方解石矿物包裹体中水的氢同位素组成在线测试方法

水是矿物流体包裹体的重要组成,承载着流体性质和演化信息。提取矿物包裹体中水的方法主要有真空破碎法及爆裂法。为了减少真空破碎法表面积增大引起水的吸附以及爆裂法在高温下发生同位素交换反应,本文自制了一个在线提取装置,以高纯He作为载气,与高温裂解装置—稳定同位素质谱仪(EA/HT-IRMS)相连,进行一系列的条件实验,确认了方解石矿物包裹体中水的氢同位素组成在线测试的关键技术参数。实验证实,当爆裂温度为420℃、爆裂时间为5 min、含水量为0.1～0.3μL时,利用在线提取装置—EA/HT-IRMS对方解石矿物包裹体中水的δD进行测试的精密度优于±1.5‰(1σ)。相对于传统离线分析方法,本方法实现方解石矿物包裹体中水的在线提取及氢同位素组成的在线测试,简化了操作流程,并提高实验测试效率。     

Predicting the surface tension of aqueous 1:1 electrolyte solutions at high salinity

The surface tension of the air/water interface is a phenomenon of particular interest in the water-unsaturated zone of porous media because it influences the contact angle and consequently the capillary water volume. A mechanistic model based on the modified Poisson-Boltzmann equation and the Pitzer theory is described and used to predict, under isothermal and isobaric conditions, the surface tension of 1:1 electrolytes at high salinity. These theories enable the determination of the electrical potential at the air/water interface and the activity coefficient of the ionic species in the bulk pore water, respectively. Hydration free energies of the structure-making and structure-breaking ions that influence the surface tension at high salinity are taken into account. Structure-making ions flee the air/water surface because they can better organize the water dipoles in bulk water than at the interface. Structure-breaking ions are positively adsorbed at the air/water interface because the bulk water can better organize their hydrogen-bonding network without these ions. The resulting surface tension increases and decreases, respectively, compared to the surface tension of pure water. The predictions are in good agreement with the surface tension data of 1:1 electrolytes (NaCl, KCl, HCl, NaNO₃, KNO₃, HNO₃ aqueous solutions) and the optimized parameters depend on the effective electrostatic diameters of cations and on the hydration free energies of the ions at the interface.     

Oxygen isotope salt effects at high pressure and high temperature and the calibration of oxygen isotope geothermometers

The influence of NaCl, CaCl₂, and dissolved minerals on the oxygen isotope fractionation in mineral-water systems at high pressure and high temperature was studied experimentally. The salt effects of NaCl (up to 37 molal) and 5-molal CaCl₂ on the oxygen isotope fractionation between quartz and water and between calcite and water were measured at 5 and 15 kbar at temperatures from 300 to 750°C. CaCl₂ has a larger influence than NaCl on the isotopic fractionation between quartz and water. Although NaCl systematically changes the isotopic fractionation between quartz and water, it has no influence on the isotopic fractionation between calcite and water. This difference in the apparent oxygen isotope salt effects of NaCl must relate to the use of different minerals as reference phases. The term oxygen isotope salt effect is expanded here to encompass the effects of dissolved minerals on the fractionations between minerals and aqueous fluids. The oxygen isotope salt effects of dissolved quartz, calcite, and phlogopite at 15 kbar and 750°C were measured in the three-phase systems quartz-calcite-water and phlogopite-calcite-water. Under these conditions, the oxygen isotope salt effects of the three dissolved minerals range from ∼0.7 to 2.1‰. In both three-phase hydrothermal systems, the equilibrium fractionation factors between the pairs of minerals are the same as those obtained by anhydrous direct exchange between each pair of minerals, proving that the use of carbonate as exchange medium provides correct isotopic fractionations for a mineral pair.When the oxygen isotope salt effects of two minerals are different, the use of water as an indirect exchange medium will give erroneous fractionations between the two minerals. The isotope salt effect of a dissolved mineral is also the main reason for the observation that the experimentally calibrated oxygen isotope fractionations between a mineral and water are systematically 1.5 to 2‰ more positive than the results of theoretical calculations. Dissolved minerals greatly affect the isotopic fractionation in mineral-water systems at high pressure and high temperature. If the presence of a solute changes the solubility of a mineral, the real oxygen isotope salt effect of the solute at high pressure and high temperature cannot be correctly derived by using the mineral as reference phase.     

Influence of liquid structure on diffusive isotope separation in molten silicates and aqueous solutions

Molecular diffusion in natural volcanic liquids discriminates between isotopes of major ions (e.g., Fe, Mg, Ca, and Li). Although isotope separation by diffusion is expected on theoretical grounds, the dependence on mass is highly variable for different elements and in different media. Silicate liquid diffusion experiments using simple liquid compositions were carried out to further probe the compositional dependence of diffusive isotopic discrimination and its relationship to liquid structure. Two diffusion couples consisting of the mineral constituents anorthite (CaAl₂Si₂O₈; denoted AN), albite (NaAlSi₃O₈; denoted AB), and diopside (CaMgSi₂O₆; denoted DI) were held at 1450 °C for 2 h and then quenched to ambient pressure and temperature. Major-element as well as Ca and Mg isotope profiles were measured on the recovered quenched glasses. In both experiments, Ca diffuses rapidly with respect to Si. In the AB-AN experiment, D_Ca/D_Si ≈ 20 and the efficiency of isotope separation for Ca is much greater than in natural liquid experiments where D_Ca/D_Si ≈ 1. In the AB-DI experiment, D_Ca/D_Si ≈ 6 and the efficiency of isotope separation is between that of the natural liquid experiments and the AB-AN experiment. In the AB-DI experiment, D_Mg/D_Si ≈ 1 and the efficiency of isotope separation for Mg is smaller than it is for Ca yet similar to that observed for Mg in natural liquids.The results from the experiments reported here, in combination with results from natural volcanic liquids, show clearly that the efficiency of diffusive separation of Ca isotopes is systematically related to the solvent-normalized diffusivity - the ratio of the diffusivity of the cation (D_Ca) to the diffusivity of silicon (D_Si). The results on Ca isotopes are consistent with available data on Fe, Li, and Mg isotopes in silicate liquids, when considered in terms of the parameter D_cation/D_Si. Cations diffusing in aqueous solutions display a similar relationship between isotopic separation efficiency and D_cation/D_H2O, although the efficiencies are smaller than in silicate liquids. Our empirical relationship provides a tool for predicting the magnitude of diffusive isotopic effects in many geologic environments and a basis for a more comprehensive theory of isotope separation in liquid solutions. We present a conceptual model for the relationship between diffusivity and liquid structure that is consistent with available data.     

Effects of changing solution chemistry on Fe/Fe isotope fractionation in aqueous Fe-Cl solutions

The range in ⁵⁶Fe/⁵⁴Fe isotopic compositions measured in naturally occurring iron-bearing species is greater than 5‰. Both theoretical modeling and experimental studies of equilibrium isotopic fractionation among iron-bearing species have shown that significant fractionations can be caused by differences in oxidation state (i.e., redox effects in the environment) as well as by bond partner and coordination number (i.e., nonredox effects due to speciation).To test the relative effects of redox vs. nonredox attributes on total Fe equilibrium isotopic fractionation, we measured changes, both experimentally and theoretically, in the isotopic composition of an Fe²⁺-Fe³⁺-Cl-H₂O solution as the chlorinity was varied. We made use of the unique solubility of FeCl₄⁻ in immiscible diethyl ether to create a separate spectator phase against which changes in the aqueous phase could be quantified. Our experiments showed a reduction in the redox isotopic fractionation between Fe²⁺- and Fe³⁺-bearing species from 3.4‰ at [Cl⁻] = 1.5 M to 2.4‰ at [Cl⁻] = 5.0 M, due to changes in speciation in the Fe-Cl solution. This experimental design was also used to demonstrate the attainment of isotopic equilibrium between the two phases, using a ⁵⁴Fe spike.To better understand speciation effects on redox fractionation, we created four new sets of ab initio models of the ferrous chloride complexes used in the experiments. These were combined with corresponding ab initio models for the ferric chloride complexes from previous work. At 20 °C, 1000 ln β (β = ⁵⁶Fe/⁵⁴Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 6.39‰ to 5.42‰ for Fe(H₂O)₆²⁺, 5.98‰ to 5.34‰ for FeCl(H₂O)₅⁺, and 5.91‰ to 4.86‰ for FeCl₂(H₂O)₄, depending on the model. The theoretical models predict ferric-ferrous fractionation about half as large (depending on model) as the experimental results.Our results show (1) oxidation state is likely to be the dominant factor controlling equilibrium Fe isotope fractionation in solution and (2) nonredox attributes (such as ligands present in the aqueous solution, speciation and relative abundances, and ionic strength of the solution) can also have significant effects. Changes in the isotopic composition of an Fe-bearing solution will influence the resultant Fe isotopic signature of any precipitates.     

The kinetic studies of the cobalt ion removal from aqueous solutions by dolomite-based sorbent

The kinetics of Co(II) ions adsorption on thermally activated dolomite was studied with respect to the calcination temperature of natural dolomite. The sorption of Co(II) onto all samples is reasonably fast: The first 30–35 min accounts for approximately 70–80 % of Co(II) removal from feed solutions. In order to select the main rate-determining step in the overall uptake mechanism, a series of experiments were performed and data obtained were interpreted in terms of film diffusion control, intraparticle diffusion, pseudo-first-order and pseudo-second-order models. From the modeling of kinetic data, it can be concluded that adsorption of Co(II) ions from aqueous solution by heat-treated dolomite is a complex phenomenon and occurs in a mixed diffusion mode—the kinetic data are well described by the pseudo-second-order equation. The possible multistage sorption mechanism involving film diffusion and intraparticle diffusion control steps as well as chemical interaction between Co(II) ions and calcined dolomite is proposed.     

离子交换分离过程中铅同位素分馏评估及针对MC-ICPMS铅同位素测定的分离纯化方法的修正

本文对分离纯化样品过程中铅同位素的分馏进行了评估,并描述了适于MC-ICPMS同位素测定的分离纯化方法。利用AG1-X8阴离子交换树脂分离纯化样品中铅的过程确实导致了铅同位素的质量分馏。尽管分离纯化过程导致的铅同位素分馏程度较小(0.43‰amu-1),但明显超出了仪器的测试误差(0.23‰amu-1),如果样品中铅的回收率太低,会导致铅同位素测试值明显偏离真值。利用AG1-X8阴离子交换树脂,以0.2mL 1mol/L HBr溶液为上样介质,以5mL 1mol/L HBr和0.5mL 2mol/L HCl溶液为淋洗液,1.5mL 6mol/L HCl溶液为洗脱液,利用该分离流程可以保证获得样品中铅同位素的准确值。在本实验研究条件下,相对于过柱前样品,前期淋洗液富集铅的轻同位素(δ208Pb0),后期淋洗液富集铅的重同位素(δ208 Pb0),表明在该实验条件下,铅的重同位素组分比轻同位素更容易和树脂结合,AG1-X8阴离子交换树脂吸附铅的配分系数208 D/204 D大于1。解吸被树脂吸附铅的过程中,铅在不同络合形式间的交换反应可能导致了铅同位素的分馏效应,意味着无机络合物或者有机大分子参与反应的过程可能会导致铅同位素的分馏。     

A method of calculating quartz solubilities in aqueous sodium chloride solutions

The aqueous silica species that form when quartz dissolves in water or saline solutions are hydrated. Therefore, the amount of quartz that will dissolve at a given temperature is influenced by the prevailing activity of water. Using a standard state in which there are 1,000 g of water (55.51 moles) per 1,000 cm³ of solution allows activity of water in a NaCl solution at high temperature to be closely approximated by the effective density of water, p_e, in that solution, i.e. the product of the density of the NaCl solution times the weight fraction of water in the solution, corrected for the amount of water strongly bound to aqueous silica and Na⁺ as water of hydration. Generally, the hydration of water correction is negligible.The solubility of quartz in pure water is well known over a large temperature-pressure range. An empirical formula expresses that solubility in terms of temperature and density of water and thus takes care of activity coefficient and pressure-effect terms. Solubilities of quartz in NaCl solutions can be calculated by using that equation and substituting p_e, for the density of pure water. Calculated and experimentally determined quartz solubilities in NaCl solutions show excellent agreement when the experiments were carried out in non-reactive platinum, gold, or gold plus titanium containers. Reactive metal containers generally yield dissolved silica concentrations higher than calculated, probably because of the formation of metal chlorides plus NaOH and H₂. In the absence of NaOH there appears to be no detectable silica complexing in NaCl solutions, and the variation in quartz solubility with NaCl concentration at constant temperature can be accounted for entirely by variations in the activity of water.The average hydration number per molecule of dissolved SiO₂ in liquid water and NaCl solutions decreases from about 2.4 at 200°C to about 2.1 at 350°C. This suggests that H₄SiO₄ may be the dominant aqueous silica species at 350°C, but other polymeric forms become important at lower temperatures.     

TC/EA-MS online determination of hydrogen isotope composition and water concentration in eclogitic garnet

A continuous flow method, by a combination of thermal conversion elemental analyzer (TC/EA) with isotope ratio mass spectrometry (MS), is presented for determination of both H isotope composition and H₂O concentration of garnet from eclogite. Together with biotite NBS-30, the garnet was tested by preheating mineral grains at different temperatures. Preheating at 90°C for 12 h was found to be capable of eliminating adsorption water on sample surface. This results in constant δD values and total H₂O contents for the garnet, with weighted means of −93 ± 2‰ and 522 ± 11 ppm (wt), respectively. The garnet that was preheated at 350°C for 4 h also gave constant δD values of −86 ± 6‰ and H₂O contents of 281 ± 13 ppm (wt). The latter result for the H₂O contents agrees with the H₂O contents 271 ± 58 ppm (wt) measured by Fourier transform infrared spectroscopy for quantitative analysis of structural hydroxyl in the same garnet. Stepwise-heating TC/EA-MS analyses for the garnet show that the molecular H₂O are depleted in D relative to the structural OH and has higher mobility than the structural OH. Therefore, the TC/EA-MS method can be used not only for quantitative determination of both H isotope composition and H₂O concentration of hydrous and anhydrous minerals, but also for the concentration of structural hydroxyl after high-T dehydration.     

Thermodynamic properties of Pd chloride complexes and the Pd2+(aq) ion in aqueous solutions

Based on the expert review of literature data on the thermodynamic properties of species in the Cl-Pd system, stepwise and overall stability constants are recommended for species of the composition [PdCl _n ]^{2 ? n} , and the standard electrode potential of the half-cell PdCl ₄ ^2? /Pd(c) is evaluated at E _298,15° = 0.646 ± 0.007 V, which corresponds to Δ _f G _298.15° = ?400.4 ± 1.4 kJ/mol for the ion PdCl ₄ ^2? (aq). Derived from calorimetric data, Δ _f H _298.15° PdCl ₄ ^2? (aq) = ?524.6 ± 1.6 kJ/mol and Δ _f H _298.15° Pd²⁺(aq) = 189.7 ± 2.6 kJ/mol. The assumed values of the overall stability constant of the PdCl ₄ ^2? ion and the standard electrode potential of the PdCl ₄ ^2? /Pd(c) half-cell correspond to Δ _f G _298.15° = 190.1 ± 1.4 kJ/mol and S _298.15° = ?94.2 ± 10 J/(mol K) for the Pd²⁺(aq) ion.     

Solubility of silica polymorphs in electrolyte solutions, II. Activity of aqueous silica and solid silica polymorphs in deep solutions from the sedimentary Paris Basin

Activity coefficient for aqueous silica in saline waters and brines from the Paris Basin was calculated using Pitzer's specific interaction model. Quartz and chalcedony are the only reported authigenic silica minerals in the Dogger aquifer of the Paris Basin (France). However, the measured silica concentrations fall between those of these two phases. The silica concentrations measured in Dogger fluids seem to be controlled by a microcrystalline quartz phase with a grain size computed to be about 20 nm. Studies have shown that pressure can preserve small grain size for a long time at the geological scale. The effective mechanism of pressure action is probably linked to the fact that pressure simultaneously favours dissolution at the grain-contact inducing a quartz supersaturation and prohibits the increase in size of reprecipitated microcrystalline quartz grains. This hypothesis is supported by other studies reported in the literature. The proposed model, which incorporates silica mineralogy and a precise calculation of aqueous silica activity, allows us to explain measured silica concentrations in the deep sedimentary solutions of the Dogger aquifers. In the Keuper brines, silica solubility can in most cases be explained by an equilibrium with either chalcedony or quartz. Another application of the present work is shown by an example, where we examined the importance of precisely evaluating the activity coefficient in basin characterisation, as the goal of reservoir characterisation is to describe the spatial distribution of petrophysical parameters such as porosity, permeability, and saturations.     

Amorphous silica solubilities V. Predictions of solubility behavior in aqueous mixed electrolyte solutions to 300°C

Solubilities of amorphous silica in several aqueous electrolyte solutions up to 300°C (Marshall, 1980a; Chen and Marshall, 1982) fitted the Setchénow equation, $\text{log(}\text{s}{}^0\text{s}\text{) = D·m}$ as described earlier (Marshall, 1980b) where s⁰ and s are molal solubilities of silica in pure water and salt solution, respectively, m is the molality of salt, and D is a proportionality constant related to the particular salt and temperature. It is now shown that, to a first approximation, the D parameters for various salts at the same temperature are additive. For instance, D(NaCl) ? D(KCl) = D(NaNO₃) ? D(KNO₃) or D(MgSO₄) = D(MgCl₂) + D(Na₂S0₄) ? 2D(NaCl). It also follows that $\text{(}\text{s}{}_0\text{s}\text{) =}\text{∑}\text{i}\text{(D}{}_{\mathrm{i}}\text{m}{}_{\mathrm{i}}\text{)}$.This additivity principle was used to estimate amorphous silica solubilities in mixed NaCl-Na₂SO₄, NaCl-MgCl₂, NaCl-MgSO₄, Na₂SO₄-MgCl₂, Na₂SO₄-MgSO₄, and MgCl₂-MgSO₄ aqueous solutions up to 300°C. The method produces results that agree reasonably well with experimental values and would be useful for predicting silica solubilities, for example, in seawater and its hydrothermal concentrates and in geothermal energy applications.     

线-面结合的结构面粗糙系数经验计算方法

岩体结构面的剪切力学特性主要取决于其表面粗糙特征,结构面粗糙系数是表征该粗糙特征的主要方法。目前对结构面粗糙系数的研究局限于单一维度,多角度且定量化计算结构面粗糙系数能避免单一维度分析导致计算精度不准的局限性。采用立方体花岗岩,通过巴西劈裂的方式制备含结构面的试样;利用高精度三维扫描仪对试样结构面进行扫描,得到结构面的点云数据,同时借助逆向软件对点云数据进行三维重构。研究了点云数据Z方向上的分布频率,剖面线剖面比与节理粗糙系数（JRC）值的关系,结构面面积比与JRC均值的关系。研究表明：点云数据Z方向上的分布频率可以作为初步评估结构面粗糙度的手段;剖面线剖面比与JRC数值、结构面面积比与JRC均值有二次函数的关系。通过数值分析建立了结构面JRC均值与剖面比、面积比的二元函数关系,并得到结构面JRC均值的经验计算公式。本次研究为结构面粗糙度提供了一种“点-线-面”逐渐深入的多角度评估思路,得到的经验公式为计算结构面JRC均值提供了一种新的计算方法。     

Stable hydrogen isotopes in iron oxides—isotope effects associated with the dehydration of a natural goethite

The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the $\text{D}\text{H}$ ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system $\text{D}\text{H}$ fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO₂ loss from goethite during dehydration is correlated with the loss of H₂O. The CO₃ is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H₂O and CO₂ appears to be diffusion-controlled.     

湿度对盐溶液在壁画地仗中的毛细迁移影响研究

盐溶液在地仗中毛细迁移引起的盐分迁移、富集已成为壁画病害发生的重要原因。研究不同湿度条件下盐溶液在模拟地仗中的毛细迁移过程对可溶盐再分布的影响。分析不同湿度条件下毛细上升高度随时间的变化关系,含水率和电导率随高度变化关系,毛细饱和后试样表面变化情况及可溶盐含量随试样高度的分布。试验结果表明,空气相对湿度越低,毛细上升过程中水分向空气中迁移越多,水分难以向上迁移。试样的含水率随高度呈递减趋势,而电导率随试样高度增加而增大。可溶盐在毛细水上升过程中发生结晶分异,毛细前锋以NaCl结晶富集为主,亚前锋以Na2SO4结晶富集为主。其研究结果可以为壁画盐害的防治提供基础科学依据。     

An induction time model for the attachment of an air bubble to a hydrophobic sphere in aqueous solutions

A phenomenological model is developed to describe the induction time of an air bubble in contact with a hydrophobic sphere, based on an analytical solution of Reynolds approximation under the specific boundary conditions. A modified version of induction time apparatus is used to measure the induction time of an air bubble with a methylated silica bead, an untreated silica bead in dodecylamine solutions and a bitumen droplet in alkaline solutions. It was found that the induction time between an air bubble and a silica bead (or a bitumen droplet) increased with increasing bubble size. The bubble size dependence is stronger for the large silica beads (or bitumen droplets) tested. The induction time, obtained from two different methylated silica beads diameters, is used to estimate the average net driving force (F̄_o) for the intervening liquid film drainage and rupture and the critical film thickness (h_c) in the established model. Through curve fitting, the values for F̄_o and h_c are found to be 3.5×10⁻⁸ N and 150 nm, respectively, for a methylated silica–bubble system. The predicted values of critical film thickness and the net driving force for the systems used in this study are in excellent agreement with those reported in the literature, confirming the present theoretical analysis and model development. The suitability of using the liquid drainage time to represent the induction time, or the attachment time, is experimentally justified.     

Validation of a rapid and simple method for the preparation of aqueous organic compounds prior to compound specific isotope analysis

Landfill leachate comprises a complex mixture of contaminants many of which may have multiple sources in the environment confounding conventional techniques for apportioning sources. Compound specific isotope ratio mass spectrometry offers the potential to “fingerprint” compounds enabling discrimination to be made between different sources. This paper presents a rapid and highly reproducible method to prepare landfill leachate samples for compound specific isotope analysis. A suitable solid phase extraction (SPE) method was developed using artificial contaminant solutions, natural waters spiked with artificial contaminants (eucalyptol, dodecane, benzothiazole, dibutyl phthalate and naphthalene), and samples of landfill leachate. The elution of adsorbed compounds from the SPE cartridge was found to be the major cause of hydrogen and carbon isotope fractionation. Three different SPE cartridge types were tested: C18, Strata-X and ENV+. Fractionation of between 1‰ and 245‰ for hydrogen isotopes and 0–1.83‰ for carbon isotopes was observed. Part of the fractionation could be attributed to the different SPE cartridges but the major contribution was from the choice of the eluting solvent. Our results indicated hydroxylated styrene-divinylbenzene cartridges eluted with dichloromethane resulted in negligible hydrogen or carbon isotope fractionation for any of the tested organic compounds.The isotopic fractionation of hydrogen and/or carbon of most artificial contaminants were proportional to the efficiency with which they were extracted from water. Only naphthalene exhibited isotopic fractionation unrelated to its extraction efficiency but this fractionation was negligible.The comparative extraction of landfill leachate using SPE and LLE indicated SPE generally extracts slightly more of each compound from leachate than LLE. This relationship is stronger than for polar compounds. In addition, the δD composition of each compound prepared using SPE was with two standard deviations of the sample compound prepared using LLE, and the δ¹³C composition of each compound prepare using either method was mostly within two standard deviations.     

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

Experimental and theoretical study of pressure effects on hydrogen isotope fractionation in the system brucite-water at elevated temperatures

A detailed, systematic experimental and theoretical study was conducted to investigate the effect of pressure on equilibrium D/H fractionation between brucite (Mg(OH)₂) and water at temperatures from 200 to 600°C and pressures up to 800 MPa. A fine-grained brucite was isotopically exchanged with excess amounts of water, and equilibrium D/H fractionation factors were calculated by means of the partial isotope exchange method. Our experiments unambiguously demonstrated that the D/H fractionation factor between brucite and water increased by 4.4 to 12.4‰ with increasing pressure to 300 or 800 MPa at all the temperatures investigated. The observed increases are linear with the density of water under experimental conditions. We calculated the pressure effects on the reduced partition function ratios (β-factor) of brucite (300-800 K and P ≤ 800 MPa) and water (400-600°C and P ≤ 100 MPa), employing a statistical-mechanical method similar to that developed by Kieffer (1982) and a simple thermodynamic method based on the molar volumes of normal and heavy waters, respectively. Our theoretical calculations showed that the reduced partition function ratio of brucite increases linearly with pressure at a given temperature (as much as 12.6‰ at 300 K and 800 MPa). The magnitude of the pressure effects rapidly decreases with increasing temperature. On the other hand, the β-factor of water decreases 4 to 5‰ with increasing pressure to 100 MPa at 400 to 600°C. Overall D/H isotope pressure effects combined from the separate calculations on brucite and water are in excellent agreement with the experimental results under the same temperature-pressure range. Our calculations also suggest that under the current experimental conditions, the magnitude of the isotope pressure effects is much larger on water than brucite. Thus, the observed pressure effects on D/H fractionation are common to other systems involving water. It is very likely that under some geologic conditions, pressure is an important variable in controlling D/H partitioning.     

Simulation of the nucleation and growth of binary solid solutions in aqueous solutions

We present a model which, for the first time, accounts for nucleation, growth and/or resorption of particles of variable composition in aqueous solutions (AS). Devised for describing the precipitation of binary solid solutions, it yields the time evolution of all ion activities in the AS, together with the particle population characteristics: number, size and composition profile of particles as a function of time and of their time of nucleation. We apply this numerical approach to the prototypical case of (Ba,Sr)CO₃ solid solution precipitation. We demonstrate the great sensitivity of the composition profiles and particle sizes to the initial conditions under which the AS is prepared, and thus illustrate the possibility of engineering the particle characteristics into a chosen state. Finally, by comparing the precipitation of two solid solutions (Ba,Sr)CO₃ and (Ba,Sr)SO₄, we evidence the sensitivity of the particle composition profiles to the ratio of the end-member solubility products, which leads to the formation of core-shell particles in the case of (Ba,Sr)SO₄.