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1.
The nucleation kinetics of binary solid solutions, with general formula BxC1−xA, crystallising from aqueous solution can be described using a generalised expression for the nucleation rate: the function, J(x), in which supersaturation, interfacial free energy and other parameters of the classical nucleation rate equation are considered as functions of the solid composition. As an example, we studied the behaviour of such J(x) functions for the case of the (Ba,Sr)SO4 and (Ba,Sr)CO3 solid solutions. J(x) functions are very sensitive to slight changes in the composition of the aqueous solution, which result in strong modifications of the nucleation kinetics. The implications of the relationship between supersaturation and nucleation rate functions for the general nucleation behaviour in solid solution-aqueous solution (SS-AS) systems are discussed. Finally, we present a method for constructing non-equilibrium Roozeboom diagrams based on the nucleation kinetics in SS-AS systems. Our Roozeboom diagrams calculated for different departures from equilibrium conditions are consistent with previous experimental work and they can be used to predict actual distribution coefficients.  相似文献   

2.
A new approach is proposed for incorporating solid solution reactions into mass conservation equations describing reaction paths in both closed and open systems. The method is applicable to problems involving advective, dispersive, and diffusive transport in a porous medium. By representing the continuously variable solid solution composition with a discrete set of stoichiometric solids that span composition space, combined with a kinetic formulation of their rates of reaction, a self-determining spatial and temporal evolution of the solid solution concentration and composition is obtained. It is demonstrated that equilibrium of an aqueous solution with a stoichiometric solid derived from a solid solution corresponds to equilibrium of the solid solution itself if and only if equilibrium of the stoichiometric solid is stable. One advantage of this approach is that it is unnecessary to introduce any additional compositional variables to represent the solid solution. Discretization may be over the entire range of composition space, or over some subset depending on the system. A major consequence of the kinetic discrete-composition solid solution representation is that modeling solid solutions is similar to modeling pure mineral phases with the exception of a weighting factor applied to reaction rates of stoichiometric solids corresponding to a common solid solution. With this approach, precipitation leads to a discrete zonation of the solid solution that approximates the continuous variation in composition expected for the actual solid solution. The approach is demonstrated for a hypothetical ideal and non-ideal binary solid solution AxB1−xC for a reaction path formulation and reactive transport involving advection and diffusion.  相似文献   

3.
The kinetics of the formation and precipitation of nanocolloidal silica from geologically relevant aqueous solutions is investigated. Changes in monomeric (SiO2(mono)), nanocolloidal (SiO2(nano)) and precipitated silica (SiO2(ppt)) concentrations in aqueous solutions from pH 3 to 7, ionic strengths (IS) of 0.01 and 0.24 molal, and initial SiO2 concentrations of 20.8, 12.5 and 4.2 mmolal (reported in [Icopini, G.A., Brantley, S.L., Heaney, P.J., 2005. Kinetics of silica oligomerization and nanocolloid formation as a function of pH and ionic strength at 25 °C. Geochim. Cosmochim. Acta69(2), 293-303.]) were fit using two kinetic models. The first model, termed the concentration model, is taken from Icopini et al. (2005) and assumes that the rate of change of SiO2(mono) as a function of time has a fourth-order dependence on the concentration of SiO2(mono) in solution. The second model, termed the supersaturation model, incorporates the equilibrium concentration of amorphous silica and predicts that polymerization will be a function of the degree of silica supersaturation in solution with respect to amorphous silica. While both models generally predicted similar rate constants for a given set of experimental conditions, the supersaturation model described the long-term equilibrium behavior of the SiO2(mono) fraction more accurately, resulting in significantly better fits of the monomeric data. No difference was seen between the model fits of the nanocolloidal silica fraction. At lower pH values (3-4), a metastable equilibrium was observed between SiO2(mono) and SiO2(nano). This equilibrium SiO2(mono) concentration was found to be 6 mmolal, or three times the reported solubility of bulk amorphous silica under the experimental conditions studied and corresponds to the predicted solubility of amorphous silica colloids approximately 3 nm in diameter. Atomic force microscopy was used to determine the average size of the primary nanocolloidal particles to be ∼3 nm, which is in direct agreement with the solubility calculations. Larger aggregates of the primary nanocolloids were also observed to range in size from 30 to 40 nm. This work provides the first kinetic models describing the formation and evolution of nanocolloidal silica in environmentally relevant aqueous solutions. Results indicate that nanocolloidal silica is an important species at low pH and neutral pH at low ionic strengths and may play a more important role in geochemical cycles in natural aqueous systems than previously considered.  相似文献   

4.

Background

The interaction between Ca-HAP and Pb2+ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(PbxCa1?x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (PbxCa1?x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.

Results

Dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb2+ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00–0.80), the aqueous Pb2+ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.

Conclusions

The dissolution process of the solids with high XPb (0.89–1.00) was different from that of the solids with low XPb (0.00–0.80). The average K sp values were estimated to be 10?80.77±0.20 (10?80.57–10?80.96) for hydroxypyromorphite [Pb5(PO4)3OH] and 10?58.38±0.07 (10?58.31–10?58.46) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔG f o ) were determined to be ?3796.71 and ?6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1?x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1?x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1?x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution.
Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3OH] at 25??C and an initial pH of 2.00.
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5.
《Chemical Geology》2006,225(3-4):189-212
The dual-thermodynamic (DualTh) approach is shown to provide a useful alternative to other methods in: (i) forward modelling of equilibrium speciation, activities, and element partitioning in a heterogeneous system involving several variable-composition phases, such as the aqueous–solid solution system; (ii) estimation of interaction parameters of a non-ideal mixing model from known bulk compositions of coexisting aqueous and solid-solution phases; and (iii) retrieval of unknown stoichiometries and apparent standard chemical potentials of trace solid-solution end-members. Inverse-modelling tasks (ii) and (iii) can be performed when the solid solution of interest is shown experimentally to co-exist with the aqueous phase either in the equilibrium or at the minimum stoichiometric saturation state.DualTh calculations exploit the ability of Gibbs energy minimisation (GEM) algorithms to find simultaneously two numerical solutions of the isobaric–isothermal chemical equilibrium speciation problem: (1) primal solution x — a vector of amounts of components (species) in phases; and (2) dual solution u — a vector of chemical potentials of stoichiometry units (usually chemical elements and charge). Conversely, the chemical potential of a phase component can be found in two complementary ways: (i) primal via its standard-state potential, concentration and activity coefficient (the latter two are functions of the x vector); and (ii) dual through its formula stoichiometry multiplied by the u vector. The DualTh methods compare primal and dual values of the chemical potential in simple and straightforward equations that can be easily computed in a spreadsheet, or implemented in GEM geochemical modelling codes.  相似文献   

6.
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7.
FeII-III hydroxycarbonate green rust GR(CO32−), FeII4 FeIII2 (OH)12 CO3·3H2O, is oxidized in aqueous solutions with varying reaction kinetics. Rapid oxidation with either H2O2 or dissolved oxygen under neutral and alkaline conditions leads to the formation of ferric oxyhydroxycarbonate GR(CO32−)∗, FeIII6 O12 H8 CO3·3H2O, via a solid-state reaction. By decreasing the flow of oxygen bubbled in the solution, goethite α-FeOOH forms by dissolution-precipitation mechanism whereas a mixture of non-stoichiometric magnetite Fe(3−x)O4 and goethite is observed for lower oxidation rates. The intermediate FeII-III oxyhydroxycarbonate of formula FeII6(1−x) FeIII6x O12 H2(7−3x) CO3·3H2O, i.e. GR(x)∗ for which x ? [1/3, 1], is the synthetic compound that is homologous to the fougerite mineral present in hydromorphic gleysol; in situ oxidation accounts for the variation of ferric molar fraction x = [FeIII]/{[FeII]+[FeIII]} observed in the field as a function of depth and season but limited to the range [1/3, 2/3]. The domain of stability for partially oxidized green rust is observed in the Eh-pH Pourbaix diagrams if thermodynamic properties of GR(x)∗ is compared with those of lepidocrocite, γ-FeOOH, and goethite, α-FeOOH. Electrochemical equilibrium between GR(x)∗ and FeII in solution corresponds to Eh-pH conditions close to those measured in the field. Therefore, the reductive dissolution of GR(x)∗ can explain the relatively large concentration of FeII measured in aqueous medium of hydromorphic soils containing fougerite.  相似文献   

8.
The adsorption of surfactants from aqueous solution is a phenomenon of major importance in applications ranging from ore flotation and paint technology to enhanced oil recovery. As this paper will illustrate, the process is very complex and of high scientific interest; its results can be extended to the retention of organic compounds (humic and fulvic acids, pollutants...) on solids in the biosphere. For a good understanding of the mechanisms involved in surfactants adsorption at the hydrophilic solid–aqueous solution interface, thermodynamic models have to take into account: (i) the physical chemistry of the surfactant in aqueous solution for choosing the appropriate reference phase, (ii) the surface heterogeneity of the adsorbing solid, (iii) the intensity of normal adsorbate–adsorbent bonds responsible for adsorption, (iv) the intensity of lateral bonds that favour the formation of surface aggregates through cooperative process and finally, (v) suitable theoretical models to describe adsorption phenomena. Once this has been achieved, two systems can be discussed: systems characterised by strong normal adsorbate–adsorbent bonds, currently used in ore flotation, which lead, in the case of heterogeneous surfaces, to the formation of lamellar aggregates at monolayer concentration and bilayer formation for higher concentrations. Systems characterised by weak normal adsorbate–adsorbent bonds, currently used in enhanced oil recovery and hydrocarbon (bio)remediation, which correspond to: (i) formation of globular micelles at the solid surface near the CMC when the temperature is higher than the Krafft point, (ii) formation of bilayered lamellar aggregates in the opposite case, (iii) three-dimensional condensation on substrate (T<TKrafft) if the ionic surfactant interacts with cations in the bulk. To cite this article: J.-M. Cases et al., C. R. Geoscience 334 (2002) 675–688.  相似文献   

9.
Cleaved surfaces of dolomite were studied using ex-situ X-ray photoelectron spectroscopy (XPS) following exposure of the surfaces to various experimental conditions. Dolomite samples exposed to air, to a highly undersaturated solution (0.1 M NaCl, pH = 9), and to solution with a supersaturation (−Δμ/kT) of 5.5 (pH = 9) were investigated with semiquantitative methods of analysis to ascertain the degree of non-stoichiometry resulting at the dolomite surface from reactive conditions. It was found that the dolomite cleavage surface in undersaturated solution was not altered significantly from the stoichiometric surface termination. The composition of the cleaved surface after exposure to supersaturated solution, a surface known to have self-limiting growth characteristics under similar conditions, was found to be Ca2+ rich (CaxMg2 − x(CO3)2, 1.7 > x > 1.3). The observations, while underscoring differences in hydration/dehydration kinetics of the two alkaline earth cations, suggest that achievement of equilibrium at dolomite-water interfaces may be subject to significant barriers from both undersaturated and supersaturated solutions.  相似文献   

10.
Tremolite (CaxSr1–x)2Mg5[Si8O22/(OH)2] and diopside (CaxSr1–x)Mg[Si2O6] solid solutions have been synthesized hydrothermally in equilibrium with a 1 molar (Ca,Sr)Cl2 aqueous solution at 750°C and 200 MPa. The solid run products have been investigated by optical, electron scanning and high resolution transmission electron microscopy, electron microprobe, X-ray-powder diffraction and Fourier-transform infrared spectroscopy. The synthesized (Ca,Sr)-tremolites are up to 2000 µm long and 30 µm wide, the (Ca,Sr)-diopsides are up to 150 µm long and 20 µm wide. In most runs the tremolites and diopsides are well ordered and chain multiplicity faults are rare. Nearly pure Sr-tremolite (tr0.02Sr-tr0.98) and Sr-diopside (di0.01Sr-di0.99) have been synthesized. A continuous solid solution series, i.e. complete substitution of Sr2+ for Ca2+ on M4-sites exists for (Ca,Sr)-tremolite. Total substitution of Sr2+ for Ca2+ on M2-sites can be assumed for (Ca,Sr)-diopsides. For (Ca,Sr)-tremolites the lattice parameters a, b and β are linear functions of composition and increase with Sr-content whereas c is constant. For the diopside series all 4 lattice parameters are a linear function of composition; a, b, c increase and β decreases with rising Sr-content. The unit cell volume for tremolite increases 3.47% from 906.68 Å3 for tremolite to 938.21 Å3 for Sr-tremolite. For diopside the unit cell volume increases 4.87 % from 439.91 Å3 for diopside to 461.30 Å3 for Sr-diopside. The observed splitting of the OH stretching band in tremolite is caused by different configurations of the next nearest neighbors (multi mode behavior). Resolved single bands can be attributed to the following configurations on the M4-sites: SrSr, SrCa, CaCa and CaMg. The peak positions of these 4 absorption bands are a linear function of composition. They are shifted to lower wavenumbers with increasing Sr-content. No absorption band due to the SrMg configuration on the M4-site is observed. This indicates a very low or negligible cummingtonite component in Sr-rich tremolites, which is also supported by electron microprobe analysis.  相似文献   

11.
The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ18O. Interpreting speleothem δ18O records in terms of absolute paleotemperatures and δ18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C18O bonds in CO2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation.Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ18O and Δ47 values, probably inherited from prior degassing within the cave system.In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ47 in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ47 in inorganic carbonates.  相似文献   

12.
Heterogeneous equilibria in the system Ca(HSiUO6)2 · 5H2O(c)–aqueous solution were studied over broad ranges of pH, ionic strength, and ionic composition of the solution, and the pH range of stability of Ca uranyl silicate is determined. Hydrolysis products of Ca uranyl silicate are identified, and their solubility is determined. The equilibrium constant of the dissolution reaction and the standard Gibbs function of formation of Ca(HSiUO6)2 · 5H2O are calculated from experimental data, and solubility curves of uranophane and equilibrium speciation diagrams for U(VI), Si(IV), and Ca(II) in coexisting aqueous solutions and solid phases are calculated.  相似文献   

13.
The equations relating element distribution and pH are derived for systems containing an ideal solid solution in equilibrium with an ideal aqueous solution, assuming no polymeric complexes form in the aqueous solution and the solid solution does not contain molecular units with multiple atoms of the substituting elements. These expressions demonstrate that the ratio of the partition coefficients describing element distribution for a system containing a multi-component solid solution is inversely proportional to the solubilities of the end member components at any given pH raised to the power equal to the ratio of the sum of the stoichiometric coefficients of the end-member salt to the stoichiometric coefficient of the substituting radical. The coefficient describing distribution between the aqueous phase and a two-component solid solution is equal to the inverse of the ratio of the end member solubilities raised to the above power. Element distribution between the two phases will be homogenous at any pH resulting in identical solubilities for the two end-member components, and a reversal in relative solubilities will result in a corresponding reversal in the element preferentially incorporated into the solid solution. Because of the dependence of element distribution on pH, a crystal could develop both zoning and reverse zoning as a result of changes in pH. The distribution coefficient could provide information regarding the pH of the aqueous solution at the time of mineral formation if independent evidence establishes the ratio of end-member components in the aqueous phase. The equations describing element distribution may be expressed in terms of the solubility products of the end-member components and the ionization constants of the substituting radicals. Based on the relative values of the ionization constants, pH intervals can be established in which only the concentration of a single complex for each substituting radical need be considered. Within such an interval, the curve of the log of the distribution coefficient vs. pH is linear with a slope equal to the difference in the charges of the two complexes. This approach to the examination of element distribution is developed in some detail for the geologically important case of a two component solid solution having composition (A2+, B2+) X2?.  相似文献   

14.
The solubility constants of sixty-nine rock-forming minerals have been computed for temperatures between 400 and 600°C at 1000 and 2000 bar pressure using the free-energy data for aqueous solutes presented in Parts I through IV of this series combined with the thermodynamic properties of minerals from Helgesonet al. (1978). An example describing solution compositions in equilibrium with a spilite is discussed. A computer program for calculating solution compositions in equilibrium with mineral assemblages is included as an appendix.  相似文献   

15.
A hypothesis is presented that the dissolution of albite includes the exchange of sodium for hydrogen ion in a surface layer of the mineral and the structural collapse of the residual anionic lattice of the layer. The ion exchange is described by the first law of diffusion (D25°C = 3 × 10?22 and 1.5 × 10?20 cm2sec?1 at PCO2 = 0 and 26.2 atm, respectively). The surface residual layer reaches a steady-state thickness ranging from n × 10?8 to n × 10?5 cm according to the temperature and PCO2. The increase in aqueous sodium with time in a continuous ground-water system is described by a simple exponential equation. The equation is used to estimate the percolation time of ground water from the data on the chemical composition of a water sample. The probable times range from 14 to 3840 days for various ground-water systems and are compared to the times of percolation calculated from the geothermal and hydraulic data. Both estimates are found to be in general agreement. The concentrations of Al and Si in cold water from granitic rocks are shown to be controlled by the chemical equilibrium with respect to an aged aluminosilicate. The aluminosilicate precipitates from ground water as an amorphous isoelectric solid. Its chemical composition is represented by a simplified stoichiometric formula [Al(OH)3](1?x)[SiO2]x and varies linearly with pH of the solution. The atoms of Al, O and H tend to occupy a fixed position in the solid given by the gibbsite structure upon aging in the field. The solubility product of the solid is estimated from the published data on experimental and field research into the dissolution of feldspars: logK = (1 ? x) × log [Al3+] + xlog [H4SiO4] ? (3 ? 3x) log [H+] = 8.56 ? 11.26x, where x is the molar fraction of silica in the aluminosilicate.  相似文献   

16.
Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced 56Fe/54Fe ratios for Fe(II)aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO3) and ca. +0.9‰ for Ca-substituted siderite (Ca0.15Fe0.85CO3) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have 56Fe/54Fe ratios that are up to 1‰ lower than Fe(II)aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)aq.The relative order of δ56Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ56Fe >0‰, the calculated δ56Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ56Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ56Fe values. Based on this experimental study, formation of low-δ56Fe Fe(II)aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.  相似文献   

17.
The phase equilibrium and growth of mixed (Ba,Pb)(NO3)2 crystals in aqueous solutions were investigated. The microcrystallization method was adapted to systems with isomorphic components, where crystal composition deviates from the thermodynamic equilibrium even at a low supercooling. The solid phase is characterized by continuous miscibility of the components within the analyzed ranges of temperature and solution composition. The diagram is characterized by substantial nonlinearity of the solubility isotherms and nonuniformity of the solid isocomposite location. Quasiequilibrium paths change their slope depending on solution enrichment in Ba(NO3)2 and depletion in Pb(NO3)2. The area of curvature of quasiequilibrium paths is coordinated with the area of the changing isotherm slope, i.e., the area of “remarkable” points, where the behavior of the system changes drastically. Examples of theoretical zoning of a crystal approximated to a sphere were calculated for paths at a temperature decreasing from 50 to 15°C. The content of the Ba component decreases toward the periphery with the consecutive overgrowing of zones. Each zone corresponds to one gram of (Ba,Pb)(NO3)2. Crystals grown from different initial solutions consist of different numbers of zones owing to the nonlinearity of solubility isotherms. Specific features of mixed crystal formation should be taken into account in genetic interpretation of natural minerals of mixed composition.  相似文献   

18.
Thermodynamic modeling of equilibria in the system water–rock–organic acids was used to study the influence of organic acids on Ca and Mg redistribution between a solution and a solid phase in connection with the use of calcites of variable composition CaxMg1–xCO3 as indicators of paleoclimatic environments. In the thermodynamic model, high-molecular humic substances (fulvic + humic acids) were represented by a set of independent metal-binding centers. Therefore, their number was preset based on the given density of proton- or metal-binding sites. The numerical implementation of several geochemical situations involving the dissolution/deposition of calcites with different Mg contents showed that the main effect of fulvic and humic acids is the acidification of solutions and the reduction of carbonate stability. Although humic substances can play an important role in fixing Ca and Mg and removing them from solution, their actual concentrations in natural media (<<1 g/L) do not cause significant changes in the composition of CaxMg1–xCO3 phases. On the other hand, there is quantitative evidence that variations in the Mg/Ca ratio in a solution and a solid phase are significantly influenced by the evaporative concentration of Mg-oversaturated solutions, alkalization/acidification during their evolution, or CO2 content variations owing to changes in climate and lake activity.  相似文献   

19.
High-purity synthetic barite powder was added to pure water or aqueous solutions of soluble salts (BaCl2, Na2SO4, NaCl and NaHCO3) at 23 ± 2 °C and atmospheric pressure. After a short pre-equilibration time (4 h) the suspensions were spiked either with 133Ba or 226Ra and reacted under constant agitation during 120-406 days. The pH values ranged from 4 to 8 and solid to liquid (S/L) ratios varied from 0.01 to 5 g/l. The uptake of the radiotracers by barite was monitored through repeated sampling of the aqueous solutions and radiometric analysis. For both 133Ba and 226Ra, our data consistently showed a continuous, slow decrease of radioactivity in the aqueous phase.Mass balance calculations indicated that the removal of 133Ba activity from aqueous solution cannot be explained by surface adsorption only, as it largely exceeded the 100% monolayer coverage limit. This result was a strong argument in favor of recrystallization (driven by a dissolution-precipitation mechanism) as the main uptake mechanism. Because complete isotopic equilibration between aqueous solution and barite was approached or even reached in some experiments, we concluded that during the reaction all or substantial fractions of the initial solid had been replaced by newly formed barite.The 133Ba data could be successfully fitted assuming constant recrystallization rates and homogeneous distribution of the tracer into the newly formed barite. An alternative model based on partial equilibrium of 133Ba with the mineral surface (without internal isotopic equilibration of the solid) could not reproduce the measured activity data, unless multistage recrystallization kinetics was assumed. Calculated recrystallization rates in the salt solutions ranged from 2.8 × 10−11 to 1.9 × 10−10 mol m−2 s−1 (2.4-16 μmol m−2 d−1), with no specific trend related to solution composition. For the suspensions prepared in pure water, significantly higher rates (∼5.7 × 10−10 mol m−2 s−1 or ∼49 μmol m−2 d−1) were determined.Radium uptake by barite was determined by monitoring the decrease of 226Ra activity in the aqueous solution with alpha spectrometry, after filtration of the suspensions and sintering. The evaluation of the Ra uptake experiments, in conjunction with the recrystallization data, consistently indicated formation of non-ideal solid solutions, with moderately high Margules parameters (WAB = 3720-6200 J/mol, a0 = 1.5-2.5). These parameters are significantly larger than an estimated value from the literature (WAB = 1240 J/mol, a0 = 0.5).In conclusion, our results confirm that radium forms solid solutions with barite at fast kinetic rates and in complete thermodynamic equilibrium with the aqueous solutions. Moreover, this study provides quantitative thermodynamic data that can be used for the calculation of radium concentration limits in environmentally relevant systems, such as radioactive waste repositories and uranium mill tailings.  相似文献   

20.
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