EMSL: John Zachara's Publications

Fredrickson JK, JM Zachara, AE Plymale, SM Heald, JP McKinley, DW Kennedy, C Liu, and P Nachimuthu. 2009. "Oxidative Dissolution Potential of Biogenic and Abiogenic TcO2 in Subsurface Sediments." Geochimica et Cosmochimica Acta 73(8):962-976. doi:10.1016/j.gca.2009.01.027 Abstract Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Exhibiting an intermediate redox potential, Tc is highly mobile in its anionic, oxidized state [Tc(VII)O4-]; and less mobile as a poorly soluble oxyhydroxide precipitate [Tc(IV)O2•nH2O] in its reduced state. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state (FRC, RG). Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Biogenic Tc(IV)O2•nH2O was oxidized in anoxic, but unreduced RG and FRC sediments through redox interaction with Mn(III/IV) oxides. Bioreduction by Shewanella putrefaciens CN32 dissolved Mn(III/IV) oxides and generated biogenic Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. Biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO2-like phase in both sediments. Redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular speciation to RG. X-ray microprobe, electron microprobe, x-ray absorption spectroscopy, and micro x-ray diffraction were applied to the whole sediment and isolated Tc-contained particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 µm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O2 into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.

Jaisi DP, H Dong, AE Plymale, JK Fredrickson, JM Zachara, S Heald, and C Liu. 2009. "Reduction and long-term immobilization of technetium by Fe(II) associated with clay mineral nontronite ." Chemical Geology 264(1-4):127-138. doi:10.1016/j.chemgeo.2009.02.018 Abstract 99Tc is formed mostly during nuclear reactions and is released into the environment during weapons testing and inadvertent waste disposal. The long half-life, high environmental mobility (as Tc(VII)O4-) and its possible uptake into the food chain cause 99Tc to be a significant environmental contaminant. In this study, we evaluated the role of Fe(II) in biologically reduced clay mineral, nontronite (NAu-2), in reducing Tc(VII)O4- to poorly soluble Tc(IV) species as a function of pH and Fe(II) concentration. The rate of Tc(VII) reduction by Fe(II) in NAu-2 was higher at neutral pH (pH 7.0) than at acidic and basic pHs when Fe(II) concentration was low (< 1 mmol/g). The effect of pH, however, was insignificant at higher Fe(II) concentrations. The reduction of Tc(VII) by Fe(II) associated with NAu-2 was also studied in the presence of common subsurface oxidants including iron and manganese oxides, nitrate, and oxygen, to evaluate the effect of the oxidants on the enhancement and inhibition of Tc(VII) reduction, and reoxidation of Tc(IV). Addition of iron oxides (goethite and hematite) to the Tc(VII)-NAu-2 system, where Tc(VII) reduction was ongoing, enhanced reduction of Tc(VII), apparently as a result of re-distribution of reactive Fe(II) from NAu-2 to more reactive goethite/hematite surfaces. Addition of manganese oxides stopped further Tc(VII) reduction, and in case of K+-birnessite, it reoxidized previously reduced Tc(IV). Nitrate neither enhanced reduction of Tc(VII) nor promoted reoxidation of Tc(IV). Approximately 11% of Tc(IV) was oxidized by oxygen. The rate and extent of Tc(IV) reoxidation was found to strongly depend on the nature of the oxidants and concentration of Fe(II). When the same oxidants were added to aged Tc reduction products (mainly NAu-2 and TcO2•nH2O), the extent of Tc(IV) reoxidation decreased significantly relative to fresh Tc(IV) products. Increasing NAu-2 concentration also resulted in the decreased extent of Tc(IV) reoxidation. The results were attributed to the effect of NAu-2 aggregation that effectively retained Tc(IV) in the solid and decreased its vulnerability to reoxidation. Overall, our results implied that bioreduced clay minerals could play an important role in reducing Tc(VII) and in maintaining the long-term stability of reduced Tc(IV).

Liu C, Z Shi, and JM Zachara. 2009. "Kinetics of Uranium(VI) Desorption from Contaminated Sediments: Effect of Geochemical Conditions and Model Evaluation ." Environmental Science & Technology 43(17):6560-6566. Abstract Stirred-flow cell experiments were performed to investigate the kinetics of uranyl [U(VI)] desorption from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. Three influent solutions of variable pH, Ca and carbonate concentrations that affected U(VI) aqueous and surface speciation were used under dynamic flow conditions to evaluate the effect of geochemical conditions on the rate of U(VI) desorption. The measured rate of U(VI) desorption varied with solution chemical composition that evolved as a result of thermodynamic and kinetic interactions between the influent solutions and sediment. The solution chemical composition that led to a lower equilibrium U(VI) sorption to the solid phase yielded a faster desorption rate. The experimental results were used to evaluate a multi-rate, surface complexation model (SCM) that has been proposed to describe U(VI) desorption kinetics in the Hanford sediment that contained complex sorbed U(VI) species in mass transfer limited domains. The model was modified and supplemented by including multi-rate, ion exchange reactions to describe the geochemical interactions between the solutions and sediment. With the same set of model parameters, the modified model reasonably well described the evolution of major ions and the rates of U(VI) desorption under variable geochemical and flow conditions, implying that the multi-rate SCM is an effective way to describe U(VI) desorption kinetics in subsurface sediments.

Liu C, JM Zachara, L Zhong, SM Heald, Z Wang, BH Jeon, and JK Fredrickson. 2009. "Microbial Reduction of Intragrain U(VI) in Contaminated Sediment." Environmental Science & Technology 43(13):4928-4933. doi:10.1021/es8029208 Abstract The accessibility of precipitated, intragrain U(VI) in a contaminated sediment to microbial reduction was investigated to ascertain geochemical and microscopic transport phenomena controlling U(VI) bioavailability. The sediment was collected from the US DOE Hanford site, and contained uranyl precipitates in a form of Na-boltwoodite within the mm-sized granitic lithic fragments in the sediment. Microbial reduction was investigated in a culture of a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1, in bicarbonate solutions at pH 6.8 buffered by PIPES. Measurements of uranium concentration, speciation, and valence in aqueous and solid phases indicated that microbial reduction of intragrain U(VI) proceeded by two mechanisms: 1) sequentially coupled dissolution of intragrain uranyl precipitates, diffusion of dissolved U(VI) out of intragrain regions, and microbial reduction of dissolved U(VI); and 2) U(VI) reduction in the intragrain regions by soluble, diffusible biogenic reductants. The bioreduction rate in the first pathway was over 3 orders of magnitude slower than that in comparable aqueous solutions containing aqueous U(VI) only. The slower bioreduction rate was attributed to: 1) the release of calcium from the desorption/dissolution of calcium-containing minerals in the sediment, which subsequently altered U(VI) aqueous speciation and slowed U(VI) bioreduction and 2) alternative electron transfer pathways that reduced U(VI) in the intragrain regions and changed its dissolution and solubility behavior. The results implied that the overall rate of microbial reduction of intragrain U(VI) will be influenced by the reactive mass transfer of U(VI) and biogenic reductants within intragrain regions, and geochemical reactions controlling major ion concentrations that affect U(VI) aqueous speciation and microbial activity.

Marshall MJ, A Dohnalkova, DW Kennedy, AE Plymale, SH Thomas, FE Loffler, R Sanford, JM Zachara, JK Fredrickson, and AS Beliaev. 2009. "Electron donor-dependent radionuclide reduction and nanoparticle formation by Anaeromyxobacter dehalogenans strain 2CP-C." Environmental Microbiology 11(2):534-543. Abstract Anaeromyxobacter dehalogenans strain 2CP-C can rapidly reduce U(VI) or Tc(VII) to U(IV)O2(s) or Tc(IV)O2(S) using either acetate or H2 as an electron donor source. Kinetic studies reveal that the H2-driven reduction of either U(VI) or Tc(VII) is faster than the acetate-driven reduction. The sub-cellular localization of reduced UO2 is extracellular while TcO2 nanoparticles are both periplasmic and extracellular. While electron donor-specific differences in UO2 nanoparticle aggregate size were observed, the association of UO2 nanoparticles with an exopolymeric substance (EPS) was observed and found to be independent of electron donor source. Electron donor-specific localization differences were not observed in cells incubated with Tc(VII). These finding have direct implications on immobilization strategies for highly soluble radionuclide contaminants in subsurface waters and the development of microbially assisted biostimulation efforts.

Peretyazhko T, JM Zachara, JF Boily, Y Xia, PL Gassman, BW Arey, and WD Burgos. 2009. "Mineralogical transformations controlling acid mine drainage chemistry." Chemical Geology 262(3-4):169-178. Abstract The role of Fe(III) minerals in controlling acid mine drainage (AMD) chemistry was studied using samples from two AMD sites [Gum Boot (GB) and Fridays-2 (FR)] located in northern Pennsylvania. Chemical extractions, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) were used to identify and characterize Fe(III) phases. The mineralogical analysis revealed that schwertmannite and goethite were the principal Fe(III) phases in the sediments. Schwertmannite transformation occurred at the GB site where poorly-crystallized goethite rich in surface-bound sulfate was initially formed. In contrast, no schwertmannite transformation occurred at the FR site. The goethite in GB sediments had spherical morphology due to preservation of schwertmannite structure by adsorbed sulfate. Results of chemical extractions showed that poorly-crystallized goethite was subject to further crystallization accompanied by sulfate desorption. Changes in sulfate speciation preceded its desorption, with a conversion of bidentate- to monodentate-bound sulfate surface complexes. Laboratory sediment incubation experiments were conducted to evaluate the effect of mineral transformation on water chemistry. Incubation experiments were carried out with schwertmannite-containing sediments and AMD waters with different pH and chemical composition. The pH decreased to 1.9-2.2 in all suspensions and the concentrations of dissolved Fe and S increased significantly. Regardless of differences in the initial water composition, pH, Fe and S were similar in suspensions of the same sediment. XRD measurements revealed that schwertmannite transformed into goethite in GB and FR sediments during laboratory incubation. The incubation experiment demonstrated that schwertmannite transformation controlled AMD water chemistry during “closed system” laboratory contact.

Shi Z, C Liu, JM Zachara, Z Wang, and B Deng. 2009. "Inhibition Effect of Secondary Phosphate Mineral Precipitation on Uranium Release from Contaminated Sediments." Environmental Science & Technology 43(21):8344-8349. doi:10.1021/es9021359 Abstract The inhibitory effect of phosphate mineral precipitation on uranium release was evaluated using a U(VI)-contaminated sediment collected from the US Department of Energy (DOE) Hanford site. The sediment contained U(VI) that was associated with diffusion-limited intragrain regions within its mm-size granitic lithic fragments. The sediment was first treated to promote phosphate mineral precipitation in batch suspensions spiked with 1 and 50 mM aqueous phosphate, and calcium in a stoichiometric ratio of mineral hydroxyapatite. The phosphate-treated sediment was then leached to solubilize contaminant U(VI) in a column system using a synthetic groundwater that contained chemical components representative of Hanford groundwater. Phosphate treatment significantly decreased the extent of U(VI) release from the sediment. Within the experimental duration of about 200 pore volumes, the effluent U(VI) concentrations were consistently lower by over one and two orders of magnitude after the sediment was treated with 1 and 50 mM of phosphate, respectively. Measurements of solid phase U(VI) using various spectroscopes and chemical extraction of the sediment collectively indicated that the inhibition of U(VI) release from the sediment was caused by: 1) U(VI) adsorption to the secondary phosphate precipitates and 2) the transformation of initially present U(VI) mineral phases to less soluble forms.

Shi L, D Richardson, Z Wang, SN Kerisit, KM Rosso, JM Zachara, and JK Fredrickson. 2009. "The Roles of Outer Membrane Cytochromes of Shewanella and Geobacter in Extracellular Electron Transfer." Environmental Microbiology Reports 1(4):220-227. doi:10.1111/j.1758-2229.2009.00035.x Abstract As key components of the electron transfer (ET) pathways used for dissimilatory reduction of solid iron [Fe(III)] and manganese [Mn(IV)] (hydr)oxides, outer membrane cytochromes MtrC and OmcA of Shewanella oneidensis MR-1 and OmcE and OmcS of Geobacter sulfurreducens mediate ET reactions extracellularly. Cell surface-exposed MtrC and OmcA can transfer electrons directly to the metal oxides. S. oneidensis MR-1 cells also secrete flavins that can facilitate ET to the oxides. The secreted flavins are thought to serve either as chelators that form soluble Fe(III)/Mn(IV)-flavin complexes or as electron shuttles that ferry the electrons from cell-associated ET proteins to the metal oxides. Cell-surface localization may also permit MtrC and OmcA to transfer electrons extracellularly to either flavin-chelated Fe(III)/Mn(IV) or oxidized flavins. OmcE and OmcS are proposed to be located on the Geobacter cell surface where they are believed to function as the intermediates to relay electrons to type IV pili, which are then hypothesized to transfer electrons directly to the metal oxides. Thus, cell surface-localization positions these outer membrane cytochromes to transfer electrons to Fe(III)/Mn(IV) oxides external to the bacterial cells either directly, indirectly, or both, demonstrating a common strategy shared by Shewanella and Geobacter for extracellular reduction of the oxides.

Singer DM, JM Zachara, and GE Brown, JR. 2009. "Uranium Speciation As a Function of Depth in Contaminated Hanford Sediments - A Micro-XRF, Micro-XRD, and Micro- And Bulk-XAFS Study ." Environmental Science & Technology 43(3):630-636. Abstract Processing ponds at the Hanford, Washington Area 300 site were used for storing basic sodium aluminate and acidic U(VI)-Cu(II)-containing waste from 1943 to 1975. One result of this use is a groundwater plume containing elevated levels of U and Cu beneath the dry ponds and adjacent to the Columbia River. We have used synchrotron-based micro-X-ray fluorescence (XRF) imaging, micro-X-ray absorption fine structure (XANES) spectroscopy, and micro-X-ray diffraction (XRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy to determine the distribution and speciation of U and Cu through the vadose and groundwater zones beneath North Processing Pond #2 (NPP2). Sediment samples were collected from the vadose zone (8’ and 12’ depths), and a sample from the groundwater zone was collected just below the water table (12’-14’ depth). XRF imaging revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with mineral surfaces (particularly chlorite), and (2) high concentration U(VI)-containing micron-sized particles associated with surface coatings on grains of muscovite and chlorite. These U(VI) hot spots are frequently spatially correlated with Cu(II) hot spots. In the groundwater zone, these particles were identified as the copper-uranyl-silicate cuprosklodowskite and the cupper-uranyl-phosphate metatorbernite. In contrast, the U-Cu-containing particles are X-ray amorphous in the vadose zone. Fits of U LIII-edge XAFS spectra by linear-combination fitting indicate that U speciation consists of ~ 75% uranyl sorbed to clays and ~25% metatorbernite-like X-ray amorphous U-Cu-phosphates (8’ depth); nearly 100% sorbed uranyl (12’ depth); and ~70% sorbed uranyl and ~30% cuprosklodowskite/metatorbernite (ground water zone). These findings suggest that the dissolution of U(VI)-Cu(II)-bearing solids as well as the desorption of U(VI), mainly from phyllosilicates, are important sources of U(VI) in the Area 300 groundwater plume.

Stubbs JE, LA Veblen, D Elbert, JM Zachara, JA Davis, and DR Veblen. 2009. "Newly recognized hosts for uranium in the Hanford Site vadose zone." Geochimica et Cosmochimica Acta 73(6):1563-1576. Abstract 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(UO2)2(PO4)2·8H2O]; 2) coatings comprised mainly of phyllosilicates on sediment clasts; 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 Mnoxides. 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.