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J.A. Davis

Publications and source records attributed to J.A. Davis.

At least 37 records · Page 2Linked to original sources
USGS2004

Surface complexation model of uranyl sorption on Georgia kaolinite

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3–10), total U (1 and 10 μmol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uraniumwas preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO 2 , its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite.

Applied Clay Science↗
USGS2004

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10 −8 to 1 · 10 −5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999–2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca 2+ , Mg 2+ , HCO 3 − , SO 4 2− , H 4 SiO 4 , and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.

Geochimica et Cosmochimica Acta↗
USGS2003

Effects of dissolved carbonate on arsenate adsorption and surface speciation at the hematite-water interface

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite−water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [ P CO 2 = 10 - 3.5 atm and ∼0; CO 2 -free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L - 1 , [As(V)] 0 = 1.5 mM and I = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L - 1 , [As(V)] 0 = 0.5 mM and I = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems ( P CO 2 = 10 - 3.5 atm) than in the CO 2 -free argon system at pH 4−7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (≈2.8 Å) and bidentate binuclear (≈3.3 Å) bonding at pH 4.5−8 and loading levels of 0.46−3.10 μM m - 2 . Using the results of the pseudo-equilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the P CO 2 = 10 - 3.5 atm and the CO 2 -free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to electrical double-layer potentials caused by the adsorption of carbonate in the air-equilibrated system. Overall results suggest that the effects of dissolved carbonate on As(V) adsorption were influenced by the reaction conditions [e.g., available surface sites, initial As(V) concentrations, and reaction times]. Quantifying the effects of adsorbed carbonate may be important in predicting As(V) transport processes in groundwater, where iron oxide-coated aquifer materials are exposed to seasonally fluctuating partial pressures of CO 2 (g).

Environmental Science & Technology↗
USGS2003

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U L III -edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ≤ 5500 μg U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 Å was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U−P distance at 3.5−3.6 Å was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ≥ 5500 μg U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 μg U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Environmental Science & Technology↗
USGS2003

Arsenic speciation and reactivity in poultry litter

Recent U.S. government action to lower the maximum concentration levels (MCL) of total arsenic (As) (10 ppb) in drinking water has raised serious concerns about the agricultural use of As-containing biosolids such as poultry litter (PL). In this study, solid-state chemical speciation, desorbability, and total levels of As in PL and long-term amended soils were investigated using novel synchrotron-based probing techniques (microfocused (μ) synchrotron X-ray fluorescence (SXRF) and μ-X-ray absorption near-edge structure (XANES) spectroscopies) coupled with chemical digestion and batch experiments. The total As levels in the PL were as high as ≈50 mg kg - 1 , and As(II/III and V) was always concentrated in abundant needle-shaped microscopic particles (≈20 μm × 850 μm) associated with Ca, Cu, and Fe and to a lesser extent with S, Cl, and Zn. Post-edge XANES features of litter particles are dissimilar to those of the organo-As(V) compound in poultry feed (i.e., roxarsone), suggesting possible degradation/transformation of roxarsone in the litter and/or in poultry digestive tracts. The extent of As desorption from the litter increased with increasing time and pH from 4.5 to 7, but at most 15% of the total As was released after 5 d at pH 7, indicating the presence of insoluble phases and/or strongly retained soluble compounds. No significant As accumulation (<15 mg kg - 1 ) was found in long-term PL-amended agricultural surface soils. This suggests that As in the PL may have undergone surface and subsurface transport processes. Our research results raise concerns about long-term PL amendment effects on As contamination in surrounding soil−water environments.

Environmental Science & Technology↗
USGS2002

Simulation of the mobility of metal-EDTA complexes in groundwater: The influence of contaminant metals

Reactive transport simulations were conducted to model chemical reactions between metal−EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz−sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel−, zinc−, and calcium−EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created by the sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal−hydroxypolymer coatings on the aquifer sediments by the metal−EDTA complexes was kinetically restricted. All other reactions, including metal−EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal−EDTA complexes was less important than the fact that these reactions are rate controlled. Results suggest that the published solubility for ferrihydrite reasonably approximates the Fe solubility of the hydroxypolymer coatings on the sediments. Aluminum may be somewhat more soluble than represented by the equilibrium constant for gibbsite, and its dissolution may be rate controlled when reacting with Ca−EDTA complexes.

Environmental Science & Technology↗
USGS2002

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

“Two-line” ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10 −5 to 10 −3 M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(.02) Å and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) Å and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) Å in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorptionsamples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH) 6 octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH) 6 polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior.

Geochimica et Cosmochimica Acta↗
USGS2002

Effect of adsorbed metals ions on the transport of Zn- and Ni-EDTA complexes in a sand and gravel aquifer

Adsorption, complexation, and dissolution reactions strongly influenced the transport of metal ions complexed with ethylenediaminetetraacetic acid (EDTA) in a predominantly quartz-sand aquifer during two tracer tests conducted under mildly reducing conditions at pH 5.8 to 6.1. In tracer test M89, EDTA complexes of zinc (Zn) and nickel (Ni), along with excess free EDTA, were injected such that the lower portion of the tracer cloud traveled through a region with adsorbed manganese (Mn) and the upper portion of the tracer cloud traveled through a region with adsorbed Zn. In tracer test S89, Ni- and Zn-EDTA complexes, along with excess EDTA complexed with calcium (Ca), were injected into a region with adsorbed Mn. The only discernable chemical reaction between Ni-EDTA and the sediments was a small degree of reversible adsorption leading to minor retardation. In the absence of adsorbed Zn, the injected Zn was displaced from EDTA complexes by iron(III) [Fe(III)] dissolved from the sediments. Displacement of Zn by Fe(III) on EDTA became increasingly thermodynamically favorable with decreasing total EDTA concentration. The reaction was slow compared to the time-scale of transport. Free EDTA rapidly dissolved aluminum (Al) from the sediments, which was subsequently displaced slowly by Fe. In the portion of tracer cloud M89 that traveled through the region contaminated with adsorbed Zn, little displacement of Zn complexed with EDTA was observed, and Al was rapidly displaced from EDTA by Zn desorbed from the sediments, in agreement with equilibrium calculations. In tracer test S89, desorption of Mn dominated over the more thermodynamically favorable dissolution of Al oxyhydroxides. Comparison with results from M89 suggests that dissolution of Al oxyhydroxides in coatings on these sediment grains by Ca-EDTA was rate-limited whereas that by free EDTA reached equilibrium on the time-scale of transport. Rates of desorption are much faster than rates of dissolution of Fe oxyhydroxides from sediment-grain surfaces and, therefore, adsorbed metal ions can strongly influence the speciation of ligands like EDTA in soils and sediments, especially over small temporal and spatial scales.

Geochimica et Cosmochimica Acta↗
USGS2001

Mechanisms of uranium interactions with hydroxyapatite: Implications for groundwater remediation

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U L III -edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatite-based in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 μM was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations ≤4700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 Å. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios ≥0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.

Environmental Science & Technology↗
USGS2000

Multispecies reactive tracer test in an aquifer with spatially variable chemical conditions

A field investigation of multispecies reactive transport was conducted in a well‐characterized, sand and gravel aquifer on Cape Cod, Massachusetts. The aquifer is characterized by regions of differing chemical conditions caused by the disposal of secondary sewage effluent. Ten thousand liters of groundwater with added tracers (Br, Cr(VI), and EDTA complexed with Pb, Zn, Cu, and Ni) were injected into the aquifer and distributions of the tracers were monitored for 15 months. Most of the tracers were transported more than 200 m; transport was quantified using spatial moments computed from the results of a series of synoptic samplings. Cr(VI) transport was retarded relative to Br; the retardation factor varied from 1.1 to 2.4 and was dependent on chemical conditions. At 314 days after the injection, dissolved Cr(VI) mass in the tracer cloud had decreased 85%, with the likely cause being reduction to Cr(III) in a suboxic region of the aquifer. Transport of the metal‐EDTA complexes was affected by aqueous complexation, adsorption, and dissolution‐precipitation reactions of Fe oxyhydroxide minerals in the aquifer sediments. Dissolved Pb‐EDTA complexes disappeared from the tracer cloud within 85 days, probably due to metal exchange reactions with Fe and adsorbed Zn (present prior to the injection from contamination by the sewage effluent). About 30% of the Cu‐EDTA complexes remained within the tracer cloud 314 days after injection, even though the thermodynamic stability of the Pb‐EDTA complex is greater than Cu‐EDTA. It is hypothesized that stronger adsorption of Pb 2+ to the aquifer sediments causes the Pb‐EDTA complex to disassociate to a greater degree than the Cu‐EDTA complex. The mass of dissolved Zn‐EDTA increased during the first 175 days of the tracer test to 140% of the mass injected, with the increase due to desorption of sewage‐derived Zn. Dissolved Ni‐EDTA mass remained nearly constant throughout the tracer test, apparently only participating in reversible adsorption reactions. The results of the field experiment provide a chemically complex data set that can be used in the testing of reactive transport models of flow coupled with chemical reactions.

Water Resources Research↗
USGS2000

Modeling the influence of variable pH on the transport of zinc in a contaminated aquifer using semiempirical surface complexation models

Land disposal of sewage effluent resulted in contamination of a sand and gravel aquifer (Cape Cod, Massachusetts) with zinc (Zn). The distribution of Zn was controlled by pH‐dependent adsorption; the Zn extended 15 m into the 30‐m‐thick sewage plume within approximately 100 m of the source but only 2–4 m into the plume between 100 and 400 m downgradient. A two‐dimensional vertical cross section model coupling groundwater flow with solute transport and equilibrium adsorption is used to simulate the influence of pH on Zn transport. Adsorption is described using semiempirical surface complexation models (SCM) by writing chemical reactions between dissolved Zn and mineral surface sites. SCM parameters were determined in independent laboratory experiments. A 59‐year simulation with a one‐site SCM describes the influence of pH on Zn transport well, with greater mobility at the low pH values near the upper sewage plume boundary than at the higher pH values deeper in the sewage‐contaminated zone. Simulation with a two‐site SCM describes both the sharpness and approximate location of the leading edge of the Zn‐contaminated region. Temporal variations in pH of incoming groundwater can result in large increases in Zn concentration and mobility. The influence of spatial and temporal variability in pH on adsorption and transport of Zn was accomplished much more easily with the semiempirical SCM approach than could be achieved with distribution coefficients or adsorption isotherms.

Water Resources Research↗
USGS1996

Wide angle X-ray scattering (WAXS) study of "two-line" ferrihydrite structure: Effect of arsenate sorption and counterion variation and comparison with EXAFS results

Wide angle X-ray scattering (WAXS) measurements have been made on a suite of “two-line” ferrihydrite (FHY2) samples containing varying amounts of coprecipitated arsenate. Samples prepared at pH 8 with counter ions chloride, nitrate, and a mixture of both also were examined. The raw WAXS scattering functions show that “two-line” ferrihydrite actually has a large number of non-Bragg (i.e., diffuse scattering) maxima up to our observation limit of 16 Å −1 . The type of counter ion used during synthesis produces no significant change in this function. In unarsenated samples, Radial Distribution Functions (RDFs) produced from the scattering functions show a well-defined Fe-O peak at 2.02 Å in excellent agreement with the mean distance of 2.01 Å from extended X-ray absorption fine structure (EXAFS) analysis. The area under the Fe-O peak is consistent with only octahedral oxygen coordination about iron, and an iron coordination about oxygen of 2.2, in agreement with the EXAFS results, the sample composition, and XANES measurements. The second peak observed in the RDFs is clearly divided into two populations of correlations, at 3.07 and 3.52 Å, respectively. These distances are close to the EXAFS-derived Fe-Fe subshell distances of 3.02–3.05 and 3.43–3.46 Å, respectively, though this is misleading as the RDF peaks also include contributions from O-Fe and O-O correlations. Simulated RDFs of the FeOOH polymorphs indicate how the observed RDF structure relates to the EXAFS pair-correlation function, and allow comparisons with an ordered ferrihydrite structure.

Geochimica et Cosmochimica Acta↗
USGS1996

Experimental investigation and modeling of uranium (VI) transport under variable chemical conditions

The transport of adsorbing and complexing metal ions in porous media was investigated with a series of batch and column experiments and with reactive solute transport modeling. Pulses of solutions containing U(VI) were pumped through columns filled with quartz grains, and the breakthrough of U(VI) was studied as a function of variable solution composition ( p H, total U(VI) concentration, total fluoride concentration, and p H-buffering capacity). Decreasing p H and the formation of nonadsorbing aqueous complexes with fluoride increased U(VI) mobility. A transport simulation with surface complexation model (SCM) parameters estimated from batch experiments was able to predict U(VI) retardation in the column experiments within 30%. SCM parameters were also estimated directly from transport data, using the results of three column experiments collected at different p H and U(VI) pulse concentrations. SCM formulations of varying complexity (multiple surface types and reaction stoichiometries) were tested to examine the trade-off between model simplicity and goodness of fit to breakthrough. A two-site model (weak- and strong-binding sites) with three surface complexation reactions fit these transport data well. With this reaction set the model was able to predict (1) the effects of fluoride complexation on U(VI) retardation at two different p H values and (2) the effects of temporal variability of p H on U(VI) transport caused by low p H buffering. The results illustrate the utility of the SCM approach in modeling the transport of adsorbing inorganic solutes under variable chemical conditions.

Water Resources Research↗
USGS1995

XAS study of AsO43− and SeO42− substituted schwertmannites

Synthetic schwertmannite samples with varying amounts of arsenate and selenate substituting for sulfate were examined by XAS methods in an attempt to characterize the location of the anion complexes. Selenate appears to both substitute directly for sulfate within tunnels in the structure, and sorb onto the outside of crystallites. No disruption of the basic structure appears with selenate substitution. However, arsenate appears mainly to sorb to the outside of crystallites, destabilizing the structure and poisoning growth.

Physica B: Condensed Matter↗
USGS1994

Uranium(VI) adsorption to ferrihydrite: Application of a surface complexation model

A study of U(VI) adsorption by ferrihydrite was conducted over a wide range of U(VI) concentrations, pH, and at two partial pressures of carbon dioxide. A two-site (strong- and weak-affinity sites, Fe s OH and Fe w OH, respectively) surface complexation model was able to describe the experimental data well over a wide range of conditions, with only one species formed with each site type: an inner-sphere, mononuclear, bidentate complex of the type (FeO 2 )UO 2 . The existence of such a surface species was supported by results of uranium EXAFS spectroscopy performed on two samples with U(VI) adsorption density in the upper range observed in this study (10 and 18% occupancy of total surface sites). Adsorption data in the alkaline pH range suggested the existence of a second surface species, modeled as a ternary surface complex with UO 2 CO 3 0 binding to a bidentate surface site. Previous surface complexation models for U(VI) adsorption have proposed surface species that are identical to the predominant aqueous species, e.g., multinuclear hydrolysis complexes or several U(VI)-carbonate complexes. The results demonstrate that the speciation of adsorbed U(VI) may be constrained by the coordination environment at the surface, giving rise to surface speciation for U(VI) that is significantly less complex than aqueous speciation.

Geochimica et Cosmochimica Acta↗
USGS1993

Surface chemistry of ferrihydrite: Part 1. EXAFS studies of the geometry of coprecipitated and adsorbed arsenate

EXAFS spectra were collected on both the As and Fe K-edges from samples of two-line ferrihydrite with adsorbed (ADS) and coprecipitated (CPT) arsenate prepared over a range of conditions and arsenate surface coverages. Spectra also were collected for arsenate adsorbed on the surfaces of three FeOOH crystalline polymorphs, α (goethite), β (akaganeite), and γ (lepidocrocite), and as a free ion in aqueous: solution. Analyses of the As EXAFS show clear evidence for inner sphere bidentate (bridging) arsenate complexes on the ferrihydrite surface and on the surfaces of the crystalline FeOOH polymorphs. The bridging arsenate is attached to adjacent apices of edge-sharing Fe oxyhydroxyl octahedra. The arsenic-iron distance at the interface ( 3.28 &#xB1;0.01 A &#x30A; "> 3.28 ±0.01Å ) is close to that expected for this geometry on the FeOOH polymorph surfaces, but is slightly shorter on the ferrihydrite surfaces ( 3.25 &#xB1; 0.02 A &#x30A; "> 3.25 ± 0.02Å ). Mono-dentate arsenate linkages ( 3.60 &#xB1; 0.03 A &#x30A; "> 3.60 ± 0.03Å ) also occur on the ferrihydrite, but are not generally observed on the crystalline FeOOH polymorphs. The proportion of monodentate bonds appears largest for adsorption samples with the smallest As Fe "> AsFe molar ratio. In all cases the arsenate tetrahedral complex is relatively undistorted with As-O bonds of 1.66 &#xB1; 0.01 A &#x30A; "> 1.66 ± 0.01Å . Precipitation of arsenate or scorodite-like phases was not observed for any samples, all of which were prepared at a pH value of 8. The Fe EXAFS results confirm that the Fe-Fe correlations in the ferrihydrite are progressively disrupted in the CPT samples as the As Fe "> AsFe ratio is increased. Coherent crystallite size is probably no more than 10 Å in diameter and no Fe oxyhydroxyl octahedra corner-sharing linkages (as would be present in FeOOH polymorphs) are observed at the largest As Fe "> AsFe ratios. Comparison of the number and type of Fe-Fe neighbors with the topological constraints imposed by the arsenate saturation limit in the CPT samples (about 0.7 As Fe "> AsFe ) indicates ferrihydrite units consisting mainly of Fe oxyhydroxyl octahedra arranged in short dioctahedral chains with minimal interchain linking by octahedra corners. This is consistent with an enlarged surface area and a larger proportion of sites for bidentate arsenate bonding in CPT samples as compared to the ADS samples, which saturate with arsenate at lower As Fe "> AsFe ratios. The latter samples have larger crystallite sizes and a definite proportion of ferric octahedra sharing corners. The ratio of corner-sharing to edge-sharing Fe oxyhydroxyl octahedra in the ADS samples, and CPT samples with small As loadings, is very similar to what would be present in very small particles of goethite or akaganeite. The difference in the polymeric structure of ADS and CPT samples at higher As Fe "> AsFe ratios is due to strong arsenate bidentate adsorption that poisons the surface of particles of ferrihydrite precipitated in the presence of substantial arsenate, limiting their normal crystallization, and preventing further Fe-O-Fe polymerization. If the arsenate is applied after precipitation much less adsorption occurs since polymerization has already progressed. In both ADS and CPT samples, Fe-O-Fe polymerization increases with age, though at different rates for each type of sample.

Geochimica et Cosmochimica Acta↗