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Mark O Barnett

Publications and source records attributed to Mark O Barnett.

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Effects of solid-to-solution ratio on uranium(VI) adsorption and its implications.

U(VI) adsorption onto goethite-coated sand was studied in batch experiments ata solid-to-solution ratio (SSR) ranging from 33.3 to 333 g/L. Batch kinetic experiments revealed that the presence of 10(-4) M phosphate increased both the initial rate and ultimate extent of U(VI) adsorption compared with phosphate-free systems. Our experimental U(VI) adsorption isotherms were independent of SSR in phosphate-free systems. However, the U(VI) adsorption isotherm became dependent on SSR in phosphate-containing systems (with a lower SSR resulting in stronger U(VI) adsorption). A surface complexation model (SCM) was used to conceptualize the interactions in systems containing U(VI), phosphate, and goethite contributing to this SSR effect. The SCM accounted for the effects of SSR on U(VI) adsorption reasonably well. This study implies that the extrapolation of batch-measured adsorption parameters of U(VI) (and potentially other radionuclides and metal(loid)s as well) to field conditions should be done with caution, especially in the presence of strongly interacting ligands.

Adsorption↗

Methyl tertiary hexyl ether and methyl tertiary octyl ether as gasoline oxygenates: assessing risks from atmospheric dispersion and deposition.

Methyl tertiary hexyl ether (MtHxE) and methyl tertiary octyl ether (MtOcE) are currently being developed as replacement oxygenates for methyl tertiary butyl ether (MtBE) in gasoline. As was the case with MtBE, the introduction of these ethers into fuel supplies guarantees their introduction into the environment as well. In this study, a screening-level risk assessment was performed by comparing predicted environmental concentrations (PEC) of these ethers to concentrations that might cause adverse effects to humans or ecosystems. A simple box model that has successfully estimated urban air concentrations of MtBE was adapted to predict atmospheric concentrations of MtHxE and MtOcE. Expected atmospheric concentrations of these ethers were also estimated using the European Union System for the Evaluation of Substances (EUSES) multimedia fate model, which simultaneously calculates PECs in the various environmental compartments of air, water, soil, and sediment. Because little or no data are available on the physicochemical, environmental, and toxicological properties of MtHxE and MtOcE, estimation methods were used in conjunction with EUSES to predict both the PECs and the concentrations at which these ethers might pose a threat. The results suggest that these ethers would contaminate the air of a moderately sized U.S. city (Boston, MA) at levels similar to those found previously for MtBE. The risk assessment module in EUSES predicted risk characterization ratios of 10(-3) and 10(-2) for MtHxE and MtOcE, respectively, in Boston, and 10(-2) and 10(-1) in very large urban centers, suggesting that these ethers pose only a minimal threat to ecosystems at the anticipated environmental concentrations. The assessment also indicates that these compounds are possible human carcinogens and that they may be present in urban air at concentrations that pose an unacceptable cancer risk. Therefore, testing of the toxicological properties of these compounds is recommended before they replace MtBE in gasoline.

Animals↗

Effects of dissolved carbonate on arsenic adsorption and mobility.

The effects of high aqueous carbonate concentrations on arsenic mobility and transport in the subsurface were studied in synthetic iron oxide-coated sand column experiments. Elevated aqueous carbonate concentrations in groundwater have been studied and linked, by some authors, to increased aqueous As concentrations in natural waters. This study found that increasing carbonate concentrations had relatively little effect on As(V) adsorption to the iron oxide-coated sand surface at pH 7. The adsorption of As(V) decreased marginally when the CO2(g) partial pressure increased from 10(-3.5) to 10(-1.8) atm, despite a 50-fold increase in total dissolved carbonate (0.072 to 3.58 mM). Increasing the CO2(g) partial pressure to 10(-10) atm resulted in only a slight decrease in As(V) adsorption and increase in mobility, despite a >300-fold increase in total dissolved carbonate (to 22.7 mM). When compared to phosphate, a known competitive anion, carbonate mobilized less adsorbed As(V) than was mobilized by phosphate, even when present in much higher concentrations than phosphate. This was also true for an experiment with lower pore water velocity and an experiment where As(II) was introduced instead of As(V). Our experiments conclude that while carbonate anions do compete with As for adsorption to iron oxide-coated sand, the competitive effect is relatively small with regard to the total concentration of adsorbed As and the potential competitive effects of phosphate.

Adsorption↗

Adsorption, oxidation, and bioaccessibility of As(III) in soils.

At As-contaminated sites, where the ingestion of soil by children is typically the critical human-health exposure pathway, information on the bioavailability of soil-bound As is often limited. The influence of various soil physical and chemical properties (iron and manganese oxides, pH, cation exchange capacity, total inorganic and organic carbon, and particle size) on As(III) adsorption, sequestration, bioaccessibility (as a surrogate for oral bioavailability), and oxidation was investigated in 36 well-characterized soils by use of a physiologically based extraction test (PBET). These results were compared to an earlier published study with As(V) on the same set of soils. The properties of the soils were able to explain >80% of the variability in the adsorption and sequestration (as measured by the reduction in bioaccessibility over time) of As(III) in these soils. The initial bioaccessibility of As(III) was significantly higher than the initial bioaccessibility of As(V) on the same set of soils. However, over a 6-month period of aerobic aging, a significant portion of the solid-phase As(III) on these soils was oxidized to As(V), decreasing its bioaccessibility markedly. A multivariable linear regression model previously developed to predict the steady-state bioaccessibility of As(V) in soils was able to predict the bioaccessibility in As(III)-spiked soils within a root-mean-square error (RMSE) of 16.8%. Generally, soils having a higher iron oxide content and lower soil pH exhibited lower bioaccessibility. This model was also able to predict the in vivo bioavailability of As in contaminated soils previously used in an independent juvenile swine dosing trial within an RMSE of 15.5%, providing a greatly improved yet conservative estimate of bioavailability relative to the typical default assumption of 100%. However, the model was not able to accurately predict the bioavailability of As in a different set of contaminated soils previously used in an independent Cebus monkey dosing trial, consistently overpredicting the bioavailability, resulting in an RMSE of 42.7%. This model can be used to provide an initial estimate of As bioavailability in soil to aid in screening sites and justifying expensive site-specific animal feeding studies. Further, as the model is based on major soil properties, the resulting estimates are valid as long as the major soil properties do not change, thus providing some confidence in the long-term applicability of the estimates.

Adsorption↗

Chemical reduction of U(VI) by Fe(II) at the solid-water interface using natural and synthetic Fe(III) oxides.

Abiotic reduction of 0.1 mM U(VI) by Fe(II) in the presence of synthetic iron oxides (biogenic magnetite, goethite, and hematite) and natural Fe(III) oxide-containing solids was investigated in pH 6.8 artificial groundwater containing 10 mM NaHCO3. In most experiments, more than 95% of added U(VI) was sorbed to solids. U(VI) was rapidly and extensively (> or = 80%) reduced in the presence of synthetic Fe(III) oxides and highly Fe(II) oxide-enriched (18-35 wt % Fe) Atlantic coastal plain sediments. In contrast, long-term (20-60 d) U(VI) reduction was less than 30% in suspensions of six other natural solids with relatively low Fe(III) oxide content (1-5 wt % Fe). Fe(II) sorption site density was severalfold lower on these natural solids (0.2-1.1 Fe(II) nm(-2)) compared tothe synthetic Fe(lII) oxides (1.6-3.2 Fe(II) nm(-2)), which may explain the poor U(VI) reduction in the natural solid-containing systems. Addition of the reduced form of the electron shuttling compound anthrahydroquinone-2,6-disulfonate (AH2DS; final concentration 2.5 mM) to the natural solid suspensions enhanced the rate and extent of U(VI) reduction, suggesting that AH2DS reduced U(VI) at surface sites where reaction of U(VI) with sorbed Fe(II) was limited. This study demonstrates that abiotic, Fe(II)-driven U(VI) reduction is likely to be less efficient in natural soils and sediments than would be inferred from studies with synthetic Fe(III) oxides.

Adsorption↗

Effects of phosphate on uranium(VI) adsorption to goethite-coated sand.

U(VI)-phosphate interactions are important in governing the subsurface mobility of U(VI) in both natural and contaminated environments. We studied U(VI) adsorption on goethite-coated sand (to mimic natural Fe-coated subsurface materials) as a function of pH in systems closed to the atmosphere, in both the presence and the absence of phosphate. Our results indicate that phosphate strongly affects U(VI) adsorption. The effect of phosphate on U(VI) adsorption was dependent on solution pH. At low pH, the adsorption of U(VI) increased in the presence of phosphate, and higher phosphate concentration caused a larger extent of increase in U(VI) adsorption. Phosphate was strongly bound by the goethite surface in the low pH range, and the increased adsorption of U(VI) at low pH was attributed to the formation of ternary surface complexes involving both U(VI) and phosphate. In the high pH range, the adsorption of U(VI) decreased in the presence of phosphate at low total Fe concentration, and higher phosphate concentration caused a larger extent of decrease in U(VI) adsorption. This decrease in U(VI) adsorption was attributed to the formation of soluble uranium-phosphate complexes. A surface complexation model (SCM) was proposed to describe the effect of phosphate on U(VI) adsorption to goethite. This proposed model was based on previous models that predict U(VI) adsorption to iron oxides in the absence of phosphate and previous models developed to predict phosphate adsorption on goethite. A postulated ternary surface complex of the form of (>FePO4UO2) was included in our model to account for the interactions between U(VI) and phosphate. The model we established can successfully predict U(VI) adsorption in the presence of phosphate under a range of conditions (i.e., pH, total phosphate concentration, and total Fe concentration).

Adsorption↗

Microbial reduction of U(VI) at the solid-water interface.

Microbial (Geobacter sulfurreducens) reduction of 0.1 mM U(VI) in the presence of synthetic Fe(III) oxides and natural Fe(III) oxide-containing solids was investigated in pH 6.8 artificial groundwater containing 10 mM NaHCO3. In most experiments, more than 95% of added U(VI) was sorbed to solids, so that U(VI) reduction was governed by reactions at the solid-water interface. The rate and extent of reduction of U(VI) associated with surfaces of synthetic Fe(III) oxides (hydrous ferric oxide, goethite, and hematite) was comparable to that observed during reduction of aqueous U(VI). In contrast, microbial reduction of U(VI) sorbed to several different natural Fe(III) oxide-containing solids was slower and less extensive compared to synthetic Fe(III) oxide systems. Addition of the electron shuttling agent anthraquinone-2,6-disulfonate (AQDS; 0.1 mM) enhanced the rate and extent of both Fe(III) and U(VI) reduction. These findings suggest that AQDS facilitated electron transfer from G. sulfurreducens to U(VI) associated with surface sites atwhich direct enzymatic reduction was kinetically limited. Our results demonstrate that association of U(VI) with diverse surface sites in natural soils and sediments has the potential to limit the rate and extent of microbial U(VI) reduction and thereby modulate the effectiveness of in situ U(VI) bioremediation.

Anthraquinones↗

Adsorption, sequestration, and bioaccessibility of As(V) in soils.

The influence of various soil physical and chemical properties (Fe and Mn oxides, pH, cation exchange capacity, total inorganic and organic carbon, and particle size) on As(V) adsorption, sequestration, and relative bioaccessibility (as a surrogate for oral bioavailability) was investigated in a wide range of well-characterized soils over a 6-month period. Arsenic(V) bioaccessibility was measured using a streamlined version of a physiologically based extracton test (PBET), designed to replicate the solubility-limiting conditions in a child's digestive tract. The soil's dithionite-citrate-bicarbonate (DCB) extractable Fe oxide content was the most important land only statistically significant) soil property controlling the initial degree of adsorption. Sequestration, as measured by the reduction in bioaccessibility over time, occurred to a significant extent in 17 of 36 (47.2%) soils over the first 3 months. In contrast, only 4 of 36 (11.1%) soils exhibited a significant reduction in bioaccessibility from 3 to 6 months. Soil pH was the most important (and only statistically significant) soil property affecting the decrease in bioaccessibility upon aging for 6 months. Soils with pH < 6 generally sequestered As(V) more strongly over time, whereas those with pH > 6 generally did not. The Fe oxide content and pH were the most important soil properties governing the steady-state bioaccessibility of As(V) in soil. Two multivariable linear regression models of steady-state As(V) bioaccessibility were developed using soil properties as independent variables. Generally, soils having higher Fe oxide content and lower soil pH exhibited lower bioaccessibility. These models were able to account for approximately 75-80% of the variability in steady-state bioaccessibility and independently predict bioaccessibility in five soils within a root-mean-square error (RMSE) of 8.2-10.9%. One of these models was also able to predict within an RMSE of 9.5% the in vivo bioavailability of As in nine contaminated soils previously used in swine dosing trials. These results indicate the bioaccessibility, and thus, potentially the bioavailability of otherwise soluble As(V) added to soils (i.e., the worst-case bioavailability scenario) is significantly reduced in some soils over time, particularly those with lower pH and higher Fe oxide content. These results also provide a means of estimating As(V) bioaccessibility and bioavailability on the basis of soil properties.

Adsorption↗

U(VI) adsorption to heterogeneous subsurface media: application of a surface complexation model.

The pH-dependent adsorption of U(VI) onto three heterogeneous, subsurface media from the Department of Energy (DOE) Oak Ridge Reservation, Savannah River Site, and Hanford Reservation was investigated. The three materials contained significant quantities of iron and manganese oxides with nearly identical extractable iron oxide contents (25.3-25.8 g/kg). A model independently developed for the adsorption of U(VI) to synthetic ferrihydrite (Waite, T. D.; Davis, J. A.; Payne, T. E.; Waychunas, G. A.; Xu, N. Geochim. Cosmochim. Acta 1994, 58, 5465-5478) was able to predict the major features of the pH-dependent U(VI) adsorption to the materials under the assumption that all the dithionite-citrate-bicarbonate extractable iron oxide was present as ferrihydrite. Further experiments with the Oak Ridge soil as a function of carbonate and U(VI) concentration indicated that the model could predict pH-dependent U(VI) adsorption to within a root mean square error of 0.163-0.408, even under conditions outside of those for which the model was developed. These results indicate that this model could be used as a first approximation in predicting U(VI) adsorption and transport in the subsurface. U(VI) adsorption also decreased at pH >10, even in the absence of carbonate, which is of potential importance to U(VI) mobility in extreme environments present in the subsurface at some DOE facilities. The pH-dependent adsorption of U(VI) was fundamentally different in systems with a constant CO2 partial pressure as compared to a constant total carbonate concentration. Experiments at constant CO2 partial pressure may not be representative of the conditions present in the subsurface, and a constant carbonate concentration does not always result in decreased U(VI) adsorption at higher pH values.

Adsorption↗

Adsorption and transport of arsenic(V) in experimental subsurface systems.

The adsorption and transport of As(V) in a heterogeneous, iron oxide-containing soil was investigated in batch and column laboratory experiments. The As(V) adsorbed rapidly to the soil over the first 48 h, but continued to adsorb slowly over the next several weeks, clearly indicating the potential for rate-limited transport. The equilibrium As(V) adsorption isotherm was markedly nonlinear, further indicating the potential for nonideal transport. A model developed for the adsorption of As(V) to hydrous ferric oxide (HFO) was able to predict the pH-dependent adsorption of As(V) to the soil in batch experiments within 0.116 to 0.726 root mean square error (RMSE). Arsenic(V) was significantly retarded in column transport experiments. The column transport experiments were modeled using the one-dimensional advection-dispersion equation, considering both linear and nonlinear adsorption equilibrium. Although the nonlinear local equilibrium model (NLLE, RMSE = 0.273) predicted the data better than the linear local equilibrium model (LLE, RMSE = 0.317), As(V) breakthrough occurred more rapidly than predicted by either model due to adsorption nonequilibrium. However, due to the presence of an irreversible or slowly desorbing fraction, the peak aqueous As(V) concentration (0.624 mg L(-1)) and the total amount of As(V) recovered (44%) was lower than predicted based on the two equilibrium models (NLLE and LLE). For the conditions used in this study [1 mg L(-1) As(V), pH 4.5 and 9,0-0.25 mM PO4, 0.53-1.6 cm min(-1) pore water velocity], the effect on As(V) mobility and recovery increased in the order pH < pore water velocity < PO4.

Adsorption↗