Effect of pH and organic ligands on the kinetics of smectite dissolution at 25 °C

Forward dissolution rates of Na-Montmorillonite (Wyoming) SWy-2 smectite (Ca_0.06Na_0.56)[Al_3.08Fe(III)_0.38Mg_0.54] [Si_7.93 Al_0.07]O₂₀(OH)₄ were measured at 25 °C in a mixed-flow reactor equipped with interior dialysis compartment (6-8 kDa membrane) as a function of pH (1-12), dissolved carbonate (0.5-10 mM), phosphate (10⁻⁵ to 0.03 M), and nine organic ligands (acetate, oxalate, citrate, EDTA, alginate, glucuronic acid, 3,4-dihydroxybenzoic acid, gluconate, and glucosamine) in the concentration range from 10⁻⁵ to 0.03 M. In organic-free solutions, the Si-based rates decrease with increasing pH at 1 ? pH ? 8 with a slope close to −0.2. At 9 ? pH ? 12, the Si-based rates increase with a slope of ∼0.3. In contrast, non-stoichiometric Mg release weakly depends on pH at 1 ? pH ? 12 and decreases with increasing pH. The empirical expression describing Si-release rates [R, mol/cm²/s] obtained in the present study at 25 °C, I = 0.01 M is given by

     

An experimental study of magnesite dissolution rates at neutral to alkaline conditions and 150 and 200 °C as a function of pH, total dissolved carbonate concentration, and chemical affinity

Steady-state magnesite dissolution rates were measured in mixed-flow reactors at 150 and 200 °C and 4.6 < pH < 8.4, as a function of ionic strength (0.001 M ? I ? 1 M), total dissolved carbonate concentration (10⁻⁴ M < ΣCO₂ < 0.1 M), and distance from equilibrium. Rates were found to increase with increasing ionic strength, but decrease with increasing temperature from 150 to 200 °C, pH, and aqueous CO₃²⁻ activity. Measured rates were interpreted using the surface complexation model developed by Pokrovsky et al. (1999a) in conjunction with transition state theory (Eyring, 1935). Within this formalism, magnesite dissolution rates are found to be consistent with

     

Solubility of plutonium(VI) carbonate in saline solutions

Among the plutonium oxidation states found to form in the environment, mobile plutonium(VI) can exist under oxidizing conditions and in waters with high chloride content due to radiolysis effects. We are investigating the solubility and speciation of plutonium(VI) carbonate under conditions relevant to natural waters and brines such as those found near some geologic radioactive waste repositories. The solid Pu(VI) phase PuO₂CO₃(s) was prepared and its solubility was measured in NaCl and NaClO₄ solutions in a CO₂ atmosphere as a function of pH and ionic strength (0.1-5.6 m). The concentration of soluble plutonium in solution was calculated from spectroscopic data and liquid scintillation counting. Spectroscopic measurements also revealed the plutonium oxidation state. The apparent solubility product of PuO₂CO₃(s) was determined at selected electrolyte concentrations to be, log K_s,0 = −13.95 ± 0.07 (0.1 m NaCl), log K_s,0 = −14.07 ± 0.13 (5.6 m NaCl), and log K_s,0 = −15.26 ± 0.11 (5.6 m NaClO₄). Specific ion interaction theory was used to calculate the solubility product at zero ionic strength, .     

Mechanisms of equilibrium and kinetic oxygen isotope effects in synthetic aragonite at 25 °C

Aragonite was precipitated in the laboratory at 25 °C in isotopic equilibrium with Na-Ca-Mg-Cl-CO₃ solutions at two different pH values (i.e., pH = ∼8.2 and ∼10.8) by the constant addition method. On the basis of the oxygen isotope composition of the aragonite precipitates, it was demonstrated that the equilibrium aragonite-water fractionation factor is independent of the pH of the parent solution and equal to:

1000lnα_{(aragonite-H2O)}=29.12±0.09     

Sr/Ca and Ca/Ca fractionation during inorganic calcite formation: I. Sr incorporation

Partitioning of strontium during spontaneous calcite formation was experimentally studied using an advanced CO₂-diffusion technique. Results at different precipitation rates and T = 5, 25, and 40 °C show that at constant temperature Sr incorporation into calcite is controlled by the precipitation rate (R in μmol/m²/h) according to the individual expressions

     

Dissolution kinetics of fosteritic olivine at 90-150 °C including effects of the presence of CO2

The steady state dissolution rate of San Carlos olivine [Mg_1.82Fe_0.18 SiO₄] in dilute aqueous solutions was measured at 90, 120, and 150 °C and pH ranging from 2 to 12.5. Dissolution experiments were performed in a stirred flow-through reactor, under either a nitrogen or carbon dioxide atmosphere at pressures between 15 and 180 bar. Low pH values were achieved either by adding HCl to the solution or by pressurising the reactor with CO₂, whereas high pH values were achieved by adding LiOH. Dissolution was stoichiometric for almost all experiments except for a brief start-up period. At all three temperatures, the dissolution rate decreases with increasing pH at acidic to neutral conditions with a slope of close to 0.5; by regressing all data for 2 ? pH ? 8.5 and 90 °C ? T ? 150 °C together, the following correlation for the dissolution rate in CO₂-free solutions is obtained:

     

Zinc complexation in aqueous sulfide solutions: Determination of the stoichiometry and stability of complexes via ZnS(cr) solubility measurements at 100 °C and 150 bars

The solubility of ZnS_(cr) was measured at 100 °C, 150 bars in sulfide solutions as a function of sulfur concentration (m(S_total) = 0.02-0.15) and acidity (pH_t = 2-11). The experiments were conducted using a Ti flow-through hydrothermal reactor enabling the sampling of large volumes of solutions at experimental conditions, with the subsequent concentration and determination of trace quantities of Zn. Prior to the experiments, a long-term in situ conditioning of the solid phase was performed in order to attain the reproducible Zn concentrations (i.e. solubilities). The ZnS_(cr) solubility product was monitored in the course of the experiment. The following species were found to account for Zn speciation in solution: Zn²⁺ (pH_t < 3), (pH_t 3-4.5), (pH_t 5-8), and ZnS(HS)⁻ (pH_t > 8) (pH_t predominance regions are given for m(S_total) = 0.1). Solubility data collected in this study at pH_t > 3 were combined with the ZnS_(cr) solubility product determined at lower pH to yield the following equilibrium constants (t = 100 °C, P = 150 bars):

     

The solubility of FeS

The solubility of FeS_m, synthetic nanoparticulate mackinawite, in aqueous solution was measured at 23 °C from pH 3-10 using an in situ precipitation and dissolution procedure and the solution species was investigated voltammetrically. The solubility is described by a pH-dependent reaction and a pH-independent reaction. The pH-dependent dissolution reaction can be described by

FeS_m+2H⁺→Fe²⁺+H₂S     

Calcite dissolution kinetics in Na-Ca-Mg-Cl brines

Sedimentary basins can contain close to 20% by volume of pore fluids commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of migration, dispersive mixing, or anthropogenic injection of CO₂. This study measured calcite dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (50-200 g L⁻¹ TDS). The dissolution rate dependency on brine composition, pCO₂ (0.1-1 bar), and temperature (25.0-82.5 °C) was modeled using the empirical rate equation

R=k(1-Ω)ⁿ     

Precipitation and mixing properties of the “disordered” (Mn,Ca)CO3 solid solution

The enthalpy of mixing of the calcite-rhodochrosite (Ca,Mn)CO₃ solid solution was determined at 25 °C from calorimetric measurements of the enthalpy of precipitation of solids with different compositions. A detailed study of the broadening of powder X-ray diffraction peaks shows that most of the precipitates are compositionally homogeneous. All the experimental enthalpy of mixing (ΔH^m) values are positive and fit reasonably well (R² = 0.86) to a Guggenheim function of three terms:

     

Dissolution kinetics of synthetic Na-smectite. An integrated experimental approach

The effect of pH and Gibbs energy on the dissolution rate of a synthetic Na-montmorillonite was investigated by means of flow-through experiments at 25 and 80 °C at pH of 7 and 9. The dissolution reaction took place stoichiometrically at 80 °C, whereas at 25 °C preferential release of Mg over Si and Al was observed. The TEM-EDX analyses (transmission electronic microscopy with quantitative chemical analysis) of the dissolved synthetic phase at 25 °C showed the presence of newly formed Si-rich phases, which accounts for the Si deficit. At low temperature, depletion of Si concentration was attributed to incongruent clay dissolution with the formation of detached Si tetrahedral sheets (i.e., alteration product) whereas the Al behaviour remains uncertain (e.g., possible incorporation into Al-rich phases). Hence, steady-state rates were based on the release of Mg. Ex situ AFM measurements were used to investigate the variations in reactive surface area. Accordingly, steady-state rates were normalized to the initial edge surface area (11.2 m² g⁻¹) and used to propose the dissolution rate law for the dissolution reactions as a function of ΔG_r at 25 °C and pH∼9:

     

The activity coefficients of Fe(III) hydroxide complexes in NaCl and NaClO4 solutions

The osmotic coefficients of FeCl₃ at 25 °C from 0.15 to 1.7 m [Rumyantsev et al., Z. Phys. Chem., 218, 1089-1127, 2004] have been used to determine the Pitzer parameters (β⁽⁰⁾, β⁽¹⁾ and C^?) for FeCl₃. Since the differences in the Pitzer coefficients of rare earths in NaCl and NaClO₄ are small, the values of Fe(ClO₄)₃ have been estimated using the differences between La(ClO₄)₃ and LaCl₃. The Pitzer coefficients for FeCl₃ combined with enthalpy and heat capacity data for the rare earths can be used to estimate the activity coefficients of Fe³⁺ in NaCl over a wide range of temperatures (0 to 50 °C) and ionic strength (0 to 6 m).The activity coefficients of Fe³⁺ in NaCl and NaClO₄ solutions have been used to determine the activity coefficients of Fe(OH)²⁺ in these solutions from the measured first hydrolysis constants of Fe³⁺ [Byrne et al., Mar. Chem., 97, 34-48, 2005]. The activity coefficients of , Fe(OH)₃ and from 0 to 50 °C have also been determined from the solubility measurements of Fe(III) in NaCl solutions [Liu and Millero, Geochim. Cosmochim Acta, 63, 3487-3497, 1999]. These activity coefficients have been fitted to the Pitzer equations. These results can be used to estimate the speciation of Fe(III) with OH⁻ in natural waters with high concentrations of NaCl from 0 to 50 °C.     

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,     

Water speciation and diffusion in haploandesitic melts at 743-873 K and 100 MPa

Water is an important volatile component in andesitic eruptions and deep-seated andesitic magma chambers. We report an investigation of H₂O speciation and diffusion by dehydrating haploandesitic melts containing ?2.5 wt.% water at 743-873 K and 100 MPa in cold-seal pressure vessels. FTIR microspectroscopy was utilized to measure species [molecular H₂O (H₂O_m) and hydroxyl group (OH)] and total H₂O (H₂O_t) concentration profiles on the quenched glasses from the dehydration experiments. The equilibrium constant of the H₂O speciation reaction H₂O_m+O?2OH, K = (X_OH)²/(X_H2OmX_O) where X means mole fraction on a single oxygen basis, in this Fe-free andesite varies with temperature as ln K = 1.547-2453/T where T is in K. Comparison with previous speciation data on rhyolitic and dacitic melts indicates that, for a given water concentration, Fe-free andesitic melt contains more hydroxyl groups. Water diffusivity at the experimental conditions increases rapidly with H₂O concentration, contrary to previous H₂O diffusion data in an andesitic melt at 1608-1848 K. The diffusion profiles are consistent with the model that molecular H₂O is the diffusion species. Based on the above speciation model, H₂O_m and H₂O_t diffusivity (in m²/s) in haploandesite at 743-873 K, 100 MPa, and H₂O_t ? 2.5 wt.% can be formulated as

     

Solubilities of corundum, wollastonite and quartz in H2O-NaCl solutions at 800 °C and 10 kbar: Interaction of simple minerals with brines at high pressure and temperature

Solubilities of corundum (Al₂O₃) and wollastonite (CaSiO₃) were measured in H₂O-NaCl solutions at 800 °C and 10 kbar and NaCl concentrations up to halite saturation by weight-loss methods. Additional data on quartz solubility at a single NaCl concentration were obtained as a supplement to previous work. Single crystals of synthetic corundum, natural wollastonite or natural quartz were equilibrated with H₂O and NaCl at pressure (P) and temperature (T) in a piston-cylinder apparatus with NaCl pressure medium and graphite heater sleeves. The three minerals show fundamentally different dissolution behavior. Corundum solubility undergoes large enhancement with NaCl concentration, rising rapidly from Al₂O₃ molality (m_Al2O3) of 0.0013(1) (1σ error) in pure H₂O and then leveling off to a maximum of ∼0.015 at halite saturation (X_NaCl ≈ 0.58, where X is mole fraction). Solubility enhancement relative to that in pure H₂O, , passes through a maximum at X_NaCl ≈ 0.15 and then declines towards halite saturation. Quenched fluids have neutral pH at 25 °C. Wollastonite has low solubility in pure H₂O at this P and T(m_CaSiO3=0.0167(6)). It undergoes great enhancement, with a maximum solubility relative to that in H₂O at X_NaCl ≈ 0.33, and solubility >0.5 molal at halite saturation. Solute silica is 2.5 times higher than at quartz saturation in the system H₂O-NaCl-SiO₂, and quenched fluids are very basic (pH 11). Quartz shows monotonically decreasing solubility from m_SiO2=1.248 in pure H₂O to 0.202 at halite saturation. Quenched fluids are pH neutral. A simple ideal-mixing model for quartz-saturated solutions that requires as input only the solubility and speciation of silica in pure H₂O reproduces the data and indicates that hydrogen bonding of molecular H₂O to dissolved silica species is thermodynamically negligible. The maxima in for corundum and wollastonite indicate that the solute products include hydrates and Na⁺ and/or Cl⁻ species produced by molar ratios of reactant H₂O to NaCl of 6:1 and 2:1, respectively. Our results imply that quite simple mechanisms may exist in the dissolution of common rock-forming minerals in saline fluids at high P and T and allow assessment of the interaction of simple, congruently soluble rock-forming minerals with brines associated with deep-crustal metamorphism.     

Coupled phase and aqueous species equilibrium of the H2O-CO2-NaCl-CaCO3 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite

A model is developed for the calculation of coupled phase and aqueous species equilibrium in the H₂O-CO₂-NaCl-CaCO₃ system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to saturation of halite. The vapor-liquid-solid (calcite, halite) equilibrium together with the chemical equilibrium of H⁺, Na⁺, Ca²⁺, , Ca(OH)⁺, OH⁻, Cl⁻, , , CO_2(aq) and CaCO_3(aq) in the aqueous liquid phase as a function of temperature, pressure, NaCl concentrations, CO_2(aq) concentrations can be calculated, with accuracy close to those of experiments in the stated T-P-m range, hence calcite solubility, CO₂ gas solubility, alkalinity and pH values can be accurately calculated. The merit and advantage of this model is its predictability, the model was generally not constructed by fitting experimental data.One of the focuses of this study is to predict calcite solubility, with accuracy consistent with the works in previous experimental studies. The resulted model reproduces the following: (1) as temperature increases, the calcite solubility decreases. For example, when temperature increases from 273 to 373 K, calcite solubility decreases by about 50%; (2) with the increase of pressure, calcite solubility increases. For example, at 373 K changing pressure from 10 to 500 bar may increase calcite solubility by as much as 30%; (3) dissolved CO₂ can increase calcite solubility substantially; (4) increasing concentration of NaCl up to 2 m will increase calcite solubility, but further increasing NaCl solubility beyond 2 m will decrease its solubility.The functionality of pH value, alkalinity, CO₂ gas solubility, and the concentrations of many aqueous species with temperature, pressure and NaCl_(aq) concentrations can be found from the application of this model. Online calculation is made available on www.geochem-model.org/models/h2o_co2_nacl_caco3/calc.php.     

Solubility measurements of synthetic neodymium monazite as a function of temperature at 2 kbars, and aqueous neodymium speciation in equilibrium with monazite

The solubility of synthetic NdPO₄ monazite end-member was experimentally determined from 300 up to 800 °C, at 2000 bars in pure water, and in aqueous chloride or phosphate solutions. Both the classical weight-loss method and a new method based on isotope dilution coupled with thermal ionization mass spectrometer were used. In the range of temperature studied monazite showed a prograde solubility from 10^−5.4 m at 300 °C up to 10^−2.57 m at 800 °C. Experiments in H₂O-H₃PO₄-NaCl-HCl solutions suggested Nd(OH)₃⁰ was the major species that was formed at high temperature and pressure. The equilibrium constants (log K) for the reaction:

     

Chalcopyrite leaching: The rate controlling factors

The processes that determine the rate of chalcopyrite leaching are central to understanding how chalcopyrite (CuFeS₂) behaves under the environmentally adverse conditions of acid rock drainage. To this end the effect of the acid anion on chalcopyrite leach rates using a variety of acidic media (H₂SO₄, HClO₄, HCl and H₂SO₄ with 0.25 M NaCl) under carefully controlled solution conditions (pH 1 and 2, Eh 750 mV (SHE) and 75 °C) has been examined. These conditions have been chosen to enable sufficient leach rates for accurate experimental determination and to compare to the previous mechanistic analysis carried out by Harmer et al. (2006).Extensive surface analysis of leach residues demonstrated that variations in the surface speciation could not be responsible for the observed variations in leach rate. The rate of Cu release, however, was found to be first order with respect to Fe³⁺ activity and inversely proportional with respect to H⁺ activity to the power of 0.7: