Alkali feldspar dissolution and secondary mineral precipitation in batch systems: 3. Saturation states of product minerals and reaction paths

In order to evaluate the complex interplay between dissolution and precipitation reaction kinetics, we examined the hypothesis of partial equilibria between secondary mineral products and aqueous solutions in feldspar-water systems. Speciation and solubility geochemical modeling was used to compute the saturation indices (SI) for product minerals in batch feldspar dissolution experiments at elevated temperatures and pressures and to trace the reaction paths on activity-activity diagrams. The modeling results demonstrated: (1) the experimental aqueous solutions were supersaturated with respect to product minerals for almost the entire duration of the experiments; (2) the aqueous solution chemistry did not evolve along the phase boundaries but crossed the phase boundaries at oblique angles; and (3) the earlier precipitated product minerals did not dissolve but continued to precipitate even after the solution chemistry had evolved into the stability fields of minerals lower in the paragenesis sequence. These three lines of evidence signify that product mineral precipitation is a slow kinetic process and partial equilibria between aqueous solution and product minerals were not held. In contrast, the experimental evidences are consistent with the hypothesis of strong coupling of mineral dissolution/precipitation kinetics [e.g., Zhu C., Blum A. E. and Veblen D. R. (2004a) Feldspar dissolution rates and clay precipitation in the Navajo aquifer at Black Mesa, Arizona, USA. In Water-Rock Interaction (eds. R. B. Wanty and R. R. I. Seal). A.A. Balkema, Saratoga Springs, New York. pp. 895-899]. In all batch experiments examined, the time of congruent feldspar dissolution was short and supersaturation with respect to the product minerals was reached within a short period of time. The experimental system progressed from a dissolution driven regime to a precipitation limited regime in a short order. The results of this study suggest a complex feedback between dissolution and precipitation reaction kinetics, which needs to be considered in the interpretation of field based dissolution rates.     

Modelling the baseline geochemistry of groundwater in a Chalk aquifer considering solid solutions for carbonate phases

The Chalk aquifer of Champagne (France) baseline geochemistry has been determined using a solid solution approach for the modelling of calcite dissolution. The water–rock interactions are modelled by the speciation code CHESS from field data and Ca, Mg and Sr aqueous concentrations in groundwater. The stoichiometries of solid solutions are defined in each stratigraphic unit of the Chalk aquifer from bulk geochemistry and Chalk mineralogy of samples taken from boreholes. The initial mineralisation of water at the bottom of the unsaturated zone and the characterisation of the theoretical evolution of groundwater chemistry along the flow lines associated with incongruent calcite dissolution are calculated from this approach.     

Heterogeneous Equilibria in Saturated Aqueous Solutions of Uranophane

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.     

Quantitative study of geochemical processes in the Dogger aquifer,Paris Basin,France

The quantification of geochemical reactions in hydrothermal aquifers requires an exhaustive approach because of their interdependence. All chemical elements likely to have a quantitative influence on dissolution or precipitation reactions have to be taken into account. Geochemical constraints the number of which equals the number of the chemical elements, were determined with the help of chemical analyses of the solution. In the case study of the Dogger aquifer (Paris Basin, France), 12 elements are taken into account (Al, C, Cl, Ca, F, H, K, Mg, Na, O, S, Si). Three constraints apply to water-activity, neutrality and conservation of chloride in aqueous solutions. The determination of the remaining constraints was based on saturation indices, stability diagrams of minerals and partial pressure of carbon dioxide (pCO₂). The present-day solutions are at equilibrium with respect to nine minerals (albite, anhydrite, chalcedony, calcite, dolomite, fluorite, kaolinite, K-feldspar and illite or chlorite). Thus, it was demonstrated that the composition of these solutions (including computed pCO₂) is only a function of temperature and chloride content. Moreover, it was possible to test the validity of the geochemical system by computing its speciation and comparing these theoretical results with actual chemical analyses (pH and concentrations). Finally, geochemical simulations were used in predicting what quantities would be dissolved or precipitated, as either the temperature or the chlorinity varied. Although the rock is predominantly calcareous, these quantities could not be determined if the influence of the aluminosilicates were neglected. This chemical component approach with which one can pose and solve rigorously the chemical equilibrium problem constitutes a prerequisite for the quantitative study of geochemical processes related to fluid flow.     

The kinetics of nucleation of solid solutions from aqueous solutions: a new model for calculating non-equilibrium distribution coefficients

The nucleation kinetics of binary solid solutions, with general formula B_xC_1−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.     

Simulation of the nucleation and growth of simple clay minerals in weathering processes: The NANOKIN code

We present a numerical approach which accounts for nucleation, growth and/or resorption of particles of fixed composition in aqueous solutions, and which involves functionalities suited to the formation of simple clay minerals in weathering processes, such as: formation of non-spherical particles, heterogeneous/homogeneous nucleation, several growth laws, precipitation resulting from the dissolution of primary minerals. The overall model is now embedded into a new numerical code called NANOKIN, in which several optimization procedures have been introduced in order to allow long dynamics to be followed. NANOKIN was applied to the precipitation of Al- bearing minerals from aqueous solutions: halloysite, kaolinite and Ca-montmorillonite. It allowed us to propose a stable scheme for the competitive precipitation of halloysite and kaolinite under two different types of initial conditions: (1) a given initial super-saturation state of the aqueous solution; (2) progressive super-saturation resulting from the kinetic dissolution of the minerals from a granitic rock under weathering conditions. Both yield particle sizes in the micron range, but with distinct crystal size distribution functions. The interplay between kinetic and thermodynamic effects is discussed.     

Microbial control of mineral–groundwater equilibria:Macroscale to microscale

macroscale processes that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral. In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation. Feldspars, in contrast, weather exclusively at the microscale near attached microorganisms, principally in the anoxic region of the plume. Native organisms preferentially colonize feldspars that contain trace phosphorus as apatite inclusions, apparently as a consequence of the low P concentration in the groundwater. These feldspars weather rapidly, whereas nearby feldspars without trace P are uncolonized and unweathered. Feldspar dissolution is accompanied by the precipitation of secondary minerals, sometimes on the bacterial cell wall itself. These observations suggest a tightly linked biogeochemical system whereby microbial processes control mineral diagenesis at many scales of interaction, and the mineralogy and mineral chemistry influence microbial ecology. Only the macroscale interaction, however, is easily observable by standard geochemical methods, and documentation of the microscale interactions requires microscopic examination of microorganisms on mineral surfaces and the locally intense diagenetic reactions that result. Received, May 1999/Revised, October 1999/Accepted, October 1999     

The effect of Fe-oxidizing bacteria on Fe-silicate mineral dissolution

Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe²⁺ present in natural acid solutions and also may be able to utilize Fe²⁺ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe³⁺ from the available Fe in solution in microbial experiments (compared to no production of Fe³⁺ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.

Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe²⁺, Mg²⁺ and Fe³⁺ on fayalite dissolution. Neither Fe²⁺ nor Mg²⁺ had an effect on the dissolution reaction. However, Fe³⁺, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe³⁺ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe³⁺ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment.     

Assessment of groundwater chemistry in a coastal region (Kunsan, Korea) having complex contaminant sources: a stoichiometric approach

Groundwater chemistry in a coastal region (Kunsan, Korea) having complex contaminant sources was investigated. Water analysis data for 197 groundwater samples collected from the uniformly distributed sixty-six wells were used. Chemical analysis results indicate that groundwaters show wide concentration ranges in major inorganic ions, reflecting complex hydrochemical processes. Due to the complexity of groundwater chemistry, the samples were classified into four groups based on Cl and NO₃ concentrations and the processes controlling water chemistry were evaluated based on the reaction stoichiometry. The results explained the importance of mineral weathering, anthropogenic activities (nitrification and oxidation of organic matters), and Cl-salt inputs (seawater, deicer, NaCl, etc.) on groundwater chemistry. It was revealed that mineral dissolution is the major process controlling the water chemistry of the low Cl and NO₃ group (Group 1). Groundwaters high in NO₃ (Groups 2 and 4) are acidic in nature, and their chemistry is largely influenced by nitrification, oxidation of organic matters and mineral dissolution. In the case of chloride rich waters (Group 3), groundwater chemistry is highly influenced by mineral weathering and seawater intrusion associated with cation-exchange reactions.     

Dissolution kinetics of magnesite in acidic aqueous solution: a hydrothermal atomic force microscopy study assessing step kinetics and dissolution flux

Magnesite (104) dissolution kinetics were studied in acidic aqueous solutions (2.0 < pH < 4.2) at temperatures between 60 and 90°C by atomic force microscopy (AFM). Comparison of dissolution fluxes obtained by AFM and chemical methods revealed six to seven times larger dissolution fluxes obtained by chemical analysis. Corresponding empirical activation energies were found to be 74 ±22 kJ/mol and 41 ± 4 kJ/mol (at pH 4.2) for the AFM and chemical methods, respectively. The empirical reaction order with respect to proton concentration was 0.36 ± 0.13 and 0.47 ± 0.03 for AFM and chemical methods, respectively. These comparisons suggest that the two experimental measurement methods differ as a result of the different sampling length scales associated with the methods. Negligible changes in step dissolution velocity with changes in bulk pH were found, suggesting that the principal source of increasing dissolution flux with decreasing pH is an increase in step density. However, the observed stable step orientation, which is dependent on pH, suggests that more than one proton adsorption equilibrium should be used to describe the surface chemistry of magnesite in acidic solution.     

Inorganic species in geologic fluids: correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes

Correlations among experimentally determined standard partial molal thermodynamic properties of inorganic aqueous species at 25 degrees C and 1 bar allow estimates of these properties for numerous monatomic cations and anions, polyatomic anions, oxyanions, acid oxyanions, neutral oxy-acid species, dissolved gases, and hydroxide complexes of metal cations. Combined with correlations among parameters in the revised Helgeson-Kirkham-Flowers (HKF) equation of state (Shock et al., 1992), these estimates permit predictions of standard partial molal volumes, heat capacities, and entropies, as well as apparent standard partial molal enthalpies and Gibbs free energies of formation to 1000 degrees C and 5 kb for hundreds of inorganic aqueous species of interest in geochemistry. Data and parameters for more than 300 inorganic aqueous species are presented. Close agreement between calculated and experimentally determined equilibrium constants for acid dissociation reactions and cation hydrolysis reactions supports the generality and validity of these predictive methods. These data facilitate the calculation of the speciation of major, minor, and trace elements in hydrothermal and metamorphic fluids throughout most of the crust of the Earth.     

Thermodynamic and kinetic constraints on reaction rates among minerals and aqueous solutions. III. Activated complexes and the pH-dependence of the rates of feldspar,pyroxene, wollastonite,and olivine hydrolysis

The stoichiometries of activated complexes responsible for controlling the kinetics of mineral dissolution can be inferred from experimental rate data. Constraints are provided by adsorption equilibria, surface ion exchange reactions, and the pH-dependence of the steady-state rates of surface detachment. Adsorption equilibria may lead to accelerated or decelerated rates of hydrolysis due to formation of surface species. They may also result in pH-independent dissolution rates at low pH as a consequence of hydrogen ion surface saturation. Surface exchange reactions of H⁺ or H₃O⁺ for M(2) site cations in pyroxenes, Ca²⁺ in wollastonite, and alkali cations in feldspars go essentially to completion for dissolution in solutions that are appreciably undersaturated with respect to the reactant mineral. The rate of surface exchange is proportional to the fraction of exchangeable cations on the reacting surface, which leads to an integrated exponential relation for mass transfer as a function of time. The independence of detachment rates on the degree of surface exchange indicates approximately equivalent formation of activated complexes at both exchanged and unexchanged sites. The degree of hydration or protonation of activated complexes formed from surface species at active sites can be inferred from the dependence of the steady-state hydrolysis rates on pH.     

地下水中酸性污染羽的自然净化作用数值模拟研究

酸法地浸采铀对铀矿层的地下水环境有极大的破坏作用,当开采结束后将形成酸性地下水污染羽。为恢复含矿含水层的水质,必须采取有效的污染治理措施。自然净化是一种较经济的方法,但是必须对其有效性进行评价。本研究以某退役地浸铀矿采区含矿含水层为研究对象,采用反应溶质运移模拟方法来研究酸性污染羽在含水层中的自然净化作用。研究中使用PHT3D模型模拟污染羽的运移,模拟反应组分共12种、沉淀溶解矿物共6种,模拟时长为5a。模拟结果表明：酸性污染物进入地下水后,形成了由方解石、Al(OH)3（a）和 Fe(OH)3（a）反应所控制的pH缓冲区;随着酸性污染羽的向下游高pH值地下水区域移动,方解石溶解与石膏沉淀反应可使SO42-浓度产生明显下降,其他主要金属离子污染物也有明显的自净作用。     

Surface chemistry,etch pits and mineral-water reactions

The role of surface chemistry and defects in the formation of etch pits in minerals is analyzed. Elastic properties, surface free energies, and dislocation characteristics are incorporated into a theory which predicts the outcome of dislocation-controlled dissolution for a variety of free energies of reaction with aqueous solutions. The influence of the core regions of dislocations on the etch pit formation is also developed. The predictions of the analytic theory are compared with the situations to be expected in natural solutions. Finally, the powerful Monte Carlo method is introduced as a means to study mineral dissolution. The method enables a close scrutiny of the simplified analytic theory and significantly extends it.     

磷灰石固定水溶性铅离子研究进展

羟基磷灰石与天然磷灰石均能有效地固定水溶性铅离子,１ｇ羟基磷灰石或改性活性天然磷灰石除去水溶液中的铅离子量可以高达８００ｍｇ;其反应机理以磷灰石的溶解与铅的磷酸盐矿物的沉淀为主,伴有表面吸附作用。羟基磷灰石和改性活化天然磷灰石可用于含铅废水的处理,而性能良好的天然磷灰石在对铅污染水体、土壤及废弃物进行原地改良方面具有广阔的前景。     

Multisite surface reaction versus transport control during the hydrolysis of a complex oxide

Dissolution experiments of a tholeiite basalt glass carried out at different pH and T (up to 300°C) using a rotatingdisc apparatus show that, depending on pH and T, dissolution can be controlled by one of the following steps: (1) surface reaction; (2) transport of reactants in solution; and (3) mixed reaction. The activation energies of these different processes were found to be 60, 9 and 15–50 kJ mol⁻¹, respectively. Taking account of these results, it appears likely that surface reactions are not rate limiting for the hydrolysis of most crystalline silicate minerals in hydrothermal and metamorphic processes, and that caution should be exercised when predicting rate of reactions at high temperatures solely on the basis of activation energies measured at low temperatures.

Comparison of experimental and theoretical potentiometric titrations of the basalt glass and its constituent oxides indicates that the adsorption of H⁺ and OH⁻ ions at the basalt surface is metal cation specific and that the net adsorption can be predicted from the sole knowledge of the acidity constants of the network-forming constituent oxides. We found that in the acidic pH region dissolution is promoted by the adsorption of H⁺ on al and Fe surface sites while in the basic region, dissolution is promoted by the adsorption of OH⁻ on Si sites. The combination of the two distinct types of surface sites, Al and Fe on the one hand, and Si on the other hand, results in a dissolution rate minimum at a pH-value between the pH_zpc of the two groups of oxide components. Linear regressions with a slope n=3.8 are observed both in acid and alkaline solutions in logarithmic plots of the rate of dissolution vs. the surface charge. The value of n, which represents the number of protonation or hydroxylation steps prior to metal detachment, has been found equal to the mean valence of the network-forming metals.

Combining concepts of surface coordination chemistry with transition state theory afforded characterisation of the activated complexes involved in basalt dissolution processes. From the values obtained for the thermodynamic properties of activation for basalt dissolution it is assumed that the activated complexes formed during the H₂O-promoted dissolution of the basalt glass are more tightly bonded than those formed during H⁺- or OH⁻-promoted dissolution.     

Metastable phenomena on calcite {101̄4} surfaces growing from Sr2+–Ca2+–CO32− aqueous solutions

In situ atomic force microscopy (AFM) experiments, scanning electron microscopy (SEM) imaging and composition analysis, and X-ray diffraction have provided information about the growth, dissolution and transformation processes promoted by Sr²⁺–Ca²⁺–CO₃²⁻ aqueous solutions in contact with calcite {101̄4} surfaces. Experiments have shown a wide variety of surface phenomena, such as the influence of the Sr-bearing newly-formed surface on the subsequent growth (template effect), the growth and subsequent dissolution of surfaces and the nucleation of secondary three-dimensional nuclei on calcite surfaces. These phenomena reveal the metastability of the crystallisation system and are a consequence of the interplay between thermodynamics (the relative stability of the two calcite and aragonite structure solid solutions that can be formed), supersaturation of the aqueous solution with respect to the two possible solid solutions, and the crystallographic control of the surfaces on cation incorporation.     

Development of reaction models for ground-water systems

Methods are described for developing geochemical reaction models from the observed chemical compositions of ground water along a hydrologic flow path. The roles of thermodynamic speciation programs, mass balance calculations, and reaction-path simulations in developing and testing reaction models are contrasted. Electron transfer is included in the mass balance equations to properly account for redox reactions in ground water. The mass balance calculations determine net mass transfer models which must be checked against the thermodynamic calculations of speciation and reaction-path programs. Although reaction-path simulations of ground-water chemistry are thermodynamically valid, they must be checked against the net mass transfer defined by the mass balance calculations. An example is given testing multiple reaction hypotheses along a flow path in the Floridan aquifer where several reaction models are eliminated. Use of carbon and sulfur isotopic data with mass balance calculations indicates a net reaction of incongruent dissolution of dolomite (dolomite dissolution with calcite precipitation) driven irreversibly by gypsum dissolution, accompanied by minor sulfate reduction, ferric hydroxide dissolution, and pyrite precipitation in central Florida. Along the flow path, the aquifer appears to be open to CO₂ initially, and open to organic carbon at more distant points down gradient.