Surface complexation models: An evaluation of model parameter estimation using FITEQL and oxide mineral titration data

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 [alpha]-FeOOH, [alpha]-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 [Delta]pKa up to [Delta]pKa values of 3. For [Delta]pKa 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.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/29417/1/0000493.pd

Effect of silicic acid on arsenate and arsenite retention mechanisms on 6-L ferrihydrite: A spectroscopic and batch adsorption approach

The competitive adsorption of arsenate and arsenite with silicic acid at the ferrihydrite-water interface was investigated over a wide pH range using batch sorption experiments, attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy, and density functional theory (DFT) modeling. Batch sorption results indicate that the adsorption of arsenate and arsenite on the 6-L ferrihydrite surface exhibits a strong pH-dependence, and the effect of pH on arsenic sorption differs between arsenate and arsenite. Arsenate adsorption decreases consistently with increasing pH; whereas arsenite adsorption initially increases with pH to a sorption maximum at pH 7-9, where after sorption decreases with further increases in pH. Results indicate that competitive adsorption between silicic acid and arsenate is negligible under the experimental conditions; whereas strong competitive adsorption was observed between silicic acid and arsenite, particularly at low and high pH. In-situ, flow-through ATR-FTIR data reveal that in the absence of silicic acid, arsenate forms inner-sphere, binuclear bidentate, complexes at the ferrihydrite surface across the entire pH range. Silicic acid also forms inner-sphere complexes at ferrihydrite surfaces throughout the entire pH range probed by this study (pH 2.8 - 9.0). The ATR-FTIR data also reveal that silicic acid undergoes polymerization at the ferrihydrite surface under the environmentally-relevant concentrations studied (e.g., 1.0 mM). According to ATR-FTIR data, arsenate complexation mode was not affected by the presence of silicic acid. EXAFS analyses and DFT modeling confirmed that arsenate tetrahedra were bonded to Fe metal centers via binuclear bidentate complexation with average As(V)-Fe bond distance of 3.27 Å. The EXAFS data indicate that arsenite forms both mononuclear bidentate and binuclear bidentate complexes with 6-L ferrihydrite as indicated by two As(III)-Fe bond distances of ~2.92-2.94 and 3.41-3.44 Å, respectively. The As-Fe bond distances in both arsenate and arsenite EXAFS spectra remained unchanged in the presence of Si, suggesting that whereas Si diminishes arsenite adsorption preferentially, it has a negligible effect on As-Fe bonding mechanisms.24 month embargo; published online: 18 September 2013This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Toward Identifying the Next Generation of Superfund and Hazardous Waste Site Contaminants

Reproduced with permission from Environmental Health Perspectives."This commentary evolved from a workshop sponsored by the National Institute of Environmental Health Sciences titled "Superfund Contaminants: The Next Generation" held in Tucson, Arizona, in August 2009. All the authors were workshop participants." doi:10.1289/ehp.1002497Our aim was to initiate a dynamic, adaptable process for identifying contaminants of emerging concern (CECs) that are likely to be found in future hazardous waste sites, and to identify the gaps in primary research that cause uncertainty in determining future hazardous waste site contaminants. Superfund-relevant CECs can be characterized by specific attributes: they are persistent, bioaccumulative, toxic, occur in large quantities, and have localized accumulation with a likelihood of exposure. Although still under development and incompletely applied, methods to quantify these attributes can assist in winnowing down the list of candidates from the universe of potential CECs. Unfortunately, significant research gaps exist in detection and quantification, environmental fate and transport, health and risk assessment, and site exploration and remediation for CECs. Addressing these gaps is prerequisite to a preventive approach to generating and managing hazardous waste sites.Support for the workshop, from which this article evolved, was provided by the National Institute of Environmental Health Sciences Superfund Research Program (P42-ES04940)

Toward Identifying the Next Generation of Superfund and Hazardous Waste Site Contaminants

Reproduced with permission from Environmental Health Perspectives."This commentary evolved from a workshop sponsored by the National Institute of Environmental Health Sciences titled "Superfund Contaminants: The Next Generation" held in Tucson, Arizona, in August 2009. All the authors were workshop participants." doi:10.1289/ehp.1002497Our aim was to initiate a dynamic, adaptable process for identifying contaminants of emerging concern (CECs) that are likely to be found in future hazardous waste sites, and to identify the gaps in primary research that cause uncertainty in determining future hazardous waste site contaminants. Superfund-relevant CECs can be characterized by specific attributes: they are persistent, bioaccumulative, toxic, occur in large quantities, and have localized accumulation with a likelihood of exposure. Although still under development and incompletely applied, methods to quantify these attributes can assist in winnowing down the list of candidates from the universe of potential CECs. Unfortunately, significant research gaps exist in detection and quantification, environmental fate and transport, health and risk assessment, and site exploration and remediation for CECs. Addressing these gaps is prerequisite to a preventive approach to generating and managing hazardous waste sites.Support for the workshop, from which this article evolved, was provided by the National Institute of Environmental Health Sciences Superfund Research Program (P42-ES04940)

Effects of membrane structure and operational variables on membrane distillation performance

A bench-scale, sweeping gas, flat-sheet Membrane Distillation (MD) unit was used to assess the importance of membrane architecture and operational variables to distillate production rate. Sweeping gas membrane distillation (SGMD) was simulated for various membrane characteristics (material, pore size, porosity and thickness), spacer dimensions and operating conditions (influent brine temperature, sweep gas flow rate and brine flow rate) based on coupled mass and energy balances. Model calibration was carried out using four membranes that differed in terms of material selection, effective pore size, thickness and porosity. Membrane tortuosity was the lone fitting parameter. Distillate fluxes and temperature profiles from experiments matched simulations over a wide range of operating conditions. Limitations to distillate production were then investigated via simulations, noting implications for MD design and operation. Under the majority of conditions investigated, membrane resistance to mass transport provided the primary limitation to water purification rate. The nominal or effective membrane pore size and the lumped parameter epsilon/delta tau (porosity divided by the product of membrane tortuosity and thickness) were primary determinants of membrane resistance to mass transport. Resistance to Knudsen diffusion dominated membrane resistance at pore diameters <0.3 mu m. At larger pore sizes, a combination of resistances to intra-pore molecular diffusion and convection across the gas-phase boundary layer determined mass transport resistance. Findings are restricted to the module design flow regimes considered in the modeling effort. Nevertheless, the value of performance simulation to membrane distillation design and operation is well illustrated.US Bureau of Reclamation [R10AC32089]; Water, Environmental, and Energy Solutions Program (University of Arizona); Salt River Project24 month embargo; Available online 17 November 2016This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at [email protected]

Microscale Speciation of Arsenic and Iron in Ferric-Based Sorbents Subjected to Simulated Landfill Conditions

During treatment for potable use, water utilities generate arsenic-bearing ferric wastes that are subsequently dispatched to landfills. The biogeochemical weathering of these residuals in mature landfills affects the potential mobilization of sorbed arsenic species via desorption from solids subjected to phase transformations driven by abundant organic matter and bacterial activity. Such processes are not simulated with the toxicity characteristic leaching procedure (TCLP) currently used to characterize hazard. To examine the effect of sulfate on As retention in landfill leachate, columns of As­(V) loaded amorphous ferric hydroxide were reacted biotically at two leachate sulfate concentrations (0.064 mM and 2.1 mM). After 300 days, ferric sorbents were reductively dissolved. Arsenic released to porewaters was partially coprecipitated in mixed-valent secondary iron phases whose speciation was dependent on sulfate concentration. As and Fe XAS showed that, in the low sulfate column, 75–81% of As­(V) was reduced to As­(III), and 53–68% of the Fe­(III) sorbent was transformed, dominantly to siderite and green rust. In the high sulfate column, Fe­(III) solids were reduced principally to FeS_(am), whereas As­(V) was reduced to a polymeric sulfide with local atomic structure of realgar. Multienergy micro-X-ray fluorescence (ME-μXRF) imaging at Fe and As K-edges showed that As formed surface complexes with ferrihydrite > siderite > green rust in the low sulfate column; while discrete realgar-like phases formed in the high sulfate systems. Results indicate that landfill sulfur chemistry exerts strong control over the potential mobilization of As from ferric sorbent residuals by controlling secondary As and Fe sulfide coprecipitate formation