Surface Charge Concentrations on Silica in Different 1.0 M Metal-Chloride Background Electrolytes and Implications for Dissolution Rates

The empirical rate laws formulated to describe the dissolution rates of oxide minerals include the surface charge concentration that results from the protonation and deprotonation of surface functional groups. Previous experiments on quartz and silica have shown that dissolution rates vary as a function of different background electrolyte solutions, however, such experiments are often conducted at elevated temperatures where it is difficult to estimate surface charge along with the dissolution rates. In the present study we measuresurface charge concentrations for silica in different electrolyte solutions at 298 K in order to quantify the extent to which the different counterions could affect the dissolution rates through their influence on the surface charge concentrations. The experimental solutions in the electrolyte series: LiCl, NaCl, KCl, RbCl, CaCl₂, SrCl₂ and BaCl₂ were prepared to maintain a constant metal concentration of 1.0 M. For the alkali-metal chlorides, the surface charge concentrations correlate with the size of the hydrated alkali metal, consistent with the idea that these counterions affect charge via outer-sphere coordination that shield proton surface complexes from one another. The reactivity trend for alkaline-earth cations is less clear, but the data demonstrate distinct differences in the acid-base propertiesof the silica surface in these different electrolytes. We then discuss how these trends are manifested in the rate equations used to interpret dissolution experiments.     

Dissolution of uranophane: An AFM, XPS, SEM and ICP study

Dissolution experiments on single crystals of uranophane and uranophane-β, Ca(H₂O)₅[(UO₂)(SiO₃(OH)]₂, from the Shinkolobwe mine of the Democratic Republic of Congo, were done in an aqueous HCl solution of pH 3.5 for 3 h, in HCl solutions of pH 2 for 5, 10 and 30 min, and in Pb²⁺-, Ba-, Sr-, Ca- and Mg-HCl solutions of pH 2 for 30 min. The basal surfaces of the treated uranophane crystals were examined using atomic-force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Solutions after dissolution experiments on single crystals and synthetic powders were analysed with inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectroscopy (ICP-MS). The morphology of the observed etch pits (measured by AFM) were compared to the morphology, predicted on the basis of the bond-valence deficiency of polyhedron chains along the edges of the basal surface. Etch pits form in HCl solutions of pH 2. Their decrease in depth with the duration of the dissolution experiment is explained with the stepwave dissolution model, which describes the lowering of the surrounding area of an etch pit with continuous waves of steps emanated from the etch pit into the rest of the crystal surface. Hillocks form in an HCl solution of pH 3.5, and the chemical composition of the surface (as indicated by XPS) shows that these hillocks are the result of the precipitation of a uranyl-hydroxy-hydrate phase. Well-orientated hillocks form on the surface of uranophane in a SrCl₂-HCl solution of pH 2. They are part of an aged silica coating of composition Si₂O₂(OH)₄(H₂O)_n. An amorphous layer forms on the surface of uranophane in a MgCl₂-HCl solution of pH 2, which has a composition and structure similar to silicic acid. Small crystallites of uranyl-hydroxy-hydrate phases form on the surface of uranophane after treatment in Pb(NO₃)₂-HCl and BaCl₂-HCl solutions of pH 2. Dissolution experiments on synthetic uranophane powders show that in the early stage of the experiments, the dissolution rate of uranophane increase in the sequence Pb(NO₃)₂-HCl < BaCl₂-HCl < CaCl₂-HCl < HCl < SrCl₂-HCl < MgCl₂-HCl, indicating that the dissolution of uranophane is more enhanced in solutions containing divalent cations of small ionic radii and high Lewis acidity (Mg, MgCl⁺).     

Cation sorption on the muscovite (0 0 1) surface in chloride solutions using high-resolution X-ray reflectivity

The structure and mechanism of cation sorption at the (0 0 1) muscovite-water interface were investigated in 0.01 and 0.5 m KCl, CsCl, and CaCl₂ and 0.01 m BaCl₂ solutions at slightly acidic pH by high-resolution X-ray reflectivity. Structural relaxations of atom positions in the 2M₁ muscovite were small (?0.07 Å) and occurred over a distance of 30 to 40 Å perpendicular to the interface. Cations in all solutions were sorbed dominantly in the first and second solution layers adjacent to the mineral surface. The derived heights of the first solution layer in KCl and CsCl solutions, 1.67(6)-1.77(7) and 2.15(9)-2.16(2) Å, respectively, differ in magnitude by the approximate difference in crystallographic radii between K and Cs, and correspond closely to the interlayer cation positions in bulk K- and Cs-mica structures. The first solution layer heights in CaCl₂ and BaCl₂ solutions, 2.46(5)-2.56(11) and 2.02(5) Å, respectively, differ in a sense opposite to that expected based on crystallographic or hydrated radii of the divalent cations. The derived ion heights in all solutions imply that there is no intercalated water layer between the first solution layer and the muscovite surface. Molecular compositions were assigned to the first two solution layers in the electron density profiles using models that constrain the number density of sorbed cations, water molecules, and anions by considering the permanent negative charge of the muscovite and average solution density. The models result in partial charge balance (at least 50%) by cations sorbed in the first two layers in the 0.01 m solutions and approximately full charge balance in the 0.5 m solutions. Damped oscillations of model water density away from the first two solution layers agree with previous X-ray reflectivity results on the muscovite (0 0 1) surface in pure water.     

A study of factors affecting on the zeta potential of kaolinite and quartz powder

The purpose of this study was to determine the effects of pH, ion type (salt and metal cations), ionic strength, cation valence, hydrated ionic radius, and solid concentration on the zeta potential of kaolinite and quartz powder in the presence of NaCl, KCl, CaCl₂, CuCl₂, BaCl₂, and AlCl₃ solutions. The kaolinite and quartz powder have no isoelectric point (iep) within the entire pH range (3 < pH < 11). In the presence of hydrolysable metal ions, kaolinite and quartz powder have two ieps. As the cationic valence increases, the zeta potential of kaolinite and quartz powder becomes less negative. Monovalent cation, K⁺, yields more negative zeta potential values than the divalent cation Ba²⁺. As concentration of solid increases, the zeta potential of the minerals becomes more positive under acidic conditions; however, under alkaline conditions as solid concentration increases the zeta potential becomes more negative. Hydrated ionic radius also affects the zeta potential; the larger the ion, the thicker the layer and the more negative zeta potential for both kaolinite and quartz powder.     

Kinetics of crystal nucleation in ionic solutions: Electrostatics and hydration forces

The heat of precipitation, the mean crystal size and the broadness of crystal size distribution of barium sulfate precipitating in aqueous solutions of different background electrolytes (KCl, NaCl, LiCl, NaBr or NaF), was shown to vary at constant thermodynamic driving force (supersaturation) and constant ionic strength depending on the salt present in solution. The relative inversion in the effect of respective background ions on the characteristics of barite precipitate was observed between two studied supersaturation (Ω) and ionic strength (IS) conditions. The crystal size variance (β²) increased in the presence of background electrolytes in the order LiCl < NaCl < KCl at Ω = 10^3.33 and IS = 0.03 M and KCl < NaCl < LiCl at Ω = 10^3.77 and IS = 0.09 M. At a given Ω and IS the respective size of barite crystals decreased with increasing β² in chloride salts of different cations and remained constant in sodium salts of different anions.We suggest that ionic salts affect the kinetics of barite nucleation and growth due to their influence on water of solvation and bulk solvent structure. This idea is consistent with the hypothesis that the kinetic barrier for barium sulfate nucleation depends on the frequency of water exchange around respective building units that can be modified by additives present in solution. In electrolyte solution the relative switchover between long range electrostatic interactions and short range hydration forces, which influence the dynamics of solvent exchange between an ion solvation shell and bulk fluid, results in the observed inversion in the effect of differently hydrated salts on nucleation rates and the resulting precipitate characteristics.     

The interactions between calcite particles and aqueous solutions of magnesium,barium or zinc chlorides

The interactions between calcite particles and solutions containing MgCl₂, BaCl₂ or ZnCl₂ were investigated in two different systems. In one system the solution was percolating through a column of ground calcite. In the second system the solution was equilibrated with calcite powder and the suspension was thoroughly shaken. The solid sediment was then examined by X-ray diffraction, IR spectroscopy, SEM, microprobe analysis and thermal analysis. During the percolation, the reaction which occurred at the solid-liquid interface predominated. With BaCl₂, witherite was obtained; with ZnCl₂, Zn₅(OH)₈Cl₂ was obtained. Under equilibration conditions, the products dependent on the reaction which occurred in the aqueous phase. With BaCl₂, witherite enriched with Ca was obtained, together with small amounts of alstonite. Very small amounts of calcite recrystallized to aragonite as well. With ZnCl₂, only traces of smithsonite were obtained, while there were no new phases with MgCl₂. In addition, the following reactions, which do not lead to the formation of new phases, also occurred: (1) sorption of the metallic cation onto the calcite surface, either by cation exchange or by surface hydrolysis; (2) topochemical substitution of Ca by the metallic cation inside the calcite crystal. The first was favored in the percolation system, whereas the second occurred in both.     

Distribution of barium and fulvic acid at the mica-solution interface using in-situ X-ray reflectivity

The interfacial structures of the basal surface of muscovite mica in solutions containing (1) 5 × 10⁻³ m BaCl₂, (2) 500 ppm Elliott Soil Fulvic Acid I (ESFA I), (3) 100 ppm Elliott Soil Fulvic Acid II (ESFA II), (4) 100 ppm Pahokee Peat Fulvic Acid I (PPFA), and (5) 5 × 10⁻³ m BaCl₂ and 100 ppm ESFA II were obtained with high resolution in-situ X-ray reflectivity. The derived electron-density profile in BaCl₂ shows two sharp peaks near the mica surface at 1.98(2) and 3.02(4) Å corresponding to the heights of a mixture of Ba²⁺ ions and water molecules adsorbed in ditrigonal cavities and water molecules coordinated to the Ba²⁺ ions, respectively. This pattern indicates that most Ba²⁺ ions are adsorbed on the mica surface as inner-sphere complexes in a partially hydrated form. The amount of Ba²⁺ ions in the ditrigonal cavities compensates more than 90% of the layer charge of the mica surface. The electron-density profiles of the fulvic acids (FAs) adsorbed on the mica surface, in the absence of Ba²⁺, had overall thicknesses of 4.9-10.8 Å and consisted of one broad taller peak near the surface (likely hydrophobic and positively-charged groups) followed by a broad humped pattern (possibly containing negatively-charged functional groups). The total interfacial electron density and thickness of the FA layer increased as the solution FA concentration increased. The sorbed peat FA which has higher ash content showed a higher average electron density than the sorbed soil FA. When the muscovite reacted with a pre-mixed BaCl₂-ESFA II solution, the positions of the two peaks nearest the surface matched those in the BaCl₂ solution. However, the occupancy of the second peak decreased by about 30% implying that the hydration shell of surface-adsorbed Ba²⁺ was partially substituted by FA. The two surface peaks were followed by a broad less electron-dense layer suggesting a sorption mechanism in which Ba²⁺ acts dominantly as a bridging cation between the mica surface and FA. When the muscovite reacted first with FA and subsequently with BaCl₂, more Ba²⁺ could be adsorbed on the FA-coated mica surface. The peak closest to the mica included Ba²⁺ ions adsorbed directly on the mica in an amount similar to that in the BaCl₂ solution but more broadly distributed. A second peak observed within the FA layer suggests that the FA coating provides additional sites for Ba²⁺ sorption. The results indicate that enhanced uptake of heavy metals can occur when an organic coating already exists on a mineral surface.     

Humic acids coagulation: influence of divalent cations

The effects of the ionic strength (maintained by LiCl, NaCl or KCl) and Ca²⁺ and Mg²⁺ concentration on the coagulation of purified humic acids (HA) was studied. Solutions of known ionic strengths, pcH, Ca²⁺ and Mg²⁺ concentrations were prepared with HA and filtered to obtain the fraction with a size smaller than 100 kD. After a 50 day storage, samples of these solutions were filtered again (100 kD) and the total organic C (TOC) of the filtered solutions measured. The HA coagulation increased with salt concentration, with the cationic charge, and for cations of the same charge, with the cationic charge density. The coagulation decreased for pcH values of 4 to 7–8 in the absence of and presence of Mg²⁺ and Ca²⁺. In the absence of the divalent cations, the coagulation has a constant value for pcH>8, but, in the presence of Mg²⁺ and Ca²⁺, increases at pcH values greater than 9. The coagulation of humic materials occurs whether the samples are exposed to light or kept in the dark, although the coagulation kinetics are slower for the samples kept in the dark. The size distribution of size-fractionated humic solutions changes over time to a size distribution similar to that of the original humic solution before it was size-fractionated. The results are explained by the DLVO theory.     

Simultaneous flow of water and solutes through geological membranes—I. Experimental investigation

The relative retardation by geological membranes of cations and anions generally present in subsurface waters was investigated using a high pressure and high temperature ‘filtration cell’. The solutions were forced through different clays and a disaggregated shale subjected to compaction pressures up to 9500 psi and to temperatures from 20 to 70°C.The overall efficiences measured increased with increase of exchange capacity of the material used and with decrease in concentration of the input solution. The efficiency of a given membrane increased with increasing compaction pressure but decreased slightly at higher temperatures for solutions of the same ionic concentration.The results further show that geological membranes are specific for different dissolved species. The retardation sequences varied depending on the material used and on experimental conditions. The sequences for monovalent and divalent cations at laboratory temperatures were generally as follows: Li < Na < NH₃ < K < Rb < Cs Mg < Ca < Sr < Ba.The sequences for anions at room temperature were variable, but at 70°C, the sequence was: HCO₃ < I < B < SO₄ < Cl < Br.Monovalent cations contrary to some field data were generally retarded with respect to divalent cations. The differences in the filtration ratios among the divalent cations were smaller than those between the monovalent cations. The passage rate of B, HCO₃, I and NH₃ was greatly increased at 70°C.     

A high temperature equation of state for the H2O-CaCl2 and H2O-MgCl2 systems

An equation of state (EOS) is developed for salt-water systems in the high temperature range. As an example of the applications, this EOS is parameterized for the calculation of density, immiscibility, and the compositions of coexisting phases in the CaCl₂-H₂O and MgCl₂-H₂O systems from 523 to 973 K and from saturation pressure to 1500 bar. All available volumetric and phase equilibrium measurements of these binaries are well represented by this equation. This EOS is based on a Helmholtz free energy representation constructed from a reference system containing hard-sphere and polar contributions plus an empirical correction. For the temperature and pressure range in this study, the electrolyte solutes are assumed to be associated. The water molecules are modeled as hard spheres with point dipoles and the solute molecules, MgCl₂ and CaCl₂, as hard spheres with point quadrupoles. The free energy of the reference system is calculated from an analytical representation of the Helmholtz free energy of the hard-sphere contributions and perturbative estimates of the electrostatic contributions. The empirical correction used to account for deviations of the reference system predictions from measured data is based on a virial expansion. The formalism allows generalization to aqueous systems containing insoluble gases (CO₂, CH₄), alkali chlorides (NaCl, KCl), and alkaline earth chlorides (CaCl₂, MgCl₂). The program of this model is available as an electronic annex (see EA1 and EA2) and can also be downloaded at: http://www.geochem-model.org/programs.htm.     

Ionic diffusion in naturally-occurring aqueous solutions: transition-state models that use either empirical expressions or statistically-derived relationships to predict mutual diffusion coefficients in the concentrated-solution regions of 8 binary systems

Mutual diffusion coefficients for the systems NaCl-H₂O, KCl-H₂O, CaCl₂-H₂O, SrCl₂-H₂O, BaCl₂-H₂O, MgCl₂-H₂O, Na₂SO₄-H₂O, and MgSO₄-H₂O are computed using a model that postulates exchanges between ions and water molecules. Limiting ionic equivalent conductances, a solution-density function, and a mean ionic activity-coefficient function are required as input. A region of changing solution structure extends up to concentrations ranging from about 0.01 molar in MgCl₂-H₂O to about 0.2 molar in KCl-H₂O. In the remaining concentration range to saturation, a single expression in each system containing one variable parameter can be fitted empirically to reproduce selected sets of experimentally measured D^v₁₂ with maximum errors for individual compositions ranging from about 0.25% in KCl-H₂O and Na₂SO₄-H₂O to about 4% in MgCl₂-H₂O. The experimentally measured D^v₁₂ can be reproduced with errors comparable to those of the empirical fits by further postulating that individual ion-water molecule exchanges are coupled to yield hydrated neutral exchange complexes (the activated complexes), and defining probability expressions that describe the following exchanges: Ba²⁺ + 2Cl^? for 3H₂O, 2Ca²⁺ + 4Cl^? for 6H₂O, 2Sr²⁺ + 4Cl^? for 6H₂O, Na⁺ + Cl^? for 3H₂O, 2K⁺ + 2Cl^? for 5H₂O, NaSO^?₄ + Na⁺ for 5H₂O, Mg²⁺ + SO^2?₄ (+MgSO⁰₄) for 4H₂O, and MgCl⁺ + Cl^? for 2H₂O. This calculation also contains one variable parameter. Solute transport between exchange sites is by movement of ions, except for the ion-pair contribution indicated in parentheses.     

Wollastonite solubility and free energy of supercritical aqueous CaCl2

The solubility of wollastonite in chloride solutions has been measured between 750° C and 850° C at 2kb pressure and at 800°C at 1 kb pressure. The fugacity of HCl at P and T was controlled by combining Ag+AgCl internally with magnetite +hematite+water as an external hydrogen buffer. Silica activity was fixed by the presence of quartz. The calcium and chloride contents of the solutions were measured after quench. CaCl₂ appears to be the major solute species.Using these compositional data, the Gibbs Free Energy of formation for CaCl₂ was calculated, assuming that the activity coefficient quotient is near unity. The results were combined with quartz solubility data and calculations made by Joesten (1974) to approximate the compositions of CO₂-H₂O rich fluids which prevailed during the metasomatic formation of mono-minerallic zones in calc-silicate nodules from a contact aureole in the Christmas Mountains, Texas. The largest predicted gradients in H₄SiO₄ and CaCl₂ occur across the wollastonite zone.     

The adsorption of gold(I) hydrosulphide complexes by iron sulphide surfaces

The adsorption of gold by pyrite, pyrrhotite, and mackinawite from solutions containing up to 40 mg/kg (8 μm) gold as hydrosulphidogold(I) complexes has been measured over the pH range from 2 to 10 at 25°C and at 0.10 m ionic strength (NaCl, NaClO₄). The pH of point of zero charge, pH_pzc, has been determined potentiometrically for all three iron sulphides and shown to be 2.4, 2.7, and 2.9 for pyrite, pyrrhotite, and mackinawite, respectively. In solutions containing hydrogen sulphide, the pH_pzc is reduced to values below 2. The surface charge for each sulphide is therefore negative over the pH range studied in the adsorption experiments. Adsorption was from 100% in acid solutions having pH < 5.5 (pyrite) and pH < 4 (mackinawite and pyrrhotite). At alkaline pH’s (e.g., pH = 9), the pyrite surface adsorbed 30% of the gold from solution, whereas the pyrrhotite and mackinawite surfaces did not adsorb.The main gold complex adsorbed is AuHS°, as may be deduced from the gold speciation in solution in combination with the surface charge. The adsorption of the negatively charged Au(HS)₂⁻ onto the negatively charged sulphide surfaces is not favoured. The X-ray photoelectron spectroscopic data revealed different surface reactions for pyrite and mackinawite surfaces. While no change in redox state of adsorbent and adsorbate was observed on pyrite, a chemisorption reaction has been determined on mackinawite leading to the reduction of the gold(I) solution complex to gold(0) and to the formation of surface polysulphides. The data indicate that the adsorption of gold complexes onto iron sulphide surfaces such as that of pyrite is an important process in the “deposition” of gold from aqueous solutions over a wide range of temperatures and pressures.     

Salting-out of methane in single-salt solutions at 25°C and below 800 psia

Aqueous solubilities of methane at 25°C have been determined in single-salt solutions equilibrated with a CH₄ gas phase at 350, 550, and 750 psia. Measurements were made over a range of ionic strengths in NaCl, KCl, CaCl₂, MgCl₂, Na₂SO₄, K₂SO₄, MgSO₄, Na₂CO₃, K₂CO₃, NaHCO₃, and KHCO₃ aqueous solutions.At 25°C and constant pressure and methane fugacity, methane solubilities were largely controlled by the stoichiometric ionic strength, I, and the cation of the salt. Except for an increased salting-out due to HCO₃^?, the anion effect was relatively insignificant. Different but consistent solubility trends were followed in monovalent and divalent cation salt solutions as a function of I. Solubilities increased in salt solutions having a common anion in the following cation sequence: Na⁺ < K⁺ ? Ca²⁺ < Mg²⁺.The molal salting coefficient, k_m, for each salt was constant under the experimental conditions of the study, k_m is defined by $\text{log}\text{γ}\text{ch}{}_4\text{I}$ where $\text{γ}\text{ch}{}_4$, the molal activity coefficient, is the methane solubility ratio () measured at constant temperature, pressure, and CH₄ fugacity. Single-salt k_m values are as follows: 0.121, NaCl (4m); 0.121, Na₂SO₄ (1m); 0.118, Na₂CO₃ (1.5m); 0.146, NaHCO₃ (0.5m); 0.101, KCl (4m); 0.108, K₂SO₄ (0.5m); 0.111, K₂CO₃ (2m); 0.145, KHCO₃ (0.5m); 0.071, CaCl₂ (2m); 0.063, MgCl₂ (2m); and 0.066, MgSO₄ (1.5m) where the molalities in parentheses refer to the maximum salt concentrations used in this study.     

Magnesium recovery from magnesite tailings by acid leaching and production of magnesium chloride hexahydrate from leaching solution by evaporation

The recovery of magnesium from magnesite tailings in aqueous hydrochloric acid solutions by acid leaching was studied in a batch reactor using hydrochloric acid solutions. Subsequent, production of magnesium chloride hexahydrate (MgCl₂.6H₂O) from leaching solution was also investigated. The effects of temperature, acid concentration, solid-to-liquid ratio, particle size and stirring speed on the leaching process were investigated. The pseudo-second-order reaction model seemed to be appropriate for the magnesium leaching. The activation energy of the leaching process was estimated to be 62.4 kJ mol^− 1. Finally, MgCl₂.6H₂O in a purity of 91% was produced by evaporation of leaching solution obtained at a temperature of 40 °C, 1.0 M acid, solid-to-liquid ratio of 10 g/L, particle size of 100 µm, stirring speed of 1250 rpm and leaching time of 60 min.     

Hydration-dehydration interactions between glycine and anhydrous salts: Implications for a chemical evolution of life

Polymerizations of organic monomers including amino acids, nucleotides and monosaccharides are essential processes for chemical evolution of life. Since these reactions proceed with “dehydration” reactions, they are possibly promoted if combined with thermodynamically favorable “hydration” reactions of minerals and salts. To test the possibility, we conducted heating experiments of the simplest amino acid “glycine (Gly)” mixed with four simple anhydrous salts (MgSO₄, SrCl₂, BaCl₂ and Li₂SO₄) at 140 °C up to 20 days. Gly polymerization was strongly promoted by mixing with the salts in the order of MgSO₄ > SrCl₂ > BaCl₂ > Li₂SO₄. Up to 6-mer of Gly polymers were synthesized in the Gly-MgSO₄ mixture, and a total yield of Gly polymers attained about 7% of the initial amount of Gly by the 20 days heating. The total yield was about 200 times larger than that from the heating of Gly alone. XRD measurements of the Gly-MgSO₄ mixture revealed the generation of MgSO₄ monohydrate during Gly polymerization. These observations indicate that Gly polymerization was promoted by the salt hydrations through the hydration-dehydration interactions. Based on the observations, we tried to find a relationship between thermodynamic characteristics of the interactions and the promotion effects of each salt on Gly polymerization. It was found that the salts having lower hydration Δ_rG⁰ (easier to hydrate) promote Gly polymerization more strongly. The relationship was used to estimate promotion effects of simple oxide minerals on Gly polymerization. The estimations were consistent with previous observations about the effects of these minerals on Gly polymerization. The fact suggests that the hydration-dehydration interactions between amino acids and minerals are an important mechanism for amino acids’ polymerizations on minerals.     

Controls on Ra during raffinate neutralization at the Key Lake uranium mill, Saskatchewan, Canada

This study was conducted to define the geochemical controls on ²²⁶Ra during raffinate (pH = 1.2) neutralization to pH 10 at the Key Lake U mill in northern Saskatchewan, Canada. High activities (120–150 Bq/L) of aqueous phase ²²⁶Ra are present in raffinate produced during milling of U ore. The solubility control of ²²⁶Ra in the SO₄-rich, hydrometallurgical raffinate solutions often involves the addition of BaCl₂ to form a radium-barite co-precipitate (Ba(Ra)SO₄). As such, neutralization experiments were conducted with samples of mill raffinate using Ca(OH)₂ or NaOH with and without the addition of BaCl₂. Radium-226 activity decreased from 150 to <4 Bq/L for all combinations of neutralizing agents with Ca(OH)₂ + BaCl₂ being the most effective combination (final activity ∼1.0 Bq/L; ∼99.3% removal). In the absence of BaCl₂, Ca(OH)₂ more efficiently removed ²²⁶Ra than NaOH between pH 4 and 8, due to the co-precipitation of ²²⁶Ra with gypsum. Overall, neutralization with the addition of BaCl₂ reduced ²²⁶Ra activities at lower pH values (by pH 4.5), due to co-precipitation of ²²⁶Ra with BaSO₄. At varying concentrations of BaCl₂, aqueous phase activities of ²²⁶Ra converged, but did not attain steady-state values during neutralization and would continue to decrease with time. Sequential extractions indicated that ²²⁶Ra in precipitates formed during neutralization of the mill raffinate is dominated by amorphous and crystalline Fe hydroxide phases, consistent with raffinate neutralization experiments that showed that adsorption onto ferrihydrite can remove most ²²⁶Ra in the raffinate. Data generated in this study are being used to define the long-term geochemical controls on ²²⁶Ra in U mill processes and tailings.     

A Donnan potential model for metal sorption onto Bacillus subtilis

In this study, we conducted electrophoretic mobility, potentiometric titration, and metal sorption experiments to investigate the surface charge characteristics of Bacillus subtilis and the electrostatic interactions between metal cations and the cell surface electric field. Electrophoretic mobility experiments performed as a function of pH and ionic strength show an isoelectric point of pH 2.4, with the magnitude of the electrokinetic potential increasing with increasing pH, and decreasing with increasing ionic strength. Potentiometric titration experiments conducted from pH 2.4 to 9 yield an average surface charge excess of 1.6 μmol/mg (dry mass). Corresponding cell wall charge density values were used to calculate the Donnan potential (Ψ_DON) as function of pH and ionic strength. Metal sorption experiments conducted with Ca(II), Sr(II), and Ba(II) exhibit strong ionic strength dependence, suggesting that the metal ions are bound to the bacterial cell wall via an outer-sphere complexation mechanism. Intrinsic metal sorption constants for the sorption reactions were determined by correcting the apparent sorption constant with the Boltzmann factor. A 1:2 metal-ligand stoichiometry provides the best fit to the experimental data with log K₂^int values of 5.9 ± 0.3, 6.0 ± 0.2, 6.2 ± 0.2 for Ca(II), Sr(II), and Ba(II) respectively. Electrophoretic mobility measurements of cells sorbed with Ca(II), Sr(II), and Ba(II) support the 1:2 sorption stoichiometry. These results indicate that electrical potential parameters derived from the Donnan model can be applied to predict metal binding onto bacterial surfaces over a wide range of pH and ionic strength conditions.     

CO2 solubility in aqueous solutions containing Na+, Ca2+, Cl−, SO42− and HCO3-: The effects of electrostricted water and ion hydration thermodynamics

Dissolution of CO₂ into deep subsurface brines for carbon sequestration is regarded as one of the few viable means of reducing the amount of CO₂ entering the atmosphere. Ions in solution partially control the amount of CO₂ that dissolves, but the mechanisms of the ion's influence are not clearly understood and thus CO₂ solubility is difficult to predict. In this study, CO₂ solubility was experimentally determined in water, NaCl, CaCl₂, Na₂SO_4, and NaHCO₃ solutions and a mixed brine similar to the Bravo Dome natural CO₂ reservoir; ionic strengths ranged up to 3.4 molal, temperatures to 140 °C, and CO₂ pressures to 35.5 MPa. Increasing ionic strength decreased CO₂ solubility for all solutions when the salt type remained unchanged, but ionic strength was a poor predictor of CO₂ solubility in solutions with different salts. A new equation was developed to use ion hydration number to calculate the concentration of electrostricted water molecules in solution. Dissolved CO₂ was strongly correlated (R² = 0.96) to electrostricted water concentration. Strong correlations were also identified between CO₂ solubility and hydration enthalpy and hydration entropy. These linear correlation equations predicted CO₂ solubility within 1% of the Bravo Dome brine and within 10% of two mixed brines from literature (a 10 wt % NaCl + KCl + CaCl₂ brine and a natural Na⁺, Ca²⁺, Cl⁻ type brine with minor amounts of Mg²⁺, K⁺, Sr²⁺ and Br⁻).