Geology topics

J.A. Davis

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

At least 19 recordsLinked to original sources

USGS2013

Uranium adsorption on ferrihydrite - Effects of phosphate and humic acid

Uranium adsorption on ferrihydrite was studied as a function of pH in systems equilibrated with air, in the presence and absence of added phosphate and humic acid (HA). The objective was to determine the influence of PO43- and HA on uranium uptake. Below pH 7, the sorption of UO22+ typically increases with increasing pH (the 'low pH sorption edge'), with a sharp decrease in sorption above this pH value (the 'high pH edge'). The presence of ΣPO43- of 10-4 mol/L moved the low pH edge to the left by approximately 0.8 pH units. The PO43- was strongly bound by the ferrihydrite surface, and the increased uptake of U was attributed to the formation of ternary surface complexes involving both UO22+ and PO43-. The addition of HA (9 mg/L) increased U uptake at pH values below 7, with little effect at higher pH values. The positions of the pH edges were also affected by the ionic strength and total U content. These experiments show that sorption interactions involving PO43 and HA must be considered in order to model the behavior of U in natural systems, in which these components are often present.

Radiochimica Acta↗

USGS2011

Simulating adsorption of U(VI) under transient groundwater flow and hydrochemistry: Physical versus chemical nonequilibrium model

Coupled intragrain diffusional mass transfer and nonlinear surface complexation processes play an important role in the transport behavior of U(VI) in contaminated aquifers. Two alternative model approaches for simulating these coupled processes were analyzed and compared: (1) the physical nonequilibrium approach that explicitly accounts for aqueous speciation and instantaneous surface complexation reactions in the intragrain regions and approximates the diffusive mass exchange between the immobile intragrain pore water and the advective pore water as multirate first-order mass transfer and (2) the chemical nonequilibrium approach that approximates the diffusion-limited intragrain surface complexation reactions by a set of multiple first-order surface complexation reaction kinetics, thereby eliminating the explicit treatment of aqueous speciation in the intragrain pore water. A model comparison has been carried out for column and field scale scenarios, representing the highly transient hydrological and geochemical conditions in the U(VI)-contaminated aquifer at the Hanford 300A site, Washington, USA. It was found that the response of U(VI) mass transfer behavior to hydrogeochemically induced changes in U(VI) adsorption strength was more pronounced in the physical than in the chemical nonequilibrium model. The magnitude of the differences in model behavior depended particularly on the degree of disequilibrium between the advective and immobile phase U(VI) concentrations. While a clear difference in U(VI) transport behavior between the two models was noticeable for the column-scale scenarios, only minor differences were found for the Hanford 300A field scale scenarios, where the model-generated disequilibrium conditions were less pronounced as a result of frequent groundwater flow reversals.

Water Resources Research↗

USGS2011

Acetate availability and its influence on sustainable bioremediation of Uranium-contaminated groundwater

Field biostimulation experiments at the U.S. Department of Energy's Integrated Field Research Challenge (IFRC) site in Rifle, Colorado, have demonstrated that uranium concentrations in groundwater can be decreased to levels below the U.S. Environmental Protection Agency's (EPA) drinking water standard (0.126 μM). During successive summer experiments – referred to as “Winchester” (2007) and “Big Rusty” (2008) - acetate was added to the aquifer to stimulate the activity of indigenous dissimilatory metal-reducing bacteria capable of reductively immobilizing uranium. The two experiments differed in the length of injection (31 vs. 110 days), the maximum concentration of acetate (5 vs. 30 mM), and the extent to which iron reduction (“Winchester”) or sulfate reduction (“Big Rusty”) was the predominant metabolic process. In both cases, rapid removal of U(VI) from groundwater occurred at calcium concentrations (6 mM) and carbonate alkalinities (8 meq/L) where Ca-UO 2 -CO 3 ternary complexes constitute >90% of uranyl species in groundwater. Complete consumption of acetate and increased alkalinity (>30 meq/L) accompanying the onset of sulfate reduction corresponded to temporary increases in U(VI); however, by increasing acetate concentrations in excess of available sulfate (10 mM), low U(VI) concentrations (0.1–0.05 μM) were achieved for extended periods of time (>140 days). Uniform delivery of acetate during “Big Rusty” was impeded due to decreases in injection well permeability, likely resulting from biomass accumulation and carbonate and sulfide mineral precipitation. Such decreases were not observed during the short-duration “Winchester” experiment. Terminal restriction fragment length polymorphism (TRFLP) analysis of 16S rRNA genes demonstrated that Geobacter sp. and Geobacter -like strains dominated the groundwater community profile during iron reduction, with 13 C stable isotope probing (SIP) results confirming these strains were actively utilizing acetate to replicate their genome during the period of optimal U(VI) removal. Gene transcript levels during “Big Rusty” were quantified for Geobacter -specific citrate synthase ( gltA ), with ongoing transcription during sulfate reduction indicating that members of the Geobacteraceae were still active and likely contributing to U(VI) removal. The persistence of reducible Fe(III) in sediments recovered from an area of prolonged (110-day) sulfate reduction is consistent with this conclusion. These results indicate that acetate availability and its ability to sustain the activity of iron- and uranyl-respiring Geobacter strains during sulfate reduction exerts a primary control on optimized U(VI) removal from groundwater at the Rifle IFRC site over extended time scales (>50 days).

Geomicrobiology Journal↗

USGS2010

Transport of chromium and selenium in the suboxic zone of a shallow aquifer: Influence of redox and adsorption reactions

Breakthrough of Cr(VI) (chromate), Se(VI) (selenate), and O 2 (dissolved oxygen) was observed in tracer tests conducted in a shallow, sand and gravel aquifer with mildly reducing conditions. Loss of Cr, probably due to reduction of Cr(VI) to Cr(III) and irreversible sorption of Cr(III), occurred along with slight retardation of Cr(VI), owing to reversible sorption. Reduction of Se(VI) and O 2 was thermodynamically feasible but did not occur, indicating conditions, were unfavorable to microbial reduction. Cr(VI) reduction by constituents of aquifer sediments did not achieve local equilibrium during transport. The reduction rate was probably limited by incomplete contact between Cr(VI) transported along predominant flow paths and reductants located in regions within aquifer sediments of comparatively low permeability. Scatter in the amount of Cr reduction calculated from individual breakthrough curves at identical distances downgradient probably resulted from heterogeneities in the distribution of reductants in the sediments. Predictive modeling of the transport and fate of redox-sensitive solutes cannot be based strictly on thermodynamic considerations; knowledge of reaction rates is critical. Potentially important mass transfer rate limitations between solutes and reactants in sediments as well as heterogeneities in the distribution of redox properties in aquifers complicate determination of limiting rates for use in predictive simulations of the transport of redox-sensitive contaminants in groundwater.

Water Resources Research↗

USGS2010

Transport of chromium and selenium in a pristine sand and gravel aquifer: Role of adsorption processes

Field transport experiments were conducted in an oxic sand and gravel aquifer using Br (bromide ion), Cr (chromium, injected as Cr(VI)), Se (selenium, injected as Se(VI)), and other tracers. The aquifer has mildly acidic p H values and low concentrations of dissolved salts. Within analytical errors, all mobile Cr was present as Cr(VI). All mobile Se was probably present as Se(VI). Adsorption of Cr and Se onto aquifer sediments caused retardation of both tracers. Breakthrough curves for Cr and Se had extensive tails, which caused large decreases in their maximum concentrations relative to the nonreactive Br tracer after only 2.0 m of transport. A surface complexation model was applied to the results of laboratory studies of Cr(VI) adsorption on aquifer solids from the site based on adsorption onto hydrous ferric oxide. The modeling results suggested that the dominant adsorbents in the aquifer solids have lower affinities for anion adsorption than pure hydrous ferric oxide. The steep rising limbs and extensive tails observed in most of the breakthrough curves are qualitatively consistent with the equilibrium surface complexation model; however, slow rates of adsorption and desorption may have contributed to these features. Variations during transport in the concentrations of Cr, Se, and other anions competing for adsorption sites likely gave rise to variations in the extent of adsorption. Adequate description of the observed retardation of Cr and Se would require a coupled transport-adsorption model that can account for these effects. Companion experiments in the mildly reducing zone of the aquifer (Kent et al., 1994) showed a loss of Cr mass, probably resulting from reduction to Cr(III), and little retardation of mobile Cr and Se during transport; this contrast illustrates the influence of aquifer chemistry on the transport of redox-sensitive solutes.

Water Resources Research↗

USGS2010

Modeling hexavalent chromium reduction in groundwater in field-scale transport and laboratory batch experiments

A plausible and consistent model is developed to obtain a quantitative description of the gradual disappearance of hexavalent chromium (Cr(VI)) from groundwater in a small-scale field tracer test and in batch kinetic experiments using aquifer sediments under similar chemical conditions. The data exhibit three distinct timescales. Fast reduction occurs in well-stirred batch reactors in times much less than 1 hour and is followed by slow reduction over a timescale of the order of 2 days. In the field, reduction occurs on a timescale of the order of 8 days. The model is based on the following hypotheses. The chemical reduction reaction occurs very fast, and the longer timescales are caused by diffusion resistance. Diffusion into the secondary porosity of grains causes the apparent slow reduction rate in batch experiments. In the model of the field experiments, the reducing agent, heavy Fe(II)-bearing minerals, is heterogeneously distributed in thin strata located between larger nonreducing sand lenses that comprise the bulk of the aquifer solids. It is found that reducing strata of the order of centimeters thick are sufficient to contribute enough diffusion resistance to cause the observed longest timescale in the field. A one-dimensional advection/dispersion model is formulated that describes the major experimental trends. Diffusion rates are estimated in terms of an elementary physical picture of flow through a stratified medium containing identically sized spherical grains. Both reduction and sorption reactions are included. Batch simulation results are sensitive to the fraction of reductant located at or near the surface of grains, which controls the amount of rapid reduction, and the secondary porosity, which controls the rate of slow reduction observed in batch experiments. Results of Cr(VI) transport simulations are sensitive to the thickness and relative size of the reducing stratum. Transport simulation results suggest that nearly all of the reductant must be located in the reducing stratum. Within this context and as long as there is adequate reductive capacity present, the transport simulation results are insensitive to the parameters important for the batch simulations. The results illustrate how a combination of field measurements and batch laboratory studies can be used to improve predictive modeling of contaminant transport.

Water Resources Research↗

USGS2009

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10 -8 to 10 -5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10 -3 to 6.0 ?? 10 -3 M in [Ca 2+ ], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Environmental Science & Technology↗

USGS2009

Approaches to modelling uranium (VI) adsorption on natural mineral assemblages

Component additivity (CA) and generalised composite (GC) approaches to deriving a suitable surface complexation model for description of U(VI) adsorption to natural mineral assemblages are pursued in this paper with good success. A single, ferrihydrite-like component is found to reasonably describe uranyl uptake to a number of kaolinitic iron-rich natural substrates at pH > 4 in the CA approach with previously published information on nature of surface complexes, acid-base properties of surface sites and electrostatic effects used in the model. The GC approach, in which little pre-knowledge about generic surface sites is assumed, gives even better fits and would appear to be a method of particular strength for application in areas such as performance assessment provided the model is developed in a careful, stepwise manner with simplicity and goodness of fit as the major criteria for acceptance.

Radiochimica Acta↗

USGS2009

Use of thermodynamic sorption models to derive radionuclide Kd values for performance assessment: Selected results and recommendations of the NEA sorption project

For the safe final disposal and/or long-term storage of radioactive wastes, deep or near-surface underground repositories are being considered world-wide. A central safety feature is the prevention, or sufficient retardation, of radionuclide (RN) migration to the biosphere. To this end, radionuclide sorption is one of the most important processes. Decreasing the uncertainty in radionuclide sorption may contribute significantly to reducing the overall uncertainty of a performance assessment (PA). For PA, sorption is typically characterised by distribution coefficients (Kd values). The conditional nature of Kd requires different estimates of this parameter for each set of geochemical conditions of potential relevance in a RN's migration pathway. As it is not feasible to measure sorption for every set of conditions, the derivation of Kd for PA must rely on data derived from representative model systems. As a result, uncertainty in Kd is largely caused by the need to derive values for conditions not explicitly addressed in experiments. The recently concluded NEA Sorption Project [1] showed that thermodynamic sorption models (TSMs) are uniquely suited to derive K d as a function of conditions, because they allow a direct coupling of sorption with variable solution chemistry and mineralogy in a thermodynamic framework. The results of the project enable assessment of the suitability of various TSM approaches for PA-relevant applications as well as of the potential and limitations of TSMs to model RN sorption in complex systems. ?? by Oldenbourg Wissenschaftsverlag.

Conference Paper↗

USGS2009

Uranium adsorption on weathered schist - Intercomparison of modeling approaches

Experimental data for uranium adsorption on a complex weathered rock were simulated by twelve modelling teams from eight countries using surface complexation (SC) models. This intercomparison was part of an international project to evaluate the present capabilities and limitations of SC models in representing sorption by geologic materials. The models were assessed in terms of their predictive ability, data requirements, number of optimised parameters, ability to simulate diverse chemical conditions and transferability to other substrates. A particular aim was to compare the generalised composite (GC) and component additivity (CA) approaches for modelling sorption by complex substrates. Both types of SC models showed a promising capability to simulate sorption data obtained across a range of chemical conditions. However, the models incorporated a wide variety of assumptions, particularly in terms of input parameters such as site densities and surface site types. Furthermore, the methods used to extrapolate the model simulations to different weathered rock samples collected at the same field site tended to be unsatisfactory. The outcome of this modelling exercise provides an overview of the present status of adsorption modelling in the context of radionuclide migration as practised in a number of countries worldwide.

Radiochimica Acta↗

USGS2009

Comparing approaches for simulating the reactive transport of U(VI) in ground water

The reactive transport of U(VI) in a well-characterized shallow alluvial aquifer at a former U(VI) mill located near Naturita, CO, was predicted for comparative purposes using a surface complexation model (SCM) and a constant K d approach to simulate U(VI) adsorption. The ground water at the site had U(VI) concentrations that ranged from 0.01 to 20 µM, alkalinities that ranged from 2.5 to 18 meq/L, and a nearly constant pH of 7.1. The SCM used to simulate U(VI) adsorption was previously determined independently using laboratory batch adsorption experiments. Simulations obtained using the SCM approach were compared with simulations that used a constant K d approach to simulate adsorption using previously determined site-specific K d values. In both cases, the ground water flow and transport models used a conceptual model that was previously calibrated to a chloride plume present at the site. Simulations with the SCM approach demonstrated that the retardation factor varied temporally and spatially because of the differential transport of alkalinity and dissolved U(VI) and the nonlinearity of the U(VI) adsorption. The SCM model also simulated a prolonged slow decline in U(VI) concentration, which was not simulated using a constant K d model. Simulations using the SCM approach and the constant K d approach were similar after 20 years of transport but diverged significantly after 60 years. The simulations demonstrate the need for site-specific geochemical information on U(VI) adsorption to produce credible simulations of future transport.

Mine Water and the Environment↗

USGS2009

Newly recognized hosts for uranium in the Hanford Site vadose zone

Uranium contaminated sediments from the U.S. Department of Energy’s Hanford Site have been investigated using electron microscopy. Six classes of solid hosts for uranium were identified. Preliminary sediment characterization was carried out using optical petrography, and electron microprobe analysis (EMPA) was used to locate materials that host uranium. All of the hosts are fine-grained and intergrown with other materials at spatial scales smaller than the analytical volume of the electron microprobe. A focused ion beam (FIB) was used to prepare electron-transparent specimens of each host for the transmission electron microscope (TEM). The hosts were identified as: (1) metatorbernite [Cu(UO 2 ) 2 (PO 4 ) 2 ·8H 2 O]; (2) coatings on sediment clasts comprised mainly of phyllosilicates; (3) an amorphous zirconium (oxyhydr)oxide found in clast coatings; (4) amorphous and poorly crystalline materials that line voids within basalt lithic fragments; (5) amorphous palagonite surrounding fragments of basaltic glass; and (6) Fe- and Mn-oxides. These findings demonstrate the effectiveness of combining EMPA, FIB, and TEM to identify solid-phase contaminant hosts. Furthermore, they highlight the complexity of U geochemistry in the Hanford vadose zone, and illustrate the importance of microscopic transport in controlling the fate of contaminant metals in the environment.

Geochimica et Cosmochimica Acta↗

USGS2009

The kinetics of iodide oxidation by the manganese oxide mineral birnessite

The kinetics of iodide (I − ) and molecular iodine (I 2 ) oxidation by the manganese oxide mineral birnessite (δ-MnO 2 ) was investigated over the pH range 4.5–6.25. I − oxidation to iodate ( IO 3 - ) "> (IO3-) proceeded as a two-step reaction through an I 2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I − from solution was first order with respect to I − concentration, pH, and birnessite concentration, such that − d [I − ]/ dt = k [I − ][H + ][MnO 2 ], where k , the third order rate constant, is equal to 1.08 ± 0.06 × 10 7 M −2 h −1 . The data are consistent with the formation of an inner sphere I − surface complex as the first step of the reaction, and the adsorption of I − exhibited significant pH dependence. Both I 2 , and to a lesser extent, IO 3 - "> IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I 2 and IO 3 - "> IO3- , as well as the biophilic nature of I 2 , redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

Geochimica et Cosmochimica Acta↗

USGS2008

Influence of variable chemical conditions on EDTA-enhanced transport of metal ions in mildly acidic groundwater

Adsorption of Ni and Pb on aquifer sediments from Cape Cod, Massachusetts, USA increased with increasing pH and metal-ion concentration. Adsorption could be described quantitatively using a semi-mechanistic surface complexation model (SCM), in which adsorption is described using chemical reactions between metal ions and adsorption sites. Equilibrium reactive transport simulations incorporating the SCMs, formation of metal-ion-EDTA complexes, and either Fe(III)-oxyhydroxide solubility or Zn desorption from sediments identified important factors responsible for trends observed during transport experiments conducted with EDTA complexes of Ni, Zn, and Pb in the Cape Cod aquifer. Dissociation of Pb-EDTA by Fe(III) is more favorable than Ni-EDTA because of differences in Ni- and Pb-adsorption to the sediments. Dissociation of Ni-EDTA becomes more favorable with decreasing Ni-EDTA concentration and decreasing pH. In contrast to Ni, Pb-EDTA can be dissociated by Zn desorbed from the aquifer sediments. Variability in adsorbed Zn concentrations has a large impact on Pb-EDTA dissociation.

Environmental Pollution↗

USGS2007

Modeling the movement of a pH perturbation and its impact on adsorbed zinc and phosphate in a wastewater‐contaminated aquifer

[1] Chemical conditions were perturbed in an aquifer with an ambient pH of 5.9 and wastewater-derived adsorbed zinc (Zn) and phosphate (P) contamination by injecting a pulse of amended groundwater. The injected groundwater had low concentrations of dissolved Zn and P, a pH value of 4.5 resulting from equilibration with carbon dioxide gas, and added potassium bromide (KBr). Downgradient of the injection, breakthrough of nonreactive Br and total dissolved carbonate concentrations in excess of ambient values (excess TCO 2 ) were accompanied by a decrease in pH values and over twentyfold increases in dissolved Zn concentrations above preinjection values. Peak concentrations of Br and excess TCO 2 were followed by slow increases in pH values accompanied by significant increases in dissolved P above preinjection concentrations. The injected tracers mobilized a significant mass of wastewater-derived Zn. Reactive transport simulations incorporating surface complexation models for adsorption of Zn, P, hydrogen ions, and major cations onto the aquifer sediments, calibrated using laboratory experimental data, captured most of the important trends observed during the experiment. These include increases in Zn concentrations in response to the pH perturbation, perturbations in major cation concentrations, attenuation of the pH perturbation with transport distance, and increases in alkalinity with transport distance. Observed desorption of P in response to chemical perturbations was not predicted, possibly because of a disparity between the range of chemical conditions in the calibration data set and those encountered during the field experiment. Zinc and P desorbed rapidly in response to changing chemical conditions despite decades of contact with the sediments. Surface complexation models with relatively few parameters in the form of logK values and site concentrations show considerable promise for describing the influence of variable chemistry on the transport of adsorbing contaminants.

Water Resources Research↗

USGS2007

Spectroscopic evidence for uranium bearing precipitates in vadose zone sediments at the Hanford 300-area site

Uranium (U) solid-state speciation in vadose zone sediments collected beneath the former North Process Pond (NPP) in the 300 Area of the Hanford site (Washington) was investigated using multi-scale techniques. In 30 day batch experiments, only a small fraction of total U (???7.4%) was released to artificial groundwater solutions equilibrated with 1% pCO2. Synchrotron-based micro-X-ray fluorescence spectroscopy analyses showed that U was distributed among at least two types of species: (i) U discrete grains associated with Cu and (ii) areas with intermediate U concentrations on grains and grain coatings. Metatorbernite (Cu[UO2]2[PO 4]2??8H2O) and uranophane (Ca[UO 2]2[SiO3(OH)]2?? 5H 2O) at some U discrete grains, and muscovite at U intermediate concentration areas, were identified in synchrotron-based micro-X-ray diffraction. Scanning electron microscopy/energy dispersive X-ray analyses revealed 8-10 ??m size metatorbernite particles that were embedded in C-, Al-, and Si-rich coatings on quartz and albite grains. In ??- and bulk-X-ray absorption structure (??-XAS and XAS) spectroscopy analyses, the structure of metatorbernite with additional U-C and U-U coordination environments was consistently observed at U discrete grains with high U concentrations. The consistency of the ??- and bulk-XAS analyses suggests that metatorbernite may comprise a significant fraction of the total U in the sample. The entrapped, micrometer-sized metatorbernite particles in C-, Al-, and Si-rich coatings, along with the more soluble precipitated uranyl carbonates and uranophane, likely control the long-term release of U to water associated with the vadose zone sediments. ?? 2007 American Chemical Society.

Environmental Science & Technology↗

USGS2006

Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6–0.9 m 2 g −1 ) and reductively extractable iron contents (18–26 μmol m −2 ), but with varying total manganese contents (0.5–3.5 μmol m −2 ) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the concentrations of the free oxidative surface sites and dissolved As(III), as r As ( V ) = k ox ′ [ Mn ( IV ) OH ] [ H 3 AsO 3 ] "> rAs(V)=kox′[Mn(IV)OH][H3AsO3] with apparent second-order rate constants of k ox f ′ = 6.28 × 10 - 1 "> koxf′=6.28×10-1 and k ox s ′ = 1.25 × 10 - 2 M - 1 s - 1 "> koxs′=1.25×10-2M-1s-1 for the fast and the slow oxidative sites, respectively. The As(III) removal rate decreased approximately by half for a pH increase from 4 to 7. The pH dependence was explained using the acid–base behavior of the surface oxidative sites by considering a surface p K a = 6.2 ( I = 0). In the presence of excess surface adsorptive and oxidative sites, phosphate diminished the rate of As(III) removal and As(V) production only slightly due to its interaction with the oxidative sites. The observed As(III) oxidation rate here is consistent with previous observations of As(III) oxidation over short transport distances during field-scale transport experiments. The model developed here may be incorporated into groundwater transport models to predict arsenic speciation and transport in chemically heterogeneous systems.

Geochimica et Cosmochimica Acta↗

USGS2006

The effect of calcium on aqueous uranium(VI) speciation and adsorption to ferrihydrite and quartz

Recent studies of uranium(VI) geochemistry have focused on the potentially important role of the aqueous species, CaUO 2 (CO 3 ) 3 2− and Ca 2 UO 2 (CO 3 ) 3 0 (aq), on inhibition of microbial reduction and uranium(VI) aqueous speciation in contaminated groundwater. However, to our knowledge, there have been no direct studies of the effects of these species on U(VI) adsorption by mineral phases. The sorption of U(VI) on quartz and ferrihydrite was investigated in NaNO 3 solutions equilibrated with either ambient air (430 ppm CO 2 ) or 2% CO 2 in the presence of 0, 1.8, or 8.9 mM Ca 2+ . Under conditions where the Ca 2 UO 2 (CO 3 ) 3 0 (aq) species predominates U(VI) aqueous speciation, the presence of Ca in solution lowered U(VI) adsorption on quartz from 77% in the absence of Ca to 42% and 10% at Ca concentrations of 1.8 and 8.9 mM, respectively. U(VI) adsorption to ferrihydrite decreased from 83% in the absence of Ca to 57% in the presence of 1.8 mM Ca. Surface complexation model predictions that included the formation constant for aqueous Ca 2 UO 2 (CO 3 ) 3 0 (aq) accurately simulated the effect of Ca 2+ on U(VI) sorption onto quartz and ferrihydrite within the thermodynamic uncertainty of the stability constant value. This study confirms that Ca 2+ can have a significant impact on the aqueous speciation of U(VI), and consequently, on the sorption and mobility of U(VI) in aquifers.

Geochimica et Cosmochimica Acta↗