Kim F. Hayes

Surface Complexation Models: An Evaluation of Model Parameter Estimation Using FITEQL and Oxide Mineral Titration Data

Abstract The ability of surface complexation models (SCMs) to fit sets of titration data as a function of changes in model parameters was evaluated using FITEQL and acid-base titration data of α-FeOOH, α-Al2O3, and TiO2. Three SCMs were evaluated: the triple-layer model (TLM), the constant capacitance model (CCM), and the diffuse-layer model (DLM). For all models evaluated, increasing the model input value for the total number of surface sites caused a decrease in the best-fit Log K values of the surface protolysis constants. In the case of the CCM, the best-fit surface protolysis constants were relatively insensitive to changes in the value of the capacitance fitting parameter, C1, particularly for values of C1 greater than 1.2 F/m2. Similarly, the best-fit values of TLM surface electrolyte binding constants were less influenced by changes in the value of C1 when C1 was greater than 1.2 F/m2. For a given C1 value, the best-fit TLM values of the electrolyte binding constants were sensitive to changes in ΔpKa up to ΔpKa values of 3. For ΔpKa values above 3, no changes in the best-fit electrolyte binding constants were observed. Effects of the quality and extent of titration data on the best-fit values for surface constants are discussed for each model. A method is suggested for choosing a unique set of parameter values for each of the models.

An X-ray absorption spectroscopy study of the structure and reversibility of copper adsorbed to montmorillonite clay

Abstract X-ray absorption spectroscopy (XAS) and adsorption-desorption measurements have been performed to assess the relationship between the structure and reversibility of copper complexes on montmorillonite clay. By varying the solution pH and background electrolyte concentration, the adsorption of copper on either the edge sites or permanent charge sites of montmorillonite was controlled. This allowed the structure and reversibility of copper complexes on each of these site types to be assessed independently of each other. XAS analysis of copper adsorbed on the permanent charge sites indicated outer-sphere surface complexes, with these complexes showing sorption reversibility. For copper complexes formed on the edge sites of montmorillonite, XAS data confirmed the presence of monomer and dimer copper surface complexes. Sorption irreversibility at edge sites was noted at copper coverages less than 20 μmoles/g clay at pH=4.2 and at coverages greater than 50 μmoles/g clay at pH=6.8. At pH=6.8, higher Cu-Cu coordination numbers indicated the copper sorption irreversibility may be due, in part, to the formation of dimer surface complexes. The coordination numbers at pH=4.2 indicated the irreversibility could be due to the formation of dimers or due to formation of surface complexes on high energy edge sites.

Uranium(VI) Reduction By Iron(II) Monosulfide Mackinawite

Reaction of aqueous uranium(VI) with iron(II) monosulfide mackinawite in an O(2) and CO(2) free model system was studied by batch uptake measurements, equilibrium modeling, and L(III) edge U X-ray absorption spectroscopy (XAS). Batch uptake measurements showed that U(VI) removal was almost complete over the wide pH range between 5 and 11 at the initial U(VI) concentration of 5 × 10(-5) M. Extraction by a carbonate/bicarbonate solution indicated that most of the U(VI) removed from solution was reduced to nonextractable U(IV). Equilibrium modeling using Visual MINTEQ suggested that U was in equilibrium with uraninite under the experimental conditions. X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopy showed that the U(IV) phase associated with mackinawite was uraninite. Oxidation experiments with dissolved O(2) were performed by injecting air into the sealed reaction bottles containing mackinawite samples reacted with U(VI). Dissolved U measurement and XAS confirmed that the uraninite formed from the U(VI) reduction by mackinawite did not oxidize or dissolve under the experimental conditions. This study shows that redox reactions between U(VI) and mackinawite may occur to a significant extent, implying an important role of the ferrous sulfide mineral in the redox cycling of U under sulfate reducing conditions. This study also shows that the presence of mackinawite protects uraninite from oxidation by dissolved O(2). The findings of this study suggest that uraninite formation by abiotic reduction by the iron sulfide mineral under low temperature conditions is an important process in the redistribution and sequestration of U in the subsurface environments at U contaminated sites.

X-ray absorption spectroscopy investigation of aqueous Co(II) and Sr(II) sorption at clay-water interfaces

Abstract Sorption processes typically control trace metal concentrations in aquatic systems. To illustrate the impact of various types of surface sites on metal ion sorption behavior, Co(II) and Sr(II) sorption by several clay minerals under a range pH and background electrolyte conditions was studied. X-ray absorption spectroscopy (XAS) was used to characterize the surface complexes formed to explain the basis for the sorption trends. At low pH, Co(II) could be displaced from the surface by increasing the Na ion concentration. XAS analysis of these samples showed that sorbed Co(II) retained the coordination structure of aqueous phase Co(II), suggesting the formation of weakly associated, outer-sphere, mononuclear Co complexes at permanent charge sites. At high pH, sorbed Co could not be displaced by increasing the Na ion concentration. The XAS analyses of these samples indicated the formation of Co coprecipitates. The results of the Sr(II) sorption experiments suggested weaker bonding between sorbed Sr and the solid surfaces, regardless of solution conditions and adsorbent. XAS analysis of Sr sorption samples revealed the formation of mononuclear, outer-sphere complexes of Sr at clay–water interfaces, similar to the outer-sphere Co sorption samples observed only at low pH.

Distinguishing between interlayer and external sorption sites of clay minerals using X-ray absorption spectroscopy

Metals dissolved in natural aquatic environments are often sorbed on high surface area, smectite-clay minerals. Using X-ray absorption spectroscopy (XAS), it is shown that at low pH and Na ion concentration Co(II) forms outer-sphere, mononuclear surface complexes with permanent-charge sites in the interlayer region of smectites. XAS analysis indicates that with increasing pH and Na ion concentration Co(II) is increasingly excluded from the interlayer permanent-charge sites and forms polynuclear species with external surface-hydroxyl sites. These studies demonstrate the potential of XAS for distinguishing between the sorption of trace metals on interlayer and external sites of smectites as a function of changing solution conditions.

Reduction dechlorination of carbon tetrachloride by cobalamin(II) in the presence of dithiothreitol: mechanistic study, effect of redox potential and pH.

A mechanistic study of the reductive dechlorination of carbon tetrachloride by vitamin B 12 (cyanocobalamin) in the presence of dithiothreitol was conducted as a function of redor potential and pH. The solution redor potential decreased both with an increase in the total concentration of dithiothreitol present and with an increase in pH. The pseudo-first-order rate constant of carbon tetrachloride disappearance increased with decreasing redor potential. The predominant cobalt species present under the reaction conditions was cobalamin(II) (vitamin B 12r ), as confirmed by spectrophotometric analysis, suggesting a one-electron reduction of vitamin B 12 and the involvement of two vitamin B 12 molecules per reacting carbon tetrachloride molecule

Arsenic Waste Management: A Critical Review of Testing and Disposal of Arsenic-Bearing Solid Wastes Generated during Arsenic Removal from Drinking Water

Water treatment technologies for arsenic removal from groundwater have been extensively studied due to widespread arsenic contamination of drinking water sources. Central to the successful application of arsenic water treatment systems is the consideration of appropriate disposal methods for arsenic-bearing wastes generated during treatment. However, specific recommendations for arsenic waste disposal are often lacking or mentioned as an area for future research and the proper disposal and stabilization of arsenic-bearing waste remains a barrier to the successful implementation of arsenic removal technologies. This review summarizes current disposal options for arsenic-bearing wastes, including landfilling, stabilization, cow dung mixing, passive aeration, pond disposal, and soil disposal. The findings from studies that simulate these disposal conditions are included and compared to results from shorter, regulatory tests. In many instances, short-term leaching tests do not adequately address the range of conditions encountered in disposal environments. Future research directions are highlighted and include establishing regulatory test conditions that align with actual disposal conditions and evaluating nonlandfill disposal options for developing countries.

FeS-coated sand for removal of arsenic(III) under anaerobic conditions in permeable reactive barriers

Iron sulfide (as mackinawite, FeS) has shown considerable promise as a material for the removal of As(III) under anoxic conditions. However, as a nanoparticulate material, synthetic FeS is not suitable for use in conventional permeable reactive barriers (PRBs). This study developed a methodology for coating a natural silica sand to produce a material of an appropriate diameter for a PRB. Aging time, pH, rinse time, and volume ratios were varied, with a maximum coating of 4.0 mg FeS/g sand achieved using a pH 5.5 solution at a 1:4 volume ratio (sand: 2 g/L FeS suspension), three days of aging and no rinsing. Comparing the mass deposited on the sand, which had a natural iron-oxide coating, with and without chemical washing showed that the iron-oxide coating was essential to the formation of a stable FeS coating. Scanning electron microscopy images of the FeS-coated sand showed a patchwise FeS surface coating. X-ray photoelectron spectroscopy showed a partial oxidation of the Fe(II) to Fe(III) during the coating process, and some oxidation of S to polysulfides. Removal of As(III) by FeS-coated sand was 30% of that by nanoparticulate FeS at pH 5 and 7. At pH 9, the relative removal was 400%, perhaps due to the natural oxide coating of the sand or a secondary mineral phase from mackinawite oxidation. Although many studies have investigated the coating of sands with iron oxides, little prior work reports coating with iron sulfides. The results suggest that a suitable PRB material for the removal of As(III) under anoxic conditions can be produced through the deposition of a coating of FeS onto natural silica sand with an iron-oxide coating.

Effect of cationic surfactants on organic liquid‐water capillary pressure‐saturation relationships

Many solutes, either naturally occurring or introduced, are surface active and sorb preferentially at the interfaces of subsurface systems. In multiphase systems, the sorption of surfactants affects the capillary pressure-saturation relationships, fundamental constitutive relationships in the modeling of multiphase flow. In this study, the impact of surfactant sorption on capillary pressure relationships for organic liquid-waters systems was demonstrated by qualitatively correlating measurements of sorption and zeta potential, with interfacial tension and contact angle and, in turn, quantitatively relating these measurements to changes in capillary pressure-saturation relationships for o-xylene-water-quartz systems containing a cationic surfactant, cetyltrimethylammonium bromide (CTAB). The results show that the sorption of CTAB causes the naturally hydrophilic system to become hydrophobic, as evidenced by a change in the contact angle from about 10°–15° to 155° or 180°, depending on the pH. This change in hydrophilicity is reflected in the zeta potential of the system which goes from negative to positive as the aqueous phase CTAB concentration increases. The spontaneous imbibition capillary pressure-saturation relationship is more sensitive to the sorption of CTAB than the drainage relationship. To predict the observed changes in both capillary pressure-saturation relationships, a modified form of Leveretts function was used where roughness and curvature corrections were incorporated into the intrinsic contact angle to give an operational contact angle. A comparison of the measured and predicted capillary pressure-saturation relationships showed reasonable agreement.

High-performance liquid chromatographic analysis of polydisperse ethoxylated non-ionic surfactants in aqueous samples

An adsorption HPLC method using traditionally reversed-phase solvents and a hybrid column/precolumn has been developed for the quantitative separation and analysis of ethoxylated non-ionic surfactants on the basis of the number of ethoxylate (EO) groups per molecule. This method is demonstrated to separate ethoxylated homologues of broadly distributed linear alcohol ethoxylates and alkylphenol ethoxylates, with numbers of EO groups ranging from 3 to 50 or greater. This method presents a significant advance in non-ionic surfactant analysis because it permits direct injection of aqueous samples, eliminating the need for extensive sample preparation. The method discussed here is optimized for use with an evaporative light scattering detector (ELSD), but works equally well with UV absorbance or fluorescence detectors for the analysis of surfactants with chromophores. ELSD and UV detector operating conditions and calibration methods are discussed.