Theoretical approach to evaluating plagioclase dissolution mechanisms

The more rapid dissolution of Ca-rich feldspars relative to Na, K-rich feldspars has been attributed to the preferential leaching of Al deep within the feldspar structure. Evidence from surface microanalysis (e.g., Hellmann et al., 2003), however, shows that preferential dissolution of Al is confined to the top layers of the feldspar lattice and that the amorphous surface layer most likely results from precipitation versus dissolution. It is thus critical to examine the extent of preferential Al removal. Here we present a theoretical study of plagioclase dissolution behavior using parameterized Monte Carlo simulations. Two different dissolution mechanisms, a mechanism involving preferential leaching of Al and an interfacial dissolution-reprecipitation mechanism, are tested using compositions representing the entire plagioclase solid solution series. Our modeling results indicate that under the control of the preferential Al leaching mechanism, the influence of (Al, Si) disorder on the dissolution rate is significant. At a fixed composition, an increase in the degree of (Al, Si) disorder yields an increased dissolution rate, with an 8-fold increase in dissolution rate observed for highly disordered albite (An₀) compared to low albite. Increasing anorthite content tends to decrease the variation in the dissolution rate due to disorder. The difference in the dissolution rate of 293 tested oligoclase configurations with a composition of An₂₀ is 3-fold, and the difference is reduced to 2-fold among 107 andesine configurations of An₃₀. Furthermore, feldspar configurations with completely disordered (Al, Si) distributions yield a consistent log-linear dependence of dissolution rate on the anorthite content (An), while other feldspar configurations with modest degrees of (Al, Si) disorder exhibit rates less than this trend. In contrast, when Al removal is confined to the top surface layers, a variety of feldspar configurations with different (Al, Si) disorder but a single fixed composition have similar dissolution rates; and the dissolution rate of Ca-rich feldspars departs positively from its log-linear relationship with anorthite content. This departure occurs around An₈₀ and is in good agreement with previous experimental studies. Subsequent modeling results of aluminum inhibition, ΔG dependence, and formation of altered surface layers in the framework of the interfacial dissolution-reprecipitation mechanism are all comparable with experimental investigations, and these results suggest that an interfacial dissolution-reprecipitation mechanism governs the dissolution of plagioclase feldspars.     

Dissolution kinetics of diopside as a function of solution saturation state: Macroscopic measurements and implications for modeling of geological storage of CO2

Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔG_r) in a continuously stirred flow-through reactor at 90 °C and pH_90 °C = 5.05. The overall relation between r and ΔG_r was determined over a free energy range of −130.9 < ΔG_r < −47.0 kJ mo1⁻¹. The data define a highly non-linear, sigmoidal relation between r and ΔG_r. At far-from-equilibrium conditions (ΔG_r ? −76.2 kJ mo1⁻¹), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔG_r. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔG_r region defined by −76.2 < ΔG_r ? −61.5 kJ mo1⁻¹. Dissolution closer to equilibrium (ΔG_r > −61.5 kJ mo1⁻¹) is characterised by a much weaker inverse dependence of the rates on ΔG_r. Modeling the experimental r-ΔG_r data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔG_r relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO₂ over long time spans. In order to take into account the actual experimental r-ΔG_r relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO₂ interactions performed with classical geochemical codes should be evaluated with great caution.     

Does reactive surface area depend on grain size? Results from pH 3, 25 °C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 μm were dissolved in pH 3, HCl at 25 °C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol_feldspar g⁻¹ s⁻¹. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10⁻¹² mol_biotite m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10⁻¹² mol_biotite g⁻¹ s⁻¹. For all normalising terms rates varied significantly (p ? 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over which they would change significantly.     

Reaction pathways for quartz dissolution determined by statistical and graphical analysis of macroscopic experimental data

In light of recent work on the reactivity of specific sites on large (hydr)oxo-molecules and the evolution of surface topography during dissolution, we examined the ability to extract molecular-scale reaction pathways from macroscopic dissolution and surface charge measurements of powdered minerals using an approach that involved regression of multiple datasets and statistical graphical analysis of model fits. The test case (far-from-equilibrium quartz dissolution from 25 to 300 °C, pH 1-12, in solutions with [Na⁺] ? 0.5 M) avoids the objections to this goal raised in these recent studies. The strategy was used to assess several mechanistic rate laws, and was more powerful in distinguishing between models than the statistical approaches employed previously. The best-fit model included three mechanisms—two involving hydrolysis of Si centers by H₂O next to neutral (>Si-OH⁰) and deprotonated (>Si-O⁻) silanol groups, and one involving hydrolysis of Si centers by OH⁻. The model rate law is

     

In situ atomic force microscopy measurements of biotite basal plane reactivity in the presence of oxalic acid

We have used a direct imaging technique, in situ atomic force microscopy (AFM), to observe the dissolution of the basal biotite surface by oxalic acid over a range of temperatures close to ambient conditions, using a specially designed AFM liquid cell and non-invasive intermittent contact mode of operation. From the 3-dimensional nanometre-resolution data sets, we observe a process characterised by the slow formation of shallow etch pits in the (0 0 1) surface and fast growth of etch pits from the resulting steps, which represent proxies for the {h k 0} surface. Measurements of dissolution rates as a function of temperature allow a determination of an apparent activation energy (E_a,app) for the process, via mass-loss calculations from image analysis. We obtain a value of E_a,app = 49 ± 2 kJ mol⁻¹, which is consistent with separate calculations based on planar area etch pit growth, and measurements of etch pit perimeters, indicating that this value of E_a,app is representative of {h k 0} surface dissolution. The measurement of etch pit perimeters also enables an estimation of apparent activation energy as a function of step density indicating substantially higher apparent activation energy, up to E_a,app = 140 kJ mol⁻¹, on extrapolation towards a pristine surface with no defects. We suggest that this higher value of E_a,app represents the slow formation of etch pits into the (0 0 1) surface.     

The effect of crystallinity on dissolution rates and CO2 consumption capacity of silicates

Comparison of measured far-from-equilibrium dissolution rates of natural glasses and silicate minerals at 25 °C and pH 4 reveals the systematic effects of crystallinity and elemental composition on these rates. Rates for both minerals and glasses decrease with increasing Si:O ratio, but glass dissolution rates are faster than corresponding mineral rates. The difference between glass and mineral dissolution rates increases with increasing Si:O ratio; ultra-mafic glasses (Si:O ? 0.28) dissolve at similar rates as correspondingly compositioned minerals, but Si-rich glasses such as rhyolite (Si:O ∼ 0.40) dissolve ?1.6 orders of magnitude faster than corresponding minerals. This behaviour is interpreted to stem from the effect of Si-O polymerisation on silicate dissolution rates. The rate controlling step of dissolution for silicate minerals and glasses for which Si:O > 0.28 is the breaking of Si-O bonds. Owing to rapid quenching, natural glasses will exhibit less polymerisation and less ordering of Si-O bonds than minerals, making them less resistant to dissolution. Dissolution rates summarized in this study are used to determine the Ca release rates of natural rocks at far-from-equilibrium conditions, which in turn are used to estimate their CO₂ consumption capacity. Results indicate that Ca release rates for glasses are faster than those of corresponding rocks. This difference is, however, significantly less than the corresponding difference between glass and mineral bulk dissolution rates. This is due to the presence of Ca in relatively reactive minerals. In both cases, Ca release rates increase by ∼two orders of magnitude from high to low Si:O ratios (e.g., from granite to gabbro or from rhyolitic to basaltic glass), illustrating the important role of Si-poor silicates in the long-term global CO₂ cycle.     

Probing interfacial reactions with X-ray reflectivity and X-ray reflection interface microscopy: Influence of NaCl on the dissolution of orthoclase at pOH 2 and 85 °C

The role of electrolyte ions in the dissolution of orthoclase (0 0 1) in 0.01 m NaOH (pOH ∼ 2) at 84 ± 1 °C is studied using a combination of in-situ X-ray reflectivity (XR) and ex-situ X-ray reflection interface microscopy (XRIM). The real-time XR measurements show characteristic intensity oscillations as a function of time indicative of the successive removal of individual layers. The dissolution rate in 0.01 m NaOH increases approximately linearly with increasing NaCl concentration up to 2 m NaCl. XRIM measurements of the lateral interfacial topography/structure were made for unreacted surfaces and those reacted in 0.01 m NaOH/1.0 m NaCl solution for 15, 30 and 58 min. The XRIM images reveal that the dissolution reaction leads to the formation of micron-scale regions that are characterized by intrinsically lower reflectivity than the unreacted regions, and appears to be nucleated at steps and defect sites. The reflectivity signal from these reacted regions in the presence of NaCl in solution is significantly lower than that calculated from an idealized layer-by-layer dissolution process, as observed previously in 0.1 m NaOH in the absence of added electrolyte. This difference suggests that dissolved NaCl results in a higher terrace reactivity leading to a more three-dimensional process, consistent with the real-time XR measurements. These observations demonstrate the feasibility of XRIM to gain new insights into processes that control interfacial reactivity, specifically the role of electrolytes in feldspar dissolution at alkaline conditions.     

Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10⁻⁶ mol m⁻² h⁻¹. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H₂S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.     

Dissolution of basalts and peridotite in seawater, in the presence of ligands, and CO2: Implications for mineral sequestration of carbon dioxide

Steady-state silica release rates (r_Si) from basaltic glass and crystalline basalt of similar chemical composition as well as dunitic peridotite have been determined in far-from-equilibrium dissolution experiments at 25 °C and pH 3.6 in (a) artificial seawater solutions under 4 bar pCO₂, (b) varying ionic strength solutions, including acidified natural seawater, (c) acidified natural seawater of varying fluoride concentrations, and (d) acidified natural seawater of varying dissolved organic carbon concentrations. Glassy and crystalline basalts exhibit similar r_Si in solutions of varying ionic strength and cation concentrations. Rates of all solids are found to increase by 0.3-0.5 log units in the presence of a pCO₂ of 4 bar compared to CO₂ pressure of the atmosphere. At atmospheric CO₂ pressure, basaltic glass dissolution rates were most increased by the addition of fluoride to solution whereas crystalline basalt rates were most enhanced by the addition of organic ligands. In contrast, peridotite does not display any significant ligand-promoting effect, either in the presence of fluoride or organic acids. Most significantly, Si release rates from the basalts are found to be not more than 0.6 log units slower than corresponding rates of the peridotite at all conditions considered in this study. This difference becomes negligible in seawater suggesting that for the purposes of in-situ mineral sequestration, CO₂-charged seawater injected into basalt might be nearly as efficient as injection into peridotite.     

Inner-Helmholtz potential development at the hematite (α-Fe2O3) (0 0 1) surface

Electric potentials of the (0 0 1) surface of hematite were measured as a function of pH and ionic strength in solutions of sodium nitrate and oxalic acid using the single-crystal electrode approach. The surface is predominantly charge-neutral in the pH 4-14 range, and develops a positive surface potential below pH 4 due to protonation of μ-OH⁰ sites (pK_1,1,0,int = −1.32). This site is resilient to deprotonation up to at least pH 14 (−pK_−1,1,0,int ? 19). The associated Stern layer capacitance of 0.31-0.73 F/m² is smaller than typical values of powders, and possibly arises from a lower degree of surface solvation. Acid-promoted dissolution under elevated concentrations of HNO₃ etches the (0 0 1) surface, yielding a convoluted surface populated by sites. The resulting surface potential was therefore larger under these conditions than in the absence of dissolution. Oxalate ions also promoted (0 0 1) dissolution. Associated electric potentials were strongly negative, with values as large as −0.5 V, possibly from metal-bonded interactions with oxalate. The hematite surface can also acquire negative potentials in the pH 7-11 range due to surface complexation and/or precipitation of iron species (0.0038 Fe/nm²) produced from acidic conditions. Oxalate-bearing systems also result in negative potentials in the same pH range, and may include ferric-oxalate surface complexes and/or surface precipitates. All measurements can be modeled by a thermodynamic model that can be used to predict inner-Helmholtz potentials of hematite surfaces.     

Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar

Here we report on an experimental investigation of the relation between the dissolution rate of albite feldspar and the Gibbs free energy of reaction, ΔG_r. The experiments were carried out in a continuously stirred flow-through reactor at 150 °C and pH_(150 °C) 9.2. The dissolution rates R are based on steady-state Si and Al concentrations and sample mass loss. The overall relation between ΔG_r and R was determined over a free energy range of −150 < ΔG_r < −15.6 kJ mol⁻¹. The data define a continuous and highly non-linear, sigmoidal relation between R and ΔG_r that is characterized by three distinct free energy regions. The region furthest from equilibrium, delimited by −150 < ΔG_r < −70 kJ mol⁻¹, represents an extensive dissolution rate plateau with an average rate . In this free energy range the rates of dissolution are constant and independent of ΔG_r, as well as [Si] and [Al]. The free energy range delimited by −70 ? ΔG_r ? −25 kJ mol⁻¹, referred to as the ‘transition equilibrium’ region, is characterized by a sharp decrease in dissolution rates with increasing ΔG_r, indicating a very strong inverse dependence of the rates on free energy. Dissolution nearest equilibrium, defined by ΔG_r > −25 kJ mol⁻¹, represents the ‘near equilibrium’ region where the rates decrease as chemical equilibrium is approached, but with a much weaker dependence on ΔG_r. The lowest rate measured in this study, R = 6.2 × 10⁻¹¹ mol m⁻² s⁻¹ at ΔG_r = −16.3 kJ mol⁻¹, is more than two orders of magnitude slower than the plateau rate. The data have been fitted to a rate equation (adapted from Burch et al. [Burch, T. E., Nagy, K. L., Lasaga, A. C., 1993. Free energy dependence of albite dissolution kinetics at 80 °C and pH 8.8. Chem. Geol.105, 137-162]) that represents the sum of two parallel reactions

R=k₁[1-exp(-ng^m₁)]+k₂[1-exp(-g)]^m₂,     

Sorption and catalytic oxidation of Fe(II) at the surface of calcite

The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO₃Fe⁺ and >CO₃FeCO₃H⁰. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t_1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t_1/2 = 41 ± 1 min and t_1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO₃FeCO₃H⁰, for which the species specific rate constant was estimated.     

Molecular dynamics simulations of the orthoclase (0 0 1)- and (0 1 0)-water interfaces

Molecular dynamics simulations of water in contact with the (0 0 1) and (0 1 0) surfaces of orthoclase (KAlSi₃O₈) were carried out to investigate the structure and dynamics of the feldspar-water interface, contrast the intrinsic structural properties of the two surfaces, and provide a basis for future work on the diffusion of ions and molecules in microscopic mineral fractures. Electron density profiles were computed from the molecular dynamics trajectories and compared with those derived experimentally from high-resolution X-ray reflectivity measurements by Fenter and co-workers [Fenter P., Cheng L., Park C., Zhang H. and Sturchio N. C. (2003a) Structure of the orthoclase (0 0 1)- and (0 1 0)-water interfaces by high-resolution X-ray reflectivity. Geochim. Cosmochim. Acta67, 4267-4275]. For each surface, three scenarios were considered whereby the interfacial species is potassium, water, or a hydronium ion. Excellent agreement was obtained for the (0 0 1) surface when potassium is the predominant interfacial species; however, some discrepancies in the position of the interfacial peaks were obtained for the (0 1 0) surface. The two surfaces showed similarities in the extent of water ordering at the interface, the activation energies for water and potassium desorption, and the adsorption localization of interfacial species. However, there are also important differences between the two surfaces in the coordination of a given adsorbed species, adsorption site densities, and the propensity for water molecules in surface cavities and those in the first hydration layer to coordinate to surface bridging oxygen atoms. These differences may have implications for the extent of dissolution in the low-pH regime since hydrolysis of Si(Al)OSi(Al) bonds is a major dissolution mechanism.     

An experimental study of the dissolution mechanism and rates of muscovite

Steady-state muscovite dissolution rates have been measured at temperatures from 60 to 201 °C and 1 ? pH ? 10.3 as a function of reactive solution K, Si, and Al concentration. The pegmatitic muscovite used in these experiments has a composition consistent with (Na_0.09, K_0.86)Fe_0.05Al_2.92Si_3.05O₁₀(OH_1.95, F_0.06). All experiments were performed in titanium mixed-flow reactors. All experiments were performed at far-from-equilibrium conditions with respect to muscovite. All reactive solutions were undersaturated with respect to secondary product phases other than for some experiments which were supersaturated with respect to bohemite and diaspore; steady-state dissolution was stoichiometric for all experiments that were undersaturated with respect to these phases.The variation of rates with reactive solution composition depends on the solution pH. At pH ? 7 rates were found to decrease significantly with increasing reactive fluid Al activity but be independent of aqueous SiO₂ activity. pH < 7 rates measured in the present study from 60 to 175 °C are consistent with

     

Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions

A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R_p) to the gross forward precipitation rate (R_f), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R_p has been experimentally measured under varying conditions, but the magnitude of R_f is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R_f can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R_b or k_b), since at equilibrium R_f = R_b, and R_p = 0. Hence it can be inferred that R_f ≈ R_p + R_b. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R_p (=R_f − R_b) ? R_b. For precipitation rates high enough that R_p ? R_b, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R_p ≈ R_b for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R_f for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R_p. Allowing R_b to vary as , consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R_b is constant. This model can account for most of the experimental data in the literature on the dependence of ⁴⁴Ca/⁴⁰Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for ¹⁸O/¹⁶O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R_b on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.     

Investigation of acidic dissolution of mixed clays between pH 1.0 and −3.0 using Si and Al X-ray absorption near edge structure

Although widely investigated in relation to acid mine drainage systems at pH > 1.0, we know little about the impact of sulfuric acid (H₂SO₄) on the geochemistry and mineralogy of clays at pH < 1.0 (including negative pH values). Thus, laboratory batch experiments were conducted on three mixed clay samples with different mass ratios of phyllosilicates (smectite, illite, and kaolinite) to investigate the impact of H₂SO₄ from pH 1.0 to −3.0 for exposure periods of 14, 90, 180, and 365 days. Si and Al K- and L_2,3-edge X-ray absorption near edge structure (XANES) spectroscopy were employed on these samples to determine the chemical and structural changes that occur during acidic dissolution of phyllosilicates that cannot be distinguished using X-ray diffraction analyses. A series of silicate, phyllosilicate, and Al-bearing standard compounds were also studied to provide an explanation for the observed changes in the clay samples. The Si XANES results indicated the preferential dissolution of the phyllosilicates (pH ? 1.0, t ? 14 d), the persistence of quartz even at pH ? −3.0 and t ? 365 d, and the formation of an amorphous silica-like phase that was confined to the surface layer of the altered clay samples at pH ? 0.0 and t ? 90 d). Al XANES results demonstrated dissolution of Al-octahedral layers (pH ? 1.0, t ? 14 d), the persistence of four-fold relative to six-fold coordinated Al, and the precipitation of an Al-SO₄-rich phase (pH ? −1.0, t ? 90 d). An existing conceptual model of phyllosilicate dissolution under extremely acidic conditions was modified to include the results of this study.     

In situ Atomic Force Microscopy study of dissolution of the barite (0 0 1) surface in water at 30 °C

The dissolution behavior of the barite (0 0 1) surface in pure water at 30 °C was investigated using in situ Atomic Force Microscopy (AFM), to better understand the dissolution mechanism and the microtopographical changes that occur during the dissolution, such as steps and etch pits. The dissolution of the barite (0 0 1) surface started with the slow retreat of steps, after which, about 60 min later, the <hk0> steps of one unit cell layer or multi-layers became two-step fronts (fast “f” and slow “s” steps) with a half-unit cell layer showing different retreat rates. The “f” step had a fast retreat rate (≈(14 ± 1) × 10⁻² nm/s) and tended to have a jagged step edge, whereas the “s” step (≈(1.8 ± 0.1) × 10⁻² nm/s) had a relatively straight front. The formation of the “f” steps led to the formation of a new one-layer step, where the front of the “s” step was overtaken by that of the immediate underlying “f” step. The “f” steps also led to the decrease of the <hk0> steps and the increase in the percentage of stable steps parallel to the [0 1 0] direction during the dissolution.Etch pits, which could be observed after about 90 min, were of three types: triangular etch pits with a depth of a half-unit cell, shallow etch pits, and deep etch pits. The triangular etch pits were bounded by the step edges parallel to [0 1 0], [1 2 0], and [] and had opposite orientations in the upper half and lower half layers. Shallow etch pits that had a depth of two or more half-unit cell layers had any two consecutive pits pointing in the opposite direction of each other. The triangular etch pit appeared to grow by simultaneously removal of a row of ions parallel to each direction from the three step edges. At first, deep etch pits were elongated in the [0 1 0] direction with a curved outline and then gradually developed to an angular form bounded by the {1 0 0}, {3 1 0}, and (0 0 1) faces. The retreat rate of the (0 0 1) face was much slower than those of the {1 0 0} and {3 1 0} and tended to separate into two rates ((0.13 ± 0.01) × 10⁻² nm/s for the deep etch pits derived from a screw dislocation and (0.07 ± 0.01) × 10⁻² nm/s for those from other line defects).The changes in the dissolution rate of a barite (0 0 1) surface during the dissolution were estimated using the retreat rates and densities of the various steps as well as the growth rates, density, and areas of the lateral faces of the deep etch pits that were obtained from this AFM analysis. Our results showed that the dissolution rate of the barite (0 0 1) surface gradually increased and approached the bulk dissolution rate because of the change in the main factor determining the dissolution rate from the density of the steps to the growth and the density of the deep etch pits on the surface.     

Interaction of gypsum with lead in aqueous solutions

Sorption processes on mineral surfaces are a critical factor in controlling the distribution and accumulation of potentially harmful metals in the environment. This work investigates the effectiveness of gypsum (CaSO₄⋅2H₂O) to sequester Pb. The interaction of gypsum fragments with Pb-bearing solutions (10, 100 and 1000 mg/L) was monitored by performing macroscopic batch-type experiments conducted at room temperature. The aqueous phase composition was periodically determined by Atomic Absorption Spectrometry (AAS), Ion Chromatography (IC) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP–OES). Regardless of the [Pb_aq]_initial, a [Pb_aq]_final < 4 mg/L was always reached. The uptake process was fast (t < 1 h) for [Pb_aq]_initial ? 100 mg/L and significantly slower (t > 1 week) for [Pb_aq]_initial = 10 mg/L. Speciation calculations revealed that after a long time of interaction (1 month), all the solutions reached equilibrium with respect to both gypsum and anglesite. For [Pb_aq]_initial ? 100 mg/L, sorption takes place mainly via the rapid dissolution of gypsum and the simultaneous formation of anglesite both on the gypsum surface and in the bulk solution. In the case of [Pb_aq]_initial = 10 mg/L, no anglesite precipitation was observed, but surface spectroscopy (proton Rutherford Backscattering Spectroscopy, p-RBS) confirmed the formation of Pb-bearing surface layers on the (0 1 0) gypsum surface in this case also. This study shows that the surface of gypsum can play an important role in the attenuation of Pb in contaminated waters.     

Dissolution of illite in saline-acidic solutions at 25 °C

The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K_1.38Na_0.05)(Al_2.87Mg_0.46Fe³⁺_0.39Fe²⁺_0.28Ti_0.07)[Si_7.02Al_0.98]O₂₀(OH)₄ was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H₂SO₄) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K⁺ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na⁺ from the solution and K⁺ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower R_Al (dissolution rate calculated from steady state Al release) than R_Si (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.