonema costatum, Dunaliella sp. and Monochrysis lutheri grown at salinities of 22, 26, 32 and 36% indicates that natural salinity variations have negligible effects on the isotopic composition of marine phytoplankton.  相似文献   

3.
Applications of speleothem calcite geochemistry in climate change studies require the evaluation of the accuracy and sensitivity of speleothem proxies to correctly infer paleoclimatic information. The present study of Harrison’s Cave, Barbados, uses the analysis of the modern climatology and groundwater system to evaluate controls on the C and O isotopic composition of modern speleothems. This new approach directly compares the δ18O and δ13C values of modern speleothems with the values for their corresponding drip waters in order to assess the degree to which isotopic equilibrium is achieved during calcite precipitation. If modern speleothems can be demonstrated to precipitate in isotopic equilibrium, then ancient speleothems, suitable for paleoclimatic studies, from the same cave environment may also have been precipitated in isotopic equilibrium. If modern speleothems are precipitated out of isotopic equilibrium, then the magnitude and direction of the C and O isotopic offsets may allow specific kinetic and/or equilibrium isotopic fractionation mechanisms to be identified.Carbon isotope values for the majority of modern speleothem samples from Harrison’s Cave fall within the range of equilibrium values predicted from the combined use of (1) calcite-water fractionation factors from the literature, (2) measured temperatures, and (3) measured δ13C values of the dissolved inorganic carbon of drip waters. Calcite samples range from ∼0.8‰ higher to ∼1.1‰ lower than predicted values. The 13C depletions are likely caused by kinetically driven departures in the fractionation between HCO3− (aq) and CaCO3 from equilibrium conditions, caused by rapid calcite growth. 13C enrichments can be accounted for by Rayleigh distillation of the HCO3− (aq) reservoir during degassing of 13C-depleted CO2.Modern speleothems from Harrison’s Cave are not in O isotopic equilibrium with their corresponding drip waters and are 0.2‰ to 2.3‰ enriched in 18O relative to equilibrium values. δ18O variations in modern calcite are likely controlled by kinetically driven changes in the fractionation between HCO3− (aq) and CaCO3 from equilibrium conditions to nonequilibrium conditions, consistent with rapid calcite growth. In contrast to δ13C, δ18O values of modern calcite may not be affected by Rayleigh distillation during degassing because CO2 hydration and hydroxylation reactions will buffer the O isotopic composition of the HCO3− (aq) reservoir. If the effects of Rayleigh distillation manifest themselves in the O isotopic system, they will result in 18O enrichment in the HCO3− (aq) reservoir and ultimately in the precipitated CaCO3.  相似文献   

4.
To determine oxygen isotope fractionation between aragonite and water, aragonite was slowly precipitated from Ca(HCO3)2 solution at 0 to 50°C in the presence of Mg2+ or SO42−. The phase compositions and morphologies of synthetic minerals were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The effects of aragonite precipitation rate and excess dissolved CO2 gas in the initial Ca(HCO3)2 solution on oxygen isotope fractionation between aragonite and water were investigated. For the CaCO3 minerals slowly precipitated by the CaCO3 or NaHCO3 dissolution method at 0 to 50°C, the XRD and SEM analyses show that the rate of aragonite precipitation increased with temperature. Correspondingly, oxygen isotope fractionations between aragonite and water deviated progressively farther from equilibrium. Additionally, an excess of dissolved CO2 gas in the initial Ca(HCO3)2 solution results in an increase in apparent oxygen isotope fractionations. As a consequence, the experimentally determined oxygen isotope fractionations at 50°C indicate disequilibrium, whereas the relatively lower fractionation values obtained at 0 and 25°C from the solution with less dissolved CO2 gas and low precipitation rates indicate a closer approach to equilibrium. Combining the lower values at 0 and 25°C with previous data derived from a two-step overgrowth technique at 50 and 70°C, a fractionation equation for the aragonite-water system at 0 to 70°C is obtained as follows:
  相似文献   

5.
The effect of bicarbonate (HCO3?) on the growth and development of plants varies by species. To better understand inorganic carbon and nitrogen assimilation changes of karst-adaptable plants under different HCO3? treatments, we conducted experiments on seedlings and in vitro plantlets of Orychophragmus violaceus (Ov). We found that the vital photosynthesis potential (as measured by net photosynthetic rate, actual photochemical efficiency of photosystem-II, photochemical quenching coefficient, and the instantaneous carbon isotope ratio of 3-phosphoglycerate) was consistent under different HCO3? treatments of Ov. Bicarbonate’s lack of effect on carbon assimilation of Ov may be related to carbonic anhydrase in Ov converting HCO3? to H2O and CO2. In this way, Ov could prevent HCO3? ion toxicity and high pH from harming its growth and development under HCO3? stress. This study also found that high HCO3? concentrations could promote nitrogen assimilation and utilization of Ov through changes in related indexes (foliar nitrogen isotope fractionation ratio, stable nitrogen isotope assimilation ratio, foliar stable nitrogen isotope fractionation, nitrate nitrogen utilization efficiency, and nitrate utilization share) under different HCO3? treatments. Bicarbonate has different effects on photosynthesis and on inorganic nitrogen assimilation of Ov, which may be connected to photosynthesis providing electrons for nitrate/nitrite reduction through the photosynthetic chain.  相似文献   

6.
4He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4?C6 times on each sample, and indicate a bulk 4He diffusion coefficient of 3.5?±?1.3?×?10?C8 cm2?s?C1 at 21°C, compared to previously published diffusion coefficients of 1.2?×?10?C18 cm2?s?C1 (21°C) to 3.0?×?10?C15 cm2?s?C1 (150°C) in the sands and clays. Correcting the diffusion coefficient of 4Hewater for matrix porosity (??3%) and tortuosity (??6?C13) produces effective diffusion coefficients of 1?×?10?C8 cm2?s?C1 (21°C) and 1?×?10?C7 (120°C), effectively isolating pore fluid 4He from the 4He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8?±?0.4% (SD, n?=?4) and mudstones 3.1?±?0.8% (SD, n?=?4).  相似文献   

7.
Carbonates formed from hyperalkaline aqueous solutions at the Earth?s surface are known to bear the most extreme disequilibrium isotope signatures reported so far in nature. We present here the results for stable carbon (C), oxygen (O), and barium (Ba) isotope fractionation during the precipitation of witherite (BaCO3) induced by the chemical absorption of atmospheric carbon dioxide (CO2) into an aqueous hyper-alkaline solution (at 4° and 21?°C; 1?atm total pressure). Independent from temperature, the barium carbonate formation was associated with a substantial enrichment of the lighter C and O isotopes in the solid compared to the atmosphere (C, O), close to previous results found in experiments and nature. A new approach is introduced to explain oxygen isotope fractionation upon hydroxylation of CO2. With Ba isotope enrichment factors between ?0.45 and ?0.53‰ (138/134ε) or ?0.34 and ?0.40‰ (137/134ε), respectively, the synthesized BaCO3 displays the highest kinetic enrichment of the light Ba isotope in the carbonate solid reported so far.  相似文献   

8.
The δ13C values of dissolved HCO3? in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO2 of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The δ13C values of total HCO3? indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin.The range of δ13C values for the HCO3? of these waters is ?20–28 per mil relative to PDB. This wide range of δ13C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high δ13C values of HCO3? in the shallow production zones where the subsurface temperatures are less than 80°C. The extremely low δ13C values (< ?10 per mil) are obtained in waters where concentrations of SO42? are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria (SO42? + CH3COO? → 2HCO3? + HS?). The high δ13C values probably result from the degradation of these anions by methanogenic bacteria (CH3COO? + H2OaiHCO3? + CH4).Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO2 and CH4 is probably the major source of CO2 for production zones with subsurface temperatures greater than 80°C. The δ13C values of HCO3? for waters from zones with temperatures greater than 100°C result from isotopic equilibration between CO2 and CH4. At these high temperatures, δ13C values of HCO3? decrease with increasing temperatures and decreasing concentrations of these acid anions.  相似文献   

9.
《Applied Geochemistry》1998,13(2):177-184
Calcium carbonate is one of the most common and important scale-forming minerals in oilfield produced water, but the kinetics of CaCO3 precipitation has been ignored in most scale prediction models because of the lack of reliable precipitation rate model. There are none in the open literature for oilfield conditions (temperature > 100°C, pressure > 200 bar and salinity > 0.5 mol kg− 1). In this work the kinetics of calcite (CaCO3) precipitation from high salinity waters (up to 2 mol kg−1) have been studied by a pH-free-drift method in a closed water system. This method. is much easier to operate than the often used steady-state method. The experimental results indicate that the calcite precipitation rate is not only affected by the solution CaCO3 saturation level, but also by the solution pH, ionic strength and the concentration ratios of Ca to HCO3− ions (CCa2+/CHCO3−). When the concentration ratios of Ca to HCO3− ions are close to their chemical stoichiometric ratio of 0.5, the calcite growth from a supersaturated solution is believed to be surface reaction controlled. However, at higher CCa2+CHCO3− ratios, the transportation of the lattice ions to calcite crystal surface has to be considered.  相似文献   

10.
Hydrogen isotope fractionation factors between hydroxyl-bearing minerals and water were determined at temperatures ranging between 400 and 850°C. The hydrogen isotope exchange rates for the mineral-water pairs examined were very slow. In most cases it was necessary to use an interpolation method for the determination of the hydrogen isotope equilibrium fractionation factor, αe.For the temperature range of 450–850°C the hydrogen isotope fractionation factors for the mica-water and amphibole-water systems are simply expressed as a function of temperature and the molar fractions of the six-fold coordinated cations in the crystal, regardless of mineral species, as follows: 103 In αe(mineral-water) = ? 22.4 (106T?2) + 28.2 + (2XAl ? 4XMg ? 68XFe), where X is the molar fraction of the cations. As the equation indicates, for any specific composition of the OH-bearing minerals, the change of αe with temperature, over the temperature range investigated, is the same for all minerals studied. Thus for any specified values of XAl, XMg, and XFe for these minerals, the relationship between αe and T is 103 In αe = αT?2 + k. Consequently, hydrogen isotope fractionation among coexisting minerals is temperature independent and cannot be used as a hydrogen isotope geothermometer.Some exceptions to the above general observations exist for minerals such as boehmite and kaolinite. In these minerals hydrogen bonding modifies the equilibrium hydrogen isotopic fractionation between mineral and water.  相似文献   

11.
Carbon and oxygen isotopic analyses have been performed on live-stained aragonitic and calcitic benthic foraminifera and dissolved inorganic carbon (DIC) from the Southern California Borderland to examine carbon isotopic fractionation in foraminifera. Temperature, salinity and pH data have also been collected to permit accurate determination of the δ13C of bicarbonate ion and thus aragonite-HCO3 and calcite-HCO?3 isotopic enrichment factors (?ar-b and ?cl-b, respectively). Only species which precipitate in 18O equilibrium have been considered.?ar-b values based on Hoeglundina elegans range from 1.9%. at 2.7°C to 1.1%. at 9.5°C. Only the lower temperature values agree with a tentative carbon isotope equilibrium equation for aragonite based on the data of Rubinson and Clayton (1969) and Emrich et al. (1970). The temperature dependence of ?ar-b is considerably greater than the equilibrium equation would predict and may be due to a vital effect.The calcitic foraminifera Cassidulina tortuosa, Cassidulina braziliensis, and Cassidulina limbata, Bank and Terrace dwellers, have similar δ13C values and yield an average ?cl-b value of ?0.2 ± .1%. between 8° and 10°C. Calcitic Uvigerina curticosta, Uvigerina peregrina, and megalospheric B. argentea, Slope and Basin dwellers, are ?0.7 ± .1%. enriched relative to ambient bicarbonate for 3 to 9°C. No temperature dependence for ?cl-b was observed for the species in either habitat. The ?cl-b values for Cassidulina species are close (± 0.3%.) to the values given by the tentative equilibrium curve for calcite, while Uvigerina and Bolivina species give values 0.2–0.8%. less. The ?cl-b difference between the Cassidulina species and the Uvigerina and Bolivina species is attributed to the incorporation of 13C-depleted pore water DIC by the latter group rather than to taxonomic or temperature differences.  相似文献   

12.
The oxygen isotope fractionation accompanying the hydrothermal dolomitization of CaCO3 between 252 and 295°C has been investigated. Dolomitization (which occurs via the crystallization of one or more intermediate magnesian calcite phases) is characterised by a progressive lowering in δ8O, which smoothly correlates with the change in the Mg/(Mg + Ca) and the Sr(Mg + Ca) ratios and with the sequential phase formation. The data support the proposals of Katz and Matthews (1977) that (a) all reaction occurs by solution and reprecipitation, (b) intermediate phases and dolomite form sequentially and (c) the intermediate phases form within limited solution zones surrounding the dissolving precursor. Calculated volumes of the solution zone for the aragonite → low magnesian calcite transformation are within the range 3.7–6.7 × 10?5 liters (out of 5 × 10?3 liters, the volume of the bulk solution used in the present study), and agree well with those calculated from strontium and magnesium partitioning data. Dolomite precipitates in apparent isotopic equilibrium with the bulk solution. The temperature dependence of the fractionation is defined by the equation 1000 InαD-H2O = 3.06 × 106T?2 ? 3.24 Dolomite-water fractionations from this equation are significantly lower than those obtained by extrapolation of the Northrop And Clayton (1966) calibration. The reaction zone model can be applied to explain near zero dolomite-calcite oxygen isotope fractionations reported by Epsteinet al. (1964).  相似文献   

13.
Chemolithotrophic homoacetogenic bacteria apparently express a characteristic stable carbon isotope fractionation and may contribute significantly to acetate production in anoxic environments. However, fractionation factors (ε) in bacterial cultures have rarely been determined and the effect of substrate availability has not been assessed. We therefore studied the kinetic carbon isotope effect in cultures of Thermoanaerobacter kivui grown at 55 °C. The fractionation factor in HCO3− buffered medium was ca. 15‰ more negative than that in PO43− buffered medium. To test whether the difference was caused by the initial substrate ratio of H2 and total inorganic carbon (TIC; 0.5 in HCO3− vs. 4.0 in PO43− buffered medium), T. kivui was grown in either [3-(N-morpholino) propanesulfonic acid, MOPS] buffered or PO43− buffered media with different HCO3− concentration. Indeed, the fractionation factor became more negative with increasing HCO3− concentration and decreasing H2/TIC ratio. While pH had only a small effect, the fractionation was generally more negative in MOPS buffered than in phosphate buffered media, indicating that the buffer system also affected fractionation. Collectively, the results show that substrate availability and other environmental factors affect the magnitude of isotope fractionation during acetate production by chemolithotrophic homoacetogenesis.  相似文献   

14.
The calcium isotope ratios (δ44Ca = [(44Ca/40Ca)sample/(44Ca/40Ca)standard −1] · 1000) of Orbulina universa and of inorganically precipitated aragonite are positively correlated to temperature. The slopes of 0.019 and 0.015‰ °C−1, respectively, are a factor of 13 and 16 times smaller than the previously determined fractionation from a second foraminifera, Globigerinoides sacculifer, having a slope of about 0.24‰ °C−1. The observation that δ44Ca is positively correlated to temperature is opposite in sign to the oxygen isotopic fractionation (δ18O) in calcium carbonate (CaCO3). These observations are explained by a model which considers that Ca2+-ions forming ionic bonds are affected by kinetic fractionation only, whereas covalently bound atoms like oxygen are affected by kinetic and equilibrium fractionation. From thermodynamic consideration of kinetic isotope fractionation, it can be shown that the slope of the enrichment factor α(T) is mass-dependent. However, for O. universa and the inorganic precipitates, the calculated mass of about 520 ± 60 and 640 ± 70 amu (atomic mass units) is not compatible with the expected ion mass for 40Ca and 44Ca. To reconcile this discrepancy, we propose that Ca diffusion and δ44Ca isotope fractionation at liquid/solid transitions involves Ca2+-aquocomplexes (Ca[H2O]n2+ · mH2O) rather than pure Ca2+-ion diffusion. From our measurements we calculate that such a hypothesized Ca2+-aquocomplex correlates to a hydration number of up to 25 water molecules (490 amu). For O. universa we propose that their biologically mediated Ca isotope fractionation resembles fractionation during inorganic precipitation of CaCO3 in seawater. To explain the different Ca isotope fractionation in O. universa and in G. sacculifer, we suggest that the latter species actively dehydrates the Ca2+-aquocomplex before calcification takes place. The very different temperature response of Ca isotopes in the two species suggests that the use of δ44Ca as a temperature proxy will require careful study of species effects.  相似文献   

15.
The ion-interaction model of PITZER (1973), is very effective in deriving stability relationships at high concentrations for the system Na-Cl-HCO3-CO3-OH-H2O. The solubility products of the main sodium carbonates have been calculated from solubility data between 5 and 50°C. The stability diagram in log pco2 — temperature coordinates and the invariant points deduced from the newly determined data are in good agreement with the most recent measurements.These results are used to calculate the activities of the major dissolved species in Lake Magadi brines (Kenya). The thermodynamic treatment confirms the main conclusions reached earlier by Eugster (1970, 1980) mainly from field observations. Trona precipitation occurs at equilibrium while natron is likely to form when the temperature decreases below 25°C. After the salt deposition the CO2 supply from the atmosphere is too slow to allow equilibrium between the atmosphere and the brines. In the next stages of evaporative concentration thermonatrite and halite precipitate. The deposition of the latter salts along with the observed HCO?3 depletion suggest that fractional crystallization is likely to control trona deposition.  相似文献   

16.
The paired chemical reactions, Ca2+ + 2HCO3 ? ? CaCO3 + CO2 + H2O, overestimate the ratio of CO2 flux to CaCO3 flux during the precipitation or dissolution of CaCO3 in seawater. This ratio, which has been termed ??, is about 0.6 in surface seawater at 25°C and at equilibrium with contemporary atmospheric CO2 and increases towards 1.0 as seawater cools and pCO2 increases. These conclusions are based on field observations, laboratory experiments, and equilibrium calculations for the seawater carbonate system. Yet global geochemical modeling indicates that small departures of ?? from 1.0 would cause dramatic, rapid, and unrealistic change in atmospheric CO2. ?? can be meaningfully calculated for a water sample whether or not it is in equilibrium with the atmosphere. The analysis presented here demonstrates that the atmospheric CO2 balance can be maintained constant with respect to seawater CaCO3 reactions if one considers the difference between CaCO3 precipitation and burial and differing values for ?? (both <1.0) in regions of precipitation and dissolution within the ocean.  相似文献   

17.
《Geochimica et cosmochimica acta》1999,63(13-14):2001-2007
Stable oxygen isotope ratios of foraminiferal calcite are widely used in paleoceanography to provide a chronology of temperature changes during ocean history. It was recently demonstrated that the stable oxygen isotope ratios in planktonic foraminifera are affected by changes of the seawater chemistry carbonate system: the δ18O of the foraminiferal calcite decreases with increasing CO32− concentration or pH. This paper provides a simple explanation for seawater chemistry dependent stable oxygen isotope variations in the planktonic foraminifera Orbulina universa which is derived from oxygen isotope partitioning during inorganic precipitation. The oxygen isotope fractionation between water and the dissolved carbonate species S = [H2CO3] + [HCO3−] + [CO32−] decreases with increasing pH. Provided that calcium carbonate is formed from a mixture of the carbonate species in proportion to their relative contribution to S, the oxygen isotopic composition of CaCO3 also decreases with increasing pH. The slope of shell δ18O vs. [CO32−] of Orbulina universa observed in culture experiments is −0.0022‰ (μmol kg−1)−1 (Spero et al., 1997), whereas the slope derived from inorganic precipitation is −0.0024‰ (μmol kg−1)−. The theory also provides an explanation of the nonequilibrium fractionation effects in synthetic carbonates described by Kim and O’Neil (1997) which can be understood in terms of equilibrium fractionation at different pH. The results presented here emphasize that the oxygen isotope fractionation between calcium carbonate and water does not only depend on the temperature but also on the pH of the solution from which it is formed.  相似文献   

18.
This study is the first investigation of biodegradation of carbon disulphide (CS2) in soil that provides estimates of degradation rates and identifies intermediate degradation products and carbon isotope signatures of degradation. Microcosm studies were undertaken under anaerobic conditions using soil and groundwater recovered from CS2-contaminated sites. Proposed degradation mechanisms were validated using equilibrium speciation modelling of concentrations and carbon isotope ratios. A first-order degradation rate constant of 1.25 × 10?2 h?1 was obtained for biological degradation with soil. Carbonyl sulphide (COS) and hydrogen sulphide (H2S) were found to be intermediates of degradation, but did not accumulate in vials. A 13C/12C enrichment factor of ?7.5 ± 0.8 ‰ was obtained for degradation within microcosms with both soil and groundwater whereas a 13C/12C enrichment factor of ?23.0 ± 2.1 ‰ was obtained for degradation with site groundwater alone. It can be concluded that biological degradation of both CS2-contaminated soil and groundwater is likely to occur in the field suggesting that natural attenuation may be an appropriate remedial tool at some sites. The presence of biodegradation by-products including COS and H2S indicates that biodegradation of CS2 is occurring and stable carbon isotopes are a promising tool to quantify CS2 degradation.  相似文献   

19.
The thermodynamic properties of monohydrocalcite, CaCO3 · H2O, have been obtained using a well-characterized natural specimen. Equilibration of the solid with water at 25°C under 0.97 atm CO2 led to an activity product [Ca2+][CO32?] = 10?7.60±0.03 and a free energy of formation ΔGfo = ?325,430 ± 270 calmol?. The enthalpy of solution of monohydrocalcite in 0.1 N HCl at 25°C led to a standard enthalpy of formation ΔHfo = ?358,100 ± 280 cal mol?1. Estimates of the variation of ΔGf with temperature and pressure showed monohydrocalcite to be metastable with respect to calcite and aragonite.  相似文献   

20.
Isotope fractionation during the evaporation of silicate melt and condensation of vapor has been widely used to explain various isotope signals observed in lunar soils, cosmic spherules, calcium–aluminum-rich inclusions, and bulk compositions of planetary materials. During evaporation and condensation, the equilibrium isotope fractionation factor (α) between high-temperature silicate melt and vapor is a fundamental parameter that can constrain the melt’s isotopic compositions. However, equilibrium α is difficult to calibrate experimentally. Here we used Mg as an example and calculated equilibrium Mg isotope fractionation in MgSiO3 and Mg2SiO4 melt–vapor systems based on first-principles molecular dynamics and the high-temperature approximation of the Bigeleisen–Mayer equation. We found that, at 2500 K, δ25Mg values in the MgSiO3 and Mg2SiO4 melts were 0.141?±?0.004 and 0.143?±?0.003‰ more positive than in their respective vapors. The corresponding δ26Mg values were 0.270?±?0.008 and 0.274?±?0.006‰ more positive than in vapors, respectively. The general \(\alpha - T\) equations describing the equilibrium Mg α in MgSiO3 and Mg2SiO4 melt–vapor systems were: \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.264 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\) and \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.340 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\), respectively, where m is the mass of light isotope 24Mg and m′ is the mass of the heavier isotope, 25Mg or 26Mg. These results offer a necessary parameter for mechanistic understanding of Mg isotope fractionation during evaporation and condensation that commonly occurs during the early stages of planetary formation and evolution.  相似文献   

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