Mark O. Barnett

An assessment of U(VI) removal from groundwater using biochar produced from hydrothermal carbonization.

The ever-increasing growth of biorefineries is expected to produce huge amounts of lignocellulosic biochar as a byproduct. The hydrothermal carbonization (HTC) process to produce biochar from lignocellulosic biomass is getting more attention due to its inherent advantage of using wet biomass. In the present study, biochar was produced from switchgrass at 300 °C in subcritical water and characterized using X-ray diffraction, fourier transform infra-red spectroscopy, scanning electron micrcoscopy, and thermogravimetric analysis. The physiochemical properties indicated that biochar could serve as an excellent adsorbent to remove uranium from groundwater. A batch adsorption experiment at the natural pH (~3.9) of biochar indicated an H-type isotherm. The adsorption data was fitted using a Langmuir isotherm model and the sorption capacity was estimated to be ca. 2.12 mg of U g(-1) of biochar. The adsorption process was highly dependent on the pH of the system. An increase towards circumneutral pH resulted in the maximum adsorption of ca. 4 mg U g(-1) of biochar. The adsorption mechanism of U(VI) onto biochar was strongly related to its pH-dependent aqueous speciation. The results of the column study indicate that biochar could be used as an effective adsorbent for U(VI), as a reactive barrier medium. Overall, the biochar produced via HTC is environmentally benign, carbon neutral, and efficient in removing U(VI) from groundwater.

Dynamic flux chamber measurement of gaseous mercury emission fluxes over soils: Part 2—effect of flushing flow rate and verification of a two-resistance exchange interface simulation model

Both field and laboratory tests demonstrated that soil Hg emission fluxes measured by dynamic flux chamber (DFC) operations strongly depend on the flushing air flow rates used. The general trend is an increase in the fluxes with increasing flushing flow rates followed by an asymptotic approach to flux maximum at sufficiently high (optimum) flushing flow rates. This study indicates that the DFC measurements performed at low flushing flow rates can underestimate Hg emission fluxes over soils, especially Hg-enriched soils. High flushing flow rates therefore are recommended for accurate estimation of soil Hg emission fluxes by DFC operations. The dependence of DFC-measured soil Hg emission fluxes on flushing flow rate is a physical phenomenon inherent in DFC operations, regardless of DFC design and soil physical characteristics. Laboratory tests using DFCs over different soils confirmed the predictions of a two-resistance exchange interface model and demonstrated the capability of this model in quantitatively simulating Hg emissions from soils measured by DFC operations.

Immobilization of mercury in sediment using stabilized iron sulfide nanoparticles.

Mercury (Hg) immobilization using stabilized iron sulfide (FeS) nanoparticles was investigated through a series of batch and column experiments. The nanoparticles were prepared using a low-cost, food-grade cellulose (sodium carboxymethyl cellulose, CMC) as the stabilizer. The hydrodynamic diameter of fresh FeS-CMC nanoparticles was measured to be 38.5+/-5.4nm. Batch tests showed that the nanoparticles can effectively immobilize Hg in a clay loam sediment. The Hg distribution coefficient for the nanoparticles was determined to be 8930+/-1480L/g, which is >4 orders of magnitude greater than for the sediment. When the Hg-laden sediment was treated at an FeS-to-Hg molar ratio of 26.5, the Hg concentration leached into water was reduced by 97% and the TCLP (toxicity characteristic leaching procedure) leachability of Hg was reduced by 99%. Column tests showed that water-leachable mercury from the sediment containing 3120mg/L Hg was reduced by 67% and the TCLP leachability by >77% when the sediment was treated with 67 pore volumes (PVs) of a 0.5g/L FeS nanoparticle suspension. Column tests proved that the stabilized nanoparticles were highly mobile in the sediment and full breakthrough of the nanoparticles occurred at approximately 18 PVs.

Factors Controlling the Bioaccessibility of Arsenic(V) and Lead(II) in Soil

The relative oral bioaccessibility of labile Pb(II) and As(V) added to soils was investigated in a well-characterized soil using a physiologically based extraction test (PBET) to simulate metal solubility in a childs digestive system. The effect of soil and PBET (i.e., simulated stomach and small intestine) pH, soil metal concentration, soil to solution ratio, and soil-metal aging time were investigated. Arsenic bioaccessibility was relatively unaffected by a variation in simulated stomach and small intestine pH over the range 2 to 7 and soil pH over the range 4.5 to 9.4. In contrast, Pb(II) bioaccessibility was strongly dependent on both the simulated stomach, small intestine, and soil pH, showing enhanced sequestration and decreased bioaccessibility at higher pH values in all cases. Although the bioaccessibility of Pb(II) was constant over the concentration range of approximately 10 to 10,000 mg/kg, the As(V) bioaccessibility significantly increased over this concentration range. The bioaccessibility of both arsenic and lead increased as the soil-to-solution ratio decreased from 1:40 to 1:100. Additional lead sequestration was not observed during 6 months of soil aging, but As(V) bioaccessibility decreased significantly during this period.

Potential negative consequences of adding phosphorus-based fertilizers to immobilize lead in soil

A study of the potential negative consequences of adding phosphate (P)-based fertilizers as amendments to immobilize lead (Pb) in contaminated soils was conducted. Lead-contaminated firing range soils also contained elevated concentrations of antimony (Sb), a common Pb hardening agent, and some arsenic (As) of unknown (possibly background) origin. After amending the soils with triple superphosphate, a relatively soluble P source, column leaching experiments revealed elevated concentrations of Sb, As, and Pb in the leachate, reflecting an initial spike in soluble Pb and a particularly dramatic increase in Sb and As mobility. Minimal As, Sb, and Pb leaching was observed during column tests performed on non-amended control soils. In vitro extractions tests were performed to assess changes in Pb, As, and Sb bioaccessibility on P amendment. Lead bioaccessibility was systematically lowered with increasing P dosage, but there was much less of an effect on As and Sb bioaccessibility than on mobility. Our results indicate that although P amendments may aid in lowering the bioaccessibility of soil-bound Pb, it may also produce an initial increase in Pb mobility and a significant release of Sb and As from the soil, dramatically increasing their mobility and to a lesser extent their bioavailability.

Immobilization of mercury by pyrite (FeS2)

Elemental mercury (Hg(0)) is a metal with a number of atypical properties, which has resulted in its use in myriad anthropogenic processes. However, these same properties have also led to severe local subsurface contamination at many places where it has been used. As such, we studied the influence of various parameters on Hg(II) sorption onto pyrite (pH, time, Hg(II) concentration), a potential subsurface reactive barrier. Batch sorption studies revealed that total Hg(II) removal increases with both pH and time. X-ray absorption spectroscopy analysis showed that a transformation in the coordination environment at low pH occurred during aging over 2 weeks, to form an ordered monolayer of monodentate Hg-Cl complexes on pyrite. In column studies packed with pure quartz sand, the transport of Hg(II) was significantly retarded by the presence of a thin pyrite-sand reactive barrier, although dissolved oxygen inhibited Hg(II) sorption onto pyrite in the column.

Effects of Contaminant Concentration, Aging, and Soil Properties on the Bioaccessibility of Cr(III) and Cr(VI) in Soil

Contaminated soils at numerous U.S. Department of Defense, Department of Energy, and other industrial facilities often contain huge inventories of toxic metals such as chromium. Ingestion of soil by children is often the primary risk factor that drives the need for remediation. Site assessments are typically based solely on total soil-metal concentrations and do not consider the potential for decreased bioaccessibility due to metal sequestration by soil. The objectives of this research are to investigate the effect of soil properties on the bioaccessibility of Cr(III) and Cr(VI) as a function of contaminant concentration and aging. The A and upper B horizons of two well-characterized soils, representative of Cr-contaminated soils in the southeastern United States, were treated with varying concentration of Cr(III) and Cr(VI) and allowed to age. The bioaccessibility of the contaminated soils was measured over a 200-d time period using a physiologically based extraction test (PBET) that was designed to simulate the digestive process of the stomach. The sorption of Cr(III) and Cr(VI) varied significantly as a function of soil type and horizon, and the oxidation state of the contaminant. Solid phase concentrations with Cr(III) were significantly greater than Cr(VI) for any given initial Cr concentration. This is consistent with the mechanisms of Cr(III) vs. Cr(VI) sequestration by the soils, where the formation of Cr(III)-hydroxides can result in the accumulation of large mass fractions of contaminant on mineral surfaces. Overall, Cr bioaccessibility decreased with duration of exposure for all soils and at all solid phase concentrations, with aging effects being more pronounced for Cr(III). The decrease in Cr bioaccessibility was rapid for the first 50 d and then slowed dramatically between 50 and 200 d. In general, the effects of Cr solid phase concentration on bioaccessibility was small, with Cr(III) showing the most pronounced effect; higher solid phase concentrations resulted in a decrease in bioaccessibility. Chemical extraction methods and X-ray Adsorption Spectroscopy analyses suggested that the bioaccessibility of Cr(VI) was significantly influenced by reduction processes catalyzed by soil organic carbon. Soils with sufficient organic carbon had lower Cr bioaccessibility values (∼10 to 20%) due to an enhanced reduction of Cr(VI) to Cr(III). In soils where organic carbon was limited and reduction processes were minimal, the bioaccessibility of Cr(VI) dramatically increased (∼60 to 70%).

Impact of natural organic matter on uranium transport through saturated geologic materials: from molecular to column scale.

The risk stemming from human exposure to actinides via the groundwater track has motivated numerous studies on the transport of radionuclides within geologic environments; however, the effects of waterborne organic matter on radionuclide mobility are still poorly understood. In this study, we compared the abilities of three humic acids (HAs) (obtained through sequential extraction of a peat soil) to cotransport hexavalent uranium (U) within water-saturated sand columns. Relative breakthrough concentrations of U measured upon elution of 18 pore volumes increased from undetectable levels (<0.001) in an experiment without HAs to 0.17 to 0.55 in experiments with HAs. The strength of the HA effect on U mobility was positively correlated with the hydrophobicity of organic matter and NMR-detected content of alkyl carbon, which indicates the possible importance of hydrophobic organic matter in facilitating U transport. Carbon and uranium elemental maps collected with a scanning transmission X-ray microscope (STXM) revealed uneven microscale distribution of U. Such molecular- and column-scale data provide evidence for a critical role of hydrophobic organic matter in the association and cotransport of U by HAs. Therefore, evaluations of radionuclide transport within subsurface environments should consider the chemical characteristics of waterborne organic substances, especially hydrophobic organic matter.

Sorption of the veterinary antimicrobials sulfadimethoxine and ormetoprim in soil.

Currently, limited research on the fate of antimicrobials in the environment exists, once they are discharged in human and animal wastes. Sorption of two antimicrobials, sulfadimethoxine (SDM) and ormetoprim (OMP), was investigated in two soils and sand using a series of batch experiments. Because OMP and SDM are often administered in combination, their sorption was also investigated in combination as co-solutes. The rate of SDM and OMP sorption was rapid over the first few hours of the experiments, which then slowed considerably after 16 to 68 h. OMP sorption was enhanced at high concentrations when in combination with SDM, with linear sorption coefficients ranging from 1.3 to 58.3 L.kg(-1) in the single solute experiments and 4.96 to 89.7 L.kg(-1) in the co-solute experiments. Sorption of OMP as a single solute seems to provide a better fit with the Freundlich equation, which became more linear (n approached 1) when SDM was present. Overall, SDM sorbed less than OMP in the two soils and sand. SDM linear sorption coefficients ranged from 0.4 to 25.8 L.kg(-1) as a single solute and 2.5 to 22.1 L.kg(-1) as a co-solute. Sorption of SDM becomes more nonlinear (n < 1) when SDM is present in combination with OMP. Overall, sorption of both antimicrobials increased in the selected soils and sand as the organic matter, clay content, and cation exchange capacity increased. These experiments indicate relatively low sorption of SDM and OMP in natural soils, making them a potential threat to surface and ground water.

Surface complexation modeling of the effects of phosphate on uranium(VI) adsorption

Previous published data for the adsorption of U(VI) and/or phosphate onto amorphous Fe(III) oxides (hydrous ferric oxide, HFO) and crystalline Fe(III) oxides (goethite) was examined. These data were then used to test the ability of a commonly-used surface complexation model (SCM) to describe the adsorption of U(VI) and phosphate onto pure amorphous and crystalline Fe(III) oxides and synthetic goethite-coated sand, a surrogate for a natural Fe(III)-coated material, using the component additivity (CA) approach. Our modeling results show that this model was able to describe U(VI) adsorption onto both amorphous and crystalline Fe(III) oxides and also goethite-coated sand quite well in the absence of phosphate. However, because phosphate adsorption exhibits a stronger dependence on Fe(III) oxide type than U(VI) adsorption, we could not use this model to consistently describe phosphate adsorption onto both amorphous and crystalline Fe(III) oxides and goethite-coated sand. However, the effects of phosphate on U(VI) adsorption could be incorporated into the model to describe U(VI) adsorption to both amorphous and crystalline Fe(III) oxides and goethite-coated sand, at least for an initial approximation. These results illustrate both the potential and limitations of using surface complexation models developed from pure systems to describe metal/radionuclide adsorption under more complex conditions.