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PubMed2001

Approaching zero discharge in uranium reprocessing: photochemical reduction of uranyl.

We have studied the photochemical reduction of uranyl to generate UO2 without hydrogen reduction. Formate and oxalate were examined as potential reductants that only lead to CO2 production as a side product. Despite the similar nature of the two reductants, the mechanism for quenching the uranyl excited-state changes drastically and leads to dramatically different chemistry at low pH. Oxalate quenches by unimolecular electron transfer and formate quenches by H-atom abstraction. Because of the change in mechanism, photochemical reduction of uranyl with formate works with high efficiency at low pH while photolysis in the presence of oxalate leads to the generation of CO and no net uranyl reduction. Photochemical reduction of uranyl with formate at low pH leads to U(IV) in solution that can then be precipitated as UO2 by simply raising the pH with yields as high as 99.992%.

Carbon Monoxide↗
PubMed2003

EXAFS study of Sn(IV) immobilization by hardened cement paste and calcium silicate hydrates.

In this study, the immobilization mechanisms of Sn(IV) onto calcium silicate hydrates (C-S-H) and hardened cement paste (HCP) have been investigated by combining wet chemistry experiments with X-ray absorption spectroscopy (XAS). Evidence is presented which demonstrates the formation of a Sn(IV) inner-sphere surface complex on C-S-H with a CaO/SiO2 weight ratio of 0.7. Two possible structural models, implying a corner sharing between the Sn octahedra and Q1 or Q2b Si tetrahedra, have been developed based on the experimentally determined structural parameters. In HCP, the formation of a different type of Sn(IV) inner-sphere complex has been observed, indicating that C-S-H may not be the uptake-controlling phase for Sn(IV) in the cement matrix. An alternative structural model for Sn(IV) binding in HCP has been developed, assuming that ettringite is the uptake-controlling phase. At high Sn(IV) concentrations, Sn(IV) immobilization in HCP occurs due to the formation of CaSn(OH)6.

Calcium Compounds↗
PubMed2003

Performance evaluation of a permeable reactive barrier using reaction products as tracers.

A method incorporating laboratory analysis of constituents that formed as reaction products was developed and used to determine the flux of groundwater through a zerovalent iron-based permeable reactive barrier (PRB) installed to treat U-contaminated groundwater. Concentrations of three nonvolatile constituents (Ca, U, and V) that formed as reaction products in the PRB were analyzed in 279 samples. Areal distributions of the reaction products indicate that groundwater flowed through all portions of the PRB and that nearly the entire volume of reactive material is treating the groundwater. Almost 9 t of calcium carbonate precipitated in the PRB during the first 2.7 yr of operation, but only 24 kg of combined U- and V-bearing minerals precipitated during the same period. Concentration gradients of Ca, U, and V dissolved in the groundwater indicate that a hydraulically upgradient portion of the PRB lost some reactivity during the first 2.7 yr of operation. Calculations that partially couple porosity changes to ZVI reactivity suggest that loss of reactivity may be more limiting than porosity reduction for long-term performance of the PRB. Calculations using groundwater concentration gradients and solid-phase concentrations indicate that the mean groundwater flux ranged from 11 to 24 L/min, considerably less than the design flux of 185 L/min. Flux values calculated with all three constituents were in good agreement. This method provides a more accurate determination of groundwater flux than is possible with flow sensor measurements, dissolved tracers, or Darcy's law computations.

Calcium↗
PubMed2003

Uptake of Cm(III) and Eu(III) by calcium silicate hydrates: a solution chemistry and time-resolved laser fluorescence spectroscopy study.

The interaction of the two chemical homologues [Cm(III) and Eu(III)] with calcium silicate hydrates (CSH phases) at pH 13.3 has been investigated in batch-type sorption studies using Eu(III) and complemented with time-resolved laser fluorescence spectroscopy (TRLFS) using Cm(III). The sorption data for Eu(III) reveal fast sorption kinetics and a strong uptake by CSH phases with distribution ratios of (6 +/- 3) x 10(5) L kg(-1). Three different Cm(III) species have been identified: A nonfluorescing species, which was identified as a curium hydroxide (surface) precipitate, and two fluorescing Cm(III)/CSH-sorbed species. The fluorescing sorbed species have characteristic emission spectra with main peak maxima at 618.9 and 620.9 nm and fluorescence emission lifetimes of 289 +/- 11 and 1482 +/- 200 micros, respectively. From the fluorescence lifetimes, it was calculated that the two fluorescing Cm(III) species have one or two and no water molecules left in their first coordination sphere, suggesting that these species are incorporated into the CSH structure. A structural model for Cm(III) and Eu(III) incorporation into CSH phases is proposed based on the substitution for Ca at two different types of sites in the CSH structure.

Calcium Compounds↗
PubMed2004

Interaction of Eu(III)/Cm(III) with alumina-bound poly(acrylic acid): sorption, desorption, and spectroscopic studies.

This paper contributes to the comprehension of kinetic and equilibrium phenomena governing trace metal ion sorption on organic matter coated mineral particles. Sorption and desorption experiments were carried out with trivalent metal ions M(III) (M = Eu, Cm) and poly(acrylic acid) (PAA)-coated alumina colloids at pH 5 in 0.1 M NaClO4. Under these conditions, M(III) interaction with the solid is governed by sorbed PAA. The results were compared with spectroscopic data obtained by time-resolved laser-induced fluorescence spectroscopy (TRLFS). Within less than 30 s, a state of local equilibrium is reached between M(III) and adsorbed poly(acrylic acid). M(II) bound to the organic-mineral surface and to dissolved PAA keeps five water molecules in its first hydration sphere. Interaction of M(III) with alumina-bound PAA appears to be strongerthan with dissolved PAA. With increasing contact time, a change of the metal ion speciation occurs at the organic-mineral surface. This change is explained quantitatively by kinetically controlled reactions, which succeed a rapid local equilibrium. The experimental findings suggest, in agreement with model calculations, that a part of the initially sorbed M(III) is slowly converted to a kinetically stabilized species, thereby losing water molecules from the first coordination sphere as indicated by TRLFS. This species might be assigned as a ternary Al2O3-M(III)-PAA complex. The second part of the initially bound M(II) appears to experience as well kinetically controlled reactions, however, without showing changes in the first coordination sphere. We assume that the kinetic stabilization is the consequence of rearrangement processes of the PAA at the alumina surface.

Acrylates↗
PubMed2004

Use of spectroscopic techniques for uranium(VI)/montmorillonite interaction modeling.

To experimentally identify both clay sorption sites and sorption equilibria and to understand the retention mechanisms at a molecular level, we have characterized the structure of hexavalent uranium surface complexes resulting from the interaction between the uranyl ions and the surface retention groups of a montmorillonite clay. We have performed laser-induced fluorescence spectroscopy (LIFS) and X-ray photoelectron spectroscopy (XPS) on uranyl ion loaded montmorillonite. These structural results were then compared to those obtained from the study of uranyl ions sorbed onto an alumina and also from U(VI) sorbed on an amorphous silica. This experimental approach allowed for a clear determination of the reactive surface sites of montmorillonite for U(VI) sorption. The lifetime values and the U4f XPS spectra of uranium(VI) sorbed on montmorillonite have shown that this ion is sorbed on both exchange and edge sites. The comparison of U(VI)/clay and U(VI)/oxide systems has determined that the interaction between uranyl ions and montmorillonite edge sites occurs via both [triple bond]AlOH and [triple bond]SiOH surface groups and involves three distinct surface complexes. The surface complexation modeling of the U(VI)/montmorillonite sorption edges was determined using the constant capacitance model and the above experimental constraints. The following equilibria were found to account for the uranyl sorption mechanisms onto montmorillonite for metal concentrations ranged from 10(-6) to 10(-3) M and two ionic strengths (0.1 and 0.5 M): 2[triple bond]XNa + UO2(2+) <==> ([triple bond]X)2UO2 + 2Na+, log K0(exch) = 3.0; [triple bond]Al(OH)2 + UO2(2+) <==> [triple bond]Al(OH)2UO2(2+), log K0(Al) = 14.9; [triple bond]Si(OH)2 + UO2(2+) <==> [triple bond]SiO2UO2 + 2H+, log K0(Si1) = -3.8; and [triple bond]Si(OH)2 + 3UO2(2+) + 5H2O <==> [triple bond]SiO2(UO2)3(OH)5- + 7H+, log K0(Si2) = -20.0.

Bentonite↗
PubMed2005

Effects of Fe(II) and hydrogen peroxide interaction upon dissolving UO2 under geologic repository conditions.

Iron redox cycling is supposed to be one of the major mechanisms that control the geochemical boundary conditions in the near field of a geologic repository for UO2 spent nuclear fuel. This work investigates the impact of reactions between hydrogen peroxide (H2O2) and iron (Fe2+/Fe3+) on UO2 dissolution. The reaction partners were contacted with UO2 in oxygen-free batch reactor tests. The interaction in absence of UO2 gives a stoichiometric redox reaction of Fe2+ and H2O2 when the reactants are present in equal concentration. Predomination of H202 results in its delayed catalytic decomposition. With UO2 present, its dissolution is controlled by either a slow mechanism (as typical for anoxic environments) or uranium peroxide precipitation, depending strongly on the reactant ratio. Uranium peroxide (UO4 x nH2O, m-studtite), detected on UO2 surfaces after exposure to H2O2, was not found on the surfaces exposed to solutions with stoichometric Fe(II)/ H2O2 ratios. This suggests that H2O2 was deactivated in redox reactions before a formation of UO4 took place. ESR measurements employing the spin trapping technique revealed only the DMPO-OH adduct within the first minutes after the reaction start (high initial concentrations of the OH radical); however, in the case of Fe(II) and H2O2 reacting at 10(-4) mol/L with UO2, dissolved oxygen and Fe2+ concentrations indicate the participation of further Fe intermediates and, therefore, Fenton redox activities.

Geological Phenomena↗
PubMed2005

Influence of sediment bioreduction and reoxidation on uranium sorption.

The influence of sediment bioreduction and reoxidation on U(VI) sorption was studied using Fe(II) oxide-containing saprolite from the U.S. Department of Energy (DOE) Oak Ridge site. Bioreduced sediments were generated by anoxic incubation with a metal-reducing bacterium, Shewanella putrefaciens strain CN32, supplied with lactate as an electron donor. The reduced sediments were subsequently reoxidized by air contact. U(VI) sorption was studied in NaNO3-HCO3 electrolytes that were both closed and open to atmosphere and where pH, U(VI), and carbonate concentration were varied. Mössbauer spectroscopy and chemical analyses showed that 50% of the Fe(III)-oxides were reduced to Fe(II) that was sorbed to the sediment during incubation with CN32. However, this reduction and subsequent reoxidation of the sorbed Fe(II) had negligible influence on the rate and extent of U sorption or the extractability of sorbed U by 0.2 mol/L NaHCO3. Various results indicated that U(VI) surface complexation was the primary process responsible for uranyl sorption by the bioreduced and reoxidized sediments. A two-site, nonelectrostatic surface complexation model best described U(VI) adsorption under variable pH, carbonate, and U(VI) conditions. A ferrihydrite-based diffuse double layer model provided a better estimation of U(VI) adsorption without parameter adjustment than did a goethite-based model, even though a majority of the Fe(III)-oxides in the sediments were goethite. Our results highlight the complexity of the coupled U-Fe redox system and show that sorbed Fe(II) is not a universal reductant for U(VI) as commonly assumed.

Adsorption↗
PubMed2006

Enhanced sorption of trichloroethene by smectite clay exchanged with Cs+.

Trichloroethene (TCE) is one of the most common pollutants in groundwater, and Cs+ can be a cocontaminant at nuclear facilities. Smectite clays have large surface areas, are common in soils, have high affinities for some organic contaminants, and hence can potentially influence the transport of organic pollutants entering soils and sediments. The exchangeable cations present near smectite clay surfaces can radically influence the sorption of organic pollutants by soil clays. This research was undertaken to determine the effect of Cs+, and other common interlayer cations, such as K+ and Ca2+, on the sorption of TCE by a reference smectite clay saponite. Cs-saturated clay sorbed the most TCE, up to 3500 mg/kg, while Ca-saturated smectite sorbed the least. We hypothesize that the stronger sorption of TCE by the Cs-smectite can be attributed to the lower hydration energy and hence smaller hydrated radius of Cs+, which expands the lateral clay surface domains available for sorption. Also, Cs-smectite interlayers are only one or two water layers thick, which may drive capillary condensation of TCE. Our results implicate enhanced retention of TCE in aquifer materials containing smectites accompanied by Cs+ cocontamination.

Adsorption↗
PubMed2006

Uranium and technetium bio-immobilization in intermediate-scale physical models of an in situ bio-barrier.

We investigated the long-term effects of ethanol addition on U and Tc mobility in groundwater flowing through intermediate-scale columns packed with uncontaminated sediments. The columns were operated above-ground at a contaminated field site to serve as physical models of an in situ bio-barrierfor U and Tc removal from groundwater. Groundwater containing 4 microM U and 520 pM Tc was pumped through the columns for 20 months. One column received additions of ethanol to stimulate activity of indigenous microorganisms; a second column received no ethanol and served as a control. U(VI) and Tc(VII) removal was sustained for 20 months (approximately 189 pore volumes) in the stimulated column under sulfate- and Fe(III)-reducing conditions. Less apparent microbial activity and only minor removal of U(VI) and Tc(VII) were observed in the control. Sequential sediment extractions and XANES spectra confirmed that U(IV) was present in the stimulated column, although U(IV) was also detected in the control; extremely low concentrations precluded detection of Tc(IV) in any sample. These results provide additional evidence that bio-immobilization may be effective for removing U and Tc from groundwater. However, long-term effectiveness of bio-immobilization may be limited by hydraulic conductivity reductions or depletion of bioavailable Fe(III).

Bacteria↗
PubMed1999

Vehicle emission unit risk factors for transportation risk assessments.

When the transportation risk posed by shipments of hazardous chemical and radioactive materials is being assessed, it is necessary to evaluate the risks associated with both vehicle emissions and cargo-related risks. Diesel exhaust and fugitive dust emissions from vehicles transporting hazardous shipments lead to increased air pollution, which increases the risk of latent fatalities in the affected population along the transport route. The estimated risk from these vehicle-related sources can often be as large or larger than the estimated risk associated with the material being transported. In this paper, data from the U.S. Environmental Protection Agency's Motor Vehicle-Related Air Toxics Study are first used to develop latent cancer fatality estimates per kilometer of travel in rural and urban areas for all diesel truck classes. These unit risk factors are based on studies investigating the carcinogenic nature of diesel exhaust. With the same methodology, the current per-kilometer latent fatality risk factor used in transportation risk assessments for heavy diesel trucks in urban areas is revised and the analysis expanded to provide risk factors for rural areas and all diesel truck classes. These latter fatality estimates may include, but are not limited to, cancer fatalities and are based primarily on the most recent epidemiological data available on mortality rates associated with ambient air PM-10 concentrations.

Hazardous Substances↗
PubMed1999

Factors in exposure assessment: ethnic and socioeconomic differences in fishing and consumption of fish caught along the Savannah River.

South Carolina has issued fish consumption advisories for the Savannah River based on mercury and radionuclide levels. We examine differences in fishing rates and fish consumption of 258 people interviewed while fishing along the Savannah River, as a function of age, education, ethnicity, employment history, and income, and test the assumption that the average consumption of fish is less than the recreational value of 19 kg/year assumed by risk assessors. Ethnicity and education contributed significantly to explaining variations in number of fish meals per month, serving size, and total quantity of fish consumed per year. Blacks fished more often, ate more fish meals of slightly larger serving sizes, and consumed more fish per year than did Whites. Although education and income were correlated, education contributed most significantly to behavior; people who did not graduate from high school ate fish more often, ate more fish per year, and ate more whole fish than people who graduated from high school. Computing consumption of fish for each person individually indicates that (1) people who eat fish more often also eat larger portions, (2) a substantial number of people consume more than the amount of fish used to compute risk to recreational fishermen, (3) some people consume more than the subsistence level default assumption (50 kg/year) and (4) Blacks consume more fish per year than Whites, putting them at greater risk from contaminants in fish. Overall, ethnicity, age, and education contributed to variations in fishing behavior and consumption.

Adolescent↗
PubMed1999

Economic impact of accelerated cleanup on regions surrounding the U.S. DOE's major nuclear weapons sites.

The regional economic impacts of the U.S. Department of Energy's accelerated environmental cleanup plan are estimated for the major nuclear weapons sites in Colorado, Idaho, New Mexico, South Carolina, Tennessee, and Washington. The analysis shows that the impact falls heavily on the three relatively rural regions around the Savannah River (SC), Hanford (WA), and Idaho National Engineering and Environmental Laboratory (ID) sites. A less aggressive phase-down of environmental management funds and separate funds to invest in education and infrastructure in the regions helps buffer the impacts on jobs, personal income, and gross regional product. Policy options open to the federal and state and local governments are discussed.

Government Agencies↗
PubMed1999

Risk perception in context: the Savannah River Site Stakeholder Study.

Environmental managers are increasingly charged with involving the public in the development and modification of policies regarding risks to human health and the environment. Involving the public in environmental decision making first requires a broad understanding of how and why the public perceives various risks. The Savannah River Stakeholder Study was conducted with the purpose of investigating individual, economic, and social characteristics of risk perceptions among those living near the Savannah River Nuclear Weapons Site. A number of factors were found to impact risk perceptions among those living near the site. One's estimated proximity to the site and relative river location surfaced as strong determinants of risk perceptions among SRS residents. Additionally, living in a quality neighborhood and demonstrating a willingness to accept health risks for economic gain strongly abated heightened risk perceptions.

Environmental Health↗