Donald T. Reed

Reduction of Np(V) and precipitation of Np(IV) by an anaerobic microbial consortium

A combination of experimental, analytical, and modeling investigations shows that an anaerobic, sulfate-reducing consortium reduced Np(V) to Np(IV), with subsequent precipitation of a Np(IV) solid. Precipitation of Np(IV) during growth on pyruvate occurred before sulfate reduction began. H2 stimulated precipitation of Np(IV) when added alone to growing cells, but it slowed precipitation when added along with pyruvate. Increasing concentrations of pyruvate also retarded precipitation. Accumulation of an intermediate pyruvate-fermentation product – probably succinate – played a key role in retarding Np(IV) precipitation by complexing the Np(IV). Hydrogen appears to have two roles in controlling Np precipitation: donating electrons for Np(V) reduction and modulating intermediate levels. That Np(V) is microbially reduced and subsequently precipitated under anaerobic conditions has likely beneficial implications for the containment of Np on lands contaminated by radionuclides, but complexation by fermentation intermediates can prevent immobilization by precipitation.

Reduction of Np(VI) and Pu(VI) by organic chelating agents

The reduction of NpO{sub 2}{sup 2+} and PuO{sub 2}{sup 2+} by oxalate, citrate, and ethylenediaminetetraacetic acid (EDTA) was investigated in low ionic strength media and brines. This was done to help establish the stability of the An(VI) oxidation state depended on the pH nd relative strength of the various oxidation state-specific complexes. At low ionic strength and pH 6, NpO{sub 2}{sup 2+} was rapidly reduced to form NpO{sub 2}{sup +} organic complexes. At longer times, Np(IV) organic complexes were observed in the presence of citrate. PuO{sub 2}{sup 2+} was predominantly reduced to Pu{sup 4+}, resulting in the formation of organic complexes or polymeric/hydrolytic precipitates. The relative rates of reduction to the An(V) complex were EDTA > citrate > oxalate. Subsequent reduction to An(IV) complexes, however, occurred in the following order: citrate > EDTA > oxalate because of the stability of the An(VI)-EDTA complex. The presence of organic complexants led to the rapid reduction of NpO{sub 2}{sup 2+} and PuO{sub 2}{sup 2+} in G-Seep brine at pHs 5 and 7. At pHs 8 and 10 in ERDA-6 brine, carbonate and hydrolytic complexes predominated and slowed down or prevented the reduction of An(VI) by the organics present.

Complexation of Nd(III) with tetraborate ion and its effect on actinide (III) solubility in WIPP brine

Abstract The potential importance of tetraborate complexation on lanthanide(III) and actinide(III) solubility is recognized in the literature but a systematic study of f-element complexation has not been performed. In neodymium solubility studies in WIPP brines, the carbonate complexation effect is not observed since tetraborate ions form a moderately strong complex with neodymium(III). The existence of these tetraborate complexes was established for low and high ionic strength solutions. Changes in neodymium(III) concentrations in undersaturation experiments were used to determine the neodymium with tetraborate stability constants as a function of NaCl ionic strength. As very low Nd(III) concentrations have to be measured, it was necessary to use an extraction pre-concentration step combined with ICP-MS analysis to extend the detection limit by a factor of 50. The determined Nd(III) with borate stability constants at infinite dilution and 25 °C are equal to logβ1=4.55±0.06 using the SIT approach, equal to logβ1=4.99±0.30 using the Pitzer approach, with an apparent logβ1=4.06±0.15 (in molal units) at I=5.6 m NaCl. Pitzer ion-interaction parameters for neodymium with tetraborate and SIT interaction coefficients were also determined and reported.

Surface Complexation of Neptunium(V) onto Whole Cells and Cell Components of Shewanella alga: Modeling and Experimental Study

We systematically quantified surface complexation of Np(V) onto whole cells, cell wall, and extracellular polymeric substances (EPS) of Shewanella alga strain BrY. We first performed acid and base titrations and used the mathematical model FITEQL to estimate the concentrations and deprotonation constants of specific surface functional groups. Deprotonation constants most likely corresponded to a carboxyl group not associated with amino acids (pK(a) approximately 5), a phosphoryl site (pK(a) approximately 7.2), and an amine site (pK(a) > 10). We then carried out batch sorption experiments with Np(V) and each of the S. alga components as a function of pH. Since significant Np(V) sorption was observed on S. alga whole cells and its components in the pH range 2-5, we assumed the existence of a fourth site: a low-pK(a) carboxyl site (pK(a) approximately 2.4) that is associated with amino acids. We used the SPECIATE submodel of the biogeochemical model CCBATCH to compute the stability constants for Np(V) complexation to each surface functional group. The stability constants were similar for each functional group on S. alga bacterial whole cells, cell walls, and EPS, and they explain the complicated sorption patterns when they are combined with the aqueous-phase speciation of Np(V). For pH < 8, the aquo NpO(2)(+) species was the dominant form of Np(V), and its log K values for the low-pK(a) carboxyl, mid-pK(a) carboxyl, and phosphoryl groups were 1.8, 1.8, and 2.5-3.1, respectively. For pH greater than 8, the key surface ligand was amine >XNH(3)(+), which complexed with NpO(2)(CO(3))(3)(5-). The log K for NpO(2)(CO(3))(3)(5-) complexed onto the amine groups was 3.1-3.9. All of the log K values are similar to those of Np(V) complexes with aqueous carboxyl and N-containing carboxyl ligands. These results help quantify the role of surface complexation in defining actinide-microbiological interactions in the subsurface.

Pillared metal(IV) phosphate-phosphonate extraction of actinides

Abstract Four pillared metal(IV) phosphate-phosphonate ion exchange materials were synthesized and characterized. Studies were conducted to determine their affinity for the lanthanides (Ln´s) and actinides (An´s). It was determined that by simply manipulating the metal source (Zr or Sn) and the phosphate source (H3PO4 or Na3PO4) large differences were seen in the extraction of the Ln and An species. Kd values higher than 4×105 were observed for the AnO22+ species in nitric acid at pH 2. These basic uptake experiments are important, as the data they provide may indicate the possibility of a separation of Ln´s from An´s or even more notably americium from curium and Ln´s.

Reduction of plutonium(VI) in brine under subsurface conditions

The redox stability of PuO22+ was investigated in brine under subsurface conditions. In simulated brines, when no reducing agent was present, 0.1 mM concentrations of plutonium(VI) were stable as regards to reduction for over two years, which was the duration of the experiments performed. In these systems, the plutonyl existed as a carbonate or hydroxy-chloride species. The introduction of reducing agents (e.g. steel coupons, and aqueous Fe2+) typically present in a subsurface repository, however, led to the destabilization of the plutonium(VI) complexes and the subsequent reduction to Pu(IV) under most conditions investigated. X-ray Absorption Near-Edge Spectroscopy (XANES) confirmed that the final oxidation state in these systems was Pu(IV). This reduction lowered the overall steady state concentration of plutonium in the brine by 3−4 orders of magnitude. These results show the importance of considering repository constituents in evaluating subsurface actinide solubility/mobility and provide further evidence of the effectiveness of reduced iron species in the reduction and immobilization of higher-valent plutonium species.

Determination of ferrous and ferric iron in aqueous biological solutions

A solvent extraction method was employed to determine ferrous and ferric iron in aqueous samples. Fe(3+) is selectively extracted into the organic phase (n-heptane) using HDEHP (bis(2-ethylhexyl) hydrogen phosphate) and is then stripped using a strong acid. After separation, both oxidation states and the total iron content were determined directly by ICP-MS analysis. This extraction method was refined to allow determination of both iron oxidation states in the presence of strong complexing ligands, such as citrate, NTA and EDTA. The accuracy of the method was verified by crosschecking using a refinement of the ferrozine assay. Presented results demonstrate the ability of the extraction method to work in a microbiological system in the presence of strong chelating agents following the bioreduction of Fe(3+) by the Shewanella alga BrY. Based on the results we report, a robust approach was defined to separately analyze Fe(3+) and Fe(2+) under a wide range of potential scenarios in subsurface environments where radionuclide/metal contamination may coexist with strongly complexing organic contaminants.

Multiscale Speciation of U and Pu at Chernobyl, Hanford, Los Alamos, McGuire AFB, Mayak, and Rocky Flats.

The speciation of U and Pu in soil and concrete from Rocky Flats and in particles from soils from Chernobyl, Hanford, Los Alamos, and McGuire Air Force Base and bottom sediments from Mayak was determined by a combination of X-ray absorption fine structure (XAFS) spectroscopy and X-ray fluorescence (XRF) element maps. These experiments identify four types of speciation that sometimes may and other times do not exhibit an association with the source terms and histories of these samples: relatively well ordered PuO2+x and UO2+x that had equilibrated with O2 and H2O under both ambient conditions and in fires or explosions; instances of small, isolated particles of U as UO2+x, U3O8, and U(VI) species coexisting in close proximity after decades in the environment; alteration phases of uranyl with other elements including ones that would not have come from soils; and mononuclear Pu-O species and novel PuO2+x-type compounds incorporating additional elements that may have occurred because the Pu was exposed to extreme chemical conditions such as acidic solutions released directly into soil or concrete. Our results therefore directly demonstrate instances of novel complexity in the Å and μm-scale chemical speciation and reactivity of U and Pu in their initial formation and after environmental exposure as well as occasions of unexpected behavior in the reaction pathways over short geological but significant sociological times. They also show that incorporating the actual disposal and site conditions and resultant novel materials such as those reported here may be necessary to develop the most accurate predictive models for Pu and U in the environment.

Bacterial Pu(V) reduction in the absence and presence of Fe(III)–NTA: modeling and experimental approach

Plutonium (Pu), a key contaminant at sites associated with the manufacture of nuclear weapons and with nuclear-energy wastes, can be precipitated to “immobilized” plutonium phases in systems that promote bioreduction. Ferric iron (Fe3+) is often present in contaminated sites, and its bioreduction to ferrous iron (Fe2+) may be involved in the reduction of Pu to forms that precipitate. Alternately, Pu can be reduced directly by the bacteria. Besides Fe, contaminated sites often contain strong complexing ligands, such as nitrilotriacetic acid (NTA). We used biogeochemical modeling to interpret the experimental fate of Pu in the absence and presence of ferric iron (Fe3+) and NTA under anaerobic conditions. In all cases, Shewanella alga BrY (S. alga) reduced Pu(V)(PuO2+) to Pu(III), and experimental evidence indicates that Pu(III) precipitated as PuPO4(am). In the absence of Fe3+ and NTA, reduction of PuO2+ was directly biotic, but modeling simulations support that PuO2+ reduction in the presence of Fe3+ and NTA was due to an abiotic stepwise reduction of PuO2+ to Pu4+, followed by reduction of Pu4+ to Pu3+, both through biogenically produced Fe2+. This means that PuO2+ reduction was slowed by first having Fe3+ reduced to Fe2+. Modeling results also show that the degree of PuPO4(am) precipitation depends on the NTA concentration. While precipitation out-competes complexation when NTA is present at the same or lower concentration than Pu, excess NTA can prevent precipitation of PuPO4(am).

Subsurface Interactions of Actinide Species with Microorganisms

Subsurface microbiological processes have an important role in defining the speciation and mobility of actinide contaminants in groundwater. The relative importance of these processes, especially when groundwater conditions support high microbiological activity, has, however, only been recognized by researchers in the field since the early 1990s. The need to mechanistically understand the key interactions between actinide species and microbial processes becomes greater as we increasingly rely on more passive, long-term containment strategies, such as natural attenuation, where microbial processes are likely to predominate (NRC, 2000a).