EMSL: Zheming Wang's Publications

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.

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.

Um W, Z Wang, RJ Serne, BD Williams, CF Brown, CJ Dodge, and AROKIASAMYJ FRANCIS. 2009. "Uranium Phases in Contaminated Sediments Below Hanford's U Tank Farm ." Environmental Science & Technology 43(12):4280-4286. doi:10.1021/es900203r Abstract Macroscopic and spectroscopic investigations (XAFS, XRF and TRLIF) on Hanford contaminated vadose zone sediments from the U-tank farm showed that U(VI) exists as different surface phases as a function of depth below ground surface (bgs). Dominant U(VI) silicate precipitates (boltwoodite and uranophane) were present in shallow-depth sediments (15-16 m bgs). In the intermediate depth sediments (20-25 m bgs), adsorbed U(VI) phases dominated but small amounts of surface precipitates consisting of polynuclear U(VI) surface complex were also identified. The deep depth sediments (> 28 m bgs) showed no signs of contact with tank wastes containing Hanford-derived U(VI), but natural uranium solid phases were observed. Most of the U(VI) was preferentially associated with the silt and clay size fractions and showed strong correlation with Ca, especially for the precipitated U(VI) silicate phase in the shallow depth sediments. Because U(VI) silicate precipitates dominate the U(VI) phases in the shallow depth sediments, macroscopic (bi)carbonate leaching should result in U(VI) releases from both desorption and dissolution processes. Having several different U(VI) surface phases in the Hanford contaminated sediments indicates that the U(VI) release mechanism could be complicated and that detailed characterization of the sediments would be needed to estimate U(VI) fate and transport in vadose zone.

Wan J, Y Kim, TK Tokunaga, Z Wang, S Dixit, CI Steefel, E Saiz, M Kunz, and N Tamura. 2009. "Spatially Resolved U(VI) Partitioning and Speciation: Implications for Plume Scale Behavior of Contaminant U in the Hanford Vadose Zone." Environmental Science & Technology 43(7):2247-2253. Abstract A saline-alkaline brine containing high concentration of U(VI) was accidentally spilled at the Hanford Site in 1951, introducing 10 tons of U into sediments under storage tank BX-102. U concentrations in the deep vadose zone and groundwater plumes increase with time, yet how the U has been migrating is not fully understood. We simulated the spill event in laboratory soil columns, followed by aging, and obtained spatially resolved U partitioning and speciation along simulated plumes. We found after aging, at apparent steady state, that the pore aqueous phase U concentrations remained surprisingly high (up to 0.022 M), in close agreement with the recently reported high U concentrations (up to 0.027 M) in the vadose zone plume (1). The pH values of aged pore liquids varying from 10 to 7, consistent with the measured pH of the field borehole sediments varying from 9.5 to 7.4 (2), from near the plume source to the plume front. The direct measurements of aged pore liquids together with thermodynamic calculations using a Pitzer approach revealed that UO2(CO3)34- is the dominant aqueousUspecies within the plume body (pH 8-10), whereas Ca2UO2(CO3)3 and CaUO2(CO3)32- are also significant in the plume front vicinity (pH 7-8), consistent with that measured from field borehole pore-waters (3). U solid phase speciation varies at different locations along the plume flow path and even within single sediment grains, because of location dependent pore and micropore solution chemistry. Our results suggest that continuous gravitydriven migration of the highly stable UO2(CO3)34- in the residual carbonate and sodium rich tank waste solution is likely responsible for the detected growing U concentrations in the vadose zone and groundwater.

Di Bernardo P, PL Zanonato, A Melchior, R Portanova, M Tolazzi, GR Choppin, and Z Wang. 2008. "Thermodynamic and Spectroscopic Studies of Lanthanides(III) Complexation with Polyamines in Dimethyl Sulfoxide." Inorganic Chemistry 47(3):1155-1164. doi:10.1021/ic701337u Abstract The thermodynamic parameters of complexation of Ln(III) cations with tris(2-aminoethyl)amine (tren) and tetraethylenepentamine (tetren) were determined in dimethyl sulfoxide (DMSO) by potentiometry and calorimetry. The excitation and emission spectra and luminescence decay constants of Eu3+ and Tb3+ complexed by tren and tetren, as well as those of the same lanthanides(III) complexed with diethylenetriamine (dien) and triethylenetetramine (trien), were also obtained in the same solvent. The combination of thermodynamic and spectroscopic data showed that, in the 1:1 complexes, all nitrogens of the ligands bound to the lanthanides except in the case of tren, in which only pendant N bound. For the larger ligands (trien, tren, tetren) in the higher complexes (ML2), there was less complete binding by available donors, presumably due to steric crowding. FT-IR studies were carried out in an acetonitrile/DMSO mixture, suitably chosen in order to follow the changes in the primary solvation sphere of lanthanide(III) due to complexation of amine ligands. Results show that the mean number of molecules of DMSO removed from the inner coordination sphere of lanthanides(III) is lower than ligand denticity and that the coordination number of the metal ions increases with amine complexation from 8 to 10. Independently of the number and structure of the amines, linear trends, similar for all lanthanides, were obtained by plotting the values of *Gj°, *Hj° and T*Sj° for the complexation of ethylenediamine (en), dien, trien, tren and tetren as a function of the number of amine metal-coordinated nitrogen atoms. The main factors on which the thermodynamic functions of lanthanide(III) complexation reactions in DMSO depend are discussed.

Liu C, JM Zachara, N Qafoku, and Z Wang. 2008. "Scale-dependent desorption of uranium from contaminated subsurface sediments." Water Resources Research 44:W08413. doi:10.1029/2007WR006478 Abstract Column experiments were performed to investigate the scale-dependent desorption of uranyl [U(VI)] from a contaminated sediment collected from the Hanford 300 Area at the US Department of Energy (DOE) Hanford Site, Washington. The sediment was a coarse-textured alluvial flood deposit containing significant mass percentage of river cobble. U(VI) was, however, only associated with its minor, fine-grained (< 2mm) mass fraction. U(VI) desorption was investigated both from the field-textured sediment using a large column (80 cm length by 15 cm inner diameter), and from its < 2mm, U(VI)-associated mass fraction using a small column (10 cm length by 3.4 cm inner diameter). Dynamic advection conditions with intermittent flow and stop-flow events of variable durations were employed to investigate U(VI) desorption kinetics and its scale dependence. A multi-component kinetic model that integrated a distributed rate expression with surface complexation reactions successfully described U(VI) release from the fine-grained, U(VI)-associated materials. The field-textured sediment in the large column displayed dual domain, tracer-dependent mass transfer properties that affected the breakthrough curves of bromide, pentafluorobenzoic acid (PFBA), and tritium. The tritium breakthrough curve showed stronger non-equilibrium behavior than did PFBA and bromide, and required a larger immobile porosity to describe. The dual domain mass transfer properties were then used to scale the kinetic model of U(VI) desorption developed for the fine-grained materials to describe U(VI) release and reactive transport in the field-textured sediment. Numerical simulations indicated that the kinetic model that was integrated with the dual domain properties determined from tracer PFBA and Br best described the experimental results. The kinetic model without consideration of the dual domain properties over-predicted effluent U(VI) concentrations, while the model based on tritium mass transfer under-predicted the rate of U(VI) release. Overall, our results indicated that the kinetics of U(VI) release from the field-textured sediment were different from that of its fine-grained, U(VI)-associated mass fraction. However, the desorption kinetics measured on the U(VI)-containing mass fraction could be scaled to describe U(VI) reactive transport in the contaminated field-textured sediment after proper consideration of the physical transport properties of the sediment. The research also demonstrated a modeling approach to integrate geochemical processes into field scale reactive transport models.

Marshall MJ, AE Plymale, DW Kennedy, L Shi, Z Wang, SB Reed, A Dohnalkova, CJ Simonson, C Liu, D Saffarini, MF Romine, JM Zachara, AS Beliaev, and JK Fredrickson. 2008. "Hydrogenase- and Outer Membrane c-Type Cytochrome-Facilitated Reduction of Technetium(VII) by Shewanella oneidensis MR-1." Environmental Microbiology 10(1):125-136. doi:10.1111/j.1462-2920.2007.01438.x Abstract Pertechnetate, 99Tc(VII)O4-, is a highly mobile radionuclide contaminant at U.S. Department of Energy sites that can be enzymatically reduced by a range of anaerobic and facultatively anaerobic microorganisms, including Shewanella oneidensis MR-1, to poorly soluble Tc(IV)O2(s). In other microorganisms, Tc(VII)O4- reduction is generally considered to be catalyzed by hydrogenase. Here, we provide evidence that although the NiFe hydrogenase of MR-1 was involved in the H2-driven reduction of Tc(VII)O4- (presumably through a direct coupling of H2 oxidation and Tc(VII) reduction), the deletion of both hydrogenase genes did not completely eliminate the ability of MR-1 to reduce Tc(VII). With lactate as the electron donor, mutants lacking the outer membrane c-type cytochromes MtrC and OmcA or the proteins required for the maturation of c-type cytochromes were defective in reducing Tc(VII) to nanoparticulate TcO2·nH2O(s) relative to MR-1 or a NiFe hydrogenase mutant. In addition, reduced MtrC and OmcA were oxidized by Tc(VII)O4-, confirming the capacity for direct electron transfer from these OMCs to TcO4-. c-Type cytochrome-catalyzed Tc(VII) reduction could be a potentially important mechanism in environments where organic electron donor concentrations are sufficient to allow this reaction to dominate.

Ohno T, Z Wang, and R Bro. 2008. "PowerSlicing to determine fluorescence lifetimes of water-soluble organic matter derived from soils, plant biomass, and animal manures." Analytical and Bioanalytical Chemistry 390(8):2189-2194. doi:10.1007/s00216-008-1963-6 Abstract Time-resolved fluorescence spectroscopy was used to characterize water-soluble organic matter (WSOM) which plays an important role in soil ecosystem processes. WSOM was extracted from plant biomass, animal manures, and soils from controlled cropping systems studies with known histories of organic amendments. Lifetime constants were derived using the multi-way PowerSlicing method which provides a non-iterative, multi-exponential fitting of decay profiles. The lifetimes obtained by PowerSlicing were not significantly different from those obtained using the traditional discrete components analysis. The three components attributed to WSOM had lifetimes of 0.38± 0.14, 2.11±0.72, and 7.08±1.18 ns which are in agreement with previous lifetimes reported for humic substances. This study provides further support for the new paradigm for the structure of soil organic matter where the organic matter is composed of low-molecular-weight components held together by hydrogen bonding and hydrophobic interactions.

Shi L, S Deng, MJ Marshall, Z Wang, DW Kennedy, A Dohnalkova, HM Mottaz, EA Hill, YA Gorby, AS Beliaev, DJ Richardson, JM Zachara, and JK Fredrickson. 2008. " Direct Involvement of Type II Secretion System in Extracellular Translocation of Shewanella Oneidensis Outer Membrane Cytochromes MtrC and OmcA." Journal of Bacteriology 190(15):5512-5516. doi:10.1128/JB.00514-08 Abstract Outer membrane decaheme c-type cytochromes MtrC and OmcA of Shewanella oneidensis MR-1 are extracellular lipoproteins important for dissimilatory reduction of solid metal (hydr)oxides during anaerobic respiration. To investigate the roles of type II secretion system (T2S) in translocation of MtrC and OmcA across outer membrane, we measured the effects of deleting two T2S genes, gspD and gspG, on the secretion of MtrC and OmcA when cells were grown under anaerobic conditions. Deletion of gspD or gspG resulted in slightly yellowish supernatants, different from the pink supernatant of wild type (wt). Comparative proteomic analyses revealed that, although MtrC, OmcA and NrfA, a periplasmic nitrite reductase, were present the supernatants of wt and ΔgspD mutant, their peptides counts were much lower in ΔgspD than in wt. Subsequent analyses with heme-staining and Western blot not only confirmed that deletion of gspD or gspG reduced the abundances of MtrC and OmcA in the supernatants, but also revealed that the deletions consequently increased their abundances inside the cells. Complementation of ΔgspG mutant with functional GspG could reverse the effects of deleting gspG on the colors of the supernatants and the abundances of MtrC and OmcA. In contrast, Western results showed that the abundance of NrfA was reduced in the supernatant and the cells of ΔgspD mutant, suggesting that reduced NrfA in the periplasm, where MtrC and OmcA were accumulated, contributed to its reduction in the supernatant. Thus, our results demonstrate at the first time that T2S facilitates translocation of MtrC and OmcA across outer membrane.