D. K. Shuh

Argonne National Laboratory, Lemont, Illinois, United States

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Publications (272)506.4 Total impact

  • [show abstract] [hide abstract]
    ABSTRACT: Two isostructural series of trigonal prismatic complexes, M(Bp(Me))3 and M(Bc(Me))3 (M = Y, Tb, Dy, Ho, Er, U; [Bp(Me)](-) = dihydrobis(methypyrazolyl)borate; [Bc(Me)](-) = dihydrobis(methylimidazolyl)borate) are synthesized and fully characterized to examine the influence of ligand donor strength on slow magnetic relaxation. Investigation of the dynamic magnetic properties reveals that the oblate electron density distributions of the Tb(3+), Dy(3+), and U(3+) metal ions within the axial ligand field leads to slow relaxation upon application of a small dc magnetic field. Significantly, the magnetization relaxation is orders of magnitude slower for the N-heterocyclic carbene complexes, M(Bc(Me))3, than for the isomeric pyrazolate complexes, M(Bp(Me))3. Further, investigation of magnetically dilute samples containing 11-14 mol% of Tb(3+), Dy(3+), or U(3+) within the corresponding Y(3+) complex matrix reveals thermally-activated relaxation is favored for the M(Bc(Me))3 complexes, even when dipolar interactions are largely absent. Notably, the dilute species U(Bc(Me))3 exhibits Ueff ~33 cm(-1), representing the highest barrier yet observed for a U(3+) molecule demonstrating slow relaxation. Additional analysis through lanthanide XANES, X-band EPR, and (1)H NMR spectroscopies provides evidence that the origin of the slower relaxation derives from the greater magnetic anisotropy enforced within the strongly donating N-heterocyclic carbene coordination sphere. These results show that, like molecular symmetry, ligand donating ability is a variable that can be controlled to the advantage of the synthetic chemist in the design of single-molecule magnets with enhanced relaxation barriers.
    Journal of the American Chemical Society 03/2014; · 10.68 Impact Factor
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    ABSTRACT: The reaction of UO2Cl2·3THF with the tridentate nitrogen donor ligand 2,6-bis(2-benzimidazolyl)pyridine (H2BBP) in pyridine leads to the formation of three different complexes: [(UO2)(H2BBP)Cl2] (1), [(UO)2(HBBP)(Py)Cl] (2), and [(UO2)(BBP)(Py)2] (3) after successive deprotonation of H2BBP with a strong base. Crystallographic determination of 1-3 reveals that increased charge through ligand deprotonation and displacement of chloride leads to equatorial planarity about uranyl as well as a more compact overall coordination geometry. Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectra of 1-3 at the U-4d edges have been recorded using a soft X-ray Scanning Transmission X-ray Microscope (STXM) and reveal the uranium 4d5/2 and 4d3/2 transitions at energies associated with uranium in the hexavalent oxidation state. First-principles Density Functional Theory (DFT) electronic structure calculations for the complexes have been performed to determine and validate the coordination characteristics, which correspond well to the experimental results.
    Inorganic Chemistry 02/2014; · 4.59 Impact Factor
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    ABSTRACT: Understanding the uranium 5f/6d orbital mixing with oxygen 2p valence orbitals in uranium oxides is important for advancing nuclear technology. Unfortunately, U–O orbital mixing is difficult to probe experimentally. In this manuscript, U–O bonding is evaluated in U3O8 using O K-edge X-ray absorption spectroscopy (XAS). To confirm that the O K-edge XAS spectra were correct and did not contain contributions from surface contamination, three different sample types were investigated using three unique detection methods. Specifically an epitaxial film of U3O8 deposited on Al2O3 (PAD-U3O8) was probed using grazing-incidence fluorescence yield (GIFY) detection, a bulk powder of α-phase U3O8 was analyzed with fluorescence yield (FY) detection at normal incidence, and particles of α-phase U3O8 were studied in transmission mode using a scanning transmission X-ray microscope (STXM). Experimental spectra have been presented in the context of previously published computational results from DFT using the Heyd-Scuseria-Ernzerhof (HSE) screened hybrid functional. Overall, the comparative analyses of PAD-U3O8 and α-phase U3O8 samples enabled identification of unique signatures associated with oxygen 2p orbital mixing with both UV and UVI 5f and 6d valence orbitals.
    Journal of Electron Spectroscopy and Related Phenomena 01/2014; · 1.71 Impact Factor
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    ABSTRACT: The study addresses the possibilities of immobilizing the mobile species of actinides in the geosphere using metallic iron. Sorption on corroding iron is well known, but there have been uncertainties as to the possibilities of reducing the actinyl species to sparingly soluble oxides and, thereby, permanently immobilizing them. Resonant inelastic x-ray scattering (RIXS) measurements at the actinide 5d edges on Fe foils exposed to U(VI) and Np(V) solutions in ground water unambigiously indicate reduction of actinides to respectively U(IV) and Np(IV) on iron surfaces. The reduction manifests itself in an appearance of distinct specific signatures of U(IV) and Np(IV) in the RIXS profile of 5f-5f excitations. Such signatures and RIXS intensity/cross-section behaviour with varying energy of incident photons can be reproduced by model atomic-multiplet calculations of the RIXS spectra. By normalizing the RIXS signal of corresponding 5f-5f excitations to core-to-core 6p-to-5d characteristic fluorescence transitions of actinides, their reduction rates on Fe samples with different exposure to actinide solutions can be estimated. Observed reduction implies similar processes in the nuclear waste canister thus suggesting reduced probability of nuclear waste release with ground waters from the canister.
    Analytical Chemistry 11/2013; · 5.70 Impact Factor
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    ABSTRACT: Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.
    Journal of the American Chemical Society 09/2013; · 10.68 Impact Factor
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    ABSTRACT: Syntheses of neutral halide and aryl vanadium bisimides are described. Treatment of VCl2(NtBu)[NTMS(N(t)Bu)], 2, with PMe3, PEt3, PMe2Ph, or pyridine gave vanadium bisimides via TMSCl elimination in good yield: VCl(PMe3)2(N(t)Bu)2 3, VCl(PEt3)2(N(t)Bu)2 4, VCl(PMe2Ph)2(N(t)Bu)2 5, and VCl(Py)2(N(t)Bu)2 6. The halide series (Cl-I) was synthesized by use of TMSBr and TMSI to give VBr(PMe3)2(N(t)Bu)2 7 and VI(PMe3)2(N(t)Bu)2 8. The phenyl derivative was obtained by reaction of 3 with MgPh2 to give VPh(PMe3)2(N(t)Bu)2 9. These neutral complexes are compared to the previously reported cationic bisimides [V(PMe3)3(N(t)Bu)2][Al(PFTB)4] 10, [V(PEt3)2(N(t)Bu)2][Al(PFTB)4] 11, and [V(DMAP)(PEt3)2(N(t)Bu)2][Al(PFTB)4] 12 (DMAP = dimethylaminopyridine, PFTB = perfluoro-tert-butoxide). Characterization of the complexes by X-ray diffraction, (13)C NMR, (51)V NMR, and V L3,2-edge X-ray absorption near-edge structure (XANES) spectroscopy provides a description of the electronic structure in comparison to group 6 bisimides and the bent metallocene analogues. The electronic structure is dominated by π bonding to the imides, and localization of electron density at the nitrogen atoms of the imides is dictated by the cone angle and donating ability of the axial neutral supporting ligands. This phenomenon is clearly seen in the sensitivity of (51)V NMR shift, (13)C NMR Δδαβ, and L3-edge energy to the nature of the supporting phosphine ligand, which defines the parameters for designing cationic group 5 bisimides that would be capable of breaking stronger σ bonds. Conversely, all three methods show little dependence on the variable equatorial halide ligand. Furthermore, this analysis allows for quantification of the electronic differences between vanadium bisimides and the structurally analogous mixed Cp/imide system CpV(N(t)Bu)X2 (Cp = C5H5(1-)).
    Inorganic Chemistry 09/2013; · 4.59 Impact Factor
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    ABSTRACT: Although transition metal cyano bimetallic compounds have been well known for decades for their interesting optical and magnetic properties, reports on actinide hexacyanoferrate compounds are scarce. For instance, a thorough structural description is still lacking. Another question is the possible covalency or charge transfer effects in these materials that are known to foster electron delocalization with a large variety of transition metal cations. In this paper, new members of the actinide(IV) hexacyanoferrates have been synthesized with Th, Np and Pu. This is the first review of thorium to plutonium hexacyanoferrate compounds since the early investigations during the Manhattan Project some 70 years ago. We have carried out an extensive structural characterization using powder X-ray Diffraction (XRD), X-ray Absorption Spectroscopy (XAS) and X-ray microscopy for the plutonium adduct. The crystallographic space group of microcrystalline Th, Np and Pu hexacyanoferrate compounds appears to be very similar to that of the early lanthanide adducts, suggesting that the tetravalent actinides are arranged in a tricapped trigonal prismatic polyhedron of coordination number 9, in which the actinide atom is bonded to six nitrogen atoms and to three water molecules. Further combined analysis of the iron K-edge and actinide LIII-edge EXAFS data and XRD data provided the basis for a three-dimensional molecular model. Structural data in terms of actinide–ligand bond lengths have been compared to those reported for the parent lanthanide(III) compounds, confirming the structural similarities. In addition, two new structures with the thorium cation have been obtained and described using single-crystal XRD: (H5O2)[Th(DMF)5(H2O)]2[Fe(CN)6]3 and [Th(DMF)4(H2O)3][Fe(CN)6](NO3)·2H2O. This structural description of the Th, Np and Pu hexacyanoferrate system will be followed by a semi-quantitative electronic description of the actinide–cyano bond using NEXAFS data analysis in a coming paper.
    New Journal of Chemistry 06/2013; · 2.97 Impact Factor
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    ABSTRACT: The synthesis and study of soft-donor uranyl complexes can provide new insights into the coordination chemistry of non-aqueous [UO]2^+ Recently, the tunable N-donor ligand 2,6-Bis(2-benzimidazyl)pyridine (BBP) was employed to produce novel uranyl complexes in which the [UO]2^+ cation is ligated by anionic and covalent groups with discrete chemical differences. In this work we investigate the electronic structure of the three such uranyl-BBP complexes via near-edge X-ray absorption fine structure (NEXAFS) experiments and simulations using the eXcited electron and Core-Hole (XCH) approach [1]. The evolution of the structural as well as electronic properties across the three complexes is studied systematically. Computed N K-edge and O K-edge NEXAFS spectra are compared with experiment and spectral features assigned to specific electronic transitions in these complexes. Studying the variations in spectral features arising from N K-edge absorption provides a clear picture of ligand-uranyl bonding in these systems. References: [1] D. Prendergast and G. Galli, X-ray absorption spectra of water from first-principles calculations, Phys. Rev. Lett., 215502 (2006).
    03/2013;
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    ABSTRACT: Advancing theories of how metal-oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal MO(4)(x-) anions have formed the basis for new M-O bonding theories. Herein, relative changes in M-O orbital mixing in MO(4)(2-) (M = Cr, Mo, W) and MO(4)(-) (M = Mn, Tc, Re) are evaluated for the first time by nonresonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and time-dependent density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M-O e* (π*) mixing; for example, it more than doubles in ReO(4)(-) relative to CrO(4)(2-). Mixing in the t(2)* orbitals (σ* + π*) remains relatively constant within the same Group, but increases on moving from Group 6 to Group 7. These unexpected changes in orbital energy and composition for formally isoelectronic tetraoxometalates are evaluated in terms of periodic trends in d orbital energy and radial extension.
    Journal of the American Chemical Society 01/2013; · 10.68 Impact Factor
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    ABSTRACT: Monometallic niobium arene complexes [Nb(BDI)(NtBu)(R-C6H5)] (2a: R = H and 2b: R = Me, BDI = N,N'-diisopropylbenzene-β-diketiminate) were synthesized and were found to slowly converted into the diniobium inverted arene sandwich complexes [[(BDI)Nb(NtBu)]2(μ-RC6H5)] (7a: R = H and 7b: R = Me) in solution. The kinetics of this reaction were followed by 1H NMR spectroscopy, and is in agreement with a dissociative mechanism. Compounds 7a-b showed a lack of reactivity towards small molecules - even at elevated temperatures - which is unusual in the chemistry of inverted sandwich complexes. However, protonation of the BDI ligands occurred readily on treatment with [H(OEt2)][B(C6F5)4], resulting in the mono-protonated cationic inverted sandwich complex 8 [[(BDI#)Nb(NtBu)][(BDI)Nb(NtBu)](μ-C6H5)][B(C6F5)4] and the dicationic complex 9 [[(BDI#)Nb(NtBu)]2(μ-RC6H5)][B(C6F5)4]2 (BDI# = (ArNC(Me))2CH2). NMR, UV-vis and X-ray absorption near-edge structure (XANES) spectroscopies were used to characterize this unique series of diamagnetic molecules as a means of determining how best to describe the Nb-arene interactions. The X-ray crystal structures, UV-visible spectra, arene 1H NMR chemical shifts and large JCH coupling con-stants provide evidence for donation of electron density from the Nb d-orbitals into the antibonding π system of the arene ligands. However, Nb L3/2-edge XANES spectra and the lack of sp3 hybridization of the arene carbon indicate that the Nb→arene donation is not accompanied by an increase in formal oxidation state, and suggest that 4d2 electronic configurations are appropriate to describe the Nb atoms in all four complexes.
    Journal of the American Chemical Society 01/2013; · 10.68 Impact Factor
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    ABSTRACT: Synthetic routes to salts containing uranium bis-imido tetrahalide anions [U(NR)(2)X(4)](2-) (X = Cl(-), Br(-)) and non-coordinating NEt(4)(+) and PPh(4)(+) countercations are reported. In general, these compounds can be prepared from U(NR)(2)I(2)(THF)(x) (x = 2 and R = (t)Bu, Ph; x = 3 and R = Me) upon addition of excess halide. In addition to providing stable coordination complexes with Cl(-), the [U(NMe)(2)](2+) cation also reacts with Br(-) to form stable [NEt(4)](2)[U(NMe)(2)Br(4)] complexes. These materials were used as a platform to compare electronic structure and bonding in [U(NR)(2)](2+) with [UO(2)](2+). Specifically, Cl K-edge X-ray absorption spectroscopy (XAS) and both ground-state and time-dependent hybrid density functional theory (DFT and TDDFT) were used to probe U-Cl bonding interactions in [PPh(4)](2)[U(N(t)Bu)(2)Cl(4)] and [PPh(4)](2)[UO(2)Cl(4)]. The DFT and XAS results show the total amount of Cl 3p character mixed with the U 5f orbitals was roughly 7-10% per U-Cl bond for both compounds, which shows that moving from oxo to imido has little effect on orbital mixing between the U 5f and equatorial Cl 3p orbitals. The results are presented in the context of recent Cl K-edge XAS and DFT studies on other hexavalent uranium chloride systems with fewer oxo or imido ligands.
    Journal of the American Chemical Society 01/2013; · 10.68 Impact Factor
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    ABSTRACT: Forty-three atomic emission lines for 235U and 238U were compiled for computer simulation of isotopic analysis using laser induced breakdown spectroscopy (LIBS). The spectral line profile was assumed to be Lorentzian in shape and the magnitude of three common types of noises (detector-read, photon-shot and flicker) were experimentally determined and incorporated into the simulation. Precision and root mean square error of prediction (RMSEP) for isotopic analysis of a single U line were simulated, and it was found that analytical performance (precision) primarily depended on the signal-to-background ratio (SBR) and net intensity of the emission line, rather than on the magnitude of isotopic splitting (IS), when partial least squares (PLS) was used for calibration. This is because PLS multivariate calibration can be performed correctly even when the spectra are only partially resolved, which in turn relaxes the requirement on having IS larger than the spectral resolution. The analytical performance was found to improve with multiple-line analysis. Depending on the criteria (e.g., SBR, net intensity, magnitude of IS, or best single-line performance) used in sorting the spectral lines into the multiline pool, improvement factors ranging from 2 × to 9 × were obtained. The absolute uncertainty of isotopic analysis is practically constant and independent of isotopic abundance, which makes experimental estimation of the detection limit in isotopic analysis straightforward because one can experimentally measure this uncertainty with one arbitrary and conveniently chosen isotopic standard and then estimate the detection limit through simple extrapolation.
    Spectrochimica Acta Part B Atomic Spectroscopy 01/2013; 89:40–49. · 3.14 Impact Factor
  • 10/2012;
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    ABSTRACT: A key distinction between the lanthanide (4f) and the actinide (5f) transition elements is the increased role of f-orbital covalent bonding in the latter. Circularly polarized luminescence (CPL) is an uncommon but powerful spectroscopy which probes the electronic structure of chiral, luminescent complexes or molecules. While there are many examples of CPL spectra for the lanthanides, this report is the first for an actinide. Two chiral, octadentate chelating ligands based on orthoamide phenol (IAM) were used to complex curium(III). While the radioactivity kept the amount of material limited to micromole amounts, spectra of the highly luminescent complexes showed significant emission peak shifts between the different complexes, consistent with ligand field effects previously observed in luminescence spectra.
    Journal of the American Chemical Society 08/2012; 134(37):15545-9. · 10.68 Impact Factor
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    ABSTRACT: h i g h l i g h t s " Tc, an environmental risk for nuclear waste storage, is commonly modeled using Re. " Tc and Re valences can diverge in original and hydrothermally altered glasses. " Tc and Re spatial distributions can diverge in hydrothermally altered glasses. " Re can be an unreliable surrogate for Tc in situations where redox is important. " Using Re as a surrogate for Tc in waste glasses can provide misleading results. a b s t r a c t Technetium (99 Tc) is a significant environmental risk factor to consider for nuclear waste disposal repos-itories. Rhenium (Re), in the same column of the periodic table as Tc, is often used as a non-radioactive surrogate for Tc. Six waste glasses containing both Tc and Re were synthesized under a variety of redox conditions to produce different distributions of Tc and Re oxidation states. These glasses were exposed to vapor hydration tests (VHT) at 200 °C for 23 to 30 days; and the Tc and Re oxidation state, coordination environment, and spatial distribution within the altered coupons were determined. Compared with the original glasses, the corresponding VHT samples showed substantial reduction of Tc species, except where the original glass contained only reduced Tc (Tc 4+). Similar to earlier findings, Tc is more sensitive to redox conditions than Re with respect to both glass synthesis conditions and VHT alteration processes. Glasses that originally contained more oxidized Tc (near 100% Tc 7+) showed the most Tc enrichment in the altered VHT sample layers, where Tc was largely reduced to Tc 4+ . Re is generally more oxidized than Tc in the samples measured and has similar spatial distributions as Tc in some VHT samples, while having very different spatial distributions compared with Tc in others. Glasses that originally had a distribution of Tc oxidation states (approximately 1:1 Tc 4+ to Tc 7+), had Tc concentrations in the VHT altered layers that were approximately equal to or less than those found in the unaltered glass. However, in the same samples, Re concentrations were highest in the altered layers. Overall, with regard to spatial distributions within the altered VHT layers, the behavior of Re was not a good predictor of Tc behavior. Therefore, at least under VHT conditions, using Re as a non-radioactive surrogate for Tc in borosilicate waste glasses can provide misleading results. Ó 2012 Elsevier B.V. All rights reserved.
    Journal of Nuclear Materials 05/2012; · 1.21 Impact Factor
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    ABSTRACT: High-purity syntheses are reported for a series of first, second, and third row transition metal and actinide hexahalide compounds with equivalent, noncoordinating countercations: (Ph(4)P)(2)TiF(6) (1) and (Ph(4)P)(2)MCl(6) (M = Ti, Zr, Hf, Th, U, Np, Pu; 2-8). While a reaction between MCl(4) (M = Zr, Hf, U) and 2 equiv of Ph(4)PCl provided 3, 4, and 6, syntheses for 1, 2, 5, 7, and 8 required multistep procedures. For example, a cation exchange reaction with Ph(4)PCl and (NH(4))(2)TiF(6) produced 1, which was used in a subsequent anion exchange reaction with Me(3)SiCl to synthesize 2. For 5, 7, and 8, synthetic routes starting with aqueous actinide precursors were developed that circumvented any need for anhydrous Th, Np, or Pu starting materials. The solid-state geometries, bond distances and angles for isolated ThCl(6)(2-), NpCl(6)(2-), and PuCl(6)(2-) anions with noncoordinating counter cations were determined for the first time in the X-ray crystal structures of 5, 7, and 8. Solution phase and solid-state diffuse reflectance spectra were also used to characterize 7 and 8. Transition metal MCl(6)(2-) anions showed the anticipated increase in M-Cl bond distances when changing from M = Ti to Zr, and then a decrease from Zr to Hf. The M-Cl bond distances also decreased from M = Th to U, Np, and Pu. Ionic radii can be used to predict average M-Cl bond distances with reasonable accuracy, which supports a principally ionic model of bonding for each of the (Ph(4)P)(2)MCl(6) complexes.
    Inorganic Chemistry 05/2012; 51(10):5728-36. · 4.59 Impact Factor
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    ABSTRACT: 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.
    Environmental Science & Technology 04/2012; 46(11):5931-8. · 5.26 Impact Factor
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    ABSTRACT: Chlorine K-edge X-ray absorption spectroscopy (XAS) and ground-state and time-dependent hybrid density functional theory (DFT) were used to probe the electronic structures of O(h)-MCl(6)(2-) (M = Ti, Zr, Hf, U) and C(4v)-UOCl(5)(-), and to determine the relative contributions of valence 3d, 4d, 5d, 6d, and 5f orbitals in M-Cl bonding. Spectral interpretations were guided by time-dependent DFT calculated transition energies and oscillator strengths, which agree well with the experimental XAS spectra. The data provide new spectroscopic evidence for the involvement of both 5f and 6d orbitals in actinide-ligand bonding in UCl(6)(2-). For the MCl(6)(2-), where transitions into d orbitals of t(2g) symmetry are spectroscopically resolved for all four complexes, the experimentally determined Cl 3p character per M-Cl bond increases from 8.3(4)% (TiCl(6)(2-)) to 10.3(5)% (ZrCl(6)(2-)), 12(1)% (HfCl(6)(2-)), and 18(1)% (UCl(6)(2-)). Chlorine K-edge XAS spectra of UOCl(5)(-) provide additional insights into the transition assignments by lowering the symmetry to C(4v), where five pre-edge transitions into both 5f and 6d orbitals are observed. For UCl(6)(2-), the XAS data suggest that orbital mixing associated with the U 5f orbitals is considerably lower than that of the U 6d orbitals. For both UCl(6)(2-) and UOCl(5)(-), the ground-state DFT calculations predict a larger 5f contribution to bonding than is determined experimentally. These findings are discussed in the context of conventional theories of covalent bonding for d- and f-block metal complexes.
    Journal of the American Chemical Society 03/2012; 134(12):5586-97. · 10.68 Impact Factor
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    ABSTRACT: The existing evaluations of the 243Am neutron-induced fission cross section have been questioned by recent measurements performed at the GNEISS facility. In the neutron energy range from 1 to 6 MeV, the GNEISS data present deviations of more than 15% with respect to the evaluations. In order to solve this problem, we have measured this cross section in reference to three different standard cross sections. The first standard reaction used corresponds to the neutron on proton elastic scattering cross section, which is known with a precision better than 0.5% over a wide neutron-energy range of 1 meV to 20 MeV. The other two experiments were conducted in reference to the 235U(n,f) and 238U(n,f) reactions. The comparison between these three standard reactions ensures that systematic parameters have been correctly evaluated. Moreover, a sensitivity analysis of parameters and correlations of parameters is described and a complete variance-covariance matrix of the measurements is presented and discussed.
    Physical Review C 01/2012; · 3.72 Impact Factor
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    ABSTRACT: Carnotite minerals [X2(UO2)2(VO4)2]; X = K, Ca, Ba, Mn, Na, Cu or Pb] form the major ore of uranium in the Colorado Plateau. These deposits are highly oxidized and contain U(VI) and V(IV). The biotransformation of U(VI) bound in carnotite by bacteria during dissimilatory metal reduction presents a complex puzzle in mineral chemistry. Both U(VI) and V(V) can be respired by metal reducing bacteria, and the mineral structure can change depending on the associated counterion. We incubated anaerobic cultures of S. putrefaciens CN32 with natural carnotite minerals from southeastern Utah in a nutrient-limited defined medium. Strain CN32 is a gram negative bacterium and a terrestrial isolate from New Mexico. The mineral and metal transformations were compared to a system that contained similar concentrations of soluble U(VI) and V(V). Electron (SEM, TEM) microscopies and x-ray spectromicroscopy (STXM) were used in conjunction with XRD to track mineral changes, and bacterial survival was monitored throughout the incubations. Slow rates of metal reduction over 10 months for the treatment with carnotite minerals revealed distinct biotic and abiotic processes, providing insight on mineral transformation and bacteria-metal interactions. The bacteria existed as small flocs or individual cells attached to the mineral phase, but did not adsorb soluble U or V, and accumulated very little of the biominerals. Reduction of mineral V(V) necessarily led to a dismantling of the carnotite structure. Bioreduction of V(V) by CN32 contributed small but profound changes to the mineral system, resulting in new minerals. Abiotic cation exchange within the carnotite group minerals induced the rearrangement of the mineral structures, leading to further mineral transformation. In contrast, bacteria survival was poor for treatments with soluble U(VI) and V(V), although both metals were reduced completely and formed solid UO2 and VO2; we also detected V(III). For these treatments, the bacteria formed extensive biofilms or flocs that contained U and V in the exopolymer, but excluded these metals from the bacteria. This suggests a specific mechanism to inhibit metal sorption to cell wall components. The example illustrates the interplay between bacteria and minerals under conditions that model oligotrophic survival, and provides insight on U mobilization from common uranium ore minerals.
    AGU Fall Meeting Abstracts. 12/2011;

Publication Stats

928 Citations
506.40 Total Impact Points

Institutions

  • 2014
    • Argonne National Laboratory
      Lemont, Illinois, United States
  • 2006–2012
    • University of California, Berkeley
      • Department of Chemistry
      Berkeley, CA, United States
  • 1992–2012
    • Lawrence Berkeley National Laboratory
      • • Chemical Sciences Division
      • • Advanced Light Source Facility
      Berkeley, California, United States
  • 2011
    • Paul Scherrer Institut
      • Laboratory for Waste Management (LES)
      Villigen, AG, Switzerland
  • 2010–2011
    • Northwestern University
      • Department of Chemistry
      Evanston, IL, United States
  • 1998–2011
    • Uppsala University
      • Department of Chemistry - Ångström Laboratory
      Uppsala, Uppsala, Sweden
  • 2005
    • University of Nevada, Reno
      Reno, Nevada, United States
  • 1992–2005
    • CSU Mentor
      Long Beach, California, United States
  • 2004
    • Oak Ridge National Laboratory
      • Chemical Sciences Division
      Oak Ridge, FL, United States
  • 1997–2003
    • Lawrence Livermore National Laboratory
      • Condensed Matter and Materials Division
      Livermore, California, United States
  • 2001
    • University of Nevada, Las Vegas
      • Department of Chemistry
      Las Vegas, NV, United States
  • 1995
    • The University of Tennessee Medical Center at Knoxville
      Knoxville, Tennessee, United States
  • 1992–1995
    • University of California, Riverside
      Riverside, California, United States
  • 1987–1991
    • University of California, Los Angeles
      • Department of Chemistry and Biochemistry
      Los Angeles, California, United States
    • California State University, Los Angeles
      Los Angeles, California, United States