Environmental controls on the activity of aquifer microbial communities in the 300 area of the Hanford site.

PubMed

Konopka, Allan; Plymale, Andrew E; Carvajal, Denny A; Lin, Xueju; McKinley, James P

2013-11-01

Aquifer microbes in the 300 Area of the Hanford Site in southeastern Washington State, USA, are located in an oligotrophic environment and are periodically exposed to U(VI) concentrations that can range up to 10 μM in small sediment fractures. Assays of (3)H-leucine incorporation indicated that both sediment-associated and planktonic microbes were metabolically active, and that organic C was growth-limiting in the sediments. Although bacteria suspended in native groundwater retained high activity when exposed to 100 μM U(VI), they were inhibited by U(VI) <1 μM in synthetic groundwater that lacked added bicarbonate. Chemical speciation modeling suggested that positively charged species and particularly (UO2)3(OH)5 (+) rose in concentration as more U(VI) was added to synthetic groundwater, but that carbonate complexes dominated U(VI) speciation in natural groundwater. U toxicity was relieved when increasing amounts of bicarbonate were added to synthetic groundwater containing 4.5 μM U(VI). Pertechnetate, an oxyanion that is another contaminant of concern at the Hanford Site, was not toxic to groundwater microbes at concentrations up to 125 μM.

The U(VI) speciation influenced by a novel Paenibacillus isolate from Mont Terri Opalinus clay.

PubMed

Lütke, Laura; Moll, Henry; Bachvarova, Velina; Selenska-Pobell, Sonja; Bernhard, Gert

2013-05-21

Bacterial cell walls have a high density of ionizable functional groups available for U(VI) binding, hence have a great potential to affect the speciation of this contaminant in the environment. The studied strain of the genus Paenibacillus is a novel isolate originating from the Mont Terri Opalinus clay formations (Switzerland) which are currently investigated as a potential host rock for future nuclear waste storage. U(VI) binding to the cell surface functional groups was studied by potentiometry combined with time-resolved laser-induced fluorescence spectroscopy (TRLFS). Four bacterial U(VI) surface complexes were identified: R-COO-UO2(+), R-O-PO3-UO2, R-O-PO3H-UO2(+), and (R-O-PO3)2-UO2(2-). The corresponding complex stability constants were calculated to be 5.33 ± 0.08, 8.89 ± 0.04, 12.92 ± 0.05, and 13.62 ± 0.08, respectively. Hence UO2(2+) displays a moderate to strong interaction with the bacterial surface functional groups. In the acidic pH range (pH 3) UO2(2+) binding onto the cell envelope is governed by coordination to hydrogen phosphoryl sites. Upon increasing the pH an increasing coordination of UO2(2+) to carboxylic and deprotonated phosphoryl sites was found. At a pH greater than 7 uranyl hydroxides dominate the speciation. Additionally the bacteria-mediated release of inorganic phosphate in dependence on [U(VI)] at different pH values was studied to assess the influence of phosphate release on U(VI) mobilization.

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

USGS Publications Warehouse

Yin, J.; Haggerty, R.; Stoliker, D.L.; Kent, D.B.; Istok, J.D.; Greskowiak, J.; Zachara, J.M.

2011-01-01

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry. Copyright 2011 by the American Geophysical Union.

Transient groundwater chemistry near a river: Effects on U(VI) transport in laboratory column experiments

USGS Publications Warehouse

Yin, Jun; Haggerty, Roy; Stoliker, Deborah L.; Kent, Douglas B.; Istok, Jonathan D.; Greskowiak, Janek; Zachara, John M.

2011-01-01

In the 300 Area of a U(VI)-contaminated aquifer at Hanford, Washington, USA, inorganic carbon and major cations, which have large impacts on U(VI) transport, change on an hourly and seasonal basis near the Columbia River. Batch and column experiments were conducted to investigate the factors controlling U(VI) adsorption/desorption by changing chemical conditions over time. Low alkalinity and low Ca concentrations (Columbia River water) enhanced adsorption and reduced aqueous concentrations. Conversely, high alkalinity and high Ca concentrations (Hanford groundwater) reduced adsorption and increased aqueous concentrations of U(VI). An equilibrium surface complexation model calibrated using laboratory batch experiments accounted for the decrease in U(VI) adsorption observed with increasing (bi)carbonate concentrations and other aqueous chemical conditions. In the column experiment, alternating pulses of river and groundwater caused swings in aqueous U(VI) concentration. A multispecies multirate surface complexation reactive transport model simulated most of the major U(VI) changes in two column experiments. The modeling results also indicated that U(VI) transport in the studied sediment could be simulated by using a single kinetic rate without loss of accuracy in the simulations. Moreover, the capability of the model to predict U(VI) transport in Hanford groundwater under transient chemical conditions depends significantly on the knowledge of real-time change of local groundwater chemistry.

Long-term diffusion of U(VI) in bentonite: Dependence on density

DOE PAGES

Joseph, Claudia; Mibus, Jens; Trepte, Paul; ...

2016-10-12

As a contribution to the safety assessment of nuclear waste repositories, U(VI) diffusion through the potential buffer material MX-80 bentonite was investigated at three clay dry densities over six years. Synthetic MX-80 model pore water was used as background electrolyte. Speciation calculations showed that Ca 2UO 2(CO 3) 3(aq) was the main U(VI) species. The in- and out-diffusion of U(VI) was investigated separately. U(VI) diffused about 3 mm, 1.5 mm, and 1 mm into the clay plug at ρ = 1.3, 1.6, and 1.9 g/cm 3, respectively. No through-diffusion of the U(VI) tracer was observed. However, leaching of natural uraniummore » contained in the clay occurred and uranium was detected in all receiving reservoirs. As expected, the effective and apparent diffusion coefficients, D e and D a, decreased with increasing dry density. The D a values for the out-diffusion of natural U(VI) were in good agreement with previously determined values. Surprisingly, D a values for the in-diffusion of U(VI) were about two orders of magnitude lower than values obtained in short-term in-diffusion experiments reported in the literature. Some potential reasons for this behavior that were evaluated are changes of the U(VI) speciation within the clay (precipitation, reduction) or changes of the clay porosity and pore connectivity with time. By applying Archie's law and the extended Archie's law, it was estimated that a significantly smaller effective porosity must be present for the long-term in-diffusion of U(VI). Finally, the results suggest that long-term studies of key transport phenomena may reveal additional processes that can directly impact long-term repository safety assessments.« less

Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by titration and XAFS

NASA Astrophysics Data System (ADS)

Boyanov, Maxim I.; O'Loughlin, Edward J.; Roden, Eric E.; Fein, Jeremy B.; Kemner, Kenneth M.

2007-04-01

The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, "dead-end" U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).

Polyaniline (PANI) modified bentonite by plasma technique for U(VI) removal from aqueous solution

NASA Astrophysics Data System (ADS)

Liu, Xinghao; Cheng, Cheng; Xiao, Chengjian; Shao, Dadong; Xu, Zimu; Wang, Jiaquan; Hu, Shuheng; Li, Xiaolong; Wang, Weijuan

2017-07-01

Polyaniline (PANI) modified bentonite (PANI/bentonie) was synthesized by plasma induced polymerization of aniline on bentonite surface, and applied to uptake of uranium(VI) ions from aqueous solution. The as-synthesized PANI/bentonie was characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and X-ray photoelectron spectroscopy (XPS). Batch adsorption technique was utilized to investigate the adsorption of U(VI) on bentonite and PANI/bentonite. The adsorption of U(VI) (10 mg/L) on PANI/bentonite surface is fairly depend on solution pH, ionic strength, and temperature in solution. The modified PANI on PANI/bentonite surface significantly enhances its adsorption capability for U(VI). The presence of humic acid (HA) can sound enhance U(VI) adsorption on PANI/bentonite at pH < 6.5 because of the strong complexation, and inhibits U(VI) adsorption at pH > 6.5. According to the thermodynamic parameters, the adsorption of U(VI) on PANI/bentonite surface is a spontaneous and endothermic process. The results highlight the application of PANI/bentonite composites as candidate material for the uptake of trace U(VI) from aqueous solution.

Bio-precipitation of uranium by two bacterial isolates recovered from extreme environments as estimated by potentiometric titration, TEM and X-ray absorption spectroscopic analyses.

PubMed

Merroun, Mohamed L; Nedelkova, Marta; Ojeda, Jesus J; Reitz, Thomas; Fernández, Margarita López; Arias, José M; Romero-González, María; Selenska-Pobell, Sonja

2011-12-15

This work describes the mechanisms of uranium biomineralization at acidic conditions by Bacillus sphaericus JG-7B and Sphingomonas sp. S15-S1 both recovered from extreme environments. The U-bacterial interaction experiments were performed at low pH values (2.0-4.5) where the uranium aqueous speciation is dominated by highly mobile uranyl ions. X-ray absorption spectroscopy (XAS) showed that the cells of the studied strains precipitated uranium at pH 3.0 and 4.5 as a uranium phosphate mineral phase belonging to the meta-autunite group. Transmission electron microscopic (TEM) analyses showed strain-specific localization of the uranium precipitates. In the case of B. sphaericus JG-7B, the U(VI) precipitate was bound to the cell wall. Whereas for Sphingomonas sp. S15-S1, the U(VI) precipitates were observed both on the cell surface and intracellularly. The observed U(VI) biomineralization was associated with the activity of indigenous acid phosphatase detected at these pH values in the absence of an organic phosphate substrate. The biomineralization of uranium was not observed at pH 2.0, and U(VI) formed complexes with organophosphate ligands from the cells. This study increases the number of bacterial strains that have been demonstrated to precipitate uranium phosphates at acidic conditions via the activity of acid phosphatase. Copyright © 2011 Elsevier B.V. All rights reserved.

Field Application of 238U/235U Measurements To Detect Reoxidation and Mobilization of U(IV).

PubMed

Jemison, Noah E; Shiel, Alyssa E; Johnson, Thomas M; Lundstrom, Craig C; Long, Philip E; Williams, Kenneth H

2018-03-20

Biostimulation to induce reduction of soluble U(VI) to relatively immobile U(IV) is an effective strategy for decreasing aqueous U(VI) concentrations in contaminated groundwater systems. If oxidation of U(IV) occurs following the biostimulation phase, U(VI) concentrations increase, challenging the long-term effectiveness of this technique. However, detecting U(IV) oxidation through dissolved U concentrations alone can prove difficult in locations with few groundwater wells to track the addition of U to a mass of groundwater. We propose the 238 U/ 235 U ratio of aqueous U as an independent, reliable tracer of U(IV) remobilization via oxidation or mobilization of colloids. Reduction of U(VI) produces 238 U-enriched U(IV), whereas remobilization of solid U(IV) should not induce isotopic fractionation. The incorporation of remobilized U(IV) with a high 238 U/ 235 U ratio into the aqueous U(VI) pool produces an increase in 238 U/ 235 U of aqueous U(VI). During several injections of nitrate to induce U(IV) oxidation, 238 U/ 235 U consistently increased, suggesting 238 U/ 235 U is broadly applicable for detecting mobilization of U(IV).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joseph, Claudia; Mibus, Jens; Trepte, Paul

As a contribution to the safety assessment of nuclear waste repositories, U(VI) diffusion through the potential buffer material MX-80 bentonite was investigated at three clay dry densities over six years. Synthetic MX-80 model pore water was used as background electrolyte. Speciation calculations showed that Ca 2UO 2(CO 3) 3(aq) was the main U(VI) species. The in- and out-diffusion of U(VI) was investigated separately. U(VI) diffused about 3 mm, 1.5 mm, and 1 mm into the clay plug at ρ = 1.3, 1.6, and 1.9 g/cm 3, respectively. No through-diffusion of the U(VI) tracer was observed. However, leaching of natural uraniummore » contained in the clay occurred and uranium was detected in all receiving reservoirs. As expected, the effective and apparent diffusion coefficients, D e and D a, decreased with increasing dry density. The D a values for the out-diffusion of natural U(VI) were in good agreement with previously determined values. Surprisingly, D a values for the in-diffusion of U(VI) were about two orders of magnitude lower than values obtained in short-term in-diffusion experiments reported in the literature. Some potential reasons for this behavior that were evaluated are changes of the U(VI) speciation within the clay (precipitation, reduction) or changes of the clay porosity and pore connectivity with time. By applying Archie's law and the extended Archie's law, it was estimated that a significantly smaller effective porosity must be present for the long-term in-diffusion of U(VI). Finally, the results suggest that long-term studies of key transport phenomena may reveal additional processes that can directly impact long-term repository safety assessments.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hawkins, Cory A.; Bustillos, Christian G.; May, Iain

Conventional solvent extraction of selected f-element cations by bis(2-ethylhexyl)phosphoric acid (HDEHP) yields increased extraction from aqueous to organic solution along the series Np(V) < Cm(III) < Eu(III) < U(VI), with distribution ratios all within two orders of magnitude. However, in the presence of the water-soluble tetradentate Schiff base (N,N'-bis(5-sulfonatosalicylidene)-ethylenediamine or H 2salenSO 3), selective complexation of the two actinyl cations (Np(V) and U(VI)) resulted in an extraction order of Np(V) < U(VI) << Eu(III) < Cm(III). The extraction of neither Cm(III) or Eu(III) by HDEHP are significantly impacted by the presence of the aqueous phase Schiff base. Despite observed hydrolyticmore » decomposition of H 2salenSO 3 in aqueous solutions, the calculated high conditional stability constant (β 11 = 26) for the complex [UO 2(salenSO 3)] 2- demonstrates its capacity for aqueous hold-back of U(VI). UV-visible-NIR spectroscopy of solutions prepared with a Np(VI) stock and H 2salenSO 3 suggest that reduction of Np(VI) to Np(V) by the ligand was rapid, resulting in a pentavalent Np complex that was substantially retained in the aqueous phase. Lastly, results from 1H NMR of aqueous solutions of H 2salenSO 3 with U(VI) and La(III), Eu(III), and Lu(III) provides additional evidence that the ligand readily chelates U(VI), but has only weak interactions with trivalent lanthanide ions.« less

Study of sorption-retarded U(VI) diffusion in Hanford silt/clay material.

PubMed

Bai, Jing; Liu, Chongxuan; Ball, William P

2009-10-15

A diffusion cell method was applied to measure the effective pore diffusion coefficient (Dp) for U(VI) under strictly controlled chemical conditions in a silt/clay sediment from the U.S. Department of Energy Hanford site, WA. "Inward-flux" diffusion studies were conducted in which [U(VI)] in both aqueous and solid phases was measured as a function of distance in the diffusion cell under conditions of constant concentration at the cell boundaries. A sequential extraction method was developed to measure sorbed contaminant U(VI) in the solid phase containing extractable background U(VI). The effect of sorption kinetics on U(VI) interparticle diffusion was evaluated by comparing sorption-retarded diffusion models with sorption described either as equilibrium or intraparticle diffusion-limited processes. Both experimental and modeling results indicated that (1) a single pore diffusion coefficient can simulate the diffusion of total aqueous U(VI), and (2) the local equilibrium assumption (LEA) is appropriate for modeling sorption-retarded diffusion under the given experimental conditions. Dp of 1.6-1.7 x 10(-6) cm2/s was estimated in aqueous solution at pH 8.0 and saturated with respect to calcite, as relevant to some subsurface regions of the Hanford site.

Water-soluble Schiff base-actinyl complexes and their effect on the solvent extraction of f-elements

DOE PAGES

Hawkins, Cory A.; Bustillos, Christian G.; May, Iain; ...

2016-09-07

Conventional solvent extraction of selected f-element cations by bis(2-ethylhexyl)phosphoric acid (HDEHP) yields increased extraction from aqueous to organic solution along the series Np(V) < Cm(III) < Eu(III) < U(VI), with distribution ratios all within two orders of magnitude. However, in the presence of the water-soluble tetradentate Schiff base (N,N'-bis(5-sulfonatosalicylidene)-ethylenediamine or H 2salenSO 3), selective complexation of the two actinyl cations (Np(V) and U(VI)) resulted in an extraction order of Np(V) < U(VI) << Eu(III) < Cm(III). The extraction of neither Cm(III) or Eu(III) by HDEHP are significantly impacted by the presence of the aqueous phase Schiff base. Despite observed hydrolyticmore » decomposition of H 2salenSO 3 in aqueous solutions, the calculated high conditional stability constant (β 11 = 26) for the complex [UO 2(salenSO 3)] 2- demonstrates its capacity for aqueous hold-back of U(VI). UV-visible-NIR spectroscopy of solutions prepared with a Np(VI) stock and H 2salenSO 3 suggest that reduction of Np(VI) to Np(V) by the ligand was rapid, resulting in a pentavalent Np complex that was substantially retained in the aqueous phase. Lastly, results from 1H NMR of aqueous solutions of H 2salenSO 3 with U(VI) and La(III), Eu(III), and Lu(III) provides additional evidence that the ligand readily chelates U(VI), but has only weak interactions with trivalent lanthanide ions.« less

Transport of U(VI) through sediments amended with phosphate to induce in situ uranium immobilization.

PubMed

Mehta, Vrajesh S; Maillot, Fabien; Wang, Zheming; Catalano, Jeffrey G; Giammar, Daniel E

2015-02-01

Phosphate amendments can be added to U(VI)-contaminated subsurface environments to promote in situ remediation. The primary objective of this study was to evaluate the impacts of phosphate addition on the transport of U(VI) through contaminated sediments. In batch experiments using sediments (<2 mm size fraction) from a site in Rifle, Colorado, U(VI) only weakly adsorbed due to the dominance of the aqueous speciation by Ca-U(VI)-carbonate complexes. Column experiments with these sediments were performed with flow rates that correspond to a groundwater velocity of 1.1 m/day. In the absence of phosphate, the sediments took up 1.68-1.98 μg U/g of sediments when the synthetic groundwater influent contained 4 μM U(VI). When U(VI)-free influents were then introduced with and without phosphate, substantially more uranium was retained within the column when phosphate was present in the influent. Sequential extractions of sediments from the columns revealed that uranium was uniformly distributed along the length of the columns and was primarily in forms that could be extracted by ion exchange and contact with a weak acid. Laser induced fluorescence spectroscopy (LIFS) analysis along with sequential extraction results suggest adsorption as the dominant uranium uptake mechanism. The response of dissolved uranium concentrations to stopped-flow events and the comparison of experimental data with simulations from a simple reactive transport model indicated that uranium adsorption to and desorption from the sediments was not always at local equilibrium. Copyright © 2014 Elsevier Ltd. All rights reserved.

Decrease of U(VI) Immobilization Capability of the Facultative Anaerobic Strain Paenibacillus sp. JG-TB8 under Anoxic Conditions Due to Strongly Reduced Phosphatase Activity

PubMed Central

Reitz, Thomas; Rossberg, Andre; Barkleit, Astrid; Selenska-Pobell, Sonja; Merroun, Mohamed L.

2014-01-01

Interactions of a facultative anaerobic bacterial isolate named Paenibacillus sp. JG-TB8 with U(VI) were studied under oxic and anoxic conditions in order to assess the influence of the oxygen-dependent cell metabolism on microbial uranium mobilization and immobilization. We demonstrated that aerobically and anaerobically grown cells of Paenibacillus sp. JG-TB8 accumulate uranium from aqueous solutions under acidic conditions (pH 2 to 6), under oxic and anoxic conditions. A combination of spectroscopic and microscopic methods revealed that the speciation of U(VI) associated with the cells of the strain depend on the pH as well as on the aeration conditions. At pH 2 and pH 3, uranium was exclusively bound by organic phosphate groups provided by cellular components, independently on the aeration conditions. At higher pH values, a part (pH 4.5) or the total amount (pH 6) of the dissolved uranium was precipitated under oxic conditions in a meta-autunite-like uranyl phosphate mineral phase without supplying an additional organic phosphate substrate. In contrast to that, under anoxic conditions no mineral formation was observed at pH 4.5 and pH 6, which was clearly assigned to decreased orthophosphate release by the cells. This in turn was caused by a suppression of the indigenous phosphatase activity of the strain. The results demonstrate that changes in the metabolism of facultative anaerobic microorganisms caused by the presence or absence of oxygen can decisively influence U(VI) biomineralization. PMID:25157416

Removal of uranium from aqueous solution by a low cost and high-efficient adsorbent

NASA Astrophysics Data System (ADS)

Liu, Yun-Hai; Wang, You-Qun; Zhang, Zhi-Bin; Cao, Xiao-Hong; Nie, Wen-Bin; Li, Qin; Hua, Rong

2013-05-01

In this study, a low-cost and high-efficient carbonaceous adsorbent (HTC-COOH) with carboxylic groups was developed for U(VI) removal from aqueous solution compared with the pristine hydrothermal carbon (HTC). The structure and chemical properties of resultant adsorbents were characterized by Scanning electron microscope (SEM), N2 adsorption-desorption, Fourier transform-infrared spectra (FT-IR) and acid-base titration. The key factors (solution pH, contact time, initial U(VI) concentrations and temperature) affected the adsorption of U(VI) on adsorbents were investigated using batch experiments. The adsorption of U(VI) on HTC and HTC-COOH was pH-dependent, and increased with temperature and initial ion concentration. The adsorption equilibrium of U(VI) on adsorbents was well defined by the Langmuir isothermal equation, and the monolayer adsorption capacity of HTC-COOH was found to be 205.8 mg/g. The kinetics of adsorption was very in accordance with the pseudo-second-order rate model. The adsorption processes of U(VI) on HTC and HTC-COOH were endothermic and spontaneous in nature according to the thermodynamics of adsorption. Furthermore, HTC-COOH could selectively adsorption of U(VI) in aqueous solution containing co-existing ions (Mg2+, Co2+, Ni2+, Zn2+ and Mn2+). From the results of the experiments, it is found that the HTC-COOH is a potential adsorbent for effective removal of U(VI) from polluted water.

Diffusion of U(VI) in Opalinus Clay: Influence of temperature and humic acid

NASA Astrophysics Data System (ADS)

Joseph, C.; Van Loon, L. R.; Jakob, A.; Steudtner, R.; Schmeide, K.; Sachs, S.; Bernhard, G.

2013-05-01

The diffusion of U(VI) (c0 = 1 × 10-6 mol/L) in compacted Opalinus Clay from the Mont Terri underground laboratory, Switzerland, was studied in the absence and presence of humic acid (10 mg/L) at two different temperatures (25 °C, 60 °C) under anaerobic conditions. As background electrolyte synthetic Opalinus Clay pore water (pH 7.6, I = 0.36 mol/L) was used. The diffusion-accessible porosity, ɛ, was determined for each Opalinus Clay bore core sample by through-diffusion experiments with tritiated water (HTO) before the U(VI) diffusion experiments were carried out. The values for the effective diffusion and distribution coefficients De and Kd obtained for U(VI) and humic acid at 25 °C as well as at 60 °C showed that humic acid has no significant influence on the U(VI) diffusion. The diffusion profiles of humic acid in Opalinus Clay at 25 and 60 °C indicate the contributions of two different humic acid particle size fractions (<1 kDa and 10-100 kDa). The small-sized humic acid fraction diffused through the whole Opalinus Clay samples at both temperatures within the 3 month duration of the U(VI) diffusion experiments. At 60 °C, diffusion profiles of two different U(VI) species were observed. In a separate experiment the U(VI) speciation in the source reservoir solution at 60 °C was analyzed by laser-induced fluorescence spectroscopy, photon correlation spectroscopy and scanning electron microscopy with an energy dispersive X-ray detector. The two diffusion profiles could be attributed to an unknown colloidal and a known aquatic U(VI) species (Ca2UO2(CO3)3(aq)). The diffusion results showed that the interaction of U(VI) and of the large-sized humic acid colloid fraction with the clay is stronger at 60 °C. An increase of Kd from 0.025 ± 0.003 m3/kg at 25 °C to 0.25 ± 0.05 m3/kg for U(VI)colloidal at 60 °C was determined. In addition, the value for De of U(VI) increased with increasing temperature. Using the De values at 25 and 60 °C, a preliminary activation energy for the diffusion of U(VI) through Opalinus Clay of 10 kJ/mol was calculated. The observed increased Kd and De values for U(VI)aqueous at 60 °C compensated each other to almost equal values of the apparent diffusion coefficient Da at 25 and 60 °C. Hence, an elevated temperature of 60 °C does not impact the migration of U(VI) through OPA significantly.

Uranium Reduction by Fe(II) in the Presence of Montmorillonite and Nontronite.

PubMed

Tsarev, Sergey; Waite, T David; Collins, Richard N

2016-08-02

Uranium(VI) interactions with three smectites (one montmorillonite and two nontronites - NAu1 and NAu2) were examined with 0, 1, and 2 mM aqueous concentrations of Fe(II) over the pH range of 3-9.5 in a background electrolyte of 100 mM NaCl and 1 mM CaCl2 in equilibration with 400 ppmv CO2(g) ([U(VI)] = 4 μM and 0.5 g smectite/L). In the absence of Fe(II), no differences were observed in the U(VI) sorption curves for the three clay minerals. In the presence of 1 or 2 mM Fe(II), under anoxic conditions, U(VI) uptake by the smectites changed slightly between ∼pH 3 and 6; however, uranium uptake increased significantly above ∼pH 6 and was proportional to the concentration of Fe(II) added to the system, particularly at pH values >8. The uptake of Fe(II) showed a sharp edge starting from ∼pH 6.5 with 95%-100% uptake occurring at pH values >7.5, with no difference observed between the iron-rich nontronites and montmorillonite. After 3 days of reaction at pH 7.6 (i.e., above the Fe(II) "sorption" edge), U(VI) was transformed to a mixture of U(IV) and U(VI) sorption complexes, and after 14 days of reaction, 100% of the U was found to be reduced to U(IV) in the form of nanocrystalline uraninite. In contrast, U remained as sorbed species until 14 days of reaction at pH 6.5. Ferrihydrite (NAu1), lepidocrocite, and magnetite (NAu2) were detected as secondary mineralization products upon reaction of the nontronites with Fe(II) but appeared to have no effect on the partitioning or speciation of uranium.

Multispecies diffusion models: A study of uranyl species diffusion

NASA Astrophysics Data System (ADS)

Liu, Chongxuan; Shang, Jianying; Zachara, John M.

2011-12-01

Rigorous numerical description of multispecies diffusion requires coupling of species, charge, and aqueous and surface complexation reactions that collectively affect diffusive fluxes. The applicability of a fully coupled diffusion model is, however, often constrained by the availability of species self-diffusion coefficients, as well as by computational complication in imposing charge conservation. In this study, several diffusion models with variable complexity in charge and species coupling were formulated and compared to describe reactive multispecies diffusion in groundwater. Diffusion of uranyl [U(VI)] species was used as an example in demonstrating the effectiveness of the models in describing multispecies diffusion. Numerical simulations found that a diffusion model with a single, common diffusion coefficient for all species was sufficient to describe multispecies U(VI) diffusion under a steady state condition of major chemical composition, but not under transient chemical conditions. Simulations revealed that for multispecies U(VI) diffusion under transient chemical conditions, a fully coupled diffusion model could be well approximated by a component-based diffusion model when the diffusion coefficient for each chemical component was properly selected. The component-based diffusion model considers the difference in diffusion coefficients between chemical components, but not between the species within each chemical component. This treatment significantly enhanced computational efficiency at the expense of minor charge conservation. The charge balance in the component-based diffusion model can be enforced, if necessary, by adding a secondary migration term resulting from model simplification. The effect of ion activity coefficient gradients on multispecies diffusion is also discussed. The diffusion models were applied to describe U(VI) diffusive mass transfer in intragranular domains in two sediments collected from U.S. Department of Energy's Hanford 300A, where intragranular diffusion is a rate-limiting process controlling U(VI) adsorption and desorption. The grain-scale reactive diffusion model was able to describe U(VI) adsorption/desorption kinetics that had been previously described using a semiempirical, multirate model. Compared with the multirate model, the diffusion models have the advantage to provide spatiotemporal speciation evolution within the diffusion domains.

Sequestration of U(VI) from Acidic, Alkaline, and High Ionic-Strength Aqueous Media by Functionalized Magnetic Mesoporous Silica Nanoparticles: Capacity and Binding Mechanisms

EPA Science Inventory

Uranium (VI) exhibits little adsorption onto sediment minerals in acidic, alkaline or high ionic-strength aqueous media that often occur in U mining or contaminated sites, which makes U(VI) very mobile and difficult to sequester. In this work, magnetic mesoporous silica nanoparti...

Characterization of U(VI) reduction in contaminated sediments with slow-degrading electron donor source

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Zhang, G.; Mehlhorn, T.; Lowe, K.; Earles, J.; Phillips, J.; Kelly, S. D.; Boyanov, M.; Kemner, K. M.; Schadt, C.; Criddle, C. S.; Jardine, P. M.; Brooks, S. C.

2011-12-01

In order to select sustainable, high efficiency and cost effective electron donor source, oleate and emulsified vegetable oil (EVO) were tested uranium (VI) reduction in comparison with ethanol in microcosms using uranium contaminated sediments and groundwater from the US DOE Oak Ridge Integrated Field Research Challenge (ORIFRC) site. The effect of initial sulfate concentration on U(VI) reduction was also tested. Both oleate and EVO were effective electron donor sources for U(VI) reduction. Accumulation of acetate as a major product and the removal of aqueous U(VI) were observed and were associated with sulfate reduction. Both oleate and EVO supported U(VI) reduction but at slower rates with a comparable but slightly lower extent of reduction than ethanol. X-ray absorption near-edge spectroscopy (XANES) analysis confirmed reduction of U(VI) to U(IV). The extent of U(VI) reduction in solid phase was negatively influenced by aqueous calcium concentration. The majority of electrons of the three substrates were consumed by sulfate reduction, Fe(III) reduction, and methanogenesis. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 versus 5 mM), likely due to U(VI) desorption from the solid phase. At the higher initial sulfate concentration more U(VI) was reduced and fewer electrons were used in methanogenesis. Analysis of bacterial and archeal populations using 16S rRNA gene libraries showed a significant increase in Deltaproteobacteria after biostimulation. The microbial community structures developed with oleate and EVO were significantly distinct from those developed with ethanol. Bacteria similar to Desulforegula spp. was predominant for oleate and EVO degradation but were not observed in ethanol-amended microcosms. Known U(VI)-reducing bacteria in the microcosms amended with the three electron donor sources included iron(III) reducing Geobacter spp. but in lower abundances than sulfate-reducing Desulfovibrio spp. The test results were used for the design a field test by one-time injection of EVO to the subsurface for U(VI) reduction in Area 2 of the ORIFRC site.

HNO3 modified biochars for uranium (VI) removal from aqueous solution.

PubMed

Jin, Jie; Li, Shiwei; Peng, Xianqiang; Liu, Wei; Zhang, Chenlu; Yang, Yan; Han, Lanfang; Du, Ziwen; Sun, Ke; Wang, Xiangke

2018-05-01

The HNO 3 treatment was used to chemically modify the biochars produced from wheat straw (WH) and cow manure for U(VI) removal from aqueous solution. Macroscopic experiments proved that the enrichment of U(VI) on the biochars was regulated by surface complexation and electrostatic interactions. FTIR and XPS analyses confirmed that the highly efficient adsorption of U(VI) was due to the carboxyl groups on the biochar surfaces. The reducing agents of the R-CH 2 OH groups facilitated U(VI) adsorption on the untreated biochars. Owing to the higher contents of surface COO groups and more negative surface charge, the modified biochars showed enhanced U(VI) adsorption ability than the untreated ones. The maximum adsorption capacity of U(VI) by the oxidized WH was calculated to be 355.6 mg/g at pH 4.5 and 298 K, which was an improvement of 40 times relative to the untreated WH and was higher than that of most carbon-based adsorbents. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quantitative Analysis of Uranium Accumulation on Sediments during Field-scale Biostimulation under Variable Bicarbonate Concentrations at the Rifle IFRC Site

NASA Astrophysics Data System (ADS)

Fox, P. M.; Davis, J. A.; Bargar, J.; Williams, K. H.; Singer, D. M.; Long, P.

2011-12-01

Bioremediation of uranium in subsurface environments is an approach that has been used at numerous field sites throughout the U.S in an attempt to lower dissolved U(VI) concentrations in groundwater. At the Rifle IFRC research site in Colorado, biostimulation of the native microbial population through acetate amendment for various periods of time has been tested in order to immobilize uranium through reduction U(VI) to U(IV). While this approach has successfully decreased U(VI) concentrations in the dissolved phase, often to levels below the EPA's maximum contaminant level of 0.13 μM, little work has examined the solid-phase accumulation of U during field-scale biostimulation. The lack of information on solid-phase U accumulation is due in large part to the difficulty of obtaining comparable pre- and post-biostimulation field sediment samples. In addition, the relatively low (<10 ppm) U concentrations present in most sediments preclude the use of spectroscopic techniques such as XAS for examining solid-phase U speciation. However, a recently developed technique of performing column experiments in situ has allowed us to overcome both of these problems, obtaining sediment samples which were exposed to the same biogeochemical conditions as subsurface sediments during the course of biostimulation. During the 2010 Rifle IFRC field experiment (dubbed "Super 8"), a number of in situ columns were deployed in various wells representing regions of the aquifer affected by acetate amendment (ambient bicarbonate) and concomitant acetate and bicarbonate amendment (elevated bicarbonate). Elevated levels of bicarbonate have been shown to cause desorption of U(VI) from the solid phase at the Rifle site under non-stimulated conditions, resulting in higher dissolved U(VI) concentrations in the aquifer. The Super 8 field experiment was designed in part to test the effect of elevated bicarbonate concentrations on U sequestration during biostimulation. Results from this experiment provide a comparison of temporal aqueous and solid-phase U concentrations under ambient and elevated bicarbonate conditions during field-scale biostimulation. Additionally, a subset of in situ columns amended with 20 μM U(VI) were analyzed by XANES in order to determine the relative importance of U(VI) and U(IV) in the solid phase. While the elevated bicarbonate concentrations did not impede reduction and sequestration of U, differences in the behavior of dissolved U(VI) after acetate amendment was stopped demonstrate the importance of U adsorption-desorption reactions in controlling dissolved U concentrations post-biostimulation.

Non-enzymatic U(VI) interactions with biogenic mackinawite

NASA Astrophysics Data System (ADS)

Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

2011-12-01

Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

The application of N,N-dimethyl-3-oxa-glutaramic acid (DOGA) in the PUREX process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jianchen, Wang; Jing, Chen

2007-07-01

The new salt-free complexant, DOGA for separating trace Pu(IV) and Np(IV) from U(VI) nitric acid solution was studied. DOGA has stronger complexing abilities to Pu(IV) and Np(IV), but complexing ability of DOGA to U(VI) was weaker. The DOGA can be used in the PUREX process to separate Pu(IV) and Np(IV) from U(VI) nitric solution. On one hand, U(IV) in the nitric acid solution containing trace Pu(IV) and Np(IV) was extracted by 30%TBP - kerosene(v/v) in the presence of DOGA, but Pu(IV) and Np(IV) were kept in the aqueous phase. On the other hand, Pu(IV) and Np(IV) loading in 30% TBPmore » - kerosene were effectively stripped by DOGA into the aqueous phase, but U(VI) loading in 30% TBP - kerosene was remained in 30% TBP - kerosene. DOGA is a promising complexant to separate Pu(IV) and Np(IV) from U(VI) solution in the U-cycle of the PUREX process. (authors)« less

Uranyl adsorption and surface speciation at the imogolite-water interface: Self-consistent spectroscopic and surface complexation models

USGS Publications Warehouse

Arai, Y.; McBeath, M.; Bargar, J.R.; Joye, J.; Davis, J.A.

2006-01-01

Macro- and molecular-scale knowledge of uranyl (U(VI)) partitioning reactions with soil/sediment mineral components is important in predicting U(VI) transport processes in the vadose zone and aquifers. In this study, U(VI) reactivity and surface speciation on a poorly crystalline aluminosilicate mineral, synthetic imogolite, were investigated using batch adsorption experiments, X-ray absorption spectroscopy (XAS), and surface complexation modeling. U(VI) uptake on imogolite surfaces was greatest at pH ???7-8 (I = 0.1 M NaNO3 solution, suspension density = 0.4 g/L [U(VI)]i = 0.01-30 ??M, equilibration with air). Uranyl uptake decreased with increasing sodium nitrate concentration in the range from 0.02 to 0.5 M. XAS analyses show that two U(VI) inner-sphere (bidentate mononuclear coordination on outer-wall aluminol groups) and one outer-sphere surface species are present on the imogolite surface, and the distribution of the surface species is pH dependent. At pH 8.8, bis-carbonato inner-sphere and tris-carbonato outer-sphere surface species are present. At pH 7, bis- and non-carbonato inner-sphere surface species co-exist, and the fraction of bis-carbonato species increases slightly with increasing I (0.1-0.5 M). At pH 5.3, U(VI) non-carbonato bidentate mononuclear surface species predominate (69%). A triple layer surface complexation model was developed with surface species that are consistent with the XAS analyses and macroscopic adsorption data. The proton stoichiometry of surface reactions was determined from both the pH dependence of U(VI) adsorption data in pH regions of surface species predominance and from bond-valence calculations. The bis-carbonato species required a distribution of surface charge between the surface and ?? charge planes in order to be consistent with both the spectroscopic and macroscopic adsorption data. This research indicates that U(VI)-carbonato ternary species on poorly crystalline aluminosilicate mineral surfaces may be important in controlling U(VI) mobility in low-temperature geochemical environments over a wide pH range (???5-9), even at the partial pressure of carbon dioxide of ambient air (pCO2 = 10-3.45 atm). ?? 2006 Elsevier Inc. All rights reserved.

A Uranium Bioremediation Reactive Transport Benchmark

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yabusaki, Steven B.; Sengor, Sevinc; Fang, Yilin

A reactive transport benchmark problem set has been developed based on in situ uranium bio-immobilization experiments that have been performed at a former uranium mill tailings site in Rifle, Colorado, USA. Acetate-amended groundwater stimulates indigenous microorganisms to catalyze the reduction of U(VI) to a sparingly soluble U(IV) mineral. The interplay between the flow, acetate loading periods and rates, microbially-mediated and geochemical reactions leads to dynamic behavior in metal- and sulfate-reducing bacteria, pH, alkalinity, and reactive mineral surfaces. The benchmark is based on an 8.5 m long one-dimensional model domain with constant saturated flow and uniform porosity. The 159-day simulation introducesmore » acetate and bromide through the upgradient boundary in 14-day and 85-day pulses separated by a 10 day interruption. Acetate loading is tripled during the second pulse, which is followed by a 50 day recovery period. Terminal electron accepting processes for goethite, phyllosilicate Fe(III), U(VI), and sulfate are modeled using Monod-type rate laws. Major ion geochemistry modeled includes mineral reactions, as well as aqueous and surface complexation reactions for UO2++, Fe++, and H+. In addition to the dynamics imparted by the transport of the acetate pulses, U(VI) behavior involves the interplay between bioreduction, which is dependent on acetate availability, and speciation-controlled surface complexation, which is dependent on pH, alkalinity and available surface complexation sites. The general difficulty of this benchmark is the large number of reactions (74), multiple rate law formulations, a multisite uranium surface complexation model, and the strong interdependency and sensitivity of the reaction processes. Results are presented for three simulators: HYDROGEOCHEM, PHT3D, and PHREEQC.« less

Characterization of uranium redox state in organic-rich Eocene sediments.

PubMed

Cumberland, Susan A; Etschmann, Barbara; Brugger, Joël; Douglas, Grant; Evans, Katy; Fisher, Louise; Kappen, Peter; Moreau, John W

2018-03-01

The presence of organic matter (OM) has a profound impact on uranium (U) redox cycling, either limiting or promoting the mobility of U via binding, reduction, or complexation. To understand the interactions between OM and U, we characterised U oxidation state and speciation in nine OM-rich sediment cores (18 samples), plus a lignite sample from the Mulga Rock polymetallic deposit in Western Australia. Uranium was unevenly dispersed within the analysed samples with 84% of the total U occurring in samples containing >21 wt % OM. Analyses of U speciation, including x-ray absorption spectroscopy and bicarbonate extractions, revealed that U existed predominately (∼71%) as U(VI), despite the low pH (4.5) and nominally reducing conditions within the sediments. Furthermore, low extractability by water, but high extractability by a bi-carbonate solution, indicated a strong association of U with particulate OM. The unexpectedly high proportion of U(VI) relative to U(IV) within the OM-rich sediments implies that OM itself does not readily reduce U, and the reduction of U is not a requirement for immobilizing uranium in OM-rich deposits. The fact that OM can play a significant role in limiting the mobility and reduction of U(VI) in sediments is important for both U-mining and remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Removing uranium (VI) from aqueous solution with insoluble humic acid derived from leonardite.

PubMed

Meng, Fande; Yuan, Guodong; Larson, Steven L; Ballard, John H; Waggoner, Charles A; Arslan, Zikri; Han, Fengxiang X

2017-12-01

The occurrence of uranium (U) and depleted uranium (DU)-contaminated wastes from anthropogenic activities is an important environmental problem. Insoluble humic acid derived from leonardite (L-HA) was investigated as a potential adsorbent for immobilizing U in the environment. The effect of initial pH, contact time, U concentration, and temperature on U(VI) adsorption onto L-HA was assessed. The U(VI) adsorption was pH-dependent and achieved equilibrium in 2 h. It could be well described with pseudo-second-order model, indicating that U(VI) adsorption onto L-HA involved chemisorption. The U(VI) adsorption mass increased with increasing temperature with maximum adsorption capacities of 91, 112 and 120 mg g -1 at 298, 308 and 318 K, respectively. The adsorption reaction was spontaneous and endothermic. We explored the processes of U(VI) desorption from the L-HA-U complex through batch desorption experiments in 1 mM NaNO 3 and in artificial seawater. The desorption process could be well described by pseudo-first-order model and reached equilibrium in 3 h. L-HA possessed a high propensity to adsorb U(VI). Once adsorbed, the release of U(VI) from L-HA-U complex was minimal in both 1 mM NaNO 3 and artificial seawater (0.06% and 0.40%, respectively). Being abundant, inexpensive, and safe, L-HA has good potential for use as a U adsorbent from aqueous solution or immobilizing U in soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geochemical control on the reduction of U(VI) to mononuclear U(IV) species in lacustrine sediments

NASA Astrophysics Data System (ADS)

Stetten, L.; Mangeret, A.; Brest, J.; Seder-Colomina, M.; Le Pape, P.; Ikogou, M.; Zeyen, N.; Thouvenot, A.; Julien, A.; Alcalde, G.; Reyss, J. L.; Bombled, B.; Rabouille, C.; Olivi, L.; Proux, O.; Cazala, C.; Morin, G.

2018-02-01

Contaminated systems in which uranium (U) concentrations slightly exceed the geochemical background are of particular interest to identify natural processes governing U trapping and accumulation in Earth's surface environments. For this purpose, we examined the role of early diagenesis on the evolution of U speciation and mobility in sediments from an artificial lake located downstream from a former mining site. Sediment and pore water chemistry together with U and Fe solid state speciation were analyzed in sediment cores sampled down to 50 cm depth at four locations in the lake. These organic-rich sediments (∼12% organic C) exhibited U concentrations in the 40-80 mg kg-1 range. The sediment columns were anoxic 2-3 mm below the sediment-water interface and pore waters pH was circumneutral. Pore water chemistry profiles showed that organic carbon mineralization was associated with Fe and Mn reduction and was correlated with a decrease in dissolved U concentration with depth. Immobilization of U in the sediment was correlated with the reduction of U(VI) to U(IV) at depth, as shown by U LIII-edge XANES spectroscopic analysis. XANES and EXAFS spectroscopy at the Fe K-edge showed the reduction of structural Fe(III) to Fe(II) in phyllosilicate minerals with depth, coincident with U(VI) to U(IV) reduction. Thermodynamic modeling suggests that Fe(II) could act as a major reducing agent for U(VI) during early diagenesis of these sediments, leading to complete U reduction below ∼30 cm depth. Shell-by-shell and Cauchy-Wavelet analysis of U LIII-EXAFS spectra indicates that U(VI) and U(IV) are mainly present as mononuclear species bound to C, P or Si ligands. Chemical extractions confirmed that ∼60-80% of U was present as non-crystalline species, which emphasizes that such species should be considered when evaluating the fate of U in lacustrine environments and the efficiency of sediment remediation strategies.

Incorporation of Np(V) and U(VI) in Carbonate and Sulfate Minerals Crystallized from Aqueous Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming

2015-02-15

The neptunyl Np(V)O2 + and uranyl U(VI)O2 2+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is coprecipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factorsmore » that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals.« less

Thermodynamic Insight into the Solvation and Complexation Behavior of U(VI) in Ionic Liquid: Binding of CMPO with U(VI) Studied by Optical Spectroscopy and Calorimetry.

PubMed

Wu, Qi; Sun, Taoxiang; Meng, Xianghai; Chen, Jing; Xu, Chao

2017-03-06

The complexation of U(VI) with octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO, denoted as L) in ionic liquid (IL) C 4 mimNTf 2 was investigated by UV-vis absorption spectrophotometry and isothermal titration calorimetry. Spectro-photometric titration suggests that three successive complexes, UO 2 L j 2+ (j = 1-3), formed both in "dry" (water content < 250 ppm) and "wet" (water content ≈ 12 500 ppm) ionic liquid. However, the thermodynamic parameters are distinctly different in the two ILs. In dry IL, the complexation strength between CMPO and U(VI) is much stronger, with stability constants of the respective complexes more than 1 order of magnitude higher than that in wet IL. Energetically, the complexation of U(VI) with CMPO in dry IL is mainly driven by negative enthalpies. In contrast, the complexation in wet IL is overwhelmingly driven by highly positive entropies as a result of the release of a large amount of water molecules from the solvation sphere of U(VI). Moreover, comparisons between the fitted absorption spectra of complexes in wet IL and that of extractive samples from solvent extraction have identified the speciation involved in the extraction of U(VI) by CMPO in ionic liquid. The results from this study not only offer a thermodynamic insight into the complexation behavior of U(VI) with CMPO in IL but also provide valuable information for understanding the extraction behavior in the corresponding solvent extraction system.

Complexation of Eu(III), Pb(II), and U(VI) with a Paramecium glycoprotein: Microbial transformation of heavy elements in the aquatic environment.

PubMed

Kozai, Naofumi; Sakamoto, Fuminori; Tanaka, Kazuya; Ohnuki, Toshihiko; Satoh, Takahiro; Kamiya, Tomihiro; Grambow, Bernd

2018-04-01

This study investigated the interaction of inorganic aqueous Eu(III), Pb(II), and U(VI) with Paramecium sp., a representative single-celled protozoan that lives in freshwater. Living and prekilled Paramecium cells were tested. The prekilled cells were killed with a fixative. After 24 h exposure of the cells to inorganic aqueous solutions containing Eu(III) or U(VI), analyses by microparticle-induced X-ray emission with a focused beam (<1 μm) did not detect Eu and U in the living cells, whereas Eu and U were detected in the prekilled cells. Size exclusion chromatography coupled with on-line ultraviolet-visible detection and elemental detection by inductively coupled plasma mass spectrometry of the aqueous phases collected after the living cell experiments revealed that a fraction of the Eu, Pb, and U in the aqueous phase bound to a large (ca. 250 kDa) Paramecium biomolecule and formed a metal-organic complex. The characteristics of the biomolecule were consistent with those of the soluble glycoproteins covering the surfaces of Paramecium cells. These results show that Paramecium cells transform inorganic aqueous Eu, Pb, and U to organic complexes. This paper discusses the relation between this novel complexation and the sorption of these heavy elements on Paramecium cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

USGS Publications Warehouse

Arai, Yuji; Fuller, C.C.

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na2SO4 solutions to simulate the major chemical composition of U-contaminatedgroundwater (i.e., [SO42-]~13 mM L-1) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO2-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite–water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55–7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO2, there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO2 fluctuates between 1 and 2 pCO2%.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces.

PubMed

Arai, Yuji; Fuller, C C

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na(2)SO(4) solutions to simulate the major chemical composition of U-contaminated groundwater (i.e., [SO(4)(2-)] ~13 mM L(-1)) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO(2)-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite-water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55-7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO(2), there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO(2) fluctuates between 1 and 2 pCO(2)%. Copyright © 2011 Elsevier Inc. All rights reserved.

Surface Engineering of PAMAM-SDB Chelating Resin with Diglycolamic Acid (DGA) Functional Group for Efficient Sorption of U(VI) and Th(IV) from Aqueous Medium.

PubMed

Ilaiyaraja, P; Deb, A K Singha; Ponraju, D; Ali, Sk Musharaf; Venkatraman, B

2017-04-15

A novel chelating resin obtained via growth of PAMAM dendron on surface of styrene divinyl benzene resin beads, followed by diglycolamic acid functionalization of the dendrimer terminal. Batch experiments were conducted to study the effects of pH, nitric acid concentration, amount of adsorbent, shaking time, initial metal ion concentration and temperature on U(VI) and Th(IV) adsorption efficiency. Diglycolamic acid terminated PAMAM dendrimer functionalized styrene divinylbenzene chelating resin (DGA-PAMAM-SDB) is found to be an efficient candidate for the removal of U(VI) and Th(IV) ions from aqueous (pH >4) and nitric acid media (>3M). The sorption equilibrium could be reached within 60min, and the experimental data fits with pseudo-second-order model. Langmuir sorption isotherm model correlates well with sorption equilibrium data. The maximum U(VI) and Th(IV) sorption capacity onto DGA-PAMAMG 5 -SDB was estimated to be about 682 and 544.2mgg -1 respectively at 25°C. The interaction of actinides and chelating resin is reversible and hence, the resin can be regenerated and reused. DFT calculation on the interaction of U(VI) and Th(IV) ions with chelating resin validates the experimental findings. Copyright © 2017 Elsevier B.V. All rights reserved.

Efficient sorption and reduction of U(VI) on zero-valent iron-polyaniline-graphene aerogel ternary composite.

PubMed

Chen, Lili; Feng, Shaojie; Zhao, Donglin; Chen, Shaohua; Li, Feifei; Chen, Changlun

2017-03-15

In this work, zero-valent iron-polyaniline-graphene aerogel composite (Fe-PANI-GA) was prepared and applied in the removal of U(VI) from aqueous solutions by batch sorption experiments. The experimental results showed that the Fe-PANI-GA composite had an excellent removal capacity for the removal of U(VI) in acidic solutions. The results also showed that the maximum removal capacity of the Fe-PANI-GA toward U(VI) was 350.47mg/g at pH 5.5. The sorption kinetics data were well-described by pseudo-second-order. The sorption isotherms of U(VI) fitted well with Langmuir isotherm and exhibited better removal efficiency with the increase of temperature. The thermodynamic parameters (ΔG, ΔS, ΔH) indicated that the sorption of U(VI) on the Fe-PANI-GA was an endothermic and spontaneous process. Moreover, removal mechanisms were studied based on the results of XRD, FTIR and XPS. Both U(VI) sorption and partially reductive precipitation of U(VI) to U(IV) contributed to the removal of U(VI) on Fe-PANI-GA. Therefore, Fe-PANI-GA was an economic and effective material for the removal of uranium from nuclear waste in practical application. Copyright © 2016 Elsevier Inc. All rights reserved.

Ship-in-a-bottle CMPO in MIL-101(Cr) for selective uranium recovery from aqueous streams through adsorption.

PubMed

De Decker, Jeroen; Folens, Karel; De Clercq, Jeriffa; Meledina, Maria; Van Tendeloo, Gustaaf; Du Laing, Gijs; Van Der Voort, Pascal

2017-08-05

Mesoporous MIL-101(Cr) is used as host for a ship-in-a-bottle type adsorbent for selective U(VI) recovery from aqueous environments. The acid-resistant cage-type MOF is built in-situ around N,N-Diisobutyl-2-(octylphenylphosphoryl)acetamide (CMPO), a sterically demanding ligand with high U(VI) affinity. This one-step procedure yields an adsorbent which is an ideal compromise between homogeneous and heterogeneous systems, where the ligand can act freely within the pores of MIL-101, without leaching, while the adsorbent is easy separable and reusable. The adsorbent was characterized by XRD, FTIR spectroscopy, nitrogen adsorption, XRF, ADF-STEM and EDX, to confirm and quantify the successful encapsulation of the CMPO in MIL-101, and the preservation of the host. Adsorption experiments with a central focus on U(VI) recovery were performed. Very high selectivity for U(VI) was observed, while competitive metal adsorption (rare earths, transition metals...) was almost negligible. The adsorption capacity was calculated at 5.32mg U/g (pH 3) and 27.99mg U/g (pH 4), by fitting equilibrium data to the Langmuir model. Adsorption kinetics correlated to the pseudo-second-order model, where more than 95% of maximum uptake is achieved within 375min. The adsorbed U(VI) is easily recovered by desorption in 0.1M HNO 3 . Three adsorption/desorption cycles were performed. Copyright © 2017 Elsevier B.V. All rights reserved.

Facile synthesis of magnetic Fe3O4/graphene composites for enhanced U(VI) sorption

NASA Astrophysics Data System (ADS)

Zhao, Donglin; Zhu, Hongyu; Wu, Changnian; Feng, Shaojie; Alsaedi, Ahmed; Hayat, Tasawar; Chen, Changlun

2018-06-01

A novel magnetic Fe3O4/graphene composite (FGC) was fabricated by a facile one-step reaction route and shown to be effective for sorbing U(VI) from aqueous solution. The structure, properties and application of the prepared FGC composite were well evaluated. The high saturation magnetization (45.6 emu/g) made FGC easier to be separated from the media within several seconds under an external magnetic. Effects of different ambient conditions (i.e., pH and ionic strength, contact time, temperatures) on sorption behaviors of U(VI) on FGC were carried out by batch experiments. According to the calculation of Langmuir model, the maximum sorption capacity of U(VI) on the FGC at pH 5.5 and 298 K was 176.47 mg/g. The sorption was correlated with the effects of pH, contact time, and temperature. X-ray photoelectron spectroscopy analysis revealed that U(VI) was sorbed on FGC via oxygen-containing functional groups. This work demonstrated that FGC could be recycled and used as an effective recyclable sorbent for sorption of U(VI).

Surface catalysis of uranium(VI) reduction by iron(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liger, E.; Charlet, L.; Van Cappellen, P.

1999-10-01

Colloidal hematite ({alpha}-Fe{sub 2}O{sub 3}) is used as model solid to investigate the kinetic effect of specific adsorption interactions on the chemical reduction of uranyl (U{sup VI}O{sub 2}{sup 2+}) by ferrous iron. Acid-base titrations and Fe(II) and uranyl adsorption experiments are performed on hematite suspensions, under O{sub 2}- and CO{sub 2}-free conditions. The results are explained in terms of a constant capacitance surface complexation model of the hematite-aqueous solution interface. Two distinct Fe(II) surface complexes are required to reproduce the data: ({equivalent{underscore}to}Fe{sup III}OFe{sup II}){sup +} (or {equivalent{underscore}to}Fe{sup III}OFe{sup II}(OH{sub 2}){sub n}{sup +}) and {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0} (or {equivalent{underscore}to}Fe{sup III}OFe{supmore » II}(OH{sub 2}){sub n{minus}1}OH{sup 0}). The latter complex represents a significant fraction of total adsorbed Fe(II) at pH {gt} 6.5. Uranyl binding to the hematite particles is characterized by a sharp adsorption edge between pH 4 and pH 5.5. Because of the absence of competing aqueous carbonate complexes, uranyl remains completely adsorbed at pH {gt} 7. A single mononuclear surface complex accounts for the adsorption of uranyl over the entire range of experimental conditions. Although thermodynamically feasible, no reaction between uranyl and Fe(II) is observed in homogeneous solution at pH 7.5, for periods of up to three days. In hematite suspensions, however, surface-bound uranyl reacts on a time scale of hours. Based on Fourier Transformed Infrared spectra, chemical reduction of U(VI) is inferred to be the mechanism responsible for the disappearance of uranyl. The kinetics of uranyl reduction are quantified by measuring the decrease with time of the concentration of U(VI) extractable from the hematite particles by NaHCO{sub 3}. In the presence of excess Fe(II), the initial rate of U(VI) reduction exhibits a first-order dependence on the concentration of adsorbed uranyl. The pseudo-first-order rate constant varies with pH (range, 6--7.5) and the total (dissolved + adsorbed) concentration of Fe(II) (range, 2--160 {micro}M). When analyzing the rate data in terms of the calculated surface speciation, the variability of the rate constant can be accounted for entirely by changes in the concentration of the Fe(II) monohydroxo surface complex {equivalent{underscore}to}Fe{sup III}OFe{sup II}OH{sup 0}. Therefore, the rate law is derived for the hematite-catalyzed reduction of uranyl by Fe(II), where the bimolecular rate constant {kappa} has a value of 399 {+-} 25 M{sup {minus}1} min{sup {minus}1} at 25 C. The hydroxo surface complex is the rate-controlling reductant species, because it provides the most favorable coordination environment in which electrons are removed from Fe(II). Natural particulate matter collected in the hypolimnion of a seasonally stratified lake also causes the rapid reduction of uranyl by Fe(II), Ferrihydrite, identified in the particulate matter by X-ray diffraction, is one possible mineral phase accelerating the reaction between U(VI) and Fe(II). At near-neutral pH and total Fe(II) levels less than 1 mM, the pseudo-first-order rate constants of chemical U(VI) reduction, measured in the presence of the hematite and lake particles, are of the same order of magnitude as the highest corresponding rate coefficients for enzymatic U(VI) reduction in bacterial cultures. Hence, based on the results of this study, surface-catalyzed U(VI) reduction by Fe(II) is expected to be a major pathway of uranium immobilization in a wide range of redox-stratified environments.« less

Microbial reduction of U(VI) under alkaline conditions: implications for radioactive waste geodisposal.

PubMed

Williamson, Adam J; Morris, Katherine; Law, Gareth T W; Rizoulis, Athanasios; Charnock, John M; Lloyd, Jonathan R

2014-11-18

Although there is consensus that microorganisms significantly influence uranium speciation and mobility in the subsurface under circumneutral conditions, microbiologically mediated U(VI) redox cycling under alkaline conditions relevant to the geological disposal of cementitious intermediate level radioactive waste, remains unexplored. Here, we describe microcosm experiments that investigate the biogeochemical fate of U(VI) at pH 10-10.5, using sediments from a legacy lime working site, stimulated with an added electron donor, and incubated in the presence and absence of added Fe(III) as ferrihydrite. In systems without added Fe(III), partial U(VI) reduction occurred, forming a U(IV)-bearing non-uraninite phase which underwent reoxidation in the presence of air (O2) and to some extent nitrate. By contrast, in the presence of added Fe(III), U(VI) was first removed from solution by sorption to the Fe(III) mineral, followed by bioreduction and (bio)magnetite formation coupled to formation of a complex U(IV)-bearing phase with uraninite present, which also underwent air (O2) and partial nitrate reoxidation. 16S rRNA gene pyrosequencing showed that Gram-positive bacteria affiliated with the Firmicutes and Bacteroidetes dominated in the post-reduction sediments. These data provide the first insights into uranium biogeochemistry at high pH and have significant implications for the long-term fate of uranium in geological disposal in both engineered barrier systems and the alkaline, chemically disturbed geosphere.

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Hung D.; Cao, Bin; Mishra, Bhoopesh

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000more » μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state.« less

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium.

PubMed

Nguyen, Hung Duc; Cao, Bin; Mishra, Bhoopesh; Boyanov, Maxim I; Kemner, Kenneth M; Fredrickson, Jim K; Beyenal, Haluk

2012-01-01

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H(2), pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H(2) concentrations were heterogeneous at the microscale (<500-1000 μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H(2) under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L(III)-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state. Copyright © 2011 Elsevier Ltd. All rights reserved.

Method for separating actinides. [Patent application; stripping of Np from organic extractant

DOEpatents

Friedman, H.A.; Toth, L.M.

1980-11-10

An organic solution used for processing spent nuclear reactor fuels is contacted with an aqueous nitric acid solution to strip Np(VI), U(VI), and Pu(IV) from the organic solution into the acid solution. The acid solution is exposed to ultraviolet light, which reduces Np(VI) to Np(V) without reducing U(VI) and Pu(IV). Since the solubility of Np(V) in the organic solution is much lower than that of Np(VI), U(VI), and Pu(IV), a major part of the Np is stripped from the organic solution while leaving most of the U and Pu therein.

U(VI) adsorption on aquifer sediments at the Hanford Site.

PubMed

Um, Wooyong; Serne, R Jeffrey; Brown, Christopher F; Last, George V

2007-08-15

Aquifer sediments collected via split-spoon sampling in two new groundwater wells in the 200-UP-1 operable unit at the Hanford Site were characterized and showed typical Ringold Unit E Formation properties dominated by gravel and sand. High iron-oxide content in Fe oxide/clay coatings caused the highest U(VI) adsorption as quantified by batch K(d) values, indicating iron oxides are the key solid adsorbent in the 200-UP-1 sediments that affect U(VI) fate and mobility. Even though U(VI) adsorption on the gravel-sized fraction of the sediments is considered to be negligible, careful characterization should be conducted to determine U(VI) adsorption on gravel, because of presence of Fe oxides coatings and diffusion-controlled adsorption into the gravel particles' interior surfaces. A linear adsorption isotherm was observed up to 10(-6) M (238 microg/L) of total U(VI) concentration in batch U(VI) adsorption tests with varying total U(VI) concentrations in spiked groundwater. U(VI) adsorption decreased with increasing concentrations of dissolved carbonate, because strong anionic aqueous uranium-carbonate complexes formed at high pH and high alkalinity conditions. Noticeable uranium desorption hysteresis was observed in a flow-through column experiment, suggesting that desorption K(d) values for aged uranium-contaminated sediments at the Hanford Site can be larger than adsorption K(d) values determined in short-term laboratory experiments and slow uranium release from contaminated sediments into the groundwater is expected.

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

NASA Astrophysics Data System (ADS)

Davis, James A.; Meece, David E.; Kohler, Matthias; Curtis, Gary P.

2004-09-01

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10 -8 to 1 · 10 -5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca 2+, Mg 2+, HCO 3-, SO 42-, H 4SiO 4, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

USGS Publications Warehouse

Davis, J.A.; Meece, D.E.; Kohler, M.; Curtis, G.P.

2004-01-01

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 ?? 10-8 to 1 ?? 10-5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca2+, Mg2+, HCO3-, SO42-, H4SiO4, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters. ?? 2004 Elsevier Ltd.

Enhanced adsorption of U(VI) and 241Am(III) from wastewater using Ca/Al layered double hydroxide@carbon nanotube composites.

PubMed

Chen, Haijun; Chen, Zhe; Zhao, Guixia; Zhang, Zhibin; Xu, Chao; Liu, Yunhai; Chen, Jing; Zhuang, Li; Haya, Tasawar; Wang, Xiangke

2018-04-05

Ca/Al layered double hydroxide decorated carbon nanotube (Ca/Al-LDH@CNTs) composites were fabricated by co-precipitation method and hydrothermal aged treatment. The prepared Ca/Al-LDH@CNTs was characterized by SEM, TEM, EDS, XRD, FT-IR, UV-vis and XPS techniques, and applied to remove U(VI) from aqueous solutions under various environmental conditions (i.e., pH, ionic strength, temperature and contact time). The results indicated that the adsorption of U(VI) on Ca/Al-LDH@CNTs was four times higher than that of U(VI) on bare CNTs. The kinetic investigations reflected the chemisorption of U(VI) on Ca/Al-LDH@CNTs through oxygen-containing functional groups. The adsorption isotherms demonstrated that the adsorption of U(VI) was well fitted by Langmuir model and the maximum adsorption capacity of U(VI) on Ca/Al-LDH@CNTs was calculated to be 382.9 mg g -1 at 289.15 K. The thermodynamic parameters calculated from temperature-dependent isotherms suggested that U(VI) adsorption on Ca/Al-LDH@CNTs were endothermic and spontaneous process. Furthermore, Ca/Al-LDH@CNTs could remove ∼91% of 241 Am(III) at pH = 8.0, which confirmed Ca/Al-LDH@CNTs as a promising material for multiply low level radionuclides' pollution remediation. Copyright © 2017 Elsevier B.V. All rights reserved.

Plasma-induced grafting of acrylic acid on bentonite for the removal of U(VI) from aqueous solution

NASA Astrophysics Data System (ADS)

Hongshan, ZHU; Shengxia, DUAN; Lei, CHEN; Ahmed, ALSAEDI; Tasawar, HAYAT; Jiaxing, LI

2017-11-01

Fabrication of reusable adsorbents with satisfactory adsorption capacity and using environment-friendly preparation processes is required for the environment-related applications. In this study, acrylic acid (AA) was grafted onto bentonite (BT) to generate an AA-graft-BT (AA-g-BT) composite using a plasma-induced grafting technique considered to be an environment-friendly method. The as-prepared composite was characterized by scanning electron microscopy, x-ray powder diffraction, thermal gravity analysis, Fourier transform infrared spectroscopy and Barrett-Emmett-Teller analysis, demonstrating the successful grafting of AA onto BT. In addition, the removal of uranium(VI) (U(VI)) from contaminated aqueous solutions was examined using the as-prepared composite. The influencing factors, including contact time, pH value, ionic strength, temperature, and initial concentration, for the removal of U(VI) were investigated by batch experiments. The experimental process fitted best with the pseudo-second-order kinetic and the Langmuir models. Moreover, thermodynamic investigation revealed a spontaneous and endothermic process. Compared with previous adsorbents, AA-g-BT has potential practical applications in treating U(VI)-contaminated solutions.

Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles.

PubMed

Pidchenko, Ivan; Kvashnina, Kristina O; Yokosawa, Tadahiro; Finck, Nicolas; Bahl, Sebastian; Schild, Dieter; Polly, Robert; Bohnert, Elke; Rossberg, André; Göttlicher, Jörg; Dardenne, Kathy; Rothe, Jörg; Schäfer, Thorsten; Geckeis, Horst; Vitova, Tonya

2017-02-21

Uranium redox states and speciation in magnetite nanoparticles coprecipitated with U(VI) for uranium loadings varying from 1000 to 10 000 ppm are investigated by X-ray absorption spectroscopy (XAS). It is demonstrated that the U M 4 high energy resolution X-ray absorption near edge structure (HR-XANES) method is capable to clearly characterize U(IV), U(V), and U(VI) existing simultaneously in the same sample. The contributions of the three different uranium redox states are quantified with the iterative transformation factor analysis (ITFA) method. U L 3 XAS and transmission electron microscopy (TEM) reveal that initially sorbed U(VI) species recrystallize to nonstoichiometric UO 2+x nanoparticles within 147 days when stored under anoxic conditions. These U(IV) species oxidize again when exposed to air. U M 4 HR-XANES data demonstrate strong contribution of U(V) at day 10 and that U(V) remains stable over 142 days under ambient conditions as shown for magnetite nanoparticles containing 1000 ppm U. U L 3 XAS indicates that this U(V) species is protected from oxidation likely incorporated into octahedral magnetite sites. XAS results are supported by density functional theory (DFT) calculations. Further characterization of the samples include powder X-ray diffraction (pXRD), scanning electron microscopy (SEM) and Fe 2p X-ray photoelectron spectroscopy (XPS).

Lithological and hydrochemical controls on distribution and speciation of uranium in groundwaters of hard-rock granitic aquifers of Madurai District, Tamil Nadu (India).

PubMed

Thivya, C; Chidambaram, S; Keesari, Tirumalesh; Prasanna, M V; Thilagavathi, R; Adithya, V S; Singaraja, C

2016-04-01

Uranium is a radioactive element normally present in hexavalent form as U(VI) in solution and elevated levels in drinking water cause health hazards. Representative groundwater samples were collected from different litho-units in this region and were analyzed for total U and major and minor ions. Results indicate that the highest U concentration (113 µg l(-1)) was found in granitic terrains of this region and about 10 % of the samples exceed the permissible limit for drinking water. Among different species of U in aqueous media, carbonate complexes [UO2(CO3)(2)(2-)] are found to be dominant. Groundwater with higher U has higher pCO2 values, indicating weathering by bicarbonate ions resulting in preferential mobilization of U in groundwater. The major minerals uraninite and coffinite were found to be supersaturated and are likely to control the distribution of U in the study area. Nature of U in groundwater, the effects of lithology on hydrochemistry and factors controlling its distribution in hard rock aquifers of Madurai district are highlighted in this paper.

Facile functionalized of SBA-15 via a biomimetic coating and its application in efficient removal of uranium ions from aqueous solution.

PubMed

Gao, Jun-Kai; Hou, Li-An; Zhang, Guang-Hui; Gu, Ping

2015-04-09

A novel dopamine-functionalized mesoporous silica (DMS), synthesized by grafting dopamine onto a mesoporous molecular sieve (SBA-15), was developed as a sorbent to extract U(VI) from aqueous solution. The method used to modify SBA-15 was simple, facile and cost-effective. The DMS was characterized by SEM, TEM, XRD and BET, showing that the material had an ordered mesoporous structure and a large surface area. The effect of contact time, pH, ionic strength, temperature, and solid-liquid ratio on the sorption process was investigated. It was demonstrated that the adsorption of U(VI) by DMS was fast and that it can be described by the pseudo-second order-equation where the equilibrium time was 20 min. Additionally, the adsorption isotherm data were fitted well by the Langmuir model with the maximum adsorption capacity of DMS of 196 mg/g at pH 6.0. Furthermore, the influence of the K(+) and Na(+) concentrations and solid-to-liquid ratio on the sorption was very weak, and the values of the thermodynamic parameters revealed that the sorption process was exothermic and spontaneous. All the results suggested that the DMS could be used as an excellent adsorbent to remove U(VI) from aqueous solution. Copyright © 2014 Elsevier B.V. All rights reserved.

Batch and fixed-bed column study for p-nitrophenol, methylene blue, and U(VI) removal by polyvinyl alcohol-graphene oxide macroporous hydrogel bead.

PubMed

Chen, Dan; Zhou, Jun; Wang, Hongyu; Yang, Kai

2018-01-01

There is an increasing need to explore effective and clean approaches for hazardous contamination removal from wastewaters. In this work, a novel bead adsorbent, polyvinyl alcohol-graphene oxide (PVA-GO) macroporous hydrogel bead was prepared as filter media for p-nitrophenol (PNP), dye methylene blue (MB), and heavy metal U(VI) removal from aqueous solution. Batch and fixed-bed column experiments were carried out to evaluate the adsorption capacities of PNP, MB, and U(VI) on this bead. From batch experiments, the maximum adsorption capacities of PNP, MB, and U(VI) reached 347.87, 422.90, and 327.55 mg/g. From the fixed-bed column experiments, the adsorption capacities of PNP, MB, and U(VI) decreased with initial concentration increasing from 100 to 400 mg/L. The adsorption capacities of PNP, MB, and U(VI) decreased with increasing flow rate. Also, the maximum adsorption capacity of PNP decreased as pH increased from 3 to 9, while MB and U(VI) presented opposite tendencies. Furthermore, the bed depth service Time (BDST) model showed good linear relationships for the three ions' adsorption processes in this fixed-bed column, which indicated that the BDST model effectively evaluated and optimized the adsorption process of PVA-GO macroporous hydrogel bead in fixed-bed columns for hazardous contaminant removal from wastewaters.

New Synthesis of nZVI/C Composites as an Efficient Adsorbent for the Uptake of U(VI) from Aqueous Solutions.

PubMed

Liu, Haibo; Li, Mengxue; Chen, Tianhu; Chen, Changlun; Alharbi, Njud S; Hayat, Tasawar; Chen, Dong; Zhang, Qiang; Sun, Yubing

2017-08-15

New nanoscale zerovalent iron/carbon (nZVI/C) composites were successfully prepared via heating natural hematite and pine sawdust at 800 °C under nitrogen conditions. Characterization by SEM, XRD, FTIR, and XPS analyses indicated that the as-prepared nZVI/C composites contained a large number of reactive sites. The lack of influence of the ionic strength revealed inner-sphere complexation dominated U(VI) uptake by the nZVI/C composites. Simultaneous adsorption and reduction were involved in the uptake process of U(VI) according to the results of XPS and XANES analyses. The presence of U-C/U-U shells demonstrated that innersphere complexation and surface coprecipitation dominated the U(VI) uptake at low and high pH conditions, respectively. The uptake behaviors of U(VI) by the nZVI/C composites were fitted well by surface complexation modeling with two weak and two strong sites. The maximum uptake capacity of U(VI) by the nZVI/C composites was 186.92 mg/g at pH 4.0 and 328 K. Additionally, the nZVI/C composites presented good recyclability and recoverability for U(VI) uptake in regeneration experiments. These observations indicated that the nZVI/C composites can be considered as potential adsorbents to remove radionuclides for environmental remediation.

Fate of Adsorbed U(VI) during Sulfidization of Lepidocrocite and Hematite

PubMed Central

2017-01-01

The impact on U(VI) adsorbed to lepidocrocite (γ-FeOOH) and hematite (α-Fe2O3) was assessed when exposed to aqueous sulfide (S(-II)aq) at pH 8.0. With both minerals, competition between S(-II) and U(VI) for surface sites caused instantaneous release of adsorbed U(VI). Compared to lepidocrocite, consumption of S(-II)aq proceeded slower with hematite, but yielded maximum dissolved U concentrations that were more than 10 times higher, representing about one-third of the initially adsorbed U. Prolonged presence of S(-II)aq in experiments with hematite in combination with a larger release of adsorbed U(VI), enhanced the reduction of U(VI): after 24 h of reaction about 60–70% of U was in the form of U(IV), much higher than the 25% detected in the lepidocrocite suspensions. X-ray absorption spectra indicated that U(IV) in both hematite and lepidocrocite suspensions was not in the form of uraninite (UO2). Upon exposure to oxygen only part of U(IV) reoxidized, suggesting that monomeric U(IV) might have become incorporated in newly formed iron precipitates. Hence, sulfidization of Fe oxides can have diverse consequences for U mobility: in short-term, desorption of U(VI) increases U mobility, while reduction to U(IV) and its possible incorporation in Fe transformation products may lead to long-term U immobilization. PMID:28121137

Effect of bicarbonate on aging and reactivity of nanoscale zerovalent iron (nZVI) toward uranium removal.

PubMed

Hua, Yilong; Wang, Wei; Huang, Xiaoyue; Gu, Tianhang; Ding, Dexin; Ling, Lan; Zhang, Wei-Xian

2018-06-01

Bicarbonate, ubiquitous in natural and waste waters is an important factor regulating the rate and efficiency of pollutant separation and transformation. For example, it can form complexes with U(VI) in the aqueous phase and at the solid-water interface. In this work, we investigated the effect of bicarbonate on the aging of nanoscale zero-valent (nZVI) in the context of U(VI) reduction and removal from wastewater. For fresh nZVI, over 99% aqueous uranium was separated in less than 10 min, of which 83% was reduced from U(VI) to U(IV). When nZVI was aged in water, its activity for U(VI) sequestration and reduction was significantly reduced. Batch experiments showed that for nZVI aged in the presence of 10 mM bicarbonate, only 20.3% uranium was reduced to U(IV) after 6 h reactions. Characterizations of the iron nanoparticles with spherical aberration corrected scanning transmission electron microscopy (Cs-STEM) suggest that in fresh nZVI, uranium was concentrated at the nanoparticle center; whereas in nZVI aged in bicarbonate, uranium was largely deposited on the outer surface of the nanoparticles. Furthermore, aged nZVI without bicarbonate contained more lepidocrocite (γ-FeOOH) while aged nZVI in the presence of bicarbonate had more magnetite/maghemite (Fe 3 O 4 /γ-Fe 2 O 3 ). This could be attributed to the formation of carbonate green rust and pH buffer effect of . Primary mechanisms for U(VI) removal with nZVI include reduction, sorption and/or precipitation. Results demonstrate that bicarbonate alter the aging products of nZVI, and reduces the separation efficiency and reduction capability for uranium removal. Copyright © 2018. Published by Elsevier Ltd.

Kinetic and equilibrium characterization of uranium(VI) adsorption onto carboxylate-functionalized poly(hydroxyethylmethacrylate)-grafted lignocellulosics.

PubMed

Anirudhan, T S; Divya, L; Suchithra, P S

2009-01-01

This study investigated the feasibility of using a new adsorbent prepared from coconut coir pith, CP (a coir industry-based lignocellulosic residue), for the removal of uranium [U(VI)] from aqueous solutions. The adsorbent (PGCP-COOH) having a carboxylate functional group at the chain end was synthesized by grafting poly(hydroxyethylmethacrylate) onto CP using potassium peroxydisulphate-sodium thiosulphite as a redox initiator and in the presence of N,N'-methylenebisacrylamide as a crosslinking agent. IR spectroscopy results confirm the graft copolymer formation and carboxylate functionalization. XRD studies confirm the decrease of crystallinity in PGCP-COOH compared to CP, and it favors the protrusion of the functional group into the aqueous medium. The thermal stability of the samples was studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was determined using potentiometric titration. The ability of PGCP-COOH to remove U(VI) from aqueous solutions was assessed using a batch adsorption technique. The maximum adsorption capacity was observed at the pH range 4.0-6.0. Maximum removal of 99.2% was observed for an initial concentration of 25mg/L at pH 6.0 and an adsorbent dose of 2g/L. Equilibrium was achieved in approximately 3h. The experimental kinetic data were analyzed using a first-order kinetic model. The temperature dependence indicates an endothermic process. U(VI) adsorption was found to decrease with an increase in ionic strength due to the formation of outer-sphere surface complexes on PGCP-COOH. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as DeltaG(0), DeltaH(0) and DeltaS(0) were derived to predict the nature of adsorption. Adsorption experiments were also conducted using a commercial cation exchanger, Ceralite IRC-50, with carboxylate functionality for comparison. Utility of the adsorbent was tested by removing U(VI) from simulated nuclear industry wastewater. Adsorbed U(VI) ions were desorbed effectively (about 96.2+/-3.3%) by 0.1M HCl. The adsorbent was suitable for repeated use (more than four cycles) without any noticeable loss of capacity.

ISSUES IN SIMULATING ELEMENTAL MERCURY AIR/WATER EXCHANGE AND AQUEOUS MONOMETHYLMERCURY SPECIATION

EPA Science Inventory

This presentation focuses on two areas relevant to assessing the global fate and bioavailability of mercury: elemental mercury air/water exchange and aqueous environmental monomethylmercury speciation.

Competing retention pathways of uranium upon reaction with Fe(II)

NASA Astrophysics Data System (ADS)

Massey, Michael S.; Lezama-Pacheco, Juan S.; Jones, Morris E.; Ilton, Eugene S.; Cerrato, José M.; Bargar, John R.; Fendorf, Scott

2014-10-01

Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3·nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway's contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation state of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ∼7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended X-ray absorption fine structure (EXAFS) spectroscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14-89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ⩽50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64-89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron oxides as a retention process of U across a wide range of biogeochemical environments and the sensitivity of uranium retention processes to operative (bio)geochemical conditions.

Competing retention pathways of uranium upon reaction with Fe(II)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Massey, Michael S.; Lezama Pacheco, Juan S.; Jones, Morris

Biogeochemical retention processes, including adsorption, reductive precipitation, and incorporation into host minerals, are important in contaminant transport, remediation, and geologic deposition of uranium. Recent work has shown that U can become incorporated into iron (hydr)oxide minerals, with a key pathway arising from Fe(II)-induced transformation of ferrihydrite, (Fe(OH)3•nH2O) to goethite (α-FeO(OH)); this is a possible U retention mechanism in soils and sediments. Several key questions, however, remain unanswered regarding U incorporation into iron (hydr)oxides and this pathway’s contribution to U retention, including: (i) the competitiveness of U incorporation versus reduction to U(IV) and subsequent precipitation of UO2; (ii) the oxidation statemore » of incorporated U; (iii) the effects of uranyl aqueous speciation on U incorporation; and, (iv) the mechanism of U incorporation. Here we use a series of batch reactions conducted at pH ~7, [U(VI)] from 1 to 170 μM, [Fe(II)] from 0 to 3 mM, and [Ca] at 0 or 4 mM) coupled with spectroscopic examination of reaction products of Fe(II)-induced ferrihydrite transformation to address these outstanding questions. Uranium retention pathways were identified and quantified using extended x-ray absorption fine structure (EXAFS) spectroscopy, x-ray powder diffraction, x-ray photoelectron spectroscopy, and transmission electron microscopy. Analysis of EXAFS spectra showed that 14 to 89% of total U was incorporated into goethite, upon reaction with Fe(II) and ferrihydrite. Uranium incorporation was a particularly dominant retention pathway at U concentrations ≤ 50 μM when either uranyl-carbonato or calcium-uranyl-carbonato complexes were dominant, accounting for 64 to 89% of total U. With increasing U(VI) and Fe(II) concentrations, U(VI) reduction to U(IV) became more prevalent, but U incorporation remained a functioning retention pathway. These findings highlight the potential importance of U(V) incorporation within iron oxides as a retention process of U across a wide range of biogeochemical environments and the sensitivity of uranium retention processes to operative (bio)geochemical conditions.« less

Selective separation of uranium using alizarin red S (ARS)-modified anion-exchange resin or by flotation of U-ARS chelate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khalifa, M.E.

An alizarin red S (ARS)-modified anion exchange resin was prepared by a simple reaction of ARS with the anion exchange Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2.8--5) with a maximum sorption capacity of 0.68 mmol/g at pH 3.2 to 4.0. Iron(III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II),more » Cd(II), Al(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0.2 mol/L HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH {approx} 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures.« less

Speciation and reactivity of uranium products formed during in situ bioremediation in a shallow alluvial aquifer.

PubMed

Alessi, Daniel S; Lezama-Pacheco, Juan S; Janot, Noémie; Suvorova, Elena I; Cerrato, José M; Giammar, Daniel E; Davis, James A; Fox, Patricia M; Williams, Kenneth H; Long, Philip E; Handley, Kim M; Bernier-Latmani, Rizlan; Bargar, John R

2014-11-04

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans.

Speciation and Reactivity of Uranium Products Formed during in Situ Bioremediation in a Shallow Alluvial Aquifer

PubMed Central

2015-01-01

In this study, we report the results of in situ U(VI) bioreduction experiments at the Integrated Field Research Challenge site in Rifle, Colorado, USA. Columns filled with sediments were deployed into a groundwater well at the site and, after a period of conditioning with groundwater, were amended with a mixture of groundwater, soluble U(VI), and acetate to stimulate the growth of indigenous microorganisms. Individual reactors were collected as various redox regimes in the column sediments were achieved: (i) during iron reduction, (ii) just after the onset of sulfate reduction, and (iii) later into sulfate reduction. The speciation of U retained in the sediments was studied using X-ray absorption spectroscopy, electron microscopy, and chemical extractions. Circa 90% of the total uranium was reduced to U(IV) in each reactor. Noncrystalline U(IV) comprised about two-thirds of the U(IV) pool, across large changes in microbial community structure, redox regime, total uranium accumulation, and reaction time. A significant body of recent research has demonstrated that noncrystalline U(IV) species are more suceptible to remobilization and reoxidation than crystalline U(IV) phases such as uraninite. Our results highlight the importance of considering noncrystalline U(IV) formation across a wide range of aquifer parameters when designing in situ remediation plans. PMID:25265543

Rapid removal of uranium from aqueous solutions using magnetic Fe3O4@SiO2 composite particles.

PubMed

Fan, Fang-Li; Qin, Zhi; Bai, Jing; Rong, Wei-Dong; Fan, Fu-You; Tian, Wei; Wu, Xiao-Lei; Wang, Yang; Zhao, Liang

2012-04-01

Rapid removal of U(VI) from aqueous solutions was investigated using magnetic Fe(3)O(4)@SiO(2) composite particles as the novel adsorbent. Batch experiments were conducted to study the effects of initial pH, amount of adsorbent, shaking time and initial U(VI) concentrations on uranium sorption efficiency as well as the desorbing of U(VI). The sorption of uranium on Fe(3)O(4)@SiO(2) composite particles was pH-dependent, and the optimal pH was 6.0. In kinetics studies, the sorption equilibrium can be reached within 180 min, and the experimental data were well fitted by the pseudo-second-order model, and the equilibrium sorption capacities calculated by the model were almost the same as those determined by experiments. The Langmuir sorption isotherm model correlates well with the uranium sorption equilibrium data for the concentration range of 20-200 mg/L. The maximum uranium sorption capacity onto magnetic Fe(3)O(4)@SiO(2) composite particles was estimated to be about 52 mg/g at 25 °C. The highest values of uranium desorption (98%) was achieved using 0.01 M HCl as the desorbing agent. Fe(3)O(4)@SiO(2) composite particles showed a good selectivity for uranium from aqueous solution with other interfering cation ions. Present study suggested that magnetic Fe(3)O(4)@SiO(2) composite particles can be used as a potential adsorbent for sorption uranium and also provided a simple, fast separation method for removal of heavy metal ion from aqueous solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

Electrode Induced Removal and Recovery of Uranium (VI) from Acidic Subsurfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gregory, Kelvin

2013-08-12

The overarching objective of this research is to provide an improved understanding of how aqueous geochemical conditions impact the removal of U and Tc from groundwater and how engineering design may be utilized to optimize removal of these radionuclides. Experiments were designed to address the unique conditions in Area 3 of ORNL while also providing broader insight into the geochemical effectors of the removal rates and extent for U and Tc. The specific tasks of this work were to: 1) quantify the impact of common aqueous geochemical and operational conditions on the rate and extent of U removal and recoverymore » from water, 2) investigate the removal of Tc with polarized graphite electrode, and determine the influence of geochemical and operational conditions on Tc removal and recovery, 3) determine whether U and Tc may be treated simultaneous from Area 3 groundwater, and examine the bench-scale performance of electrode-based treatment, and 4) determine the capacity of graphite electrodes for U(VI) removal and develop a mathematical, kinetic model for the removal of U(VI) from aqueous solution. Overall the body of work suggests that an electrode-based approach for the remediation of acidic subsurface environments, such as those observed in Area 3 of ORNL may be successful for the removal for both U(VI) and Tc. Carbonaceous (graphite) electrode materials are likely to be the least costly means to maximize removal rates and efficiency by maximizing the electrode surface area.« less

Novel Metal-Organic Framework (MOF) Based Composite Material for the Sequestration of U(VI) and Th(IV) Metal Ions from Aqueous Environment.

PubMed

Alqadami, Ayoub Abdullah; Naushad, Mu; Alothman, Zeid Abdullah; Ghfar, Ayman A

2017-10-18

The combination of magnetic nanoparticles and metal-organic frameworks (MOFs) has demonstrated their prospective for pollutant sequestration. In this work, a magnetic metal-organic framework nanocomposite (Fe 3 O 4 @AMCA-MIL53(Al) was prepared and used for the removal of U(VI) and Th(IV) metal ions from aqueous environment. Fe 3 O 4 @AMCA-MIL53(Al) nanocomposite was characterized by TGA, FTIR, SEM-EDX, XRD, HRTEM, BET, VSM (vibrating sample magnetometry), and XPS analyses. A batch technique was applied for the removal of the aforesaid metal ions using Fe 3 O 4 @AMCA-MIL53(Al) at different operating parameters. The isotherm and kinetic data were accurately described by the Langmuir and pseudo-second-order models. The adsorption capacity was calculated to be 227.3 and 285.7 mg/g for U(VI) and Th(IV), respectively, by fitting the equilibrium data to the Langmuir model. The kinetic studies demonstrated that the equilibrium time was 90 min for each metal ion. Various thermodynamic parameters were evaluated which indicated the endothermic and spontaneous nature of adsorption. The collected outcomes showed that Fe 3 O 4 @AMCA-MIL53(Al) was a good material for the exclusion of these metal ions from aqueous medium. The adsorbed metals were easily recovered by desorption in 0.01 M HCl. The excellent adsorption capacity and the response to the magnetic field made this novel material an auspicious candidate for environmental remediation technologies.

Bicarbonate Impact on U(VI) Bioreduction in a Shallow Alluvial Aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Long, Philip E.; Williams, Kenneth H.; Davis, James A.

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al. 2003, Williams et al. 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al. 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggestedmore » the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, that the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ~3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.« less

Bicarbonate impact on U(VI) bioreduction in a shallow alluvial aquifer

NASA Astrophysics Data System (ADS)

Long, Philip E.; Williams, Kenneth H.; Davis, James A.; Fox, Patricia M.; Wilkins, Michael J.; Yabusaki, Steven B.; Fang, Yilin; Waichler, Scott R.; Berman, Elena S. F.; Gupta, Manish; Chandler, Darrell P.; Murray, Chris; Peacock, Aaron D.; Giloteaux, Ludovic; Handley, Kim M.; Lovley, Derek R.; Banfield, Jillian F.

2015-02-01

Field-scale biostimulation and desorption tracer experiments conducted in a uranium (U) contaminated, shallow alluvial aquifer have provided insight into the coupling of microbiology, biogeochemistry, and hydrogeology that control U mobility in the subsurface. Initial experiments successfully tested the concept that Fe-reducing bacteria such as Geobacter sp. could enzymatically reduce soluble U(VI) to insoluble U(IV) during in situ electron donor amendment (Anderson et al., 2003; Williams et al., 2011). In parallel, in situ desorption tracer tests using bicarbonate amendment demonstrated rate-limited U(VI) desorption (Fox et al., 2012). These results and prior laboratory studies underscored the importance of enzymatic U(VI)-reduction and suggested the ability to combine desorption and bioreduction of U(VI). Here we report the results of a new field experiment in which bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Results confirm that bicarbonate amendment to alluvial aquifer sediments desorbs U(VI) and increases the abundance of Ca-uranyl-carbonato complexes. At the same time, the rate of acetate-promoted enzymatic U(VI) reduction was greater in the presence of added bicarbonate in spite of the increased dominance of Ca-uranyl-carbonato aqueous complexes. A model-simulated peak rate of U(VI) reduction was ∼3.8 times higher during acetate-bicarbonate treatment than under acetate-only conditions. Lack of consistent differences in microbial community structure between acetate-bicarbonate and acetate-only treatments suggest that a significantly higher rate of U(VI) reduction in the bicarbonate-impacted sediment may be due to a higher intrinsic rate of microbial reduction induced by elevated concentrations of the bicarbonate oxyanion. The findings indicate that bicarbonate amendment may be useful in improving the engineered bioremediation of uranium in aquifers.

Using 238U/235U ratios to understand the formation and oxidation of reduced uranium solids in naturally reduced zones

NASA Astrophysics Data System (ADS)

Jemison, N.; Johnson, T. M.; Druhan, J. L.; Davis, J. A.

2016-12-01

Uranium occurs in groundwater primarily as soluble and mobile U(VI), which can be reduced to immobile U(IV), often observed in sediments as uraninite. Numerous U(VI)-contaminated sites, such as the DOE field site in Rifle, CO, contain naturally reduced zones (NRZ's) that have relatively high concentrations of organic matter. Reduction of heavy metals occurs within NRZ's, producing elevated concentrations of iron sulfides and U(IV). Slow, natural oxidation of U(IV) from NRZ's may prolong U(VI) contamination of groundwater. The reduction of U(VI) produces U(IV) with a higher 238U/235U ratio. Samples from two NRZ sediment cores recovered from the Rifle site revealed that the outer fringes of the NRZ contain U(IV) with a high 238U/235U ratio, while lower values are observed in the center . We suggest that as aqueous U(VI) was reduced in the NRZ, it was driven to lower 238U/235U values, such that U(IV) formed in the core of the NRZ reflects a lower 238U/235U. Two oxidation experiments were conducted by injecting groundwater containing between 14.9 and 21.2 mg/L dissolved O2 as an oxidant into the NRZ. The oxidation of U(IV) from this NRZ increased aqueous U(VI) concentrations and caused a shift to higher 238U/235U in groundwater as U(IV) was oxidized primarily on the outer fringes of the NRZ. In total these observations suggest that the stability of solid phase uranium is governed by coupled reaction and transport processes. To better understand various reactive transport scenarios we developed a model for the formation and oxidation of NRZ's utilizing the reactive transport software CrunchTope. These simulations suggest that the development of isotopically heterogeneous U(IV) within NRZ's is largely controlled by permeability of the NRZ and the U(VI) reduction rate. Oxidation of U(IV) from the NRZ's is constrained by the oxidation rate of U(IV) as well as iron sulfides, which can prevent oxidation of U(IV) by scavenging dissolved oxygen.

XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate.

PubMed

Qiu, Muqing; Wang, Min; Zhao, Qingzhou; Hu, Baowei; Zhu, Yuling

2018-06-01

Effect of phosphate on the reduction of U(VI) on nZVI was determined by batch, XPS, XANES and EXAFS techniques. The batch experiments showed that nZVI was quite effective for the removal of uranium under the anaerobic conditions, whereas the addition of phosphate enhanced uranium removal over wide pH range. At low pH, the reduction of U(VI) to U(IV) significantly decreased with increasing phosphate concentration by XPS and XANES analysis. According to EXAFS analysis, the occurrence of UU shell at 10 mg/L phosphate and pH 4.0 was similar to that of U (IV) O 2 (s), whereas the UP and UFe shells were observed at 50 mg/L phosphate, revealing that reductive co-precipitate (U (IV) O 2 (s)) and precipitation of uranyl-phosphate were observed at low and high phosphate, respectively. The findings are crucial for the prediction of the effect of phosphate on the speciation and binding of uranium by nZVI at low pH, which is significant in controlling the mobility of U(VI) in contaminated environments. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mechanism of Uranium Reduction and Immobilization in Desulfovibrio vulgaris Biofilms.

PubMed

Stylo, Malgorzata; Neubert, Nadja; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan

2015-09-01

The prevalent formation of noncrystalline U(IV) species in the subsurface and their enhanced susceptibility to reoxidation and remobilization, as compared to crystalline uraninite, raise concerns about the long-term sustainability of the bioremediation of U-contaminated sites. The main goal of this study was to resolve the remaining uncertainty concerning the formation mechanism of noncrystalline U(IV) in the environment. Controlled laboratory biofilm systems (biotic, abiotic, and mixed biotic-abiotic) were probed using a combination of U isotope fractionation and X-ray absorption spectroscopy (XAS). Regardless of the mechanism of U reduction, the presence of a biofilm resulted in the formation of noncrystalline U(IV). Our results also show that biotic U reduction is the most effective way to immobilize and reduce U. However, the mixed biotic-abiotic system resembled more closely an abiotic system: (i) the U(IV) solid phase lacked a typically biotic isotope signature and (ii) elemental sulfur was detected, which indicates the oxidation of sulfide coupled to U(VI) reduction. The predominance of abiotic U reduction in our systems is due to the lack of available aqueous U(VI) species for direct enzymatic reduction. In contrast, in cases where bicarbonate is present at a higher concentration, aqueous U(VI) species dominate, allowing biotic U reduction to outcompete the abiotic processes.

Uranium speciation as a function of depth in contaminated hanford sediments--a micro-XRF, micro-XRD, and micro- and bulk-XAFS study.

PubMed

Singer, David M; Zachara, John M; Brown, Gordon E

2009-02-01

The distribution and speciation of U and Cu in contaminated vadose zone and aquifer sediments from the U.S. DOE Hanford site (300 Area) were determined using a combination of synchrotron-based micro-X-ray fluorescence (microXRF) imaging, micro-X-ray absorption near edge structure (microXANES) spectroscopy, and micro-X-ray diffraction (microXRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy. Samples were collected from within the inactive North Process Pond (NPP2) at 8 ft (2.4 m, NPP2-8) depth and 12 ft (3.7 m, NPP2-12) depth in the vadose zone, and fines were isolated from turbid groundwater just below the water Table (12-14 ft, approximately 4 m, NPP2-GW). microXRF imaging, microXRD, and microXANES spectroscopy revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with fine-textured grain coatings that were consistently found to contain clinochlore (referred to here as chlorite) observed in all three samples, and (2) U(VI)-Cu(II) hotspots consisting of micrometer-sized particles associated with surface coatings on grains of muscovite and chlorite observed in samples NPP2-8' and NPP2-GW. In the aquifer fines (NPP2-GW), these particles were identified as cuprosklodowskite (cps: Cu[(UO2)(SiO2OH)]2 x 6H2O) and metatorbernite (mtb: Cu(UO2)2(PO4)2 x 8H2O). In contrast, the U-Cu-containing particles in the vadose zone were X-ray amorphous. Analyses of U LIII-edge XAFS spectra by linear-combination fitting indicated that U speciation consisted of (1) approximately 75% uranyl sorbed to chlorite and approximately 25% mtb-like X-ray amorphous U-Cu-phosphates (8 ft depth), (2) nearly 100% sorbed uranyl (12 ft depth), and (3) approximately 70% uranyl sorbed to chlorite and approximately 30% cps/mtb (groundwater zone). These findings suggest that dissolution of U(VI)-Cu(II)-bearing solids as well as desorption of U(VI), mainly from phyllosilicates, are important persistent sources of U(VI) to the associated uranium groundwater plume in Hanford Area 300.

Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Lenhart, John J.; Davis, James A.

2000-01-01

We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 μM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH ≥ 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline β-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Modeling uranium(VI) adsorption onto montmorillonite under varying carbonate concentrations: A surface complexation model accounting for the spillover effect on surface potential

DOE PAGES

Tournassat, C.; Tinnacher, R. M.; Grangeon, S.; ...

2017-10-06

The prediction of U(VI) adsorption onto montmorillonite clay is confounded by the complexities of: (1) the montmorillonite structure in terms of adsorption sites on basal and edge surfaces, and the complex interactions between the electrical double layers at these surfaces, and (2) U(VI) solution speciation, which can include cationic, anionic and neutral species. Previous U(VI)-montmorillonite adsorption and modeling studies have typically expanded classical surface complexation modeling approaches, initially developed for simple oxides, to include both cation exchange and surface complexation reactions. However, previous models have not taken into account the unique characteristics of electrostatic surface potentials that occur at montmorillonitemore » edge sites, where the electrostatic surface potential of basal plane cation exchange sites influences the surface potential of neighboring edge sites (‘spillover’ effect).« less

Incorporation of oxidized uranium into Fe (hydr)oxides during Fe(II) catalyzed remineralization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nico, Peter S.; Stewart, Brandy D.; Fendorf, Scott

2009-07-01

The form of solid phase U after Fe(II) induced anaerobic remineralization of ferrihydrite in the presence of aqueous and absorbed U(VI) was investigated under both abiotic batch and biotic flow conditions. Experiments were conducted with synthetic ground waters containing 0.168 mM U(VI), 3.8 mM carbonate, and 3.0 mM Ca{sup 2+}. In spite of the high solubility of U(VI) under these conditions, appreciable removal of U(VI) from solution was observed in both the abiotic and biotic systems. The majority of the removed U was determined to be substituted as oxidized U (U(VI) or U(V)) into the octahedral position of the goethitemore » and magnetite formed during ferrihydrite remineralization. It is estimated that between 3% and 6% of octahedral Fe(III) centers in the new Fe minerals were occupied by U(VI). This site specific substitution is distinct from the non-specific U co-precipitation processes in which uranyl compounds, e.g. uranyl hydroxide or carbonate, are entrapped with newly formed Fe oxides. The prevalence of site specific U incorporation under both abiotic and biotic conditions and the fact that the produced solids were shown to be resistant to both extraction (30 mM KHCO{sub 3}) and oxidation (air for 5 days) suggest the potential importance of sequestration in Fe oxides as a stable and immobile form of U in the environment.« less

Influence of Reactive Transport on the Reduction of U(VI) in the Presence of Fe(III) and Nitrate: Implications for U(VI) Immobilization by Bioremediation / Biobarriers- Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

B.D. Wood

2007-01-01

Subsurface contamination by metals and radionuclides represent some of the most challenging remediation problems confronting the Department of Energy (DOE) complex. In situ remediation of these contaminants by dissimilatory metal reducing bacteria (DMRB) has been proposed as a potential cost effective remediation strategy. The primary focus of this research is to determine the mechanisms by which the fluxes of electron acceptors, electron donors, and other species can be controlled to maximize the transfer of reductive equivalents to the aqueous and solid phases. The proposed research is unique in the NABIR portfolio in that it focuses on (i) the role ofmore » flow and transport in the initiation of biostimulation and the successful sequestration of metals and radionuclides [specifically U(VI)], (ii) the subsequent reductive capacity and stability of the reduced sediments produced by the biostimulation process, and (iii) the potential for altering the growth of biomass in the subsurface by the addition of specific metabolic uncoupling compounds. A scientifically-based understanding of these phenomena are critical to the ability to design successful bioremediation schemes. The laboratory research will employ Shewanella putrefaciens (CN32), a facultative DMRB that can use Fe(III) oxides as a terminal electron acceptor. Sediment-packed columns will be inoculated with this organism, and the reduction of U(VI) by the DMRB will be stimulated by the addition of a carbon and energy source in the presence of Fe(III). Separate column experiments will be conducted to independently examine: (1) the importance of the abiotic reduction of U(VI) by biogenic Fe(II); (2) the influence of the transport process on Fe(III) reduction and U(VI) immobilization, with emphasis on methods for controlling the fluxes of aqueous species to maximize uranium reduction; (3) the reductive capacity of biologically-reduced sediments (with respect to re-oxidation by convective fluxes of O2 and NO3-) and the long-term stability of immobilized uranium mineral phases after bioremediation processes are complete, and (4) the ability for metabolic uncoupling compounds to maintain microbial growth while limiting biomass production. The results of the laboratory experiments will be used to develop mathematical descriptive models for the coupled transport and reduction processes.« less

Great Salt Lake Composition and Rare Earth Speciation Analysis

DOE Data Explorer

Jiao, Yongqin; Lammers, Laura; Brewer, Aaron

2017-04-19

We have conducted aqueous speciation analyses of the Great Salt Lake (GSL) brine sample (Table 1) and a mock geo sample (Table 2) spiked with 1 ppb Tb and 100 ppb Tb. The GSL speciation (Figure 1) aligns with our basic speciation expectations that strong carbonate complexes would form at mid to higher pH's. Although we expected strong aqueous complexes with fluorides at neutral pH and with chlorides, and hydroxides at low pH, we observe that the dominant species in the low to mid pH range to be Tb3+ as a free ion. Still, we do see the presence of fluoride and chloride complexes within the expected low to mid pH range.

U(VI) biosorption by bi-functionalized Pseudomonas putida @ chitosan bead: Modeling and optimization using RSM.

PubMed

Sohbatzadeh, Hozhabr; Keshtkar, Ali Reza; Safdari, Jaber; Fatemi, Faezeh

2016-08-01

In this work, Pseudomonas putida cells immobilized into chitosan beads (PICB) were synthesized to investigate the impact of microorganism entrapment on biosorption capacity of prepared biosorbent for U(VI) biosorption from aqueous solutions. Response Surface Methodology (RSM) based on Central Composite Design (CCD) was utilized to evaluate the performance of the PICB in comparison with chitosan beads (CB) under batch mode. Performing experiments under optimal condition sets viz. pH 5, initial U(VI) concentration 500mg/L, biosorbent dosage 0.4g/L and 20wt.% bacterial cells showed that the observed biosorption capacity enhanced by 1.27 times from 398mg/g (CB) to 504mg/g (PICB) that confirmed the effectiveness of cells immobilization process. FTIR and potentiometric titration were then utilized to characterize the prepared biosorbents. While the dominant functional group in the binding process was NH3(+) (4.78meq/g) in the CB, the functional groups of NH3(+), NH2, OH, COOH (6.00meq/g) were responsible for the PICB. The equilibrium and kinetic studies revealed that the Langmuir isotherm model and the pseudo-second-order kinetic model were in better fitness with the CB and PICB experimental data. In conclusion, the present study indicated that the PICB could be a suitable biosorbent for uranium (VI) biosorption from aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Extraction of U(VI) from oxalate solutions using tetradecylammonium oxalate (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuzina, M.G.; Lipovskii, A.A.

1973-07-01

The extraction of U(VI) from oxalate solutions at various pH values was studied. It was shown that, as a function of the extractant and uranium concentration ratios, the latter was extracted in the form of different acido and hydroxyacido complexes. With excess extractant, the compounds were (R/sub 4/N)/ sub 2/UO/sub 2/Ox/sub 2/ at lo w pH values of the aqueous solution and (R/sub 4/ N)/sub 2/UO/sub 2/Ox(OH)/sub 2/ at h igh values. When there was a deficit of the extractant, different hydroxyacido complexes were formed. (tr-auth)

Potential Aquifer Vulnerability in Regions Down-Gradient from Uranium In Situ Recovery (ISR) Sites

EPA Science Inventory

Sandstone-hosted roll-front uranium ore deposits originate when U(VI) dissolved in groundwater is reduced and precipitated as insoluble U(IV) minerals. Groundwater redox geochemistry, aqueous complexation, and solute migration are instrumental in leaching uranium from source rock...

Cloud iron speciation: Experimental simulations

NASA Astrophysics Data System (ADS)

Sofikitis, A. M.; Colin, J. L.; Desboeufs, K. V.; Losno, R.

2003-04-01

The aim of our contribution is to identify major processes controlling iron speciation in the atmospheric aqueous phase. Fe is known to participate in a variety of redox reactions in cloud chemistry, as well as controlling free radical production in the troposphere. Iron cycling is slower than cycles with other catalytic transition metals (Cu, Mn). The residence time of each iron species is around ten minutes, this allows analytical separation and determination of each iron redox species and therefore its ratio. As the only source of trace metals in aqueous atmospheric phase is due to the solubilization of aerosols, we present here dissolution rate measurements obtained by laboratory experiments with an open flow reactor. This reactor enables us to reproduce the dissolution of a particle in aqueous atmospheric water. The dissolution rate and the speciation of iron are dependent on the mineralogy of the solid phase. Our experiments included Goethite, hematite and vermiculite, which are typical mineral constituents of dust particles. Comparisons were made with natural loess which is a blend of various crystalline and amorphous phases. We will present results of crustal origin particles dissolution experiments where kinetic parameters are determined, including iron speciation. Major functions of variation are pH and photochemistry in the aqueous weathering solution.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catalano, Jeffrey G.; Giammar, Daniel E.; Wang, Zheming

Phosphate addition is an in situ remediation approach that may enhance the sequestration of uranium without requiring sustained reducing conditions. However, the geochemical factors that determine the dominant immobilization mechanisms upon phosphate addition are insufficiently understood to design efficient remediation strategies or accurately predict U(VI) transport. The overall objective of our project is to determine the dominant mechanisms of U(VI)-phosphate reactions in subsurface environments. Our research approach seeks to determine the U(VI)-phosphate solid that form in the presence of different groundwater cations, characterize the effects of phosphate on U(VI) adsorption and precipitation on smectite and iron oxide minerals, examples ofmore » two major reactive mineral phases in contaminated sediments, and investigate how phosphate affects U(VI) speciation and fate during water flow through sediments from contaminated sites. The research activities conducted for this project have generated a series of major findings. U(VI) phosphate solids from the autunite mineral family are the sole phases to form during precipitation, with uranyl orthophosphate not occurring despite its predicted greater stability. Calcium phosphates may take up substantial quantities of U(VI) through three different removal processes (adsorption, coprecipitation, and precipitation) but the dominance of each process varies with the pathway of reaction. Phosphate co-adsorbs with U(VI) onto smectite mineral surfaces, forming a mixed uranium-phosphate surface complex over a wide range of conditions. However, this molecular-scale association of uranium and phosphate has not effect on the overall extent of uptake. In contrast, phosphate enhanced U(VI) adsorption to iron oxide minerals at acidic pH conditions but suppresses such adsorption at neutral and alkaline pH, despite forming mixed uranium-phosphate surface complexes during adsorption. Nucleation barriers exist that inhibit U(VI) phosphate solids from precipitating in the presence of smectite and iron oxide minerals as well as sediments from contaminated sites. Phosphate addition enhances retention of U(VI) by sediments from the Rifle, CO and Hanford, WA field research sites, areas containing substantial uranium contamination of groundwater. This enhanced retention is through adsorption processes. Both fast and slow uptake and release behavior is observed, indicating that diffusion of uranium between sediment grains has a substantial effect of U(VI) fate in flowing groundwater systems. This project has revealed the complexity of U(VI)-phosphate reactions in subsurface systems. Distinct chemical processes occur in acidic and alkaline groundwater systems. For the latter, calcium phosphate formation, solution complexation, and competition between phosphate and uranium for adsorption sites may serve to either enhance or inhibit U(VI) removal from groundwater. Under the groundwater conditions present at many contaminated sites in the U.S., phosphate appears to general enhance U(VI) retention and limit transport. However, formation of low-solubility uranium phosphate solids does not occur under field-relevant conditions, despite this being the desired product of phosphate-based remediation approaches. In addition, simple equilibrium approaches fail to well-predict uranium fate in contaminated sediments amended with phosphate, with reactive transport models that include reaction rates and mass transport through occluded domains needed to properly describe the system. Phosphate addition faces challenges to being effective as a stand-alone groundwater treatment approach but would prove beneficial as an add-on to other treatment methods that will further limit uranium migration in the subsurface.« less

SPECIATION OF ORGANICS IN WATER WITH RAMAN SPECTROSCOPY: UTILITY OF IONIC STRENGTH VARIATION

EPA Science Inventory

We have developed and are applying an experimental and mathematical method for describing the micro-speciation of complex organic contaminants in aqueous media. For our case, micro-speciation can be defined as qualitative and quantitative identification of all discrete forms of ...

Spectroscopic study on the role of TiO{sub 2} in the adsorption of Eu(III) and U(VI) on silica surfaces in aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Im, Hee-Jung, E-mail: imhj@kaeri.re.kr; Park, Kyoung Kyun; Jung, Euo Chang

2014-10-15

Highlights: • Enhanced adsorption of Eu(III) and U(VI) onto TiO{sub 2}-coated silica. • Enhanced Eu(III) luminescence and lifetime on TiO{sub 2}-coated silica. • Energy transfer from TiO{sub 2} of TiO{sub 2}-coated silica to Eu(III) in solutions. - Abstract: To determine the effects of TiO{sub 2} on the adsorption of actinides onto mineral surfaces in groundwater, silica was partially coated with TiO{sub 2}, and Eu(III) and U(VI) were individually adsorbed from separate 0.1 mM concentration solutions. The TiO{sub 2}-coated silica showed higher Eu(III) and U(VI) adsorption capacities for increasing amounts of TiO{sub 2} coated on the silica surfaces, and thus themore » existence of TiO{sub 2} can decrease the mobility of Eu(III) and U(VI) contaminants. In luminescence studies, it was found that TiO{sub 2} considerably enhanced the luminescence of the adsorbed Eu(III) indicating that TiO{sub 2}–Eu(III) forms surface complexes which may decrease the number of water molecules at the inner sphere of Eu(III), but this was not observed for U(VI). An energy transfer from the TiO{sub 2} to the Eu(III) was confirmed in this case of amorphous TiO{sub 2}-coated silica in Eu(III) solutions, and an increase of the luminescence lifetime of Eu(III) for increasing concentrations of coated TiO{sub 2} was also observed.« less

Biogeochemical controls of uranium bioavailability from the dissolved phase in natural freshwaters

USGS Publications Warehouse

Croteau, Marie-Noele; Fuller, Christopher C.; Cain, Daniel J.; Campbell, Kate M.; Aiken, George R.

2016-01-01

To gain insights into the risks associated with uranium (U) mining and processing, we investigated the biogeochemical controls of U bioavailability in the model freshwater speciesLymnaea stagnalis (Gastropoda). Bioavailability of dissolved U(VI) was characterized in controlled laboratory experiments over a range of water hardness, pH, and in the presence of complexing ligands in the form of dissolved natural organic matter (DOM). Results show that dissolved U is bioavailable under all the geochemical conditions tested. Uranium uptake rates follow first order kinetics over a range encompassing most environmental concentrations. Uranium uptake rates in L. stagnalis ultimately demonstrate saturation uptake kinetics when exposure concentrations exceed 100 nM, suggesting uptake via a finite number of carriers or ion channels. The lack of a relationship between U uptake rate constants and Ca uptake rates suggest that U does not exclusively use Ca membrane transporters. In general, U bioavailability decreases with increasing pH, increasing Ca and Mg concentrations, and when DOM is present. Competing ions did not affect U uptake rates. Speciation modeling that includes formation constants for U ternary complexes reveals that the aqueous concentration of dicarbonato U species (UO2(CO3)2–2) best predicts U bioavailability to L. stagnalis, challenging the free-ion activity model postulate.

Kinetics of triscarbonato uranyl reduction by aqueous ferrous iron: a theoretical study.

PubMed

Wander, Matthew C F; Kerisit, Sebastien; Rosso, Kevin M; Schoonen, Martin A A

2006-08-10

Uranium is a pollutant whose mobility is strongly dependent on its oxidation state. While U(VI) in the form of the uranyl cation is readily reduced by a range of natural reductants, by contrast complexation of uranyl by carbonate greatly reduces its reduction potential and imposes increased electron transfer (ET) distances. Very little is known about the elementary processes involved in uranium reduction from U(VI) to U(V) to U(IV) in general. In this study, we examine the theoretical kinetics of ET from ferrous iron to triscarbonato uranyl in aqueous solution. A combination of molecular dynamics (MD) simulations and density functional theory (DFT) electronic structure calculations is employed to compute the parameters that enter into Marcus' ET model, including the thermodynamic driving forces, reorganization energies, and electronic coupling matrix elements. MD simulations predict that two ferrous iron atoms will bind in an inner-sphere fashion to the three-membered carbonate ring of triscarbonato uranyl, forming the charge-neutral ternary Fe(2)UO(2)(CO(3))(3)(H(2)O)(8) complex. Through a sequential proton-coupled electron-transfer mechanism (PCET), the first ET step converting U(VI) to U(V) is predicted by DFT to occur with an electronic barrier that corresponds to a rate on the order of approximately 1 s(-1). The second ET step converting U(V) to U(IV) is predicted to be significantly endergonic. Therefore, U(V) is a stabilized end product in this ET system, in agreement with experiment.

Method for selectively reducing plutonium values by a photochemical process

DOEpatents

Friedman, Horace A.; Toth, Louis M.; Bell, Jimmy T.

1978-01-01

The rate of reduction of Pu(IV) to Pu(III) in nitric acid solution containing a reducing agent is enhanced by exposing the solution to 200-500 nm electromagnetic radiation. Pu values are recovered from an organic extractant solution containing Pu(IV) values and U(VI) values by the method of contacting the extractant solution with an aqueous nitric acid solution in the presence of a reducing agent and exposing the aqueous solution to electromagnetic radiation having a wavelength of 200-500 nm. Under these conditions, Pu values preferentially distribute to the aqueous phase and U values preferentially distribute to the organic phase.

Biosorption and Biomineralization of U(VI) by the Marine Bacterium Idiomarina loihiensis MAH1: Effect of Background Electrolyte and pH

PubMed Central

Morcillo, Fernando; González-Muñoz, María T.; Reitz, Thomas; Romero-González, María E.; Arias, José M.; Merroun, Mohamed L.

2014-01-01

The main goal of this study is to compare the effects of pH, uranium concentration, and background electrolyte (seawater and NaClO4 solution) on the speciation of uranium(VI) associated with the marine bacterium Idiomarina loihiensis MAH1. This was done at the molecular level using a multidisciplinary approach combining X-ray Absorption Spectroscopy (XAS), Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), and High Resolution Transmission Electron Microscopy (HRTEM). We showed that the U(VI)/bacterium interaction mechanism is highly dependent upon pH but also the nature of the used background electrolyte played a role. At neutral conditions and a U concentration ranging from 5·10−4 to 10−5 M (environmentally relevant concentrations), XAS analysis revealed that uranyl phosphate mineral phases, structurally resembling meta-autunite [Ca(UO2)2(PO4)2 2–6H2O] are precipitated at the cell surfaces of the strain MAH1. The formation of this mineral phase is independent of the background solution but U(VI) luminescence lifetime analyses demonstrated that the U(VI) speciation in seawater samples is more intricate, i.e., different complexes were formed under natural conditions. At acidic conditions, pH 2, 3 and 4.3 ([U] = 5·10−4 M, background electrolyte  = 0.1 M NaClO4), the removal of U from solution was due to biosorption to Extracellular Polysaccharides (EPS) and cell wall components as evident from TEM analysis. The L III-edge XAS and TRLFS studies showed that the biosorption process observed is dependent of pH. The bacterial cell forms a complex with U through organic phosphate groups at pH 2 and via phosphate and carboxyl groups at pH 3 and 4.3, respectively. The differences in the complexes formed between uranium and bacteria on seawater compared to NaClO4 solution demonstrates that the actinide/microbe interactions are influenced by the three studied factors, i.e., the pH, the uranium concentration and the chemical composition of the solution. PMID:24618567

Application of Brazilian kaolinite clay as adsorbent to removal of U(VI) from aqueous solution: Kinetic and thermodynamic of cation-basic interactions

NASA Astrophysics Data System (ADS)

Guerra, Denis L.; Leidens, Victor L.; Viana, Rúbia R.; Airoldi, Claudio

2010-05-01

The compound N 1-[3-(trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route. The modified and natural kaolinite samples were characterized by transmission electron microscopy, scanning electron microscopic, X-ray diffraction, and nuclear magnetic nuclei of 29Si and 13C. The well-defined peaks obtained in the 13C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0. The kinetic parameters analyzed by the Lagergren and Elovich models gave a good fit for a pseudo-second order reaction with k2 values 16.0 and 25.1 mmol g -1 min -1 ranges for natural and modified kaolinite clays, respectively. The energetic effects caused by metal ion adsorption were determined through calorimetric titrations.

MONITORING THE SPECIATION OF AQUEOUS FREE CHLORINE FROM PH 1-12 WITH RAMAN SPECTROSCOPY TO DETERMINE THE IDENTITY OF THE POTENT LOW-PH OXIDANT

EPA Science Inventory

The speciation of aqueous free chlorine above pH 5 is a well-understood equilibrium of H2O + HOCl (equilibrium) OCl- + H3O+ with a pKa of 7.5. However, the identity of another very potent oxidant present at low pH (below 5) has been attributed by some researchers to Cl2 (aq), a...

Enhanced U(VI) release from autunite mineral by aerobic Arthrobacter sp. in the presence of aqueous bicarbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsenovich, Yelena P.; Carvajal, Denny A.; Wellman, Dawn M.

2012-05-01

The bacterial effect on U(VI) release from the autunite mineral (Ca[(UO2)(PO4)]2•3H2O) was investigated to provide a more comprehensive understanding of the important microbiological processes affecting autunite stability within subsurface bicarbonate-bearing environments. Experiments were performed in a culture of the Arthrobacter oxydans G975 strain, herein referred to as G975, a soil bacterium previously isolated from Hanford Site soil. 91 mg of autunite powder and 50 mL of phosphorous-limiting sterile media were amended with bicarbonate (ranging between 1 and 10 mM) in glass reactor bottles and inoculated with the G975 strain after the dissolution of autunite was at steady state. SEM observationsmore » indicated that G975 formed a biofilm on the autunite surface and penetrated the mineral cleavages. The mineral surface colonization by bacteria tended to increase concomitantly with bicarbonate concentrations. Additionally, a sterile culture-ware with inserts was used in non-contact dissolution experiments where autunite and bacteria cells were kept separately. The data suggest that G975 bacteria is able to enhance the release of U(VI) from autunite without direct contact with the mineral. In the presence of bicarbonate, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for total organic carbon (TOC) degradation and cell density compared to U(VI)-free controls. The presence of active bacterial cells greatly enhanced the release of U(VI) from autunite in bicarbonate-amended media.« less

Enhanced U(VI) release from autunite mineral by aerobic Arthrobacter sp. in the presence of aqueous bicarbonate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsenovich, Yelena; Carvajal, Denny A.; Wellman, Dawn M.

2012-04-20

The bacterial effect on U(VI) leaching from the autunite mineral (Ca[(UO{sub 2})(PO{sub 4})]{sub 2} {center_dot} 3H{sub 2}O) was investigated to provide a more comprehensive understanding into important microbiological processes affecting autunite stability within subsurface bicarbonate-bearing environments. Experiments were performed in a culture of G975 Arthrobacter oxydans strain, herein referred to as G975, a soil bacterium previously isolated from Hanford Site soil. 91 mg of autunite powder and 50 mL of phosphorus-limiting sterile media were amended with bicarbonate ranging between 1-10 mM in glass reactor bottles and inoculated with G975 strain after the dissolution of autunite was at steady state. SEMmore » observations indicated G975 formed a biofilm on the autunite surface and penetrated the mineral cleavages. The mineral surface colonization by bacteria tended to increase concomitantly with bicarbonate concentrations. Additionally, a sterile cultureware with inserts was used in non-contact bioleaching experiments where autunite and bacteria cells were kept separately. The data suggest the G975 bacteria is able to enhance U(VI) leaching from autunite without the direct contact with the mineral. In the presence of bicarbonate, the damage to bacterial cells caused by U(VI) toxicity was reduced, yielding similar values for total organic carbon (TOC) degradation and cell density compared to U(VI)-free controls. The presence of active bacterial cells greatly enhanced the U(VI) bioleaching from autunite in bicarbonate-amended media.« less

Coumarin-modified microporous-mesoporous Zn-MOF-74 showing ultra-high uptake capacity and photo-switched storage/release of U(VI) ions.

PubMed

Zhang, Le; Wang, Lin Lin; Gong, Le Le; Feng, Xue Feng; Luo, Ming Biao; Luo, Feng

2016-07-05

Driven by an energy crisis but consequently puzzled by various environmental problems, uranium, as the basic material of nuclear energy, is now receiving extensive attentions. In contrast to numerous sorbents applied in this field, metal-organic framework (MOFs), as a renovated material platform, has only recently been developed. How to improve the adsorption capacity of MOF materials towards U(VI) ions, as well as taking advantage of the nature of these MOFs to design photo-switched behaviour for photo-triggered storage/release of U(VI) ions are at present urgent problems and great challenges to be solved. Herein, we show a simple and facile method to target the goal. Through coordination-based post-synthetic strategy, microporous- mesoporous Zn-MOF-74 was easily functionalized by grafting coumarin on coordinatively unsaturated Zn(II) centers, yielding a series of coumarin-modified Zn-MOF-74 materials. The obtained samples displayed ultra-high adsorption capacity for U(VI) ions from water at pH value of 4 with maximum adsorption capacities as high as 360 mg/g (the record value in MOFs) and a remarkable photo-switched capability of 50 mg/g at pH value of 4. To the best of knowledge, and in contrast to the well-known photo-switched behaviour towards CO2, dye (propidium iodide), as well as fluorescence observed in MOFs, this is the first study that shows a photo-switched behaviour towards radioactive U(VI) ions in aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Fe(III) reduction and U(VI) immobilization by Paenibacillus sp. strain 300A, isolated from Hanford 300A subsurface sediments.

PubMed

Ahmed, Bulbul; Cao, Bin; McLean, Jeffrey S; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K; Beyenal, Haluk

2012-11-01

A facultative iron-reducing [Fe(III)-reducing] Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes [Fe(III)-nitrilotriacetic acid and Fe(III)-citrate] but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 μM) of either of the electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 μM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We also found that Paenibacillus sp. 300A could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ∼7:3 in PIPES [piperazine-N,N'-bis(2-ethanesulfonic acid)] and ∼1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments.

Fe(III) Reduction and U(VI) Immobilization by Paenibacillus sp. Strain 300A, Isolated from Hanford 300A Subsurface Sediments

PubMed Central

Ahmed, Bulbul; Cao, Bin; McLean, Jeffrey S.; Ica, Tuba; Dohnalkova, Alice; Istanbullu, Ozlem; Paksoy, Akin; Fredrickson, Jim K.

2012-01-01

A facultative iron-reducing [Fe(III)-reducing] Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes [Fe(III)-nitrilotriacetic acid and Fe(III)-citrate] but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 μM) of either of the electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 μM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We also found that Paenibacillus sp. 300A could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ∼7:3 in PIPES [piperazine-N,N′-bis(2-ethanesulfonic acid)] and ∼1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments. PMID:22961903

Fe(III) Reduction and U(VI) Immobilization by Paenibacillus sp. Strain 300A, Isolated from Hanford 300A Subsurface Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahmed, B.; Cao, B.; McLean, Jeffrey S.

2012-11-07

A facultative iron-reducing (Fe(III)-reducing) Paenibacillus sp. strain was isolated from Hanford 300A subsurface sediment biofilms that was capable of reducing soluble Fe(III) complexes (Fe(III)-NTA and Fe(III)-citrate) but unable to reduce poorly crystalline ferrihydrite (Fh). However, Paenibacillus sp. 300A was capable of reducing Fh in the presence of low concentrations (2 µM) of either of electron transfer mediators (ETMs) flavin mononucleotide (FMN) or anthraquinone-2,6-disulfonate (AQDS). Maximum initial Fh reduction rates were observed at catalytic concentrations (<10 µM) of either FMN or AQDS. Higher FMN concentrations inhibited Fh reduction, while increased AQDS concentrations did not. We found that Paenibacillus sp. 300A alsomore » could reduce Fh in the presence of natural ETMs from Hanford 300A subsurface sediments. In the absence of ETMs, Paenibacillus sp. 300A was capable of immobilizing U(VI) through both reduction and adsorption. The relative contributions of adsorption and microbial reduction to U(VI) removal from the aqueous phase were ~7:3 in PIPES and ~1:4 in bicarbonate buffer. Our study demonstrated that Paenibacillus sp. 300A catalyzes Fe(III) reduction and U(VI) immobilization and that these reactions benefit from externally added or naturally existing ETMs in 300A subsurface sediments.« less

Large-Pore 3D Cubic Mesoporous (KIT-6) Hybrid Bearing a Hard-Soft Donor Combined Ligand for Enhancing U(VI) Capture: An Experimental and Theoretical Investigation.

PubMed

Yuan, Li-Yong; Zhu, Lin; Xiao, Cheng-Liang; Wu, Qun-Yan; Zhang, Nan; Yu, Ji-Pan; Chai, Zhi-Fang; Shi, Wei-Qun

2017-02-01

A preorganized tetradentate phenanthrolineamide (DAPhen) ligand with hard and soft donors combined in the same molecule has been found to possess high extraction ability toward actinides over lanthanides from acidic aqueous solution in our previous work. Herein we grafted phenanthrolineamide groups onto a large-pore three-dimensional cubic silica support by the reaction of DAPhen siloxane with KIT-6 substrate to prepare a novel uranium-selective sorbent, KIT-6-DAPhen. The as-synthesized sorbent was well-characterized by scanning electron microscopy, high-resolution transmission electron microscopy, N 2 adsorption/desorption, X-ray diffraction, FT-IR, 13 C cross-polarization magic-angle spinning NMR, and TGA techniques, which confirmed the consummation of the functionalization. Subsequently, the effects of contact time, solution pH, initial U(VI) concentration, and the presence of competing metal ions on the U(VI) sorption onto KIT-6-DAPhen sorbent were investigated in detail. It was found that KIT-6-DAPhen showed largely enhanced sorption capacity and excellent selectivity toward U(VI). The maximum sorption capacity of KIT-6-DAPhen at pH 5.0 reaches 328 mg of U/g of sorbent, which is superior to most of functionalized mesoporous silica materials. Density functional theory coupled with quasi-relativistic small-core pseudopotentials was used to explore the sorption interaction between U(VI) and KIT-6-DAPhen, which gives a sorption reaction of KIT-6-DAPhen + [UO 2 (H 2 O) 5 ] 2+ + NO 3 - ⇄ [UO 2 (KIT-6-DAPhen)(NO 3 )] + + 5H 2 O. The findings of the present work provide new clues for developing new actinide sorbents by combining new ligands with various mesoporous matrixes.

The short-term reduction of uranium by nanoscale zero-valent iron (nZVI): role of oxide shell, reduction mechanism and the formation of U( v )-carbonate phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsarev, Sergey; Collins, Richard N.; Ilton, Eugene S.

Nanoscale zero-valent iron (nZVI) is a potential remediation agent for uranium-contaminated groundwaters, however, a complete mechanistic understanding of the processes that lead to uranium immobilization has yet to be achieved. In this study, the short-term anoxic reaction of U(VI) with fresh, (anoxic) aged and corroded nZVI particles was investigated under aqueous conditions conducive to the formation of thermodynamically stable U(VI)-Ca-CO3 ternary aqueous complexes. The first stage of the reaction between U(VI) and nZVI was assigned to sorption processes with the formation of surface U(VI)-carbonate complexes. Aged nZVI removed U(VI) faster than either fresh or corroded nZVI and it is hypothesizedmore » that U reduction initially occurs through the transfer of one electron from Fe(II) in the nZVI surface oxide layer. Evidence for reduction to U(V) was obtained through X-ray photoelectron spectroscopy and by determination of U-O bond distances of ~2.05 Å and 2.27 Å by U LIII-edge X-ray absorption spectroscopy detection of U-O bond distances at ~2.05 Å and 2.27 Å with these distances , similar to thoseat observed for the U(V) site in the mixed U(V)/U(VI) carbonate mineral wyartite. Scanning transmission electron microscopy also demonstrated that U was present as a nanoparticulate phase after one day of reaction, rather than a surface complex. Further reduction to U(IV), as observed in previous studies, would appear to be rate-limiting and coincident with the transformation of this meta-stable U-carbonate phase to uraninite (UO2).« less

AN ASSESSMENT OF THERMODYNAMIC REACTION CONSTANTS FOR SIMULATING AQUEOUS ENVIRONMENTAL MONOMETHYLMERCURY SPECIATION

EPA Science Inventory

Monomethylmercury (CH3Hg+) is both the most ecologically significant and the least well characterized species of mercury in environmental settings. Our understanding of the environmental speciation behavior of this compound is limited both as the result of lesser available labor...

Assessing the Role of Iron Sulfides in the Long Term Sequestration of Uranium by Sulfate-Reducing Bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, Kim F.; Bi, Yuqiang; Carpenter, Julian

2013-12-31

This overarching aim of this project was to identify the role of biogenic and synthetic iron-sulfide minerals in the long-term sequestration of reduced U(IV) formed under sulfate-reducing conditions when subjected to re-oxidizing conditions. The work reported herein was achieved through the collaborative research effort conducted at Arizona State University (ASU) and the University of Michigan (UM). Research at ASU, focused on the biogenesis aspects, examined the biogeochemical bases for iron-sulfide production by Desulfovibrio vulgaris, a Gram-negative bacterium that is one of the most-studied strains of sulfate-reducing bacteria. A series of experimental studies were performed to investigate comprehensively important metabolic andmore » environmental factors that affect the rates of sulfate reduction and iron-sulfide precipitation, the mineralogical characteristics of the iron sulfides, and how uranium is reduced or co-reduced by D. vulagaris. FeS production studies revealed that controlling the pH affected the growth of D. vulgaris and strongly influenced the formation and growth of FeS solids. In particular, lower pH produced larger-sized mackinawite (Fe 1+xS). Greater accumulation of free sulfide, from more sulfate reduction by D. vulgaris, also led to larger-sized mackinawite and stimulated mackinawite transformation to greigite (Fe 3S 4) when the free sulfide concentration was 29.3 mM. On the other hand, using solid Fe(III) (hydr)oxides as the iron source led to less productivity of FeS due to their slow and incomplete dissolution and scavenging of sulfide. Furthermore, sufficient free Fe 2+, particularly during Fe(III) (hydr)oxide reductions, led to the additional formation of vivianite [Fe 3(PO 4) 2•8(H 2O)]. The U(VI) reduction studies revealed that D. vulgaris reduced U(VI) fastest when accumulating sulfide from concomitant sulfate reduction, since direct enzymatic and sulfide-based reductions of U(VI) occurred in parallel. The UO 2 produced in presence of ferrous iron was poorly crystalline. At UM, laboratory-scale reactor studies were performed to assess the potential for the predominant abiotic reductants formed under sulfate reducing conditions (SRCs) to: (1) reduce U(VI) in contaminated groundwater sediments), and (2) inhibit the re-oxidation of U(IV) species, and in particular, uraninite (UO 2(s)). Under SRCs, mackinawite and aqueous sulfide are the key reductants expected to form. To assess their potential for abiotic reduction of U(VI) species, a series of experiments were performed in which either FeS or S(-II) was added to solutions of U(VI), with the rates of conversion to U(IV) solids monitored as a function of pH, and carbonate and calcium concentration. In the presence of FeS and absence of oxygen or carbonate, U(IV) was completely reduced uraninite. S(-II) was also found to be an effective reductant of aqueous phase U(VI) species and produced uraninite, with the kinetics and extent of reduction depending on geochemical conditions. U(VI) reduction to uraninite was faster under higher S(-II) concentrations but was slowed by an increase in the dissolved Ca or carbonate concentration. Rapid reduction of U(VI) occurred at circumneutral pH but virtually no reduction occurred at pH 10.7. In general, dissolved Ca and carbonate slowed abiotic U(VI) reduction by forming stable Ca-U(VI)-carbonate soluble complexes that are resistant to reaction with aqueous sulfide. To investigate the stability of U(IV) against re-oxidation in the presence of iron sulfides by oxidants in simulated groundwater environments, and to develop a mechanistic understanding the controlling redox processes, continuously-mixed batch reactor (CMBR) and flow-through reactor (CMFR) studies were performed at UM. In these studies a series of experiments were conducted under various oxic groundwater conditions to examine the effectiveness of FeS as an oxygen scavenger to retard UO 2 dissolution. The results indicate that FeS is an effective oxygen scavenger, and can lower the rate of oxidative dissolution of UO 2 by over an order of magnitude compared to the absence of FeS, depending on pH, FeS content, and DO concentrations. Column reactor studies were performed at UM to assess the impact of mackinawite on uraninite oxidation under hydrodynamic flow conditions more representative of packed porous media at contaminated groundwater sites. In these studies, Rifle sediments were packed in the two columns which were subjected to different bioreduction steps and then run in parallel. The first column was bioreduced under SRCs (i.e., with sulfate in the influent) to generate mackinawite, mixed with uraninite, gamma-sterilized to inhibit subsequent microbiological activity, and then subjected to groundwater influent containing first nitrite and then oxygen. The second column was bioreduced (but in absence of sulfate in the influent) so that no iron sulfides would form, and then subjected to identical steps and influent as the first column. When nitrite was introduced in the influent of both columns, no significant release of U(VI) relative to the anoxic flow prior to nitrite addition occurred. However, when oxygen was introduced, the column which had undergone sulfate reduction (and had produced mackinawite as later verified by XAS) significantly lowered the peak U(VI) effluent concentrations, and in general, slowed U(VI) release considerably compared to the column with no FeS. Overall, these studies demonstrated that the presence of mackinawite can be a significant scavenger of oxygen and inhibit the oxidation of uraninite by oxygen, whereas nitrite had little impact on uraninite oxidation either in the presence or absence of FeS.« less

The relationship between mantle pH and the deep nitrogen cycle

NASA Astrophysics Data System (ADS)

Mikhail, Sami; Barry, Peter H.; Sverjensky, Dimitri A.

2017-07-01

Nitrogen is distributed throughout all terrestrial geological reservoirs (i.e., the crust, mantle, and core), which are in a constant state of disequilibrium due to metabolic factors at Earth's surface, chemical weathering, diffusion, and deep N fluxes imposed by plate tectonics. However, the behavior of nitrogen during subduction is the subject of ongoing debate. There is a general consensus that during the crystallization of minerals from melts, monatomic nitrogen behaves like argon (highly incompatible) and ammonium behaves like potassium and rubidium (which are relatively less incompatible). Therefore, the behavior of nitrogen is fundamentally underpinned by its chemical speciation. In aqueous fluids, the controlling factor which determines if nitrogen is molecular (N2) or ammonic (inclusive of both NH4+ and NH30) is oxygen fugacity, whereas pH designates if ammonic nitrogen is NH4+ or NH30. Therefore, to address the speciation of nitrogen at high pressures and temperatures, one must also consider pH at the respective pressure-temperature conditions. To accomplish this goal we have used the Deep Earth Water Model (DEW) to calculate the activities of aqueous nitrogen from 1-5 GPa and 600-1000 °C in equilibrium with a model eclogite-facies mineral assemblage of jadeite + kyanite + quartz/coesite (metasediment), jadeite + pyrope + talc + quartz/coesite (metamorphosed mafic rocks), and carbonaceous eclogite (metamorphosed mafic rocks + elemental carbon). We then compare these data with previously published data for the speciation of aqueous nitrogen across these respective P-T conditions in equilibrium with a model peridotite mineral assemblage (Mikhail and Sverjensky, 2014). In addition, we have carried out full aqueous speciation and solubility calculations for the more complex fluids in equilibrium with jadeite + pyrope + kyanite + diamond, and for fluids in equilibrium with forsterite + enstatite + pyrope + diamond. Our results show that the pH of the fluid is controlled by mineralogy for a given pressure and temperature, and that pH can vary by several units in the pressure-temperature range of 1-5 GPa and 600-1000 °C. Our data show that increasing temperature stabilizes molecular nitrogen and increasing pressure stabilizes ammonic nitrogen. Our model also predicts a stark difference for the dominance of ammonic vs. molecular and ammonium vs. ammonia for aqueous nitrogen in equilibrium with eclogite-facies and peridotite mineralogies, and as a function of the total dissolved nitrogen in the aqueous fluid where lower N concentrations favor aqueous ammonic nitrogen stabilization and higher N concentrations favor aqueous N2. Overall, we present thermodynamic evidence for nitrogen to be reconsidered as an extremely dynamic (chameleon) element whose speciation and therefore behavior is determined by a combination of temperature, pressure, oxygen fugacity, chemical activity, and pH. We show that altering the mineralogy in equilibrium with the fluid can lead to a pH shift of up to 4 units at 5 GPa and 1000 °C. Therefore, we conclude that pH imparts a strong control on nitrogen speciation, and thus N flux, and should be considered a significant factor in high temperature geochemical modeling in the future. Finally, our modelling demonstrates that pH plays an important role in controlling speciation, and thus mass transport, of Eh-pH sensitive elements at temperatures up to at least 1000 °C.

MINTEQA2

EPA Science Inventory

MINTEQA2 is a equilibrium speciation model that can be used to calculate the equilibrium composition of dilute aqueous solutions in the laboratory or in natural aqueous systems. The model is useful for calculating the equilibrium mass distribution among dissolved species, adsorb...

Variations of uranium concentrations in a multi-aquifer system under the impact of surface water-groundwater interaction

NASA Astrophysics Data System (ADS)

Wu, Ya; Li, Junxia; Wang, Yanxin; Xie, Xianjun

2018-04-01

Understanding uranium (U) mobility is vital to minimizing its concentrations in potential drinking water sources. In this study, we report spatial-seasonal variations in U speciation and concentrations in a multi-aquifer system under the impact of Sanggan River in Datong basin, northern China. Hydrochemical and H, O, Sr isotopic data, thermodynamic calculations, and geochemical modeling are used to investigate the mechanisms of surface water-groundwater mixing-induced mobilization and natural attenuation of U. In the study site, groundwater U concentrations are up to 30.2 μg/L, and exhibit strong spatial-seasonal variations that are related to pH and Eh values, as well as dissolved Ca2+, HCO3-, and Fe(III) concentrations. For the alkaline aquifers of this site (pH 7.02-8.44), U mobilization is due to the formation and desorption of Ca2UO2(CO3)30 and CaUO2(CO3)32- caused by groundwater Ca2+ elevation via mineral weathering and Na-Ca exchange, incorporated U(VI) release from calcite, and U(IV) oxidation by Fe(OH)3. U immobilization is linked to the adsorption of CaUO2(CO3)32- and UO2(CO3)34- shifted from Ca2UO2(CO3)30 because of HCO3- elevation and Ca2+ depletion, U(VI) co-precipitation with calcite, and U(VI) reduction by adsorbed Fe2+ and FeS. Those results are of great significance for the groundwater resource management of this and similar other surface water-groundwater interaction zones.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bone, Sharon E.; Dynes, James J.; Cliff, John

2017-01-09

Uranium is an important fuel source and a global environmental contaminant. It accumulates in the tetravalent state, U(IV), in anoxic sediments, including ore deposits, marine basins, and contaminated aquifers. However, very little is known about the speciation of U(IV) in low temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2) in anoxic sediments; yet studies now show that UO 2 is not often dominant in these environments. However, a model of U(IV) speciation under environmentally relevant conditions has not yetmore » been developed. Here we show that complexes of U(IV) adsorb on organic carbon and organic carbon-coated clays in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that the U(IV) product depended on the reduction pathway, our results demonstrate that UO 2 formation can be inhibited simply by decreasing the U:solid ratio. Thus, it is the number and type of surface ligands that controls U(IV) speciation subsequent to U(VI) reduction. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider retention of U(IV) ions within the local sediment environment.« less

Uranium fate in Hanford sediment altered by simulated acid waste solutions

DOE PAGES

Gartman, Brandy N.; Qafoku, Nikolla P.; Szecsody, James E.; ...

2015-07-31

Many aspects of U(VI) behavior in sediments that are previously exposed to acidic waste fluids for sufficiently long times to induce significant changes in pH and other physical, mineralogical and chemical properties, are not well documented in the literature. For this reason, we conducted a series of macroscopic batch experiments combined with a variety of bulk characterization studies (Mössbauer and laser spectroscopy), micro-scale inspections (µ-XRF), and molecular scale interrogations (XANES) with the objectives to: i) determine the extent of U(VI) partitioning to Hanford sediments previously exposed to acidic waste simulants (pH = 2 and pH = 5) and under neutralmore » conditions (pH = 8) at varying background solution concentrations (i.e., NaNO 3); ii) determine micron-scale solid phase associated U valence state and phase identity; and iii) provide information for a plausible conceptual model of U(VI) attenuation under waste plume acidic conditions. The results of the batch experiments showed that the acid pre-treated sediment had high affinity for aqueous U(VI), which was removed from solution via two pH dependent and apparently different mechanisms (adsorption at pH = 2 and precipitation at pH = 5). The micro-scale inspections and XANES analyses confirmed that high concentration areas were rich mainly in U(VI), demonstrating that most of the added U(VI) was not reduced to U(IV). The laser spectroscopy data showed that uranyl phosphates {e.g. metaautunite [Ca(UO 2) 2(PO 4) 2•10-12H 2O] and phosphuranylite [KCa(H 3O) 3(UO 2) 7(PO 4) 4O 4•8(H 2O)]} were present in the sediments. They also showed clear differences between the U bearing phases in the experiments conducted in the presence or absence of air. As a result, the data generated from these experiments will help in a better understanding of the reactions and processes that have a significant effect and/or control U mobility.« less

Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

PubMed

Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

2014-03-30

The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

238U and 235U isotope fractionation upon oxidation of uranium-bearing rocks by fracture waters

NASA Astrophysics Data System (ADS)

Chernyshev, I. V.; Golubev, V. N.; Chugaev, A. V.; Mandzhieva, G. V.

2016-10-01

The variations in 238U/235U values accompanying mobilization of U by fracture waters from uranium-bearing rocks, in which U occurs as a fine impregnation of oxides and silicates, were studied by the high-precision (±0.07‰) MC-ICP-MS method. Transition of U into the aqueous phase in the oxidized state U(VI) is accompanied by its isotope fractionation with enrichment of dissolved U(VI) in the heavy isotope 238U up to 0.32‰ in relation to the composition of the solid phases. According to the sign, this effect is consistent with the tendency of the behavior of 238U and 235U upon interaction of river waters with rocks of the catchment areas [11] and with the effect observed during oxidation of uraninite by the oxygen-bearing NaHCO3 solution [12].

Uranium Bioreduction Rates across Scales: Biogeochemical Hot Moments and Hot Spots during a Biostimulation Experiment at Rifle, Colorado

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bao, Chen; Wu, Hongfei; Li, Li

2014-09-02

We aim to understand the scale-dependent evolution of uranium bioreduction during a field experiment at a former uranium mill site near Rifle, Colorado. Acetate was injected to stimulate Fe-reducing bacteria (FeRB) and to immobilize aqueous U(VI) to insoluble U(IV). Bicarbonate was coinjected in half of the domain to mobilize sorbed U(VI). We used reactive transport modeling to integrate hydraulic and geochemical data and to quantify rates at the grid block (0.25 m) and experimental field scale (tens of meters). Although local rates varied by orders of magnitude in conjunction with biostimulation fronts propagating downstream, field-scale rates were dominated by thosemore » orders of magnitude higher rates at a few selected hot spots where Fe(III), U(VI), and FeRB were at their maxima in the vicinity of the injection wells. At particular locations, the hot moments with maximum rates negatively corresponded to their distance from the injection wells. Although bicarbonate injection enhanced local rates near the injection wells by a maximum of 39.4%, its effect at the field scale was limited to a maximum of 10.0%. We propose a rate-versus-measurement-length relationship (log R' = -0.63« less

The effect of Si and Al concentrations on the removal of U(VI) in the alkaline conditions created by NH3 gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsenovich, Yelena P.; Cardona, Claudia; Lapierre, Robert

2016-10-01

Remediation of uranium in the deep unsaturated zone is a challenging task, especially in the presence of oxygenated, high-carbonate alkalinity soil and pore water composition typical for arid and semi-arid environments of the western regions of the U.S. This study evaluates the effect of various pore water constituencies on changes of uranium concentrations in alkaline conditions, created in the presence of reactive gases such as NH3 to effectively mitigate uranium contamination in the vadose zone sediments. This contaminant is a potential source for groundwater pollution through slow infiltration of soluble and highly mobile uranium species towards the water table. Themore » objective of this research was to evaluate uranium sequestration efficiencies in the alkaline synthetic pore water solutions prepared in a broad range of Si, Al, and bicarbonate concentrations typically present in field systems of the western U.S. regions and identify solid uranium-bearing phases that result from ammonia gas treatment. In previous studies (Szecsody et al. 2012; Zhong et al. 2015), although uranium mobility was greatly decreased, solid phases could not be identified at the low uranium concentrations in field-contaminated sediments. The chemical composition of the synthetic pore water used in the experiments varied for silica (5–250 mM), Al3+ (2.8 or 5 mM), HCO3- (0–100 mM) and U(VI) (0.0021–0.0084 mM) in the solution mixture. Experiment results suggested that solutions with Si concentrations higher than 50 mM exhibited greater removal efficiencies of U(VI). Solutions with higher concentrations of bicarbonate also exhibited greater removal efficiencies for Si, Al, and U(VI). Overall, the silica polymerization reaction leading to the formation of Si gel correlated with the removal of U(VI), Si, and Al from the solution. If no Si polymerization was observed, there was no U removal from the supernatant solution. Speciation modeling indicated that the dominant uranium species in the presence of bicarbonate were anionic uranyl carbonate complexes (UO2(CO3)2-2 and UO2(CO3)3-4) and in the absence of bicarbonate in the solution, U(VI) major species appeared as uranyl-hydroxide (UO2(OH)3- and UO2(OH)4-2) species. The model also predicted the formation of uranium solid phases. Uranyl carbonates as rutherfordine [UO2CO3], cejkaite [Na4(UO2)(CO3)3] and hydrated uranyl silicate phases as Na-boltwoodite [Na(UO2)(SiO4)·1.5H2O] were anticipated for most of the synthetic pore water compositions amended from medium (2.9 mM) to high (100 mM) bicarbonate concentrations.« less

Microanalytical X-ray imaging of depleted uranium speciation in environmentally aged munitions residues.

PubMed

Crean, Daniel E; Livens, Francis R; Stennett, Martin C; Grolimund, Daniel; Borca, Camelia N; Hyatt, Neil C

2014-01-01

Use of depleted uranium (DU) munitions has resulted in contamination of the near-surface environment with penetrator residues. Uncertainty in the long-term environmental fate of particles produced by impact of DU penetrators with hard targets is a specific concern. In this study DU particles produced in this way and exposed to the surface terrestrial environment for longer than 30 years at a U.K. firing range were characterized using synchrotron X-ray chemical imaging. Two sites were sampled: a surface soil and a disposal area for DU-contaminated wood, and the U speciation was different between the two areas. Surface soil particles showed little extent of alteration, with U speciated as oxides U3O7 and U3O8. Uranium oxidation state and crystalline phase mapping revealed these oxides occur as separate particles, reflecting heterogeneous formation conditions. Particles recovered from the disposal area were substantially weathered, and U(VI) phosphate phases such as meta-ankoleite (K(UO2)(PO4) · 3H2O) were dominant. Chemical imaging revealed domains of contrasting U oxidation state linked to the presence of both U3O7 and meta-ankoleite, indicating growth of a particle alteration layer. This study demonstrates that substantial alteration of DU residues can occur, which directly influences the health and environmental hazards posed by this contamination.

Metal-organic complexes in geochemical processes: temperature dependence of the standard thermodynamic properties of aqueous complexes between metal cations and dicarboxylate ligands

NASA Astrophysics Data System (ADS)

Prapaipong, Panjai; Shock, Everett L.; Koretsky, Carla M.

1999-10-01

By combining results from regression and correlation methods, standard state thermodynamic properties for aqueous complexes between metal cations and divalent organic acid ligands (oxalate, malonate, succinate, glutarate, and adipate) are evaluated and applied to geochemical processes. Regression of experimental standard-state equilibrium constants with the revised Helgeson-Kirkham-Flowers (HKF) equation of state yields standard partial molal entropies (S¯°) of aqueous metal-organic complexes, which allow determination of thermodynamic properties of the complexes at elevated temperatures. In cases where S¯° is not available from either regression or calorimetric measurement, the values of S¯° can be estimated from a linear correlation between standard partial molal entropies of association (ΔS¯°r) and standard partial molal entropies of aqueous cations (S¯°M). The correlation is independent of cation charge, which makes it possible to predict S¯° for complexes between divalent organic acids and numerous metal cations. Similarly, correlations between standard Gibbs free energies of association of metal-organic complexes (ΔḠ°r) and Gibbs free energies of formation (ΔḠ°f) for divalent metal cations allow estimates of standard-state equilibrium constants where experimental data are not available. These correlations are found to be a function of ligand structure and cation charge. Predicted equilibrium constants for dicarboxylate complexes of numerous cations were included with those for inorganic and other organic complexes to study the effects of dicarboxylate complexes on the speciation of metals and organic acids in oil-field brines. Relatively low concentrations of oxalic and malonic acids affect the speciation of cations more than similar concentrations of succinic, glutaric, and adipic acids. However, the extent to which metal-dicarboxylate complexes contribute to the speciation of dissolved metals depends on the type of dicarboxylic acid ligand; relative concentration of inorganic, mono-, and dicarboxylate ligands; and the type of metal cation. As an example, in the same solution, dicarboxylic acids have a greater influence on the speciation of Fe+2 and Mg+2 than on the speciation of Zn+2 and Mn+2.

GEOSURF: a computer program for modeling adsorption on mineral surfaces from aqueous solution

NASA Astrophysics Data System (ADS)

Sahai, Nita; Sverjensky, Dimitri A.

1998-11-01

A new program, GEOSURF, has been developed for calculating aqueous and surface speciation consistent with the triple-layer model of surface complexation. GEOSURF is an extension of the original programs MINEQL, MICROQL and HYDRAQL. We present, here, the basic algorithm of GEOSURF along with a description of the new features implemented. GEOSURF is linked to internally consistent data bases for surface species (SURFK.DAT) and for aqueous species (AQSOL.DAT). SURFK.DAT contains properties of minerals such as site densities, and equilibrium constants for adsorption of aqueous protons and electrolyte ions on a variety of oxides and hydroxides. The Helgeson, Kirkham and Flowers version of the extended Debye-Huckel Equation for 1:1 electrolytes is implemented for calculating aqueous activity coefficients. This permits the calculation of speciation at ionic strengths greater than 0.5 M. The activity of water is computed explicitly from the osmotic coefficient of the solution, and the total amount of electrolyte cation (or anion) is adjusted to satisfy the electroneutrality condition. Finally, the use of standard symbols for chemical species rather than species identification numbers is included to facilitate use of the program. One of the main limitations of GEOSURF is that aqueous and surface speciation can only be calculated at fixed pH and at fixed concentration of total adsorbate. Thus, the program cannot perform reaction-path calculations: it cannot determine whether or not a solution is over- or under-saturated with respect to one or more solid phases. To check the proper running of GEOSURF, we have compared results generated by GEOSURF with those from two other programs, HYDRAQL and EQ3. The Davies equation and the "bdot" equation, respectively, are used in the latter two programs for calculating aqueous activity coefficients. An example of the model fit to experimental data for rutile in 0.001 M-2.0 M NaNO 3 is included.

Pore-scale characterization of biogeochemical controls on iron and uranium speciation under flow conditions.

PubMed

Pearce, Carolyn I; Wilkins, Michael J; Zhang, Changyong; Heald, Steve M; Fredrickson, Jim K; Zachara, John M

2012-08-07

Etched silicon microfluidic pore network models (micromodels) with controlled chemical and redox gradients, mineralogy, and microbiology under continuous flow conditions are used for the incremental development of complex microenvironments that simulate subsurface conditions. We demonstrate the colonization of micromodel pore spaces by an anaerobic Fe(III)-reducing bacterial species (Geobacter sulfurreducens) and the enzymatic reduction of a bioavailable Fe(III) phase within this environment. Using both X-ray microprobe and X-ray absorption spectroscopy, we investigate the combined effects of the precipitated Fe(III) phases and the microbial population on uranium biogeochemistry under flow conditions. Precipitated Fe(III) phases within the micromodel were most effectively reduced in the presence of an electron shuttle (AQDS), and Fe(II) ions adsorbed onto the precipitated mineral surface without inducing any structural change. In the absence of Fe(III), U(VI) was effectively reduced by the microbial population to insoluble U(IV), which was precipitated in discrete regions associated with biomass. In the presence of Fe(III) phases, however, both U(IV) and U(VI) could be detected associated with biomass, suggesting reoxidation of U(IV) by localized Fe(III) phases. These results demonstrate the importance of the spatial localization of biomass and redox active metals, and illustrate the key effects of pore-scale processes on contaminant fate and reactive transport.

Application of Brazilian kaolinite clay as adsorbent to removal of U(VI) from aqueous solution: Kinetic and thermodynamic of cation-basic interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guerra, Denis L., E-mail: denis@cpd.ufmt.b; Leidens, Victor L.; Viana, Rubia R.

2010-05-15

The compound N{sup 1}-[3-(trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route. The modified and natural kaolinite samples were characterized by transmission electron microscopy, scanning electron microscopic, X-ray diffraction, and nuclear magnetic nuclei of {sup 29}Si and {sup 13}C. The well-defined peaks obtained in the {sup 13}C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0.more » The kinetic parameters analyzed by the Lagergren and Elovich models gave a good fit for a pseudo-second order reaction with k{sub 2} values 16.0 and 25.1 mmol g{sup -1} min{sup -1} ranges for natural and modified kaolinite clays, respectively. The energetic effects caused by metal ion adsorption were determined through calorimetric titrations. - Graphical abstract: This investigation reports the use of original and modified kaolinites as alternative absorbents. The compound N-[3-trimethoxysilyl)propyl]diethylenetriamine was anchored onto Amazon kaolinite surface by heterogeneous route.« less

Preparation of graphene oxide-manganese dioxide for highly efficient adsorption and separation of Th(IV)/U(VI).

PubMed

Pan, Ning; Li, Long; Ding, Jie; Li, Shengke; Wang, Ruibing; Jin, Yongdong; Wang, Xiangke; Xia, Chuanqin

2016-05-15

Manganese dioxide decorated graphene oxide (GOM) was prepared via fixation of crystallographic MnO2 (α, γ) on the surface of graphene oxide (GO) and was explored as an adsorbent material for simultaneous removal of thorium/uranium ions from aqueous solutions. In single component systems (Th(IV) or U(VI)), the α-GOM2 (the weight ratio of GO/α-MnO2 of 2) exhibited higher maximum adsorption capacities toward both Th(IV) (497.5mg/g) and U(VI) (185.2 mg/g) than those of GO. In the binary component system (Th(IV)/U(VI)), the saturated adsorption capacity of Th(IV) (408.8 mg/g)/U(VI) (66.8 mg/g) on α-GOM2 was also higher than those on GO. Based on the analysis of various data, it was proposed that the adsorption process may involve four types of molecular interactions including coordination, electrostatic interaction, cation-pi interaction, and Lewis acid-base interaction between Th(IV)/U(VI) and α-GOM2. Finally, the Th(IV)/U(VI) ions on α-GOM2 can be separated by a two-stage desorption process with Na2CO3/EDTA. Those results displayed that the α-GOM2 may be utilized as an potential adsorbent for removing and separating Th(IV)/U(VI) ions from aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

pH-specific synthesis and spectroscopic, structural, and magnetic studies of a chromium(III)-citrate species. Aqueous solution speciation of the binary chromium(III)-citrate system.

PubMed

Gabriel, C; Raptopoulou, C P; Terzis, A; Tangoulis, V; Mateescu, C; Salifoglou, A

2007-04-16

In an attempt to understand the aqueous interactions of Cr(III) with the low-molecular-mass physiological ligand citric acid, the pH-specific synthesis in the binary Cr(III)-citrate system was explored, leading to the complex (NH4)4[Cr(C6H4O7)(C6H5O7)].3H2O (1). 1 crystallizes in the monoclinic space group I2/a, with a = 19.260(10) A, b = 10.006(6) A, c = 23.400(10) A, beta = 100.73(2) degrees , V = 4431(4) A3, and Z = 8. 1 was characterized by elemental analysis and spectroscopic, structural, thermal, and magnetic susceptibility studies. Detailed aqueous speciation studies in the Cr(III)-citrate system suggest the presence of a number of species, among which is the mononuclear [Cr(C6H4O7)(C6H5O7)]4- complex, optimally present around pH approximately 5.5. The structure of 1 reveals a mononuclear octahedral complex of Cr(III) with two citrate ligands bound to it. The two citrate ligands have different deprotonation states, thus signifying the importance of the mixed deprotonation state in the coordination sphere of the Cr(III) species in aqueous speciation. The latter reveals the distribution of numerous species, including 1, for which the collective structural, spectroscopic, and magnetic data point out its physicochemical profile in the solid state and in solution. The importance of the synthetic efforts linked to 1 and the potential ramifications of Cr(III) reactivity toward both low- and high-molecular-mass biotargets are discussed in light of (a) the quest for well-characterized soluble Cr(III) species that could be detected and identified in biologically relevant fluids, (b) ongoing efforts to delineate the aqueous speciation of the Cr(III)-citrate system and its link to biotoxic Cr(III) manifestations, and (c) the synthetic utility of convenient Cr(III) precursors in the synthesis of advanced materials.

Aqueous suspensions of carbon nanotubes: surface oxidation, colloidal stability and uranium sorption.

PubMed

Schierz, A; Zänker, H

2009-04-01

The objective of this study is to obtain information on the behaviour of carbon nanotubes (CNTs) as potential carriers of pollutants in the case of accidental CNT release to the environment and on the properties of CNTs as a potential adsorbent material in water purification. The effects of acid treatment of CNTs on (i) the surface properties, (ii) the colloidal stability and (iii) heavy metal sorption are investigated, the latter being exemplified by uranium(VI) sorption. There is a pronounced influence of surface treatment on the behaviour of the CNTs in aqueous suspension. Results showed that acid treatment increases the amount of acidic surface groups on the CNTs. Therefore, acid treatment has an increasing effect on the colloidal stability of the CNTs and on their adsorption capacity for U(VI). Another way to stabilise colloids of pristine CNTs in aqueous suspension is the addition of humic acid.

Derivation of Pitzer Interaction Parameters for an Aqueous Species Pair of Sodium and Iron(II)-Citrate Complex

NASA Astrophysics Data System (ADS)

Jang, J. H.; Nemer, M.

2015-12-01

The U.S. DOE Waste Isolation Pilot Plant (WIPP) is a deep underground repository for the permanent disposal of transuranic (TRU) radioactive waste. The WIPP is located in the Permian Delaware Basin near Carlsbad, New Mexico, U.S.A. The TRU waste includes, but is not limited to, iron-based alloys and the complexing agent, citric acid. Iron is also present from the steel used in the waste containers. The objective of this analysis is to derive the Pitzer activity coefficients for the pair of Na+ and FeCit- complex to expand current WIPP thermodynamic database. An aqueous model for the dissolution of Fe(OH)2(s) in a Na3Cit solution was fitted to the experimentally measured solubility data. The aqueous model consists of several chemical reactions and related Pitzer interaction parameters. Specifically, Pitzer interaction parameters for the Na+ and FeCit- pair (β(0), β(1), and Cφ) plus the stability constant for species of FeCit- were fitted to the experimental data. Anoxic gloveboxes were used to keep the oxygen level low (<1 ppm) throughout the experiments due to redox sensitivity. EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations, packaged in EQ3/6 v.8.0a, calculates the aqueous speciation and saturation index using an aqueous model addressed in EQ3/6's database. The saturation index indicates how far the system is from equilibrium with respect to the solid of interest. Thus, the smaller the sum of squared saturation indices that the aqueous model calculates for the given number of experiments, the more closely the model attributes equilibrium to each individual experiment with respect to the solid of interest. The calculation of aqueous speciation and saturation indices was repeated by adjusting stability constant of FeCit-, β(0), β(1), and Cφ in the database until the values are found that make the sum of squared saturation indices the smallest for the given number of experiments. Results will be presented at the time of conference.

Uranium bioreduction rates across scales: biogeochemical hot moments and hot spots during a biostimulation experiment at Rifle, Colorado.

PubMed

Bao, Chen; Wu, Hongfei; Li, Li; Newcomer, Darrell; Long, Philip E; Williams, Kenneth H

2014-09-02

We aim to understand the scale-dependent evolution of uranium bioreduction during a field experiment at a former uranium mill site near Rifle, Colorado. Acetate was injected to stimulate Fe-reducing bacteria (FeRB) and to immobilize aqueous U(VI) to insoluble U(IV). Bicarbonate was coinjected in half of the domain to mobilize sorbed U(VI). We used reactive transport modeling to integrate hydraulic and geochemical data and to quantify rates at the grid block (0.25 m) and experimental field scale (tens of meters). Although local rates varied by orders of magnitude in conjunction with biostimulation fronts propagating downstream, field-scale rates were dominated by those orders of magnitude higher rates at a few selected hot spots where Fe(III), U(VI), and FeRB were at their maxima in the vicinity of the injection wells. At particular locations, the hot moments with maximum rates negatively corresponded to their distance from the injection wells. Although bicarbonate injection enhanced local rates near the injection wells by a maximum of 39.4%, its effect at the field scale was limited to a maximum of 10.0%. We propose a rate-versus-measurement-length relationship (log R' = -0.63 log L - 2.20, with R' in μmol/mg cell protein/day and L in meters) for orders-of-magnitude estimation of uranium bioreduction rates across scales.

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

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

PubMed

Batuk, Olga N; Conradson, Steven D; Aleksandrova, Olga N; Boukhalfa, Hakim; Burakov, Boris E; Clark, David L; Czerwinski, Ken R; Felmy, Andrew R; Lezama-Pacheco, Juan S; Kalmykov, Stepan N; Moore, Dean A; Myasoedov, Boris F; Reed, Donald T; Reilly, Dallas D; Roback, Robert C; Vlasova, Irina E; Webb, Samuel M; Wilkerson, Marianne P

2015-06-02

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.

Uranium speciation in Fernald soils. Progress report, January 1--May 31, 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morris, D.E.; Conradson, S.D.; Tait, C.D.

1992-05-31

This report details progress made from January 1 to May 31, 1992 in this analytical support task to determine the speciation of uranium in contaminated soil samples from the Fernald Environmental Management Project site under the auspices of the Uranium in Soils Integrated Demonstration funded through the US DOE`s Office of Technology Development. The authors` efforts have focused on characterization of soil samples collected by S.Y. Lee (Oak Ridge National Laboratory) from five locales at the Fernald site. These were chosen to sample a broad range of uranium source terms. On the basis of x-ray absorption spectroscopy data, they havemore » determined that the majority of uranium (> 80--90%) exists in the hexavalent oxidation state for all samples examined. This is a beneficial finding from the perspective of remediation, because U(VI) species are more soluble in general than uranium species in other oxidation states. Optical luminescence data from many of the samples show the characteristic structured yellow-green emission from the uranyl (UO{sub 2}{sup 2+}) moiety. The luminescence data also suggest that much of the uranium in these soils is present as well-crystallized UO{sub 2}{sup 2+} species. Some clear spectroscopic distinctions have been noted for several samples that illustrate significant differences in the speciation (1) from site to site, (2) within different horizons at the same site, and (3) within different size fractions of the soils in the same horizon at the same site. This marked heterogeneity in uranyl speciation suggests that several soil washing strategies may be necessary to reduce the total uranium concentrations within these soils to regulatory limits.« less

Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

DOE PAGES

Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui; ...

2017-12-05

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. Here, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO 4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K 2(UO 2) 6O 4(OH) 6·8H 2O]- and becquerelite [Ca(UO 2) 6O 4(OH) 6·8H 2O]-like species.more » Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO 2) 2O 4(HSiO 4) 2•0.5(H 2O)]-like species of uranium at 180 and 365 days. When present, PO 4 exerted a direct and strong control over U speciation. Furthermore, the detection of meta-ankoleite, [K 2(UO 2) 2O 4(PO 4) 2·6H 2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO 4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO 4 present, nearly all uranium would have precipitated in the upper soil.« less

Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. In this study, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO(4)(-)reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K-2(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-and becquerelite [Ca(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-like species. Subsequent further removal of uranium coincided withmore » that of Si and accumulation of boltwoodite, [(K, Na)(UO2)(2)O-4(HSiO4)(2)center dot 0.5(H2O)]-like species of uranium at 180 and 365 days. When present, PO4 exerted a direct and strong control over U speciation. The detection of meta-ankoleite, [K-2(UO2)(2)O-4(PO4)(2)center dot 6H(2)O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO4 present, nearly all uranium would have precipitated in the upper soil.« less

Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. Here, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO 4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K 2(UO 2) 6O 4(OH) 6·8H 2O]- and becquerelite [Ca(UO 2) 6O 4(OH) 6·8H 2O]-like species.more » Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO 2) 2O 4(HSiO 4) 2•0.5(H 2O)]-like species of uranium at 180 and 365 days. When present, PO 4 exerted a direct and strong control over U speciation. Furthermore, the detection of meta-ankoleite, [K 2(UO 2) 2O 4(PO 4) 2·6H 2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO 4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO 4 present, nearly all uranium would have precipitated in the upper soil.« less

Uranium and Cesium sorption to bentonite colloids in high salinity and carbonate-rich environments: Implications for radionuclide transport

NASA Astrophysics Data System (ADS)

Tran, E. L.; Teutsch, N.; Klein-BenDavid, O.; Weisbrod, N.

2017-12-01

When radionuclides are leaked into the subsurface due to engineered waste disposal container failure, the ultimate barrier to migration of radionuclides into local aquifers is sorption to the surrounding rock matrix and sediments, which often includes a bentonite backfill. The extent of this sorption is dependent on pH, ionic strength, surface area availability, radionuclide concentration, surface mineral composition, and solution chemistry. Colloidal-sized bentonite particles eroded from the backfill have been shown to facilitate the transport of radionuclides sorbed to them away from their source. Thus, sorption of radionuclides such as uranium and cesium to bentonite surfaces can be both a mobilization or retardation factor. Though numerous studies have been conducted to-date on sorption of radionuclides under low ionic strength and carbonate-poor conditions, there has been little research conducted on the behavior of radionuclides in high salinities and carbonate rich conditions typical of aquifers in the vicinity of some potential nuclear repositories. This study attempts to characterize the sorption properties of U(VI) and Cs to bentonite colloids under these conditions using controlled batch experiments. Results indicated that U(VI) undergoes little to no sorption to bentonite colloids in a high-salinity (TDS= 9000 mg/L) artificial groundwater. This lack of sorption was attributed to the formation of CaUO2(CO3)22- and Ca2UO2(CO3)3 aqueous ions which stabilize the UO22+ ions in solution. In contrast, Cs exhibited greater sorption, the extent to which was influenced greatly by the matrix water's ionic strength and the colloid concentration used. Surprisingly, when both U and Cs were together, the presence of U(VI) in solution decreased Cs sorption, possibly due to the formation of stabilizing CaUO2(CO3)22- anions. The implications of this research are that rather than undergoing colloid-facilitated transport, U(VI) is expected to migrate similarly to a conservative dissolved species under these conditions, and little retardation through sorption onto the surrounding rock matrix is predicted. Cs is expected to undergo more sorption, though U(VI) presence may have a mobilizing effect.

Contribution of extracellular polymeric substances from Shewanella sp. HRCR-1 biofilms to U(VI) immobilization.

PubMed

Cao, Bin; Ahmed, Bulbul; Kennedy, David W; Wang, Zheming; Shi, Liang; Marshall, Matthew J; Fredrickson, Jim K; Isern, Nancy G; Majors, Paul D; Beyenal, Haluk

2011-07-01

The goal of this study was to quantify the contribution of extracellular polymeric substances (EPS) to U(VI) immobilization by Shewanella sp. HRCR-1. Through comparison of U(VI) immobilization using cells with bound EPS (bEPS) and cells with minimal EPS, we show that (i) bEPS from Shewanella sp. HRCR-1 biofilms contribute significantly to U(VI) immobilization, especially at low initial U(VI) concentrations, through both sorption and reduction; (ii) bEPS can be considered a functional extension of the cells for U(VI) immobilization and they likely play more important roles at lower initial U(VI) concentrations; and (iii) the U(VI) reduction efficiency is dependent upon the initial U(VI) concentration and decreases at lower concentrations. To quantify the relative contributions of sorption and reduction to U(VI) immobilization by EPS fractions, we isolated loosely associated EPS (laEPS) and bEPS from Shewanella sp. HRCR-1 biofilms grown in a hollow fiber membrane biofilm reactor and tested their reactivity with U(VI). We found that, when reduced, the isolated cell-free EPS fractions could reduce U(VI). Polysaccharides in the EPS likely contributed to U(VI) sorption and dominated the reactivity of laEPS, while redox active components (e.g., outer membrane c-type cytochromes), especially in bEPS, possibly facilitated U(VI) reduction.

Pore-Scale Characterization of Biogeochemical Controls on Iron and Uranium Speciation under Flow Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pearce, Carolyn I.; Wilkins, Michael J.; Zhang, Changyong

2012-09-17

Etched silicon microfluidic pore network models (micromodels) with controlled chemical and redox gradients, mineralogy, and microbiology under continuous flow conditions are used for the incremental development of complex microenvironments that simulate subsurface conditions. We demonstrate the colonization of micromodel pore spaces by an anaerobic Fe(III)-reducing bacterial species (Geobacter sulfurreducens) and the enzymatic reduction of a bioavailable Fe(III) phase within this environment. Using both X-ray Microprobe and X-ray Absorption Spectroscopy, we investigate the combined effects of the precipitated Fe(III) phases and the microbial population on uranium biogeochemistry under flow conditions. Precipitated Fe(III) phases within the micromodel were most effectively reduced inmore » the presence of an electron shuttle (AQDS), and Fe(II) ions adsorbed onto the precipitated mineral surface without inducing any structural change. In the absence of Fe(III), U(VI) was effectively reduced by the microbial population to insoluble U(IV), which was precipitated in discrete regions associated with biomass. In the presence of Fe(III) phases, however, both U(IV) and U(VI) could be detected associated with biomass, suggesting re-oxidation of U(IV) by localized Fe(III) phases. These results demonstrate the importance of the spatial localization of biomass and redox active metals, and illustrate the key effects of pore-scale processes on contaminant fate and reactive transport.« less

Contribution of Extracellular Polymeric Substances from Shewanella sp. HRCR-1 Biofilms to U(VI) Immobilization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Bin; Ahmed, B.; Kennedy, David W.

2011-06-05

The goal of this study was to quantify the contribution of extracellular polymeric substances (EPS) in U(VI) immobilization by Shewanella sp. HRCR-1. Through comparison of U(VI) immobilization using cells with bound EPS (bEPS) and cells without EPS, we showed that i) bEPS from Shewanella sp. HRCR-1 biofilms contributed significantly to U(VI) immobilization, especially at low initial U(VI) concentrations, through both sorption and reduction; ii) bEPS could be considered as a functional extension of the cells for U(VI) immobilization and they likely play more important roles at initial U(VI) concentrations; and iii) U(VI) reduction efficiency was found to be dependent uponmore » initial U(VI) concentration and the efficiency decreased at lower concentrations. To quantify relative contribution of sorption and reduction in U(VI) immobilization by EPS fractions, we isolated loosely associated EPS (laEPS) and bEPS from Shewanella sp. HRCR-1 biofilms grown in a hollow fiber membrane biofilm reactor and tested their reactivity with U(V). We found that, when in reduced form, the isolated cell-free EPS fractions could reduce U(VI). Polysaccharides in the EPS likely contributed to U(VI) sorption and dominated reactivity of laEPS while redox active components (e.g., outer membrane c-type cytochromes), especially in bEPS, might facilitate U(VI) reduction.« less

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U(VI) removed increased as the Si/Al ratios were increased. However, higher Ca concentrations correlated with higher U(VI) removal, ranging between 96% and 99%, at low Si/Al ratios. The SEM images of dried precipitates displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentages. The formation of uranyl silicate and carbonate minerals was also predicted by the speciation modeling. XRD analysis revealed the presence of uranyl carbonate mineral phases (andersonite, grimselite); however, uranyl silicates predicted (Na-boltwoodite) were not identified experimentally, possibly due to the amorphous nature of the silica solid phases observed in our experiments.« less

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH 3 gas

DOE PAGES

Katsenovich, Yelena; Cardona, Claudia; Szecsody, Jim; ...

2018-03-06

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NHmore » 3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH 3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al 3+, HCO 3 -, and Ca 2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO 3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca 2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5 mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca 2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U(VI) removed increased as the Si/Al ratios were increased. However, higher Ca concentrations correlated with higher U(VI) removal, ranging between 96% and 99%, at low Si/Al ratios. The SEM images of dried precipitates displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentages. The formation of uranyl silicate and carbonate minerals was also predicted by the speciation modeling. XRD analysis revealed the presence of uranyl carbonate mineral phases (andersonite, grimselite); however, uranyl silicates predicted (Na-boltwoodite) were not identified experimentally, possibly due to the amorphous nature of the silica solid phases observed in our experiments.« less

Metaproteomics Identifies the Protein Machinery Involved in Metal and Radionuclide Reduction in Subsurface Microbiomes and Elucidates Mechanisms and U(VI) Reduction Immobilization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pfiffner, Susan M.; Löffler, Frank; Ritalahti, Kirsti

The overall goal for this funded project was to develop and exploit environmental metaproteomics tools to identify biomarkers for monitoring microbial activity affecting U speciation at U-contaminated sites, correlate metaproteomics profiles with geochemical parameters and U(VI) reduction activity (or lack thereof), elucidate mechanisms contributing to U(VI) reduction, and provide remediation project managers with additional information to make science-based site management decisions for achieving cleanup goals more efficiently. Although significant progress has been made in elucidating the microbiology contribution to metal and radionuclide reduction, the cellular components, pathway(s), and mechanisms involved in U trans-formation remain poorly understood. Recent advances in (meta)proteomicsmore » technology enable detailed studies of complex samples, including environmental samples, which differ between sites and even show considerable variability within the same site (e.g., the Oak Ridge IFRC site). Additionally, site-specific geochemical conditions affect microbial activity and function, suggesting generalized assessment and interpretations may not suffice. This research effort integrated current understanding of the microbiology and biochemistry of U(VI) reduction and capitalize on advances in proteomics technology made over the past few years. Field-related analyses used Oak Ridge IFRC field ground water samples from locations where slow-release substrate biostimulation has been implemented to accelerate in situ U(VI) reduction rates. Our overarching hypothesis was that the metabolic signature in environmental samples, as deciphered by the metaproteome measurements, would show a relationship with U(VI) reduction activity. Since metaproteomic and metagenomic characterizations were computationally challenging and time-consuming, we used a tiered approach that combines database mining, controlled laboratory studies, U(VI) reduction activity measurements, phylogenetic analyses, and gene expression studies to support the metaproteomics characterizations. Growth experiments of target microorganisms (Anaeromyxobacter, Shewanella, Geobacter) revealed tremendous respiratory versatility, as evidenced by the ability to utilize a range of electron donors (e.g. acetate, hydrogen, pyruvate, lactate, succinate, formate) and electron acceptors (e.g. nitrate, fumarate, halogenated phenols, ferric iron, nitrous oxide, etc.). In particular, the dissimilatory metabolic reduction of metals, including radionuclides, by target microorganisms spurred interest for in situ bioremediation of contaminated soils and sediments. Distinct c-type cytochrome expression patterns were observed in target microorganisms grown with the different electron acceptors. For each target microorganism, the core proteome covered almost all metabolic pathways represented by their corresponding pan-proteomes. Unique proteins were detected for each target microorganism, and their expression and possible functionalities were linked to specific growth conditions through proteomics measurements. Optimization of the proteomic tools included in-depth comprehensive metagenomic and metaproteomic analyses on a limited number of samples. The optimized metaproteomic analyses were then applied to Oak Ridge IFRC field samples from the slow-release substrate biostimulation. Metaproteomic analysis and pathway mapping results demonstrated the distinct effects of metal and non-metal growth conditions on the proteome expression. With these metaproteomic tools, we identified which previously hypothetical metabolic pathways were active during the analyzed time points of the slow release substrate biostimulation. Thus, we demonstrated the utility of these tools for site assessment, efficient implementation of bioremediation and long-term monitoring. This research of detailed protein analysis linked with metal reduction activity did (1) show that c-type cytochrome isoforms, previously associated with radionuclide reduction activity, are suitable biomarkers, (2) identify new biomarker targets for site assessment and bioremediation monitoring, and (3) provide new information about specific proteins and mechanisms involved in U(VI) reduction and immobilization. This expanded metagenomic and metaproteomic toolbox contributed to implementing science-driven site management with broad benefits to the DOE mission.« less

Understanding Uranium Behavior in a Reduced Aquifer

NASA Astrophysics Data System (ADS)

Janot, N.; Lezama-Pacheco, J. S.; Williams, K. H.; Bernier-Latmani, R.; Long, P. E.; Davis, J. A.; Fox, P. M.; Yang, L.; Giammar, D.; Cerrato, J. M.; Bargar, J.

2012-12-01

Uranium contamination of groundwater is a concern at several US Department of Energy sites, such Old Rifle, CO. Uranium transport in the environment is mainly controlled by its oxidation state, since oxidized U(VI) is relatively mobile, whereas U(IV) is relatively insoluble. Bio-remediation of contaminated aquifers aims at immobilizing uranium in a reduced form. Previous laboratory and field studies have shown that adding electron donor (lactate, acetate, ethanol) to groundwater stimulates the activity of metal- and sulfate-reducing bacteria, which promotes U(VI) reduction in contaminated aquifers. However, obtaining information on chemical and physical forms of U, Fe and S species for sediments biostimulated in the field, as well as kinetic parameters such as U(VI) reduction rate, is challenging due to the low concentration of uranium in the aquifers (typically < 10 ppm) and the expense of collecting large number of cores. An in-situ technique has been developed for studying uranium, iron and sulfur reduction dynamics during such bioremediation episodes. This technique uses in-well columns to obtain direct access to chemical and physical forms of U(IV) produced in the aquifer, evolving microbial communities, and trace and major ion groundwater constituents. While several studies have explored bioreduction of uranium under sulfate-reducing conditions, less attention has been paid to the initial iron-reducing phase, noted as being of particular importance to uranium removal. The aim of this work was to assess the formation of U(IV) during the early stages of a bio-remediation experiment at the Old Rifle site, CO, from early iron-reducing conditions to the transition to sulfate-reducing conditions. Several in-well chromatographic columns packed with sediment were deployed and were sampled at different days after the start of bio-reduction. X-ray absorption spectroscopy and X-ray microscopy were used to obtain information on Fe, S and U speciation and distribution. Chemical extractions of the reduced sediments have also been performed, to determine the rate of Fe(II) and U(IV) accumulation.

Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

Reduction of uranium by Desulfovibrio desulfuricans

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.

1992-01-01

The possibility that sulfate-reducing microorganisms contribute to U(VI) reduction in sedimentary environments was investigated. U(VI) was reduced to U(IV) when washed cells of sulfate-grown Desulfovibrio desulfuricans were suspended in a bicarbonate buffer with lactate or H2 as the electron donor. There was no U(VI) reduction in the absence of an electron donor or when the cells were killed by heat prior to the incubation. The rates of U(VI) reduction were comparable to those in respiratory Fe(III)-reducing microorganisms. Azide or prior exposure of the cells to air did not affect the ability of D. desulfuricans to reduce U(VI). Attempts to grow D. desulfuricans with U(VI) as the electron acceptor were unsuccessful. U(VI) reduction resulted in the extracellular precipitation of the U(IV) mineral uraninite. The presence of sulfate had no effect on the rate of U(VI) reduction. Sulfate and U(VI) were reduced simultaneously. Enzymatic reduction of U(VI) by D. desulfuricans was much faster than nonenzymatic reduction of U(VI) by sulfide, even when cells of D. desulfuricans were added to provide a potential catalytic surface for the nonenzymatic reaction. The results indicate that enzymatic U(VI) reduction by sulfate-reducing microorganisms may be responsible for the accumulation of U(IV) in sulfidogenic environments. Furthermore, since the reduction of U(VI) to U(IV) precipitates uranium from solution, D. desulfuricans might be a useful organisms for recovering uranium from contaminated waters and waste streams.

BeerOz, a set of Matlab routines for the quantitative interpretation of spectrophotometric measurements of metal speciation in solution

NASA Astrophysics Data System (ADS)

Brugger, Joël

2007-02-01

The modelling of the speciation and mobility of metals under surface and hydrothermal conditions relies on the availability of accurate thermodynamic properties for all relevant minerals, aqueous species, gases and surface species. Spectroscopic techniques obeying the Beer-Lambert law can be used to obtain thermodynamic properties for reactions among aqueous species (e.g., ligand substitution; protonation). BeerOz is a set of Matlab routines designed to perform both qualitative and quantitative analysis of spectroscopic data following the Beer-Lambert law. BeerOz is modular and can be customised for particular experimental strategies or for simultaneous refinement of several datasets obtained using different techniques. Distribution of species calculations are performed using an implementation of the EQBRM code, which allows for customised activity coefficient calculations. BeerOz also contains routines to study the n-dimensional solution space, in order to provide realistic estimates of errors and test for the existence of multiple local minima and correlation between the different refined variables. The paper reviews the physical principles underlying the qualitative and quantitative analysis of spectroscopic data collected on aqueous speciation, in particular for studying successive ligand replacement reactions, and presents the non-linear least-squares algorithm implemented in BeerOz. The discussion is illustrated using UV-Vis spectra collected on acidic Fe(III) solutions containing varying LiCl concentrations, and showing the change from the hexaaquo Fe(H 2O) 63+ complex to the tetrahedral FeCl 4- complex.

Subsurface Uranium Fate and Transport: Integrated Experiments and Modeling of Coupled Biogeochemical Mechanisms of Nanocrystalline Uraninite Oxidation by Fe(III)-(hydr)oxides - Project Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peyton, Brent M.; Timothy, Ginn R.; Sani, Rajesh K.

2013-08-14

Subsurface bacteria including sulfate reducing bacteria (SRB) reduce soluble U(VI) to insoluble U(IV) with subsequent precipitation of UO 2. We have shown that SRB reduce U(VI) to nanometer-sized UO 2 particles (1-5 nm) which are both intra- and extracellular, with UO 2 inside the cell likely physically shielded from subsequent oxidation processes. We evaluated the UO 2 nanoparticles produced by Desulfovibrio desulfuricans G20 under growth and non-growth conditions in the presence of lactate or pyruvate and sulfate, thiosulfate, or fumarate, using ultrafiltration and HR-TEM. Results showed that a significant mass fraction of bioreduced U (35-60%) existed as a mobile phasemore » when the initial concentration of U(VI) was 160 µM. Further experiments with different initial U(VI) concentrations (25 - 900 M) in MTM with PIPES or bicarbonate buffers indicated that aggregation of uraninite depended on the initial concentrations of U(VI) and type of buffer. It is known that under some conditions SRB-mediated UO 2 nanocrystals can be reoxidized (and thus remobilized) by Fe(III)-(hydr)oxides, common constituents of soils and sediments. To elucidate the mechanism of UO 2 reoxidation by Fe(III) (hydr)oxides, we studied the impact of Fe and U chelating compounds (citrate, NTA, and EDTA) on reoxidation rates. Experiments were conducted in anaerobic batch systems in PIPES buffer. Results showed EDTA significantly accelerated UO 2 reoxidation with an initial rate of 9.5 M day-1 for ferrihydrite. In all cases, bicarbonate increased the rate and extent of UO 2 reoxidation with ferrihydrite. The highest rate of UO 2 reoxidation occurred when the chelator promoted UO 2 and Fe(III) (hydr)oxide dissolution as demonstrated with EDTA. When UO 2 dissolution did not occur, UO 2 reoxidation likely proceeded through an aqueous Fe(III) intermediate as observed for both NTA and citrate. To complement to these laboratory studies, we collected U-bearing samples from a surface seep at the Rifle field site and have measured elevated U concentrations in oxic iron-rich sediments. To translate experimental results into numerical analysis of U fate and transport, a reaction network was developed based on Sani et al. (2004) to simulate U(VI) bioreduction with concomitant UO 2 reoxidation in the presence of hematite or ferrihydrite. The reduction phase considers SRB reduction (using lactate) with the reductive dissolution of Fe(III) solids, which is set to be microbially mediated as well as abiotically driven by sulfide. Model results show the oxidation of HS– by Fe(III) directly competes with UO 2 reoxidation as Fe(III) oxidizes HS– preferentially over UO 2. The majority of Fe reduction is predicted to be abiotic, with ferrihydrite becoming fully consumed by reaction with sulfide. Predicted total dissolved carbonate concentrations from the degradation of lactate are elevated (log(pCO 2) ~ –1) and, in the hematite system, yield close to two orders-of-magnitude higher U(VI) concentrations than under initial carbonate concentrations of 3 mM. Modeling of U(VI) bioreduction with concomitant reoxidation of UO 2 in the presence of ferrihydrite was also extended to a two-dimensional field-scale groundwater flow and biogeochemically reactive transport model for the South Oyster site in eastern Virginia. This model was developed to simulate the field-scale immobilization and subsequent reoxidation of U by a biologically mediated reaction network.« less

Uranium aqueous speciation in the vicinity of the former uranium mining sites using the diffusive gradients in thin films and ultrafiltration techniques.

PubMed

Drozdzak, Jagoda; Leermakers, Martine; Gao, Yue; Elskens, Marc; Phrommavanh, Vannapha; Descostes, Michael

2016-03-24

The performance of the Diffusive Gradients in Thin films (DGT) technique with Chelex(®)-100, Metsorb™ and Diphonix(®) as binding phases was evaluated in the vicinity of the former uranium mining sites of Chardon and L'Ecarpière (Loire-Atlantique department in western France). This is the first time that the DGT technique with three different binding agents was employed for the aqueous U determination in the context of uranium mining environments. The fractionation and speciation of uranium were investigated using a multi-methodological approach using filtration (0.45 μm, 0.2 μm), ultrafiltration (500 kDa, 100 kDa and 10 kDa) coupled to geochemical speciation modelling (PhreeQC) and the DGT technique. The ultrafiltration data showed that at each sampling point uranium was present mostly in the 10 kDa truly dissolved fraction and the geochemical modelling speciation calculations indicated that U speciation was markedly predominated by CaUO2(CO3)3(2-). In natural waters, no significant difference was observed in terms of U uptake between Chelex(®)-100 and Metsorb™, while similar or inferior U uptake was observed on Diphonix(®) resin. In turn, at mining influenced sampling spots, the U accumulation on DGT-Diphonix(®) was higher than on DGT-Chelex(®)-100 and DGT-Metsorb™, probably because their performance was disturbed by the extreme composition of the mining waters. The use of Diphonix(®) resin leads to a significant advance in the application and development of the DGT technique for determination of U in mining influenced environments. This investigation demonstrated that such multi-technique approach provides a better picture of U speciation and enables to assess more accurately the potentially bioavailable U pool. Copyright © 2016 Elsevier B.V. All rights reserved.

Uranium(VI) Reduction by Anaeromyxobacter dehalogenans Strain 2CP-C

PubMed Central

Wu, Qingzhong; Sanford, Robert A.; Löffler, Frank E.

2006-01-01

Previous studies demonstrated growth of Anaeromyxobacter dehalogenans strain 2CP-C with acetate or hydrogen as the electron donor and Fe(III), nitrate, nitrite, fumarate, oxygen, or ortho-substituted halophenols as electron acceptors. In this study, we explored and characterized U(VI) reduction by strain 2CP-C. Cell suspensions of fumarate-grown 2CP-C cells reduced U(VI) to U(IV). More-detailed growth studies demonstrated that hydrogen was the required electron donor for U(VI) reduction and could not be replaced by acetate. The addition of nitrate to U(VI)-reducing cultures resulted in a transitory increase in U(VI) concentration, apparently caused by the reoxidation of reduced U(IV), but U(VI) reduction resumed following the consumption of N-oxyanions. Inhibition of U(VI) reduction occurred in cultures amended with Fe(III) citrate, or citrate. In the presence of amorphous Fe(III) oxide, U(VI) reduction proceeded to completion but the U(VI) reduction rates decreased threefold compared to control cultures. Fumarate and 2-chlorophenol had no inhibitory effects on U(VI) reduction, and both electron acceptors were consumed concomitantly with U(VI). Since cocontaminants (e.g., nitrate, halogenated compounds) and bioavailable ferric iron are often encountered at uranium-impacted sites, the metabolic versatility makes Anaeromyxobacter dehalogenans a promising model organism for studying the complex interaction of multiple electron acceptors in U(VI) reduction and immobilization. PMID:16672509

Impact of different environmental conditions on the aggregation of biogenic U(IV) nanoparticles synthesized by Desulfovibrio alaskensis G20

DOE Office of Scientific and Technical Information (OSTI.GOV)

Şengör, S. Sevinç; Singh, Gursharan; Dohnalkova, Alice

This study investigates the impact of specific environmental conditions on the formation of colloidal U(IV) nanoparticles by the sulfate reducing bacteria (SRB, Desulfovibrio alaskensis G20). The reduction of soluble U(VI) to less soluble U(IV) was quantitatively investigated under growth and non-growth conditions in bicarbonate or 1,4-piperazinediethanesulfonic acid (PIPES) buffered environments. The results showed that under non-growth conditions, the majority of the reduced U nanoparticles aggregated and precipitated out of solution. High resolution transmission electron microscopy revealed that only a very small fraction of cells had reduced U precipitates in the periplasmic spaces in the presence of PIPES buffer, whereas inmore » the presence of bicarbonate buffer, reduced U was also observed in the cytoplasm with greater aggregation of biogenic U(IV) particles at higher initial U(VI) concentrations. The same experiments were repeated under growth conditions using two different electron donors (lactate and pyruvate) and three electron acceptors (sulfate, fumarate, and thiosulfate). In contrast to the results of the non-growth experiments, even after 0.2 m filtration, the majority of biogenic U(IV) remained in the aqueous phase resulting in potentially mobile biogenic U(IV) nanoparticles. Size fractionation results showed that U(IV) aggregates were between 18 and 200 nm in diameter, and thus could be very mobile. The findings of this study are helpful to assess the size and potential mobility of reduced U nanoparticles under different environmental conditions, and would provide insights on their potential impact affecting U(VI) bioremediation efforts at subsurface contaminated sites.« less

The unexpected teratogenicity of RXR antagonist UVI3003 via activation of PPARγ in Xenopus tropicalis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Jingmin

2017-01-01

The RXR agonist (triphenyltin, TPT) and the RXR antagonist (UVI3003) both show teratogenicity and, unexpectedly, induce similar malformations in Xenopus tropicalis embryos. In the present study, we exposed X. tropicalis embryos to UVI3003 in seven specific developmental windows and identified changes in gene expression. We further measured the ability of UVI3003 to activate Xenopus RXRα (xRXRα) and PPARγ (xPPARγ) in vitro and in vivo. We found that UVI3003 activated xPPARγ either in Cos7 cells (in vitro) or Xenopus embryos (in vivo). UVI3003 did not significantly activate human or mouse PPARγ in vitro; therefore, the activation of Xenopus PPARγ by UVI3003more » is novel. The ability of UVI3003 to activate xPPARγ explains why UVI3003 and TPT yield similar phenotypes in Xenopus embryos. Our results indicate that activating PPARγ leads to teratogenic effects in Xenopus embryos. More generally, we infer that chemicals known to specifically modulate mammalian nuclear hormone receptors cannot be assumed to have the same activity in non-mammalian species, such as Xenopus. Rather they must be tested for activity and specificity on receptors of the species in question to avoid making inappropriate conclusions. - Highlights: • UVI3003 is a RXRs antagonist and shows teratogenicity to Xenopus embryos. • UVI3003 activated xPPARγ either in Cos7 cells or Xenopus embryos. • UVI3003 did not activate human or mouse PPARγ in Cos7 cells. • Activating PPARγ leads to teratogenic effects in Xenopus embryos.« less

Efficacy of a novel chelator BPCBG for removing uranium and protecting against uranium-induced renal cell damage in rats and HK-2 cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bao, Yizhong; Wang, Dan; Li, Zhiming

2013-05-15

Chelation therapy is a known effective method to increase the excretion of U(VI) from the body. Until now, no any uranium chelator has been approved for emergency medical use worldwide. The present study aimed to evaluate the efficacy of new ligand BPCBG containing two catechol groups and two aminocarboxylic acid groups in decorporation of U(VI) and protection against acute U(VI) nephrotoxicity in rats, and further explored the detoxification mechanism of BPCBG for U(VI)-induced nephrotoxicity in HK-2 cells with comparison to DTPA-CaNa{sub 3}. Chelating agents were administered at various times before or after injections of U(VI) in rats. The U(VI) levelsmore » in urine, kidneys and femurs were measured 24 h after U(VI) injections. Histopathological changes in the kidney and serum urea and creatinine and urine protein were examined. After treatment of U(VI)-exposed HK-2 cells with chelating agent, the intracellular U(VI) contents, formation of micronuclei, lactate dehydrogenase (LDH) activity and production of reactive oxygen species (ROS) were assessed. It was found that prompt, advanced or delayed injections of BPCBG effectively increased 24 h-urinary U(VI) excretion and decreased the levels of U(VI) in kidney and bone. Meanwhile, BPCBG injection obviously reduced the severity of the U(VI)-induced histological alterations in the kidney, which was in parallel with the amelioration noted in serum indicators, urea and creatinine, and urine protein of U(VI) nephrotoxicity. In U(VI)-exposed HK-2 cells, immediate and delayed treatment with BPCBG significantly decreased the formation of micronuclei and LDH release by inhibiting the cellular U(VI) intake, promoting the intracellular U(VI) release and inhibiting the production of intracellular ROS. Our data suggest that BPCBG is a novel bi-functional U(VI) decorporation agent with a better efficacy than DTPA-CaNa{sub 3}. - Highlights: ► BPCBG accelerated the urine U(VI) excretion and reduced the tissues U(VI) in rats. ► BPCBG can effectively protect against the U(VI)-induced nephrotoxicity in rats. ► BPCBG increased the U(VI) release and reduced the U(VI) uptake in HK-2 cells. ► BPCBG decreased the U(VI)-induced MN formation and LDH release in HK-2 cells. ► BPCBG eliminated the U(VI)-induced intracellular ROS in HK-2 cells.« less

EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wolery, T.J.

1992-09-14

EQ3NR is an aqueous solution speciation-solubility modeling code. It is part of the EQ3/6 software package for geochemical modeling. It computes the thermodynamic state of an aqueous solution by determining the distribution of chemical species, including simple ions, ion pairs, and complexes, using standard state thermodynamic data and various equations which describe the thermodynamic activity coefficients of these species. The input to the code describes the aqueous solution in terms of analytical data, including total (analytical) concentrations of dissolved components and such other parameters as the pH, pHCl, Eh, pe, and oxygen fugacity. The input may also include a desiredmore » electrical balancing adjustment and various constraints which impose equilibrium with special pure minerals, solid solution end-member components (of specified mole fractions), and gases (of specified fugacities). The code evaluates the degree of disequilibrium in terms of the saturation index (SI = 1og Q/K) and the thermodynamic affinity (A = {minus}2.303 RT log Q/K) for various reactions, such as mineral dissolution or oxidation-reduction in the aqueous solution itself. Individual values of Eh, pe, oxygen fugacity, and Ah (redox affinity) are computed for aqueous redox couples. Equilibrium fugacities are computed for gas species. The code is highly flexible in dealing with various parameters as either model inputs or outputs. The user can specify modification or substitution of equilibrium constants at run time by using options on the input file.« less

Polynuclear Speciation of Trivalent Cations near the Surface of an Electrolyte Solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bera, Mrinal K.; Antonio, Mark R.

Despite long-standing efforts, there is no agreed upon structural model for electrolyte solutions at air-liquid interfaces. We report the simultaneous detection of the near-surface and bulk coordination environments of a trivalent metal cation (europium) in an aqueous solution by use of X-ray absorption spectroscopy. Within the first few nanometers of the liquid surface, the cations exhibit oxygen coordination typical of inner-sphere hydration of an aquated Eu3+ cation. Beyond that, outer-sphere ion-ion correlations are observed that are otherwise not present in the bulk electrolyte. The combination of near-surface and bulk sensitivities to probe metal ion speciation in electrolyte solutions is achievedmore » by detecting electron-yield and X-ray fluorescence signals from an inverted pendant drop. The results provide new knowledge about the near-surface chemistry of aqueous solutions of relevance to aerosols and ion transport processes in chemical separations and biological systems.« less

Effect of Humic Substances on the Trapping and Transformations of U(VI) by Ferrihydrite

NASA Astrophysics Data System (ADS)

Dublet, G.; Brown, G. E.; Bargar, J.; Fendorf, S. E.; Janot, N.

2013-12-01

The Old Rifle DOE site in Colorado was a major site for milling uranium ore. U concentrations up to 1.8 uM persist in the Rifle aquifer, even after 'cleaning' the waste source of contaminations [1]. Understanding the behavior of U(VI) in this anthropogenically perturbed system is crucial for controlling the level of U contamination. Direct investigations of U speciation at this site have shown that U is associated with a wide variety of minerals as well as with natural organic matter (NOM) [2]. NOM has multiple functional groups which can be highly reactive with respect to aqueous metal ions, including actinides. Such interactions result in the formation of organo-mineral-metal (ternary) complexes and catalyze redox transformations; in addition, they can enhance mineral dissolution and metal transport [3,4,5]. In the complex soil/sediment system, aqueous, mineral, and organic phases are intimately mixed and their interactions are difficult to characterize by direct investigation [1]. The nanoparticulate iron hydroxide ferrihydrite (Fh), which is ubiquitous in many natural soils and highly reactive toward metal ions, is expected to significantly influence the fate of U in natural soils and is abundant in the subsurface at the Rifle site. NOM is also abundant at this site; however, little is known about the effect of NOM associated with ferrihydrite on the fate of U in such subsurface environments. To date, simple model systems composed mainly of two components (Fh and NOM) [6], (U and NOM or simple organic molecules) [7], or (Fh and U) [8,9], and more rarely composed of three components [10,11] have been studied in an effort to understand interactions among these components. In order to extend this earlier work to ternary systems, we have carried out batch reactions of U, a humic acid standard - Eliott soil humic acid (ESHA), and Fh under conditions that mimic those in the subsurface at Rifle. We have used U L3- and Fe K-edge XANES and EXAFS spectroscopy coupled with macroscopic uptake measurements to study the effect of this model humic acid on U uptake by Fh in these batch experimental systems. Results from this study will be presented and discussed mainly in terms of the affinity of U towards ESHA vs. Fh under the different conditions tested. [1] Campbell K.M. et al. (2012) Applied Geochemistry 27, 1499-1511 [2] Maher K. et al. (2012) Inorganic Chemistry 52, 3510-3532. [3] Means J.L. and Crerar D.A. (1978) Science 200, 1477-1481 [4] Ludwig C. et al. (1995) Nature 375, 44-47 [5] Gu B. et al. (2005) 39, 5268-5275 [6] Stewart B.D. et al. (2009) Environmental Science & Technology 43, 4922-4927 [7] Sachs S. and Bernhard G. (2011) Journal of Radioanalytical and Nuclear Chemistry 290, 17-29 [8] Nico P.S. et al. (2009) Environmental Science & Technology 43, 7391-7396 [9] Boland D.D. et al. (2011) Environmental Science & Technology 45, 1327-1333 [10] Gustafsson J.P. et al. (2009) Applied Geochemistry 24, 454-462 [11] Payne T.E. et al. (1996) Radiochimica Acta 74, 239-243

Application of ESI-HRMS for molybdenum speciation in natural waters: An investigation of molybdate-halide reactions.

PubMed

Dang, Duc Huy; Evans, R Douglas

2018-03-01

High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdate in interaction with halides (Cl, F, Br). Desolvation during electrospray ionization induced alteration of aqueous species but method optimization successfully suppressed artefact compounds. At low Mo concentrations, chloro(oxo)molybdate and fluoro(oxo)molybdate species were found and in natural samples, MoO 3 Cl was detected for the first time, to the best of our knowledge. Apparent equilibrium constants for Cl substitution on molybdate were calculated for a range of pH values from 4.5 to 8.5. A minor alteration in speciation during the gas phase (conversion of doubly charged MoO 4 2- to HMoO 4 - ) did not allow investigation of the molybdate acid-base properties; however this could be determined by speciation modeling. This study provides further evidence that ESI-HRMS is a fast and suitable tool to Deceasedassess the speciation of inorganic compounds such as Mo. Copyright © 2017 Elsevier B.V. All rights reserved.

Modulation of Medium pH by Caulobacter crescentus Facilitates Recovery from Uranium-Induced Growth Arrest

PubMed Central

Park, Dan M.

2014-01-01

The oxidized form of uranium [U(VI)] predominates in oxic environments and poses a major threat to ecosystems. Due to its ability to mineralize U(VI), the oligotroph Caulobacter crescentus is an attractive candidate for U(VI) bioremediation. However, the physiological basis for U(VI) tolerance is unclear. Here we demonstrated that U(VI) caused a temporary growth arrest in C. crescentus and three other bacterial species, although the duration of growth arrest was significantly shorter for C. crescentus. During the majority of the growth arrest period, cell morphology was unaltered and DNA replication initiation was inhibited. However, during the transition from growth arrest to exponential phase, cells with shorter stalks were observed, suggesting a decoupling between stalk development and the cell cycle. Upon recovery from growth arrest, C. crescentus proliferated with a growth rate comparable to that of a control without U(VI), although a fraction of these cells appeared filamentous with multiple replication start sites. Normal cell morphology was restored by the end of exponential phase. Cells did not accumulate U(VI) resistance mutations during the prolonged growth arrest, but rather, a reduction in U(VI) toxicity occurred concomitantly with an increase in medium pH. Together, these data suggest that C. crescentus recovers from U(VI)-induced growth arrest by reducing U(VI) toxicity through pH modulation. Our finding represents a unique U(VI) detoxification strategy and provides insight into how microbes cope with U(VI) under nongrowing conditions, a metabolic state that is prevalent in natural environments. PMID:25002429

Using High Performance Computing to Understand Roles of Labile and Nonlabile U(VI) on Hanford 300 Area Plume Longevity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichtner, Peter C.; Hammond, Glenn E.

Evolution of a hexavalent uranium [U(VI)] plume at the Hanford 300 Area bordering the Columbia River is investigated to evaluate the roles of labile and nonlabile forms of U(VI) on the longevity of the plume. A high fidelity, three-dimensional, field-scale, reactive flow and transport model is used to represent the system. Richards equation coupled to multicomponent reactive transport equations are solved for times up to 100 years taking into account rapid fluctuations in the Columbia River stage resulting in pulse releases of U(VI) into the river. The peta-scale computer code PFLOTRAN developed under a DOE SciDAC-2 project is employed inmore » the simulations and executed on ORNL's Cray XT5 supercomputer Jaguar. Labile U(VI) is represented in the model through surface complexation reactions and its nonlabile form through dissolution of metatorbernite used as a surrogate mineral. Initial conditions are constructed corresponding to the U(VI) plume already in place to avoid uncertainties associated with the lack of historical data for the waste stream. The cumulative U(VI) flux into the river is compared for cases of equilibrium and multirate sorption models and for no sorption. The sensitivity of the U(VI) flux into the river on the initial plume configuration is investigated. The presence of nonlabile U(VI) was found to be essential in explaining the longevity of the U(VI) plume and the prolonged high U(VI) concentrations at the site exceeding the EPA MCL for uranium.« less

In situ Bioreduction of Uranium (VI) in Groundwater and Sediments with Edible Oil as the Electron Donor

NASA Astrophysics Data System (ADS)

Wu, W.; Watson, D. B.; Mehlhorn, T.; Zhang, G.; Earles, J.; Lowe, K.; Phillips, J.; Boyanov, M.; Kemner, K. M.; Schadt, C. W.; Brooks, S. C.; Criddle, C.; Jardine, P.

2009-12-01

In situ bioremediation of a uranium-contaminated aquifer was conducted at the US DOE Environmental Remediation Sciences Program (ERSP) Integrated Field Research Challenge (IFRC) site, in Oak Ridge, TN. Edible oil was tested as a slow-release electron donor for microbially mediated U (VI) reduction. Uranium contaminated sediments from the site were used in laboratory microcosm tests to study the feasibility of using this electron donor under anaerobic, ambient temperature conditions. Parallel microcosms were established using ethanol as electron donor for comparison. The tests also examined the impact of sulfate concentrations on U (VI) reduction. The oil was degraded by indigenous microorganisms with acetate as a major product but at a much slower rate than ethanol. The rapid removal of U (VI) from the aqueous phase occurred concurrently with acetate production and sulfate reduction. Initial U(VI) concentration in the aqueous phase increased with increased sulfate concentration (1 vs. 5 mM), likely due to U(VI) desorption from the solid phase, but more U(VI) was reduced with higher initial sulfate level. Finally, the bioreaction in microcosms progressed to methanogenesis. Subsequently, a field test with the edible oil was conducted in a highly permeable gravelly layer (hydraulic conductivity 0.076 cm/sec). Groundwater at the site contained 5-6 μM U; 1.0-1.2 mM sulfate; 3-4 mM Ca; pH 6.8. Diluted emulsified oil (20% solution) was injected into three injection wells within 2 hrs. Geochemical analysis of site groundwater demonstrated the sequential reduction of nitrate, Mn, Fe(III) and sulfate. Transient accumulation of acetate was observed as an intermediate in the oil degradation. Reduction and removal of uranium from groundwater was observed in all wells connected to the injection wells after 2-4 weeks. Uranium concentrations in groundwater were reduced to below 0.126 μM (EPA drinking water standard), at some well locations. Rebound of U in groundwater was observed together with the rebound of sulfate concentrations as the oil was consumed. Uranium (VI) reduction to U (IV) in the microcosm and in situ field tests was confirmed by X-ray near-edge absorption spectroscopy analysis. Bacterial populations in microcosms and field samples were analyzed using 16S rRNA gene libraries and Geochip analysis.

Effect of pH and Fe/U ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2

NASA Astrophysics Data System (ADS)

Fu, Yukui; Luo, Yingfeng; Fang, Qi; Xie, Yanpei; Wang, Zhihong; Zhu, Xiangyu

2018-02-01

As for the decommissioned uranium deposits of acid in-situ leaching, both of the concentrations of U(VI) and Fe(II) are relatively high in groundwater. In the presence of O2, the oxidation of Fe(II) into Fe(III) that forms Fe-hydroxides could effectively remove U(VI) in the forms of sorption or co-precipitation. In this process, pH condition and Fe content will have a significant effect on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. In the present work, a series of batch experiments were carried out to investigate the effect of pH values and Fe/U mass ratio on the U(VI) removal rate by the synergistic effect of Fe(II) and O2. Experiment results show that the removal rate of U(VI) is mainly controlled by pH and secondly by Fe/U mass ratio. In the neutral conditions with pH at 7 and 8, the removal rate of U(VI) reaches up to 90% for all solutions with different initial Fe(II) concentrations. The optimal pH for the removal rate of U(VI) is above 7. In the acidic conditions with pH below 6, the effect of Fe/U mass ratio on the removal rate of U(VI) becomes more obvious and the optimal Fe/U mass ratio for U(VI) removal is 1:2.

THERMODYNAMIC REACTION CONSTANTS FOR MODELING AQUEOUS ENVIRONMENTAL MERCURY SPECIATION

EPA Science Inventory

Unacceptably high fish tissue mercury residues are responsible for the majority of fish consumption advisories issued in 48 states of the United States of America. Mercury also has emerged as a transboundary contaminant of global concern. Although monomethylmercury is generally...

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Diwu, Juan; Wang, Shuao; Good, Justin J.

2011-06-06

The heterobimetallic actinide compound UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O, UO₂Ce(H₂O)[C₆H₄(PO₃H)₂]₂·H₂O, and UO₂[C₆H₄(PO₃H)₂](H₂O)·H₂O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C₆H₄(PO₃H)₂]₂·2H₂O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U 0.9Pu 0.1)O₂[C₆H₄(PO₃H)₂](H₂O)·H₂O, and themore » Pu(IV) phosphonate, Pu[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Np) and M[C₆H₄(PO₃H)₂]₂·2H₂O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO₂[C₆H₄(PO₃H)₂](H₂O)·3H₂O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C₆H₄(PO₃H)(PO₃H₂)][C₆H₄(PO₃H)(PO₃)]·2H₂O (M = Np, Pu) and An[C₆H₄(PO₃H)₂]₂·2H₂O (M = Np, Pu) formulas.« less

Investigating In-Situ Mass Transfer Processes in a Groundwater U Plume Influenced by Groundwater-River Hydrologic and Geochemical Coupling (Invited)

NASA Astrophysics Data System (ADS)

Zachara, J. M.

2009-12-01

The Hanford Integrated Field Research Challenge (IFRC) site is a DOE/BER-supported experimental and monitoring facility focused on multi-scale mass transfer processes (hanfordifc@pnl.gov). It is located within the footprint of a historic uranium (U) waste disposal pond that overlies a contaminated vadose zone and a 1 km+ groundwater U plume. The plume is under a regulatory clean-up mandate. The site is in hydraulic connectivity with the Columbia River that is located approximately 300 m distant. Dramatic seasonal variations in Columbia River stage cause 2m+ variations in water table and associated changes in groundwater flow directions and composition that are believed to recharge contaminant U to the plume through lower vadose zone pumping. The 60 m triangular shaped facility contains 37 monitoring wells equipped with down-hole electrical resistance tomography electrode and thermistor arrays, pressure transducers for continual water level monitoring, and specific conductance electrodes. Well spacings allow cross-hole geophysical interrogation and dynamic plume monitoring. Various geophysical and hydrologic field characterizations were performed during and after well installation, and retrieved sediments are being subjected to a hierarchal laboratory characterization process to support geostatistical models of hydrologic properties, U(VI) distribution and speciation, and equilibrium and kinetic reaction parameters for robust but tractable field-scale reactive transport calculations. Three large scale (10,000 gal+), non-reactive tracer experiments have been performed to evaluate groundwater flowpaths and velocities, facies scale mass transfer, and subsurface heterogeneity effects under different hydrologic conditions (e.g., flow vectors toward or away from the river). A passive monitoring experiment was completed during spring and summer of 2009 that documents spatially variable U(VI) release and plume recharge from the contaminated lower vadose zone during oscillating rising and falling water table events. A large scale injection experiment to evaluate in situ U(VI) desorption kinetics controlled by mass transfer is planned for the fall of 2009. The presentation will summarize key results from these different activities, and discuss their implications to improved plume forecasting and development of an effective groundwater remedy.

Microbial communities biostimulated by ethanol during uranium (VI) bioremediation in contaminated sediment as shown by stable isotope probing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leigh, Mary Beth; Wu, Wei -Min; Cardenas, Erick

Stable isotope probing (SIP) was used to identify microbes stimulated by ethanol addition in microcosms containing two sediments collected from the bioremediation test zone at the US Department of Energy Oak Ridge site, TN, USA. One sample was highly bioreduced with ethanol while another was less reduced. Microcosms with the respective sediments were amended with 13C labeled ethanol and incubated for 7 days for SIP. Ethanol was rapidly converted to acetate within 24 h accompanied with the reduction of nitrate and sulfate. The accumulation of acetate persisted beyond the 7 d period. Aqueous U did not decline in the microcosmmore » with the reduced sediment due to desorption of U but continuously declined in the less reduced sample. Microbial growth and concomitant 13C-DNA production was detected when ethanol was exhausted and abundant acetate had accumulated in both microcosms. This coincided with U(VI) reduction in the less reduced sample. 13C originating from ethanol was ultimately utilized for growth, either directly or indirectly, by the dominant microbial community members within 7 days of incubation. The microbial community was comprised predominantly of known denitrifiers, sulfate-reducing bacteria and iron (III) reducing bacteria including Desulfovibrio, Sphingomonas, Ferribacterium, Rhodanobacter, Geothrix, Thiobacillus and others, including the known U(VI)-reducing bacteria Acidovorax, Anaeromyxobacter, Desulfovibrio, Geobacter and Desulfosporosinus. As a result, the findings suggest that ethanol biostimulates the U(VI)-reducing microbial community by first serving as an electron donor for nitrate, sulfate, iron (III) and U(VI) reduction, and acetate which then functions as electron donor for U(VI) reduction and carbon source for microbial growth.« less

Biogeochemical Modeling of In Situ U(VI) Reduction and Immobilization with Emulsified Vegetable Oil as the Electron Donor at a Field Site in Oak Ridge, Tennessee

NASA Astrophysics Data System (ADS)

Tang, G.; Parker, J.; Wu, W.; Schadt, C. W.; Watson, D. B.; Brooks, S. C.; Orifrc Team

2011-12-01

A comprehensive biogeochemical model was developed to quantitatively describe the coupled hydrologic, geochemical and microbiological processes that occurred following injection of emulsified vegetable oil (EVO) as the electron donor to immobilize U(VI) at the Oak Ridge Integrated Field Research Challenge site (ORIFRC) in Tennessee. The model couples the degradation of EVO, production and oxidation of long-chain fatty acids (LCFA), glycerol, hydrogen and acetate, reduction of nitrate, manganese, ferrous iron, sulfate and uranium, and methanoganesis with growth of multiple microbial groups. The model describes the evolution of geochemistry and microbial populations not only in the aqueous phase as typically observed, but also in the mineral phase and therefore enables us to evaluate the applicability of rates from the literature for field scale assessment, estimate the retention and degradation rates of EVO and LCFA, and assess the influence of the coupled processes on fate and transport of U(VI). Our results suggested that syntrophic bacteria or metal reducers might catalyze LCFA oxidation in the downstream locations when sulfate was consumed, and competition between methanogens and others for electron donors and slow growth of methanogen might contribute to the sustained reducing condition. Among the large amount of hydrologic, geochemical and microbiological parameter values, the initial biomass, and the interactions (e.g., inhibition) of the microbial functional groups, and the rate and extent of Mn and Fe oxide reduction appear as the major sources of uncertainty. Our model provides a platform to conduct numerical experiments to study these interactions, and could be useful for further iterative experimental and modeling investigations into the bioreductive immobiliztion of radionuclide and metal contaminants in the subsurface.

Precipitation and Dissolution of Uranyl Phosphates in a Microfluidic Pore Structure

NASA Astrophysics Data System (ADS)

Werth, C. J.; Fanizza, M.; Strathmann, T.; Finneran, K.; Oostrom, M.; Zhang, C.; Wietsma, T. W.; Hess, N. J.

2011-12-01

The abiotic precipitation of uranium (U(VI)) was evaluated in a microfluidic pore structure (i.e. micromodel) to assess the efficacy of using a phosphate amendment to immobilize uranium in groundwater and mitigate the risk of this contaminant to potential down-gradient receptor sites. U(VI) was mixed transverse to the direction of flow with hydrogen phosphate (HPO42-), in the presence or absence of calcium (Ca2+) or sulfate (SO42-), in order to identify precipitation rates, the morphology and types of minerals formed, and the stability of these minerals to dissolution with and without bicarbonate (HCO3-) present. Raman backscattering spectroscopy and micro X-ray diffraction (μ-XRD) results both showed that the only mineral precipitated was chernikovite (also known as hydrogen uranyl phosphate; UO2HPO4), even though the formation of other minerals were thermodynamically favored depending on the experimental conditions. Precipitation and dissolution rates varied with influent conditions. Relative to when only U(VI) and HPO42- were present, precipitation rates were 2.3 times slower when SO42- was present, and 1.4 times faster when Ca2+ was present. These rates were inversely related to the size of crystals formed during precipitation. Dissolution rates for chernikovite increased with increasing HCO3- concentrations, consistent with formation of uranyl carbonate complexes in aqueous solution, and they were the fastest for chernikovite formed in the presence of SO42-, and slowest for the chernikovite formed in the presence of Ca2+. These rates are related to the ratios of mineral-water interfacial area to mineral volume. Fluorescent tracer studies and laser confocal microscopy images showed that densely aggregated precipitates blocked pores and reduced permeability. The results suggest that changes in the solute conditions evaluated affect precipitation rates, crystal morphology, and crystal stability, but not mineral type.

HPLC separation post-column reaction, UV-visible and fluorescence detection of trace UO/sub 2//sup 2 +//U/sup 4 +/ species in aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Karimi, A.R.

In this study a method for the measurement of uranium in natural waters at sub-ppB concentration levels by the separation and determination of U/sup 4 +/ and UO/sub 2//sup 2 +/ species is proposed. Reversed phase high performance liquid chromatography, followed by a post-column reaction and a sensitive UV-visible detection system was the method of choice to determine qualitatively and quantitatively the two uranium species. Also a cation-exchange and fluorescence detection system was studied for separation and determination of UO/sub 2//sup 2 +/ ions. Uranyl ion was selectively complexed with L-phenylalanine moetie in the sample solution containing U/sup 4 +/more » ions. Uranium (IV)/U(VI)-ligand was separated on a C/sub 18/ column with acetate buffer. Hexanesulfonate was found to be the choice for ion-pair reagent. The separation was best done with the acetate buffer at .01 M concentration and pH of 3.5. Absorption of the two species were measured after a post-column reaction with Arsenazo-III. Chromatographic parameters were calculated and a calibration curves were constructed. The detection limit for the procedure was 0.7 ..mu..g/mo and 1.2..mu..g/ml for U(IV) and U(VI) respectively. When U(VI) was separated on the cation-exchange column the limit of detection was calculated to be 1 ..mu..g/ml. The direct fluorometric method for U(VI) measurement results in a detection limit of 2 ppB and upper concentration limit of 2 ppM. The effect of interfering ions in the direct method of determination could be eliminated by dilution of sample solution.« less

Equilibrium Speciation of Select Lanthanides in the Presence of Acidic Ligands in Homo- and Heterogeneous Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, Troy A

2011-08-01

This dissertation explores lanthanide speciation in liquid solution systems related to separation schemes involving the acidic ligands: bis(2-ethylhexyl) phosphoric acid (HDEHP), lactate, and 8-hydroxyquinoline. Equilibrium speciation of neodymium (Nd 3+), sodium (Na+), HDEHP, water, and lactate in the TALSPEAK liquid-liquid extraction system was explored under varied Nd 3+ loading of HDEHP in the organic phase and through extraction from aqueous HCl and lactate media. System speciation was probed through vapor pressure osmometry, visible and Fourier Transform Infrared (FTIR) spectroscopy, 22Na and 13C labeled lactate radiotracer distribution measurements, Karl Fischer titrations, and equilibrium pH measurements. Distribution of Nd 3+, Na +,more » lactate, and equilibrium pH were modeled using the SXLSQI software to obtain logKNd and logKNa extraction constants under selected conditions. Results showed that high Nd 3+ loading of the HDEHP led to Nd 3+ speciation that departs from the ion exchange mechanism and includes formation of highly aggregated, polynuclear [NdLactate(DEHP) 2] x; (with x > 1). By substituting lanthanum (La 3+) for Nd 3+ in this system, NMR scoping experiments using 23Na, 31P nuclei and 13C labeled lactate were performed. Results indicated that this technique is sensitive to changes in system speciation, and that further experiments are warranted. In a homogeneous system representing the TALSPEAK aqueous phase, Lactate protonation behavior at various temperatures was characterized using a combination of potentiometric titration and modeling with the Hyperquad computer program. The temperature dependent deprotonation behavior of lactate showed little change with temperature at 2.0 M NaCl ionic strength. Cloud point extraction is a non-traditional separation technique that starts with a homogeneous phase that becomes heterogeneous by the micellization of surfactants through the increase of temperature. To better understand the behavior of europium (Eu 3+) and 8-hydroxyquinoline under cloud point extraction conditions, potentiometric and spectrophotometric titrations coupled with modeling with Hyperquad and SQUAD computer programs were performed to assess europium (Eu 3+) and 8-hydroxyquinoline speciation. Experiments in both water and a 1wt% Triton X-114/water mixed solvent were compared to understand the effect of Triton X-114 on the system speciation. Results indicated that increased solvation of 8-hydroxyquinoline by the mixed solvent lead to more stable complexes involving 8-hydroxyquinoline than in water, whereas competition between hydroxide and Triton X-114 for Eu 3+ led to lower stability hydrolysis complexes in the mixed solvent than in water. Lanthanide speciation is challenging due to the trivalent oxidation state that leads to multiple ligand complexes, including some mixed complexes. The complexity of the system demands well-designed and precise experiments that capture the nuances of the chemistry. This work increased the understanding of lanthanide speciation in the explored systems, but more work is required to produce a comprehensive understanding of the speciation involved.« less

Arsenic Speciation and Cadmium Determination in Tobacco Leaves, Ash and Smoke.

PubMed

Iwai, Takahiro; Chiba, Koichi; Narukawa, Tomohiro

2016-01-01

The concentrations of arsenic (As) and cadmium (Cd) in the tobacco leaves, ash and smoke of 10 kinds of cigarettes collected from different countries worldwide were determined by ICP-MS after microwave-assisted digestion. Total As and Cd concentrations in the tobacco leaves ranged from 0.20 to 0.63 and 1.8 to 9.9 mg kg(-1), respectively. By the speciation analysis of As in tobacco leaves and ash by HPLC-ICP-MS following acid extraction, arsenite [As(III)] and arsenate [As(V)] were determined and trace amounts of monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), trimethylarsine oxide (TMAO), tetramethylarsonium (TeMA) and some unidentified As species were also found. Arsenic speciation for smoke absorbed in an aqueous solution was carried out. The sum of the As species in tobacco leaves, ash and smoke was in good agreement with the result of total As determination in each sample, and the recoveries of speciation were 100 ± 10%. The distributions and the behaviors of As species were clarified.

Arsenic speciation and sorption in natural environments

USGS Publications Warehouse

Campbell, Kate M.; Nordstrom, D. Kirk

2014-01-01

Aqueous arsenic speciation, or the chemical forms in which arsenic exists in water, is a challenging, interesting, and complicated aspect of environmental arsenic geochemistry. Arsenic has the ability to form a wide range of chemical bonds with carbon, oxygen, hydrogen, and sulfur, resulting in a large variety of compounds that exhibit a host of chemical and biochemical properties. Besides the intriguing chemical diversity, arsenic also has the rare capacity to capture our imaginations in a way that few elements can duplicate: it invokes images of foul play that range from sinister to comedic (e.g., “inheritance powder” and arsenic-spiked elderberry wine). However, the emergence of serious large-scale human health problems from chronic arsenic exposure in drinking water has placed a high priority on understanding environmental arsenic mobility, toxicity, and bioavailability, and chemical speciation is key to these important questions. Ultimately, the purpose of arsenic speciation research is to predict future occurrences, mitigate contamination, and provide successful management of water resources.

REE speciation in low-temperature acidic waters and the competitive effects of aluminum

USGS Publications Warehouse

Gimeno, Serrano M.J.; Auque, Sanz L.F.; Nordstrom, D. Kirk

2000-01-01

The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength. Geochim. Cosmochim. Acta, 56, 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions. (C) 2000 Elsevier Science B.V. All rights reserved.

Phosphate-Induced Immobilization of Uranium in Hanford Sediments.

PubMed

Pan, Zezhen; Giammar, Daniel E; Mehta, Vrajesh; Troyer, Lyndsay D; Catalano, Jeffrey G; Wang, Zheming

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred only at high initial U(VI) (>25 μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.

Phosphate-Induced Immobilization of Uranium in Hanford Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Zezhen; Giammar, Daniel E.; Mehta, Vrajesh

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred onlymore » at high initial U(VI) (>25 μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.« less

Phosphate-Induced Immobilization of Uranium in Hanford Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Zezhen; Giammar, Daniel E.; Mehta, Vrajesh

2016-12-20

Phosphate can be added to subsurface environments to immobilize U(VI) contamination. The efficacy of immobilization depends on the site-specific groundwater chemistry and aquifer sediment properties. Batch and column experiments were performed with sediments from the Hanford 300 Area in Washington State and artificial groundwater prepared to emulate the conditions at the site. Batch experiments revealed enhanced U(VI) sorption with increasing phosphate addition. X-ray absorption spectroscopy measurements of samples from the batch experiments found that U(VI) was predominantly adsorbed at conditions relevant to the column experiments and most field sites (low U(VI) loadings, <25 μM), and U(VI) phosphate precipitation occurred onlymore » at high initial U(VI) (>25μM) and phosphate loadings. While batch experiments showed the transition of U(VI) uptake from adsorption to precipitation, the column study was more directly relevant to the subsurface environment because of the high solid:water ratio in the column and the advective flow of water. In column experiments, nearly six times more U(VI) was retained in sediments when phosphate-containing groundwater was introduced to U(VI)-loaded sediments than when the groundwater did not contain phosphate. This enhanced retention persisted for at least one month after cessation of phosphate addition to the influent fluid. Sequential extractions and laser-induced fluorescence spectroscopy of sediments from the columns suggested that the retained U(VI) was primarily in adsorbed forms. These results indicate that in situ remediation of groundwater by phosphate addition provides lasting benefit beyond the treatment period via enhanced U(VI) adsorption to sediments.« less

Characterization of the biochemical-pathway of uranium (VI) reduction in facultative anaerobic bacteria.

PubMed

Mtimunye, Phalazane J; Chirwa, Evans M N

2014-10-01

Cultures of U(VI) reducing bacteria sourced from abandoned uranium mine tailing dam were evaluated for their ability to reduce U(VI) to U(IV). The species in the cultures reduced U(VI) in solutions with initial U(VI) concentration up to 400mgL(-)(1) under a near neutral pH of 6.5. The electron flow pathway and fate of reduced species was also analysed in the individual species in order to evaluate the potential for control and optimisation of the reduction potential at the biochemical level. The results showed that U(VI) reduction in live cells was completely blocked by the NADH-dehydrogenase inhibitor, rotenone (C23H22O6), and thioredoxin inhibitor, cadmium chloride (CdCl2), showing that U(VI) reduction involves the electron flow through NADH-dehydrogenase, a primary electron donor to the electron transport respiratory (ETR) system. Mass balance analysis of uranium species aided by visual and electron microscopy suggest that most U(VI) reduction occurred on the cell surface of the isolated species. This finding indicates the possibility of easy uranium recovery for beneficial use through biological remediation. Should the U(VI) be reduced inside the cell, recovery would require complete disruption of the cells and therefore would be difficult. The study contributes new knowledge on the underlying mechanisms in the U(VI) reduction in facultative anaerobes. Copyright © 2014 Elsevier Ltd. All rights reserved.

The adsorption behavior of U(VI) on granite.

PubMed

Fan, Q H; Hao, L M; Wang, C L; Zheng, Z; Liu, C L; Wu, W S

2014-03-01

The effects of pH, counter ions and temperature on the adsorption of U(VI) on Beishan granite (BsG) were investigated in the presence and absence of fulvic acid (FA) and humic acid (HA). The adsorption edge of U(VI) on BsG suggested that U(VI) adsorption was mainly controlled by ion exchange and outer-sphere complexation at low pH, whereas inner-sphere complex was the dominant adsorption species in the pH range of 4.0-9.0. Above pH 9.0, Na2U2O7 might play an important role in the rise of U(VI) adsorption again. Counter ions such as Cl(-), SO4(2-) and PO4(3-) can provoke U(VI) adsorption on BsG to some extent, which was directly correlated to the complexing ability of U(VI)-ligand. More noticeably, the large enhancement of U(VI) adsorption in the presence of phosphate can be attributed to the ternary complex formation (BsG-PO4-UO2), precipitation ((UO2)3(PO4)2(s)) and secondary phase (Na-autunite). Both FA and HA can slightly increase U(VI) adsorption at low pH, whereas they strongly inhibited U(VI) adsorption at high pH range. Artificial synthesized granite (AsG) prepared in the laboratory is impossible to use as an analogue of natural granite because of the large difference in the adsorption and surface properties.

Total electron acceptor loading and composition affect hexavalent uranium reduction and microbial community structure in a membrane biofilm reactor.

PubMed

Ontiveros-Valencia, Aura; Zhou, Chen; Ilhan, Zehra Esra; de Saint Cyr, Louis Cornette; Krajmalnik-Brown, Rosa; Rittmann, Bruce E

2017-11-15

Molecular microbiology tools (i.e., 16S rDNA gene sequencing) were employed to elucidate changes in the microbial community structure according to the total electron acceptor loading (controlled by influent flow rate and/or medium composition) in a H 2 -based membrane biofilm reactor evaluated for removal of hexavalent uranium. Once nitrate, sulfate, and dissolved oxygen were replaced by U(VI) and bicarbonate and the total acceptor loading was lowered, slow-growing bacteria capable of reducing U(VI) to U(IV) dominated in the biofilm community: Replacing denitrifying bacteria Rhodocyclales and Burkholderiales were spore-producing Clostridiales and Natranaerobiales. Though potentially competing for electrons with U(VI) reducers, homo-acetogens helped attain steady U(VI) reduction, while methanogenesis inhibited U(VI) reduction. U(VI) reduction was reinstated through suppression of methanogenesis by addition of bromoethanesulfonate or by competition from SRB when sulfate was re-introduced. Predictive metagenome analysis further points out community changes in response to alterations in the electron-acceptor loading: Sporulation and homo-acetogenesis were critical factors for strengthening stable microbial U(VI) reduction. This study documents that sporulation was important to long-term U(VI) reduction, whether or not microorganisms that carry out U(VI) reduction mediated by cytochrome c 3 , such as SRB and ferric-iron-reducers, were inhibited. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of ultraviolet irradiation treatment on porcelain bond strength of titanium surfaces.

PubMed

Kumasaka, Tomonari; Ohno, Akinori; Hori, Norio; Hoshi, Noriyuki; Maruo, Katsuichiro; Kuwabara, Atsushi; Seimiya, Kazuhide; Toyoda, Minoru; Kimoto, Katsuhiko

2018-01-26

To determine the effect of titanium (Ti) surface modification by ultraviolet irradiation (UVI) on the bond strength between Ti and porcelain. Grade 2 Ti plates were allotted to five groups: sandblasted (SA), 15 min UVI (UV), SA+5 min UVI (SA+UV5), SA+10 min UVI (SA+UV10), and SA+15 min UVI (SA+UV15). After surface treatment, porcelain was added. A precious metal (MC) was used for comparison with Ti. The effects of 24-h storage at room temperature versus thermal cycling only at 5 and 55°C in water were evaluated. Subsequently, the tensile strength of each sample was tested. Data were analyzed using one-way analysis of variance and the Tukey test. In both the room temperature and thermal cycling groups, the MC and SA+15 min UVI samples showed significantly greater bond strengths than the other samples (p<0.05). UVI processing efficiently increases the bond strength between porcelain and the Ti surface.

Element speciation during nuclear glass alteration

NASA Astrophysics Data System (ADS)

Galoisy, L.; Calas, G.; Bergeron, B.; Jollivet, P.; Pelegrin, E.

2011-12-01

Assessing the long-term behavior of nuclear glasses implies the prediction of their long-term performance. An important controlling parameter is their evolution during interaction with water under conditions simulating geological repositories. After briefly recalling the major characteristics of the local and medium-range structure of borosilicate glasses of nuclear interest, we will present some structural features of this evolution. Specific structural tools used to determine the local structure of glass surfaces include synchrotron-radiation x-ray absorption spectroscopy with total electron yield detection. The evolution of the structure of glass surface has been determined at the Zr-, Fe-, Si- and Al-K edges and U-LIII edge. During alteration in near- or under-saturated conditions, some elements such as Fe change coordination, as other elements such as Zr only suffer structural modifications in under-saturated conditions. Uranium exhibits a modification of its speciation from an hexa-coordinated U(VI) in the borosilicate glass to an uranyl group in the gel. These structural modifications may explain the chemical dependence of the initial alteration rate and the transition to the residual regime. They also illustrate the molecular-scale origin of the processes at the origin of the glass-to-gel transformation. Eventually, they explain the provisional trapping of U by the alteration gel: the uranium retention factors in the gel depend on the alteration conditions, and thus on the nature of the resulting gel and on the trapping conditions.

New Technique for Speciation of Uranium in Sediments Following Acetate-Stimulated Bioremediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

2011-06-22

Acetate-stimulated bioremediation is a promising new technique for sequestering toxic uranium contamination from groundwater. The speciation of uranium in sediments after such bioremediation attempts remains unknown as a result of low uranium concentration, and is important to analyzing the stability of sequestered uranium. A new technique was developed for investigating the oxidation state and local molecular structure of uranium from field site sediments using X-Ray Absorption Spectroscopy (XAS), and was implemented at the site of a former uranium mill in Rifle, CO. Glass columns filled with bioactive Rifle sediments were deployed in wells in the contaminated Rifle aquifer and amendedmore » with a hexavalent uranium (U(VI)) stock solution to increase uranium concentration while maintaining field conditions. This sediment was harvested and XAS was utilized to analyze the oxidation state and local molecular structure of the uranium in sediment samples. Extended X-Ray Absorption Fine Structure (EXAFS) data was collected and compared to known uranium spectra to determine the local molecular structure of the uranium in the sediment. Fitting was used to determine that the field site sediments did not contain uraninite (UO{sub 2}), indicating that models based on bioreduction using pure bacterial cultures are not accurate for bioremediation in the field. Stability tests on the monomeric tetravalent uranium (U(IV)) produced by bioremediation are needed in order to assess the efficacy of acetate-stimulation bioremediation.« less

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

PubMed

Mishra, Bhoopesh; Haack, Elizabeth A; Maurice, Patricia A; Bunker, Bruce A

2009-01-01

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

Whole-cell bioreporters and risk assessment of environmental pollution: A proof-of-concept study using lead.

PubMed

Zhang, Xiaokai; Qin, Boqiang; Deng, Jianming; Wells, Mona

2017-10-01

As the world burden of environmental contamination increases, it is of the utmost importance to develop streamlined approaches to environmental risk assessment in order to prioritize mitigation measures. Whole-cell biosensors or bioreporters and speciation modeling have both become of increasing interest to determine the bioavailability of pollutants, as bioavailability is increasingly in use as an indicator of risk. Herein, we examine whether bioreporter results are able to reflect expectations based on chemical reactivity and speciation modeling, with the hope to extend the research into a wider framework of risk assessment. We study a specific test case concerning the bioavailability of lead (Pb) in aqueous environments containing Pb-complexing ligands. Ligands studied include ethylene diamine tetra-acetic acid (EDTA), meso-2,3 dimercaptosuccinic acid (DMSA), leucine, methionine, cysteine, glutathione, and humic acid (HA), and we also performed experiments using natural water samples from Lake Tai (Taihu), the third largest lake in China. We find that EDTA, DMSA, cysteine, glutathione, and HA amendment significantly reduced Pb bioavailability with increasing ligand concentration according to a log-sigmoid trend. Increasing dissolved organic carbon in Taihu water also had the same effect, whereas leucine and methionine had no notable effect on bioavailability at the concentrations tested. We find that bioreporter results are in accord with the reduction of aqueous Pb 2+ that we expect from the relative complexation affinities of the different ligands tested. For EDTA and HA, for which reasonably accurate ionization and complexation constants are known, speciation modeling is in agreement with bioreporter response to within the level of uncertainty recognised as reasonable by the United States Environmental Protection Agency for speciation-based risk assessment applications. These findings represent a first step toward using bioreporter technology to streamline the biological confirmation or validation of speciation modeling for use in environmental risk assessment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dissolved sulfides in the oxic water column of San Francisco Bay, California

USGS Publications Warehouse

Kuwabara, J.S.; Luther, G.W.

1993-01-01

Trace contaminants enter major estuaries such as San Francisco Bay from a variety of point and nonpoint sources and may then be repartitioned between solid and aqueous phases or altered in chemical speciation. Chemical speciation affects the bioavailability of metals as well as organic ligands to planktonic and benthic organisms, and the partitioning of these solutes between phases. Our previous, work in south San Francisco Bay indicated that sulfide complexation with metals may be of particular importance because of the thermodynamic stability of these complexes. Although the water column of the bay is consistently well-oxygenated and typically unstratified with respect to dissolved oxygen, the kinetics of sulfide oxidation could exert at least transient controls on metal speciation. Our initial data on dissolved sulfides in the main channel of both the northern and southern components of the bay consistently indicate submicromolar concenrations (from <1 nM to 162 nM), as one would expect in an oxidizing environment. However, chemical speciation calculations over the range of observed sulfide concentrations indicate that these trace concentrations in the bay water column can markedly affect chemical speciation of ecologically significant trace metals such as cadmium, copper, and zinc.

Estimation of UV index in the clear-sky using OMI PROFOZ and AERONET data

NASA Astrophysics Data System (ADS)

Lee, H.; Kim, J.; Jeong, U.

2016-12-01

Due to a strong influence to the human health and ecosystem environment, continuous monitoring of the surface-level ultraviolet (UV) radiation is important nowadays. UV index (UVI) is a simple parameter to show the strength of surface UV radiation, therefore UVI has been widely utilized for the purpose of UV monitoring. In this work, we also try to develop our own retrieval algorithm for better estimation of UVI. The amount of UVA (320-400 nm) and UVB (290-320 nm) radiation at the Earth surface depends on the extent of Rayleigh scattering by atmospheric gas molecules, the radiative absorption by ozone, radiative scattering by clouds, and both absorption and scattering by airborne aerosols. Thus advanced consideration of these factors is the essential part to establish the process of UVI estimation. In this study, we estimate UV Index (UVI) at Seoul first in a clear-sky atmosphere, and then validate this estimated UVI comparing to UVI from Brewer spectrophotometer measurements located at Yonsei University in Seoul. We use the Vector Linearized Discrete Ordinate Radiative Transfer (VLIDORT) model version 2.6 for our UVI calculation. To consider the ozone and aerosol influence in a real situation, we input ozone and temperature profiles from the Ozone Monitoring Instrument (OMI) Aura vertical profile ozone (PROFOZ) data, and aerosol properties from the AErosol RObotic NETwork (AERONET) measurements at Seoul into the model. Inter-comparison of UVI is performed for the year 2011, 2012 and 2014, and resulted in a high correlation coefficient (R=0.95) under clear-sky condition. But a slight overestimation of Brewer UVI occurred under high AOD conditions in clear-sky. Because our UVI algorithm does not account for surface absorbing aerosols, it is lead to systematic overestimation of surface UV irradiances. Therefore, we also investigate the effect of absorbing aerosol on the amount of UV irradiance in the clear-sky over East Asia.

Sustained removal of uranium from contaminated groundwater following stimulation of dissimilatory metal reduction.

PubMed

N'Guessan, A Lucie; Vrionis, Helen A; Resch, Charles T; Long, Philip E; Lovley, Derek R

2008-04-15

Previous field studies on in situ bioremediation of uranium-contaminated groundwater in an aquifer in Rifle, Colorado identified two distinct phases following the addition of acetate to stimulate microbial respiration. In phase I, Geobacter species are the predominant organisms, Fe(III) is reduced, and microbial reduction of soluble U(VI) to insoluble U(IV) removes uranium from the groundwater. In phase II, Fe(III) is depleted, sulfate is reduced, and sulfate-reducing bacteria predominate. Long-term monitoring revealed an unexpected third phase during which U(VI) removal continues even after acetate additions are stopped. All three of these phases were successfully reproduced in flow-through sediment columns. When sediments from the third phase were heat sterilized, the capacity for U(VI) removal was lost. In the live sediments U(VI) removed from the groundwater was recovered as U(VI) in the sediments. This contrasts to the recovery of U(IV) in sediments resulting from the reduction of U(VI) to U(IV) during the Fe(III) reduction phase in acetate-amended sediments. Analysis of 16S rRNA gene sequences in the sediments in which U(VI) was being adsorbed indicated that members of the Firmicutes were the predominant organisms whereas no Firmicutes sequences were detected in background sediments which did not have the capacity to sorb U(VI), suggesting that the U(VI) adsorption might be due to the presence of these living organisms or at least their intact cell components. This unexpected enhanced adsorption of U(VI) onto sediments following the stimulation of microbial growth in the subsurface may potentially enhance the cost effectiveness of in situ uranium bioremediation.

ISSUES RELATED TO SOLUTION CHEMISTRY IN MERCURY SAMPLING IMPINGERS

EPA Science Inventory

Analysis of mercury (Hg) speciation in combustion flue gases is often accomplished in standardized sampling trains in which the sample is passed sequentially through a series of aqueous solutions to capture and separate oxidized Hg (Hg2+) and elemental Hg (Hgo). Such methods incl...

Speciation of mercury compounds by differential atomization - atomic absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Robinson, J.W.; Skelly, E.M.

This paper describes the dual stage atomization technique which allows speciation of several mercury-containing compounds in aqueous solution and in biological fluids. The technique holds great promise for further speciation studies. Accurate temperature control, expecially at temperatures less than 200/sup 0/C, is needed to separate the extremely volatile mercury halides and simple organomercurials from each other. Studies with mercury salts and EDTA, L-cysteine and dithioxamide demonstrate that this technique may be used to study the extent of complex formation. Investigations of biological fluids indicate that there is a single predominant form of mercury in sweat and a single predominant formmore » of mercury in urine. The mercury compound in urine is more volatile than that in sweat. Both quantitative and qualitative analyses are possible with this technique.« less

Long-term Kinetics of Uranyl Desorption from Sediments Under Advective Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shang, Jianying; Liu, Chongxuan; Wang, Zheming

2014-02-15

Long-term (> 4 months) column experiments were performed to investigate the kinetics of uranyl (U(VI)) desorption in sediments collected from the Integrated Field Research Challenge (IFRC) site at the US Department of Energy (DOE) Hanford 300 Area. The experimental results were used to evaluate alternative multi-rate surface complexation reaction (SCR) approaches to describe the short- and long-term kinetics of U(VI) desorption under flow conditions. The SCR stoichiometry, equilibrium constants, and multi-rate parameters were independently characterized in batch and stirred flow-cell reactors. Multi-rate SCR models that were either additively constructed using the SCRs for individual size fractions (e.g., Shang et al.,more » 2011), or composite in nature could effectively describe short-term U(VI) desorption under flow conditions. The long-term desorption results, however, revealed that using a labile U concentration measured by carbonate extraction under-estimated desorbable U(VI) and the long-term rate of U(VI) desorption. An alternative modeling approach using total U as the desorbable U(VI) concentration was proposed to overcome this difficulty. This study also found that the gravel size fraction (2-8 mm), which is typically treated as non-reactive in modeling U(VI) reactive transport because of low external surface area, can have an important effect on the U(VI) desorption in the sediment. This study demonstrates an approach to effectively extrapolate U(VI) desorption kinetics for field-scale application, and identifies important parameters and uncertainties affecting model predictions.« less

Gender differences in the association between the incidence of cutaneous melanoma and geographic UV exposure

PubMed Central

Liu-Smith, Feng; Farhat, Ahmed Majid; Arce, Anthony; Ziogas, Argyrios; Taylor, Thomas; Wang, Zi; Yourk, Vandy; Liu, Jing; Wu, Jun; McEligot, Archana J.; Anton-Culver, Hoda; Meyskens, Frank L.

2016-01-01

Background Cutaneous melanoma (CM) incidence rates continue to increase, and the reasons are unknown. Previously, we reported a unique age-specific gender difference in melanoma that suggested additional causes other than solar UV radiation. Objective This study attempted to understand whether and how UV radiation differentially impacts the CM incidence in men and women. Methods CM data and daily UV index (UVI) from 31 cancer registries were collected for association analysis. A second dataset from 42 states of the U.S.A. was used for validation. Results There was no association between log-transformed female CM rates and levels of UVI but there was a significant association between male rates and UVI and a significant association between overall rates and UVI. The 5 year age-specific rate-UVI association levels (represented by Pearson’s coefficient ρ) increased with age in men, but age-specific ρ levels remained low and unchanged in women. The significant rate-UVI association in men and non-association in women was validated in the US white population. Limitations Confounders including temperature and latitude are difficult to separate from UVI Conclusions: Ambient UVI appears to be associated with melanoma incidence in males but not in females. PMID:28413057

Microbial reduction of uranium

USGS Publications Warehouse

Lovley, D.R.; Phillips, E.J.P.; Gorby, Y.A.; Landa, E.R.

1991-01-01

REDUCTION of the soluble, oxidized form of uranium, U(VI), to insoluble U(IV) is an important mechanism for the immobilization of uranium in aquatic sediments and for the formation of some uranium ores1-10. U(VI) reduction has generally been regarded as an abiological reaction in which sulphide, molecular hydrogen or organic compounds function as the reductant1,2,5,11. Microbial involvement in U(VI) reduction has been considered to be limited to indirect effects, such as microbial metabolism providing the reduced compounds for abiological U(VI) reduction and microbial cell walls providing a surface to stimulate abiological U(VI) reduction1,12,13. We report here, however, that dissimilatory Fe(III)-reducing microorganisms can obtain energy for growth by electron transport to U(VI). This novel form of microbial metabolism can be much faster than commonly cited abiological mechanisms for U(VI) reduction. Not only do these findings expand the known potential terminal electron acceptors for microbial energy transduction, they offer a likely explanation for the deposition of uranium in aquatic sediments and aquifers, and suggest a method for biological remediation of environments contaminated with uranium.

KINETICS OF ARSENATE REDUCTION BY DISSOLVED SULFIDE. (R825399)

EPA Science Inventory

Arsenic toxicity and mobility in soil and aquatic environments depends on its
speciation, with reducing environments generally leading to more hazardous
conditions with respect to this element. Aqueous sulfide (H₂S or
HS^-) is a strong reductan...

The Speciation of Sulfur in an Ocean on Europa

NASA Technical Reports Server (NTRS)

Zolotov, M. Yu.; Shock, E. L.

2002-01-01

Stability of native sulfur, iron sulfides, and aqueous sulfur compounds is evaluated at assumed P-T conditions of the Europa's ocean floor. Pyrite, gypsum, and ferric hydroxides can coexist in contact with sulfate-rich oceanic water. Additional information is contained in the original extended abstract.

TETRAVALENT LEAD: A HITHERTO UNRECOGNIZED CONTROL OF TAP WATER LEAD CONTAMINATION

EPA Science Inventory

Almost all of the theoretical framework underlying the control of plumbosolvency and lead release has been based on the presumption that the lead release is explicable by Pb(II) solubility, aqueous speciation, and reaction kinetics. Utilities struggling to comply with the Lead an...

Dissolved organic matter reduces CuO nanoparticle toxicity to duckweed in simulated natural systems.

PubMed

Rippner, Devin A; Green, Peter G; Young, Thomas M; Parikh, Sanjai J

2018-03-01

With increasing demand for recycled wastewater for irrigation purposes, there is a need to evaluate the potential for manufactured nanomaterials in waste water to impact crop production and agroecosystems. Copper oxide nanoparticles (CuO NPs) have previously been shown to negatively impact the growth of duckweed (Landoltia punctata) a model aquatic plant consumed by water fowl and widely found in agricultural runoff ditches in temperate climates. However, prior studies involving CuO NP toxicity to duckweed have focused on systems without the presence of dissolved organic matter (DOM). In the current study, duckweed growth inhibition was shown to be a function of aqueous Cu 2+ concentration. Growth inhibition was greatest from aqueous CuCl 2 and, for particles, increased with decreasing CuO particle size. The dissolution of CuO NPs in ½ Hoagland's solution was measured to increase with decreasing particle size and in the presence of Suwannee river humic and fulvic acids (HA; FA). However, the current results suggest that HA, and to a lesser extent, FA, decrease the toxicity of both CuO NPs and free ionized Cu to duckweed, likely by inhibiting Cu availability through Cu-DOM complex formation. Such results are consistent with changes to Cu speciation as predicted by speciation modeling software and suggest that DOM changes Cu speciation and therefore toxicity in natural systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Detailed Modelling of Kinetic Biodegradation Processes in a Laboratory Mmicrocosm

NASA Astrophysics Data System (ADS)

Watson, I.; Oswald, S.; Banwart, S.; Mayer, U.

2003-04-01

Biodegradation of organic contaminants in soil and groundwater usually takes places via different redox processes happening sequentially as well as simultaneously. We used numerical modelling of a long-term lab microcosm experiment to simulate the dynamic behaviour of fermentation and respiration in the aqueous phase in contact with the sandstone material, and to develop a conceptual model describing these processes. Aqueous speciation, surface complexation, mineral dissolution and precipitation were taken into account also. Fermentation can be the first step of the degradation process producing intermediate species, which are subsequently consumed by TEAPs. Microbial growth and substrate utilisation kinetics are coupled via a formulation that also includes aqueous speciation and other geochemical reactions including surface complexation, mineral dissolution and precipitation. Competitive exclusion between TEAPs is integral to the conceptual model of the simulation, and the results indicate that exclusion is not complete, but some overlap is found between TEAPs. The model was used to test approaches like the partial equilibrium approach that currently make use of hydrogen levels to diagnose prevalent TEAPs in groundwater. The observed pattern of hydrogen and acetate concentrations were reproduced well by the simulations, and the results show the relevance of kinetics, lag times and inhibition, and especially that intermediate products play a key role.

Interactions between Silicon Oxide Nanoparticles (SONPs) and U(VI) Contaminations: Effects of pH, Temperature and Natural Organic Matters

PubMed Central

Wu, Hanyu; Li, Ping; Pan, Duoqiang; Yin, Zhuoxin; Fan, Qiaohui; Wu, Wangsuo

2016-01-01

The interactions between contaminations of U(VI) and silicon oxide nanoparticles (SONPs), both of which have been widely used in modern industry and induced serious environmental challenge due to their high mobility, bioavailability, and toxicity, were studied under different environmental conditions such as pH, temperature, and natural organic matters (NOMs) by using both batch and spectroscopic approaches. The results showed that the accumulation process, i.e., sorption, of U(VI) on SONPs was strongly dependent on pH and ionic strength, demonstrating that possible outer- and/or inner-sphere complexes were controlling the sorption process of U(VI) on SONPs in the observed pH range. Humic acid (HA), one dominated component of NOMs, bounded SONPs can enhance U(VI) sorption below pH~4.5, whereas restrain at high pH range. The reversible sorption of U(VI) on SONPs possibly indicated that the outer-sphere complexes were prevalent at pH 5. However, an irreversible interaction of U(VI) was observed in the presence of HA (Fig 1). It was mainly due to the ternary SONPs-HA-U(VI) complexes (Type A Complexes). After SONPs adsorbed U(VI), the particle size in suspension was apparently increased from ~240 nm to ~350 nm. These results showed that toxicity of both SONPs and U(VI) will decrease to some extent after the interaction in the environment. These findings are key for providing useful information on the possible mutual interactions among different contaminants in the environment. PMID:26930197

Electrochemical and Spectroscopic Evidence on the One-Electron Reduction of U(VI) to U(V) on Magnetite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(VI) on mineral surfaces is often considered a one-step two-electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies Indicates U(VI) can undergo a one-electron reduction to U(V) without further progression to U(VI),. We investigated reduction pathways of uranium by reducing U(VI) electrochemically on a, magnetite electrode at,pH 3.4. Cyclic voltammetry confirms the one-electron reduction of U(VI) . Formation of nanosize uranium precipitates on the magnetite surface at reducing potentials and dissolution of the solids at oxidizing potentials are observed by in situ electrochemical atomic force microscopy. XPS, analysis Of the magnetitemore » electrodes polarized in uranium solutions at voltages - from -0.1 to -0.9 V (E-U(VI)/U(V)(0)= -0.135 V vs Ag/AgCl) show the presence of, only U(V) and U(VI). The sample with the highest U(V)/U(VI) ratio was prepared at -0.7 V, where the longest average U-O-axial distance of 2.05 + 0.01 A was evident in the same sample revealed by extended X-ray absorption fine structure analysis. The results demonstrate that the electrochemical reduction of U(VI) On magnetite only yields,U(V), even at a potential of -0.9 V, which favors the one-electron reduction mechanism, U(V) does not disproportionate but stabilizes on magnetite through precipitation Of mixed-valence state -U(V)/U(VI) solids.« less

Speciation in Aqueous MgSO4 Fluid at High Pressures and Temperatures Studied by First-Principles Modeling and Raman Spectroscopy

NASA Astrophysics Data System (ADS)

Jahn, S.; Schmidt, C.

2008-12-01

Aqueous fluids play an essential role in mass and energy transfer in the lithosphere. Their presence has also a large effect on physical properties of rocks, e.g. the electrical conductivity. Many chemical and physical properties of aqueous fluids strongly depend on the speciation, but very little is known about this fundamental parameter at high pressures and temperatures, e.g. at subduction zone conditions. Here we use a combined approach of first-principles molecular dynamics simulation and Raman spectroscopy to study the molecular structure of aqueous 2~mol/kg MgSO4 fluids up to pressures of 3~GPa and temperatures of 750~°C. MgSO4-H2O is selected as a model system for sulfate bearing subduction zone fluids. The simulations are performed using Car-Parrinello dynamics, a system size of 120 water and four MgSO4 molecules with production runs of at least 10~ps at each P and T. Raman spectra were obtained in situ using a Bassett-type hydrothermal diamond anvil cell with external heating. Both simulation and spectroscopic data show a dynamic co-existence of various associated molecular species as well as dissociated Mg2+ and SO42- in the single phase fluid. Fitting the Raman signal in the frequency range of the ν1-SO42- stretching mode yields the P-T dependence of the relative proportions of different peaks. The latter can be assigned to species based on literature data and related to the species found in the simulation. The dominant associated species found in the P-T range of interest here are Mg-SO4 ion pairs with one (monodentate) and two (bidentate) binding sites. At the highest P and T, an additional peak is identified. At low pressures and high temperature (T>230~°C), kieserite, MgSO4·H2O, nucleated in the experiment. At the same conditions the simulations show a clustering of Mg, which is interpreted as a precursor of precipitation. In conclusion, the speciation of aqueous MgSO4 fluid shows a complex behavior at high P and T that cannot be extrapolated from ambient conditions. The combination of molecular modeling and in situ spectroscopic experiments is a promising approach towards quantitative understanding of geochemical processes in subduction zones.

High levels of ultraviolet radiation observed by ground-based instruments below the 2011 Arctic ozone hole

NASA Astrophysics Data System (ADS)

Bernhard, G.; Dahlback, A.; Fioletov, V.; Heikkilä, A.; Johnsen, B.; Koskela, T.; Lakkala, K.; Svendby, T.

2013-11-01

Greatly increased levels of ultraviolet (UV) radiation were observed at thirteen Arctic and sub-Arctic ground stations in the spring of 2011, when the ozone abundance in the Arctic stratosphere dropped to the lowest amounts on record. Measurements of the noontime UV Index (UVI) during the low-ozone episode exceeded the climatological mean by up to 77% at locations in the western Arctic (Alaska, Canada, Greenland) and by up to 161% in Scandinavia. The UVI measured at the end of March at the Scandinavian sites was comparable to that typically observed 15-60 days later in the year when solar elevations are much higher. The cumulative UV dose measured during the period of the ozone anomaly exceeded the climatological mean by more than two standard deviations at 11 sites. Enhancements beyond three standard deviations were observed at seven sites and increases beyond four standard deviations at two sites. At the western sites, the episode occurred in March, when the Sun was still low in the sky, limiting absolute UVI anomalies to less than 0.5 UVI units. At the Scandinavian sites, absolute UVI anomalies ranged between 1.0 and 2.2 UVI units. For example, at Finse, Norway, the noontime UVI on 30 March was 4.7, while the climatological UVI is 2.5. Although a UVI of 4.7 is still considered moderate, UV levels of this amount can lead to sunburn and photokeratitis during outdoor activity when radiation is reflected upward by snow towards the face of a person or animal. At the western sites, UV anomalies can be well explained with ozone anomalies of up to 41% below the climatological mean. At the Scandinavian sites, low ozone can only explain a UVI increase of 50-60%. The remaining enhancement was mainly caused by the absence of clouds during the low-ozone period.

High levels of ultraviolet radiation observed by ground-based instruments below the 2011 Arctic ozone hole

NASA Astrophysics Data System (ADS)

Bernhard, G.; Dahlback, A.; Fioletov, V.; Heikkilä, A.; Johnsen, B.; Koskela, T.; Lakkala, K.; Svendby, T. M.

2013-06-01

Greatly increased levels of ultraviolet (UV) radiation were observed at thirteen Arctic and sub-Arctic ground stations in the spring of 2011 when the ozone abundance in the Arctic stratosphere dropped to the lowest amounts on record. Measurements of the noontime UV Index (UVI) during the low-ozone episode exceeded the climatological mean by up to 77% at locations in the western Arctic (Alaska, Canada, Greenland) and by up to 161% in Scandinavia. The UVI measured at the end of March at the Scandinavian sites was comparable to that typically observed 15-60 days later in the year when solar elevations are much higher. The cumulative UV dose measured during the period of the ozone anomaly exceeded the climatological mean by more than two standard deviations at 11 sites. Enhancements beyond three standard deviations were observed at seven sites and increases beyond four standard deviations at two sites. At the western sites, the episode occurred in March when the Sun was still low in the sky, limiting absolute UVI anomalies to less than 0.5 UVI units. At the Scandinavian sites, absolute UVI anomalies ranged between 1.0 and 2.2 UVI units. For example, at Finse, Norway, the noontime UVI on 30 March was 4.7 while the climatological UVI is 2.5. Although a UVI of 4.7 is still considered moderate, UV levels of this amount can lead to sunburn and photokeratitis during outdoor activity when radiation is reflected upward by snow towards the face of a person or animal. At the western sites, UV anomalies can be well explained with ozone anomalies of up to 41% below the climatological mean. At the Scandinavian sites, low ozone can only explain a UVI increase by 50-60%. The remaining enhancement was mainly caused by the absence of clouds during the low-ozone period.

Kinetics of microbial reduction of Solid phase U(VI).

PubMed

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming; Dohnalkova, Alice; Fredrickson, James K

2006-10-15

Sodium boltwoodite (NaUO2SiO3OH x 1.5 H2O) was used to assess the kinetics of microbial reduction of solid-phase U(VI) by a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. The bioreduction kinetics was studied with Na-boltwoodite in suspension or within alginate beads in a nongrowth medium with lactate as electron donor at pH 6.8 buffered with PIPES. Concentrations of U(VI)tot and cell number were varied to evaluate the coupling of U(VI) dissolution, diffusion, and microbial activity. Microscopic and spectroscopic analyses with transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and laser-induced fluorescence spectroscopy (LIFS) collectively indicated that solid-phase U(VI) was first dissolved and diffused out of grain interiors before it was reduced on bacterial surfaces and/or within the periplasm. The kinetics of solid-phase U(VI) bioreduction was well described by a coupled model of bicarbonate-promoted dissolution of Na-boltwoodite, intragrain uranyl diffusion, and Monod type bioreduction kinetics with respect to dissolved U(VI) concentration. The results demonstrated that microbial reduction of solid-phase U(VI) is controlled by coupled biological, chemical, and physical processes.

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models.

PubMed

Flores-Alsina, Xavier; Kazadi Mbamba, Christian; Solon, Kimberly; Vrecko, Darko; Tait, Stephan; Batstone, Damien J; Jeppsson, Ulf; Gernaey, Krist V

2015-11-15

There is a growing interest within the Wastewater Treatment Plant (WWTP) modelling community to correctly describe physico-chemical processes after many years of mainly focusing on biokinetics. Indeed, future modelling needs, such as a plant-wide phosphorus (P) description, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry standard models. The module accounts for extensive consideration of non-ideality, including ion activities instead of molar concentrations and complex ion pairing. The general equilibria are formulated as a set of Differential Algebraic Equations (DAEs) instead of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method to increase the robustness of the solver making the system not so dependent of the initial conditions. Simulation results show pH predictions when describing Biological Nutrient Removal (BNR) by the activated sludge models (ASM) 1, 2d and 3 comparing the performance of a nitrogen removal (WWTP1) and a combined nitrogen and phosphorus removal (WWTP2) treatment plant configuration under different anaerobic/anoxic/aerobic conditions. The same framework is implemented in the Benchmark Simulation Model No. 2 (BSM2) version of the Anaerobic Digestion Model No. 1 (ADM1) (WWTP3) as well, predicting pH values at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling studies can be complemented with a rigorous description of aqueous phase and ion chemistry (pH, speciation, complexation). Copyright © 2015 Elsevier Ltd. All rights reserved.

Micro- and Nano-scale Diffusion Domains Acting as Kinetic Controls for U(VI) Release to the Hanford 300-Area Aquifer

NASA Astrophysics Data System (ADS)

Stoliker, D. L.; Hay, M. B.; Davis, J. A.; Zachara, J. M.

2008-12-01

The 300-Area of the Hanford reservation, a cold-war era nuclear processing facility, is plagued by long-term elevated concentrations of U(VI) in the underlying aquifer. While the sediment U(VI) concentration is relatively low, it continues to act as a source and sink for the contaminant, allowing for persistent groundwater concentrations well above the maximum contamination limit (MCL). Simple Kd modeling of the attenuation of U(VI) in the aquifer predicted that groundwater U(VI) concentrations would decrease to below the drinking water standard by the year 2002. However, grain-scale morphology of the aquifer material suggests that intra-grain flow paths and mineral coatings, in which sorption complexes and precipitates formed over years of waste disposal, provide a significant kinetic constraint that slows groundwater flushing of the sediments. In order to quantify the impact of diffusion kinetics on the release of U(VI), high-resolution, non-reactive tracer studies were conducted on vadose zone sediments in both column and batch reactors. Systems were equilibrated for long time scales with tritated artificial groundwater and then flushed with flow and stop-flow events included for columns. Previously collected U(VI) release data from batch dissolution/desorption studies is compared with tritium tracer diffusion kinetics as well as porosimetry and detailed microscopy characterization. The micro-scale and nano-scale diffusion regimes, including intra-granular regions as well as mineral coatings, represent a significant potential long-term source of contaminant U(VI). Understanding the physical kinetic limitations coupled with the complex chemistry of U(VI) sorption processes within natural systems is an important step forward in providing information to strengthen field-scale reactive transport simulations.

Uranium Isotopes in Calcium Carbonate: A Possible Proxy for Paleo-pH and Carbonate Ion Concentration?

NASA Astrophysics Data System (ADS)

Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

2015-12-01

Natural variations of 238U/235U in marine carbonates are being explored as a paleoredox proxy. However, in order for this proxy to be robust, it is important to understand how pH and alkalinity affect the fractionation of 238U/235U during coprecipitation with calcite and aragonite. Recent work suggests that the U/Ca ratio of foraminiferal calcite may vary with seawater [CO32-] concentration due to changes in U speciation[1]. Here we explore analogous isotopic consequences in inorganic laboratory co-precipitation experiments. Uranium coprecipitation experiments with calcite and aragonite were performed at pH 8.5 ± 0.1 and 7.5 ± 0.1 using a constant addition method [2]. Dissolved U in the remaining solution was periodically collected throughout the experiments. Samples were purified with UTEVA resin and 238U/235U was determined using a 233U-236U double-spike and MC-ICP-MS, attaining a precision of ± 0.10 ‰ [3]. Small but resolvable U isotope fractionation was observed in aragonite experiments at pH ~8.5, preferentially enriching heavier U isotopes in the solid phase. 238U/235U of the dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00002 - 1.00009. In contrast, no resolvable U isotope fractionation was detected in an aragonite experiment at pH ~7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among dissolved U species is the most likely mechanism driving these isotope effects. Our quantitative model of this process assumes that charged U species are preferentially incorporated into CaCO3 relative to the neutral U species Ca2UO2(CO3)3(aq), which we hypothesize to have a lighter equilibrium U isotope composition than the charged U species. According to this model, the magnitude of U isotope fractionation should scale with the fraction of the neutral U species in the solution, in agreement with our experimental results. These findings suggest that U isotope variations in abiotic CaCO3 reflect changes in aqueous U(VI) speciation, which are in turn a function of carbonate ion chemistry and pH. Hence, the door is opened to the development of a possible 238U/235U proxy for the carbonate ion system. [1] DeCarlo et al., (2015), GCA, 162,151-165. [2] Reeder et a., (2001), GCA, 65, 3491-3503. [3] Weyer et al., (2008) GCA 72, 345-359.

Updates to WFC3/UVIS Filter-Dependent and Filter-Distinct Distortion Corrections

NASA Astrophysics Data System (ADS)

Martlin, Catherine; Kozhurina-Platais, Vera; McKay, Myles; Sabbi, Elena

2018-06-01

The WFC3/UVIS filter wheel contains 63 filters that cover a large range of wavelengths from near ultraviolet to the near infrared. Previously, analysis was completed on the 14 most used UVIS filters to calibrate geometric distortions. These distortions are due to a combination of the optical assembly of HST as well as the variabilities in the composition of individual filters. We report recent updates to reference files that aid in correcting for these distortions of an additional 22 UVIS narrow and medium band filters and 4 unique UVIS filters. They were created following a calibration of the large-scale optical distortions and fine-scale filter-dependent distortions. Furthermore, we present results on a study into a selection of unique polynomial coefficient terms from all solved filters which allows us to better investigate the filter-dependent patterns across a large range of wavelengths.These updates will provide important enhancements for HST/WFC3 users as they allow more accurate alignment of images across the range of UVIS filters.

Measured solubilities and speciations of neptunium, plutonium, and americium in a typical groundwater (J-13) from the Yucca Mountain region; Milestone report 3010-WBS 1.2.3.4.1.3.1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nitsche, H.; Gatti, R.C.; Standifer, E.M.

1993-07-01

Solubility and speciation data are important in understanding aqueous radionuclide transport through the geosphere. They define the source term for transport retardation processes such as sorption and colloid formation. Solubility and speciation data are useful in verifying the validity of geochemical codes that are part of predictive transport models. Results are presented from solubility and speciation experiments of {sup 237}NpO{sub 2}{sup +}, {sup 239}Pu{sup 4+}, {sup 241}Am{sup 3+}/Nd{sup 3+}, and {sup 243}Am{sup 3+} in J-13 groundwater (from the Yucca Mountain region, Nevada, which is being investigated as a potential high-level nuclear waste disposal site) at three different temperatures (25{degree}, 60{degree},more » and 90{degree}C) and pH values (5.9, 7.0, and 8.5). The solubility-controlling steady-state solids were identified and the speciation and/or oxidation states present in the supernatant solutions were determined. The neptunium solubility decreased with increasing temperature and pH. Plutonium concentrations decreased with increasing temperature and showed no trend with pH. The americium solutions showed no clear solubility trend with increasing temperature and increasing pH.« less

Comparing the ACS/WFC and WFC3/UVIS Calibration and Photometry

NASA Astrophysics Data System (ADS)

Deustua, S. E.; Mack, J.

2018-03-01

A study was undertaken using synthetic photometry of CALSPEC stars to compare the ACS Wide Field Channel (WFC) photometry to the WFC3 UVIS imaging channel in eight similarly named passbands corresponding to the broadband filters F435W (ACS/WFC) F438W (WFC3/UVIS) and F475W, F555W, F606W, F625W, F775W, F814W and F850LP (both ACS/WFC and WFC3/UVIS). The uncertainty of the photometric calibration of ACS/WFC and WFC3/UVIS with respect to the white dwarf standard stars is within ± 0.5% for F814W, F775W, F606W and F475W, and within ±1% for F625W and F850LP. For F555W the apparent difference in the calibration is 2% for F555W and 6% for UVIS/F438W and ACS/F435W due to inherent differences in the filter passbands. Comparing the ACS/WFC to WFC3/UVIS mean flux for stars having a range of spectral types shows a color dependence. The WFC to UVIS F814W color dependence is ± 0.02 mags for F814W, F775W, F475W and F606W. For the other filters the range is -0.06 to +0.02 mags. Aperture photometry of the 47 Tucanae cluster confirm the results from using synthetic photometry of CALSPEC stars.

Macroscopic and Microscopic Investigation of U(VI) and Eu(III) Adsorption on Carbonaceous Nanofibers.

PubMed

Sun, Yubing; Wu, Zhen-Yu; Wang, Xiangxue; Ding, Congcong; Cheng, Wencai; Yu, Shu-Hong; Wang, Xiangke

2016-04-19

The adsorption mechanism of U(VI) and Eu(III) on carbonaceous nanofibers (CNFs) was investigated using batch, IR, XPS, XANES, and EXAFS techniques. The pH-dependent adsorption indicated that the adsorption of U(VI) on the CNFs was significantly higher than the adsorption of Eu(III) at pH < 7.0. The maximum adsorption capacity of the CNFs calculated from the Langmuir model at pH 4.5 and 298 K for U(VI) and Eu(III) were 125 and 91 mg/g, respectively. The CNFs displayed good recyclability and recoverability by regeneration experiments. Based on XPS and XANES analyses, the enrichment of U(VI) and Eu(III) was attributed to the abundant adsorption sites (e.g., -OH and -COOH groups) of the CNFs. IR analysis further demonstrated that -COOH groups were more responsible for U(VI) adsorption. In addition, the remarkable reducing agents of the R-CH2OH groups were responsible for the highly efficient adsorption of U(VI) on the CNFs. The adsorption mechanism of U(VI) on the CNFs at pH 4.5 was shifted from inner- to outer-sphere surface complexation with increasing initial concentration, whereas the surface (co)precipitate (i.e., schoepite) was observed at pH 7.0 by EXAFS spectra. The findings presented herein play an important role in the removal of radionuclides on inexpensive and available carbon-based nanoparticles in environmental cleanup applications.

Electrochemical and spectroscopic evidence on the one-electron reduction of U(VI) to U(V) on magnetite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yuan, Ke; Ilton, Eugene S.; Antonio, Mark R.

2015-05-19

Reduction of U(VI) to U(IV) on mineral surfaces has been considered as a one-step two electron process. However, stabilized U(V), with no evidence of U(IV), found in recent studies indicates U(VI) can undergo a one electron reduction to U(V) without further progression to U(IV). We investigated the mechanisms of uranium reduction by reducing U(VI) electrochemically on a magnetite electrode at pH 3.4 . The one electron reduction of U(VI) was first confirmed using the cyclic voltammetry method. Formation of nano-size uranium precipitates on the surface of magnetite at reducing potentials and dissolution of the solids at oxidizing potentials were observedmore » by in situ electrochemical AFM. XPS analysis of the magnetite electrodes polarized in uranium solutions at voltages from 0.1 ~ 0.9 V (vs. Ag/AgCl) showed the presence of only U(V) and U(VI). The highest amount of U(V) relative to U(VI) was prepared at 0.7 V, where the longest average U–Oaxial distance of 2.05 ± 0.01 Å was evident in the same sample revealed by EXAFS analysis. The results demonstrate that the electrochemical reduction of U(VI) on magnetite only yields U(V), even at a potential of 0.9 V, which favors the one-electron reduction mechanism. U(V) did not disproportionate but stabilized on magnetite through precipitation of mixed-valence state U(VI)/U(V) solids.« less

Computer modeling of the mineralogy of the Martian surface, as modified by aqueous alteration

NASA Technical Reports Server (NTRS)

Zolensky, M. E.; Bourcier, W. L.; Gooding, J. L.

1988-01-01

Mineralogical constraints can be placed on the Martian surface by assuming chemical equilibria among the surface rocks, atmosphere and hypothesized percolating groundwater. A study was made of possible Martian surface mineralogy, as modified by the action of aqueous alteration, using the EQ3/6 computer codes. These codes calculate gas fugacities, aqueous speciation, ionic strength, pH, Eh and concentration and degree of mineral saturation for complex aqueous systems. Thus, these codes are also able to consider mineralogical solid solutions. These codes are able to predict the likely alteration phases which will occur as the result of weathering on the Martian surface. Knowledge of the stability conditions of these phases will then assist in the definition of the specifications for the sample canister of the proposed Martian sample return mission. The model and its results are discussed.

Fate of Uranium During Transport Across the Groundwater-Surface Water Interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaffe, Peter R.; Kaplan, Daniel I.

Discharge of contaminated groundwater to surface waters is of concern at many DOE facilities. For example, at F-Area and TNX-Area on the Savannah River Site, contaminated groundwater, including uranium, is already discharging into natural wetlands. It is at this interface where contaminants come into contact with the biosphere. These this research addressed a critical knowledge gap focusing on the geochemistry of uranium (or for that matter, any redox-active contaminant) in wetland systems. Understanding the interactions between hydrological, microbial, and chemical processes will make it possible to provide a more accurate conceptual and quantitative understanding of radionuclide fate and transport undermore » these unique conditions. Understanding these processes will permit better long-term management and the necessary technical justification for invoking Monitored Natural Attenuation of contaminated wetland areas. Specifically, this research did provide new insights on how plant-induced alterations to the sediment biogeochemical processes affect the key uranium reducing microorganisms, the uranium reduction, its spatial distribution, the speciation of the immobilized uranium, and its long-term stability. This was achieved by conducting laboratory mesocosm wetland experiments as well as field measurements at the SRNL. Results have shown that uranium can be immobilized in wetland systems. To a degree some of the soluble U(VI) was reduced to insoluble U(IV), but the majority of the immobilized U was incorporated into iron oxyhydroxides that precipitated onto the root surfaces of wetland plants. This U was immobilized mostly as U(VI). Because it was immobilized in its oxidized form, results showed that dry spells, resulting in the lowering of the water table and the exposure of the U to oxic conditions, did not result in U remobilization.« less

Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site.

PubMed

Li, Dien; Seaman, John C; Chang, Hyun-Shik; Jaffe, Peter R; Koster van Groos, Paul; Jiang, De-Tong; Chen, Ning; Lin, Jinru; Arthur, Zachary; Pan, Yuanming; Scheckel, Kirk G; Newville, Matthew; Lanzirotti, Antonio; Kaplan, Daniel I

2014-05-01

Uranium speciation and retention mechanisms onto Savannah River Site (SRS) wetland sediments was studied using batch (ad)sorption experiments, sequential extraction, U L3-edge X-ray absorption near-edge structure (XANES) spectroscopy, fluorescence mapping and μ-XANES. Under oxidized conditions, U was highly retained by the SRS wetland sediments. In contrast to other similar but much lower natural organic matter (NOM) sediments, significant sorption of U onto the SRS sediments was observed at pH < 4 and pH > 8. Sequential extraction indicated that the U species were primarily associated with the acid soluble fraction (weak acetic acid extractable) and organic fraction (Na-pyrophosphate extractable). Uranium L3-edge XANES spectra of the U-bound sediments were nearly identical to that of uranyl acetate. Based on fluorescence mapping, U and Fe distributions in the sediment were poorly correlated, U was distributed throughout the sample and did not appear as isolated U mineral phases. The primary oxidation state of U in these oxidized sediments was U(VI), and there was little evidence that the high sorptive capacity of the sediments could be ascribed to abiotic or biotic reduction to the less soluble U(IV) species or to secondary mineral formation. Collectively, this study suggests that U may be strongly bound to wetland sediments, not only under reducing conditions by reductive precipitation, but also under oxidizing conditions through NOM-uranium bonding. Published by Elsevier Ltd.

Surface reactions kinetics between nanocrystalline magnetite and uranyl.

PubMed

Missana, Tiziana; Maffiotte, César; García-Gutiérrez, Miguel

2003-05-01

Magnetite is the most important end member of iron corrosion products under reducing environment, which is the condition expected in a deep geological high level radioactive waste disposal. Nanocrystalline magnetite was synthesized in the laboratory and its physicochemical properties were analyzed in detail. The kinetics of the adsorption of U(VI) and the kinetics of the actinide reduction to a lower oxidation state, in presence of the oxide, were studied by means of batch sorption techniques and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that the uranium sorption and reduction processes on the magnetite surface have very fast kinetics (hours), the reduction process being triggered by sorption. XPS measurements showed that the speciation of uranium at the surface does not show significant changes with time (from 1 day to 3 months), as well as the quantity of uranium detected at the surface. The surface speciation depended on the initial pH of the contact solution. Considering that the Eh of equilibrium between magnetite and the solution, under our experimental conditions, is slightly positive (50-100 mV), the uranium reduction would also be thermodynamically possible within the liquid phase. However, the kinetics of reduction in the liquid occur at a much slower rate which, in turn, has to depend on the attainment of the magnetite/solution equilibrium. The decrease of uranium in solution, observed after the uranyl adsorption stage, and particularly at acidic pH, is most probably due to the precipitation of U(IV) formed in the solution.

Charge distribution and local structure and speciation in the UO 2+x and PuO 2+x binary oxides for x⩽0.25

NASA Astrophysics Data System (ADS)

Conradson, Steven D.; Begg, Bruce D.; Clark, David L.; den Auwer, Christophe; Ding, Mei; Dorhout, Peter K.; Espinosa-Faller, Francisco J.; Gordon, Pamela L.; Haire, Richard G.; Hess, Nancy J.; Hess, Ryan F.; Webster Keogh, D.; Lander, Gerard H.; Manara, Dario; Morales, Luis A.; Neu, Mary P.; Paviet-Hartmann, Patricia; Rebizant, Jean; Rondinella, Vincenzo V.; Runde, Wolfgang; Drew Tait, C.; Kirk Veirs, D.; Villella, Phillip M.; Wastin, Franck

2005-02-01

The local structure and chemical speciation of the mixed valence, fluorite-based oxides UO 2+x (0.00⩽ x⩽0.20) and PuO 2+x/PuO 2+x-y(OH) 2y· zH 2O have been determined by U/Pu L III XAFS spectroscopy. The U spectra indicate (1) that the O atoms are incorporated as oxo groups at short (1.75 Å) U-O distances consistent with U(VI) concomitant with a large range of U displacements that reduce the apparent number of U neighbors and (2) that the UO 2 fraction remains intact implying that these O defects interact to form clusters and give the heterogeneous structure consistent with the diffraction patterns. The PuO 2+x system, which does not show a separate phase at its x=0.25 endpoint, also displays (1) oxo groups at longer 1.9 Å distances consistent with Pu(V+ δ), (2) a multisite Pu-O distribution even when x is close to zero indicative of the formation of stable species with H 2O and its hydrolysis products with O 2-, and (3) a highly disordered, spectroscopically invisible Pu-Pu component. The structure and bonding in AnO 2+x are therefore more complicated than have previously been assumed and show both similarities but also distinct differences among the different elements.

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

U(VI) Reduction by Biogenic and Abiotic Hydroxycarbonate Green Rusts: Impacts on U(IV) Speciation and Stability Over Time

DOE PAGES

Yan, Sen; Boyanov, Maxim I.; Mishra, Bhoopesh; ...

2018-04-09

Green rusts (GRs) are redox active Fe II-Fe III minerals that form in the environment via various biotic and abiotic processes. Although both biogenic (BioGR) and abiotic (ChemGR) GRs have been shown to reduce U VI, the dynamics of the transformations and the speciation and stability of the resulting U IV phases are poorly understood. We used carbonate extraction and XAFS spectroscopy to investigate the products of U VI reduction by BioGR and ChemGR. The results show that both GRs can rapidly remove U VI from synthetic groundwater via reduction to U IV. The initial products in the ChemGR systemmore » are solids-associated U IV-carbonate complexes that gradually transform to nanocrystalline uraninite over time, leading to a decrease in the proportion of carbonate-extractable U from ~95% to ~10%. In contrast, solid-phase U IV atoms in the BioGR system remain relatively extractable, non-uraninite U IV species over the same reaction period. The presence of calcium and carbonate in groundwater significantly increase the extractability of U IV in the BioGR system. Furthermore, these data provide new insights into the transformations of U under anoxic conditions in groundwater that contains calcium and carbonate, and have major implications for predicting uranium stability within redox dynamic environments and designing approaches for the remediation of uranium-contaminated groundwater.« less

Reduction of uranium by cytochrome c3 of Desulfovibrio vulgaris

USGS Publications Warehouse

Lovley, D.R.; Widman, P.K.; Woodward, J.C.; Phillips, E.J.P.

1993-01-01

The mechanism for U(VI) reduction by Desulfovibrio vulgaris (Hildenborough) was investigated. The H2-dependent U(VI) reductase activity in the soluble fraction of the cells was lost when the soluble fraction was passed over a cationic exchange column which extracted cytochrome c3. Addition of cytochrome c3 back to the soluble fraction that had been passed over the cationic exchange column restored the U(VI)-reducing capacity. Reduced cytochrome c3 was oxidized by U(VI), as was a c-type cytochrome(s) in whole-cell suspensions. When cytochrome c3 was combined with hydrogenase, its physiological electron donor, U(VI) was reduced in the presence of H2. Hydrogenase alone could not reduce U(VI). Rapid U(VI) reduction was followed by a subsequent slow precipitation of the U(IV) mineral uraninite. Cytochrome c3 reduced U(VI) in a uranium-contaminated surface water and groundwater. Cytochrome c3 provides the first enzyme model for the reduction and biomineralization of uranium in sedimentary environments. Furthermore, the finding that cytochrome c3 can catalyze the reductive precipitation of uranium may aid in the development of fixed-enzyme reactors and/or organisms with enhanced U(VI)-reducing capacity for the bioremediation of uranium- contaminated waters and waste streams.

Influence of Iron Speciation on Redox Cycling and Reactivity with Persistent Organic Contaminants

ERIC Educational Resources Information Center

Kim, Dongwook

2009-01-01

Although a number of past studies have been aimed at characterizing iron's redox properties in aqueous systems and its contribution to natural attenuation processes of groundwater contaminants, many questions remain. It is especially important to understand the molecular properties that control the reactivity of both Fe[superscript II] and…

Performance of a Zerovalent Iron Reactive Barrier for the Treatment of Arsenic in Groundwater: Part 2. Geochemical Modeling and Solid Phase Studies

EPA Science Inventory

Arsenic uptake processes were evaluated in a zerovalent iron reactive barrier installed at a lead smelting facility using geochemical modeling, solid-phase analysis, and X-ray absorption spectroscopy techniques. Aqueous speciation of arsenic plays a key role in directing arsenic...

Selenium speciation in acidic environmental samples: application to acid rain-soil interaction at Mount Etna volcano.

PubMed

Floor, Geerke H; Iglesías, Mònica; Román-Ross, Gabriela; Corvini, Philippe F X; Lenz, Markus

2011-09-01

Speciation plays a crucial role in elemental mobility. However, trace level selenium (Se) speciation analyses in aqueous samples from acidic environments are hampered due to adsorption of the analytes (i.e. selenate, selenite) on precipitates. Such solid phases can form during pH adaptation up till now necessary for chromatographic separation. Thermodynamic calculations in this study predicted that a pH<4 is needed to prevent precipitation of Al and Fe phases. Therefore, a speciation method with a low pH eluent that matches the natural sample pH of acid rain-soil interaction samples from Etna volcano was developed. With a mobile phase containing 20mM ammonium citrate at pH 3, selenate and selenite could be separated in different acidic media (spiked water, rain, soil leachates) in <10 min with a LOQ of 0.2 μg L(-1) using (78)Se for detection. Applying this speciation analysis to study acid rain-soil interaction using synthetic rain based on H(2)SO(4) and soil samples collected at the flanks of Etna volcano demonstrated the dominance of selenate over selenite in leachates from samples collected close to the volcanic craters. This suggests that competitive behavior with sulfate present in acid rain might be a key factor in Se mobilization. The developed speciation method can significantly contribute to understand Se cycling in acidic, Al/Fe rich environments. Copyright © 2011 Elsevier Ltd. All rights reserved.

An experimental study of the solubility and speciation of tantalum in fluoride-bearing aqueous solutions at elevated temperature

DOE PAGES

Timofeev, Alexander; Migdisov, Art. A.; Williams-Jones, A. E.

2016-10-27

Here, the solubility of Ta 2O 5 (solid) and the speciation of tantalum in HF-bearing aqueous solutions have been determined at temperatures of 100-250 °C and vapour-saturated water pressure. Tantalum is transported as the species Ta(OH) 5 0 at low HF concentration and pH ~1-3. At higher HF concentration, tantalum mobility is controlled by the species TaF 3(OH) 3- and TaF 5; the presence of TaF 5 0 is only evident at ≤150 °C. Equilibrium constants range from -17.4 ± 0.45 to -16.4 ± 0.12 for the formation of Ta(OH) 5 from crystalline Ta 2O 5 and from -8.24 ±more » 0.64 to -8.55 ± 0.68 for the formation of TaF 3(OH) 3- at 100 and 250 °C, respectively. For TaF 5 0, they were determined to be 0.13 at 100 °C and -0.35 at 150 °C.« less

Final Project Report, DE-SC0001280, Characterizing the Combined Roles of Iron and Transverse Mixing on Uranium Bioremediation in Groundwater using Microfluidic Devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Finneran, Kevin; Werth, Charles; Strathmann, Timothy

2015-01-10

In situ bioremediation of U(VI) involves amending groundwater with an appropriate electron donor and limiting nutrients to promote biological reduction to the less soluble and mobile U(IV) oxidation state. Groundwater flow is laminar; mixing is controlled by hydrodynamic dispersion. Recent studies indicate that transverse dispersion along plume margins can limit mixing of the amended electron donor and accepter (such as U(VI) in remediation applications). As a result, microbial growth, and subsequently contaminant reaction, may be limited to these transverse mixing zones during bioremediation. The primary objective of this work was to characterize the combined effects of hydrology, geochemistry, and biologymore » on the (bio)remediation of U(VI). Our underlying hypothesis was that U(VI) reaction in groundwater is controlled by transverse mixing with an electron donor along plume margins, and that iron bioavailability in these zones affects U(VI) reduction kinetics and U(IV) re-oxidation. Our specific objectives were to a) quantify reaction kinetics mediated by biological versus geochemical reactions leading to U(VI) reduction and U(IV) re-oxidation, b) understand the influence of bioavailable iron on U(VI) reduction and U(IV) re-oxidation along the transverse mixing zones, c) determine how transverse mixing limitations and the presence of biomass in pores affects these reactions, and d) identify how microbial populations that develop along transverse mixing zones are influenced by the presence of iron and the concentration of electron donor. In the completed work, transverse mixing zones along plume margins were re-created in microfluidic pore networks, referred to as micromodels. We conducted a series of experiments that allowed us to distinguish among the hydraulic, biological, and geochemical mechanisms that contribute to U(VI) reduction, U(IV) re-oxidation, and U(VI) abiotic reaction with the limiting biological nutrient HP042-. This systematic approach may lead to a better understanding of U(VI) remediation, and better strategies for groundwater amendments to maximize remediation efficiency.« less

Resistance, bioaccumulation and solid phase extraction of uranium (VI) by Bacillus vallismortis and its UV-vis spectrophotometric determination.

PubMed

Ozdemir, Sadin; Oduncu, M Kadir; Kilinc, Ersin; Soylak, Mustafa

2017-05-01

Bioaccumulation, resistance and preconcentration of uranium(VI) by thermotolerant Bacillus vallismortis were investigated in details. The minimum inhibition concentration of (MIC) value of U(VI) was found as 85 mg/L and 15 mg/L in liquid and solid medium, respectively. Furthermore, the effect of various U(VI) concentrations on the growth of bacteria and bioaccumulation on B. vallismortis was examined in the liquid culture media. The growth was not significantly affected in the presence of 1.0, 2.5 and 5.0 mg/L U(VI) up to 72 h. The highest bioaccumulation value at 1 mg/L U(VI) concentration was detected at the 72nd hour (10 mg/g metal/dry bacteria), while the maximum bioaccumulation value at 5 mg/L U(VI) concentration was determined at the 48th hour (50 mg metal/dry bacteria). In addition to these, various concentration of U(VI) on α-amylase production was studied. The α-amylase activities at 0, 1, 2.5 and 5 mg/L U(VI) were found as 3313.2, 3845.2, 3687.1 and 3060.8 U/mg, respectively at 48th. Besides, uranium (VI) ions were preconcentrated with immobilized B. vallismortis onto multiwalled carbon nanotube (MWCNT) and were determined by UV-vis spectrophotometry. The surface macro structure and functionalities of B. vallismortis immobilized onto multiwalled carbon nanotube with and without U(VI) were examined by FT-IR and SEM. The optimum pH and flow rate for the biosorption of U(VI) were 4.0-5.0 and 1.0 mL/min, respectively. The quantitative elution occurred with 5.0 mL of 1 mol/L HCl. The loading capacity of immobilized B. vallismortis was determined as 23.6 mg/g. The certified reference sample was employed for the validation of developed solid phase extraction method. The new validated method was applied to the determination of U(VI) in water samples from Van Lake-Turkey. Copyright © 2017 Elsevier Ltd. All rights reserved.

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Mccollom, Tom; Schrenk, Matt; Cardace, Dawn

2011-01-01

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

The biomineralization process of uranium(VI) by Saccharomyces cerevisiae - transformation from amorphous U(VI) to crystalline chernikovite.

PubMed

Shen, Yanghao; Zheng, Xinyan; Wang, Xiaoyu; Wang, Tieshan

2018-05-01

Microorganisms play a significant role in uranium(VI) biogeochemistry and influence U(VI) transformation through biomineralization. In the present work, the process of uranium mineralization was investigated by Saccharomyces cerevisiae. The toxicity experiments showed that the viability of cell was not significantly affected by 100 mg L -1 U(VI) under 4 days of exposure time. The batch experiments showed that the phosphate concentration and pH value increased over time during U(VI) adsorption. Meanwhile, thermodynamic calculations demonstrated that the adsorption system was supersaturated with respect to UO 2 HPO 4 . The X-ray powder diffraction spectroscopy (XRD), field emission scanning electron microscopy (FE-SEM) equipped with energy dispersive spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) analyses indicated that the U(VI) was first attached onto the cell surface and reacted with hydroxyl, carboxyl, and phosphate groups through electrostatic interactions and complexation. As the immobilization of U(VI) transformed it from the ionic to the amorphous state, lamellar uranium precipitate was formed on the cell surface. With the prolongation of time, the amorphous uranium compound disappeared, and there were some crystalline substances observed extracellularly, which were well-characterized as tetragonal-chernikovite. Furthermore, the size of chernikovite was regulated at nano-level by cells, and the perfect crystal was formed finally. These findings provided an understanding of the non-reductive transformation process of U(VI) from the amorphous to crystalline state within microbe systems, which would be beneficial for the U(VI) treatment and reuse of nuclides and heavy metals.

Methods for Estimating Adsorbed Uranium(VI) and Distribution Coefficients of Contaminated Sediments

USGS Publications Warehouse

Kohler, M.; Curtis, G.P.; Meece, D.E.; Davis, J.A.

2004-01-01

Assessing the quantity of U(VI) that participates in sorption/desorption processes in a contaminated aquifer is an important task when investigating U migration behavior. U-contaminated aquifer sediments were obtained from 16 different locations at a former U mill tailings site at Naturita, CO (U.S.A.) and were extracted with an artificial groundwater, a high pH sodium bicarbonate solution, hydroxylamine hydrochloride solution, and concentrated nitric acid. With an isotopic exchange method, both a KD value for the specific experimental conditions as well as the total exchangeable mass of U(VI) was determined. Except for one sample, KD values determined by isotopic exchange with U-contaminated sediments that were in equilibrium with atmospheric CO2 agreed within a factor of 2 with KD values predicted from a nonelectrostatic surface complexation model (NEM) developed from U(VI) adsorption experiments with uncontaminated sediments. The labile fraction of U(VI) and U extracted by the bicarbonate solution were highly correlated (r2 = 0.997), with a slope of 0.96 ?? 0.01. The proximity of the slope to one suggests that both methods likely access the same reservoir of U(VI) associated with the sediments. The results indicate that the bicarbonate extraction method is useful for estimating the mass of labile U(VI) in sediments that do not contain U(IV). In-situ KD values calculated from the measured labile U(VI) and the dissolved U(VI) in the Naturita alluvial aquifer agreed within a factor of 3 with in-situ K D values predicted with the NEM and groundwater chemistry at each well.

Controlling sunbathing safety during the summer holidays - The solar UV campaign at Baltic Sea coast in 2015.

PubMed

Guzikowski, Jakub; Czerwińska, Agnieszka E; Krzyścin, Janusz W; Czerwiński, Michał A

2017-08-01

Information regarding the intensity of surface UV radiation, provided for the public, is frequently given in terms of a daily maximum UV Index (UVI), based on a prognostic model. The quality of the UV forecast depends on the accuracy of column amount of ozone and cloudiness prediction. Daily variability of UVI is needed to determine the risk of the UV overexposure during outdoor activities. Various methods of estimating the temporary UVI and the maximum duration of UV exposures (received a dose equal to minimal erythemal dose - MED), at the site of sunbathing, were compared. The UV indices were obtained during a field experiment at the Baltic Sea coast in the period from 13th to 24th July 2015. The following UVI calculation models were considered: UVI measurements by simple hand-held biometers (Silver Crest, Oregon Scientific, or more advanced Solarmeter 6.5), our smartphone models based on cloud cover observations at the site and the cloudless-sky UVI forecast (available for any site for all smartphone users) or measured UVI, and the 24h weather predictions by the ensemble set of 10 models (with various cloud parameterizations). The direct UV measurements, even by a simple biometer, provided useful UVI estimates. The smartphone applications yielded a good agreement with the UV measurements. The weather prediction models for cloudless-sky conditions could provide valuable information if almost cloudless-sky conditions (cloudless-sky or slightly scattered clouds) were observed at the sunbathing site. Copyright © 2017 Elsevier B.V. All rights reserved.

Bioreduction of U(VI) and stability of immobilized uranium under suboxic conditions.

PubMed

Hu, Nan; Ding, De-xin; Li, Shi-mi; Tan, Xiang; Li, Guang-yue; Wang, Yong-dong; Xu, Fei

2016-04-01

In order to study the bioreduction of U(VI) and stability of immobilized uranium under suboxic conditions, microcosm were amended with ethanol, lactate and glucose, and incubated under suboxic conditions. During the incubation, total dissolved U in amended microcosms decreased from 0.95 mg/L to 0.03 mg/L. Pyrosequencing results showed that, the proportion of anaerobic microorganisms capable of reducing U(VI) under suboxic conditions was small compared with that under anoxic conditions; the proportion of aerobic and facultative anaerobic microorganisms capable of consuming the dissolved oxygen was large; and some of the facultative anaerobic microorganisms could reduce U(VI). These results indicated that different microbial communities were responsible for the bioreduction of U(VI) under suboxic and anoxic conditions. After the electron donors were exhausted, total dissolved U in the amended microcosms remained unchanged, while the U(VI)/U(IV) ratio in the solid phase of sediments increased obviously. This implied that the performance of bioreduction of the U(VI) can be maintained under suboxic condition. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling Reduction of Uranium U(VI) under Variable Sulfate Concentrations by Sulfate-Reducing Bacteria

PubMed Central

Spear, John R.; Figueroa, Linda A.; Honeyman, Bruce D.

2000-01-01

The kinetics for the reduction of sulfate alone and for concurrent uranium [U(VI)] and sulfate reduction, by mixed and pure cultures of sulfate-reducing bacteria (SRB) at 21 ± 3°C were studied. The mixed culture contained the SRB Desulfovibrio vulgaris along with a Clostridium sp. determined via 16S ribosomal DNA analysis. The pure culture was Desulfovibrio desulfuricans (ATCC 7757). A zero-order model best fit the data for the reduction of sulfate from 0.1 to 10 mM. A lag time occurred below cell concentrations of 0.1 mg (dry weight) of cells/ml. For the mixed culture, average values for the maximum specific reaction rate, Vmax, ranged from 2.4 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1) at 0.25 mM sulfate to 5.0 ± 1.1 μmol of sulfate/mg (dry weight) of SRB · h−1 at 10 mM sulfate (average cell concentration, 0.52 mg [dry weight]/ml). For the pure culture, Vmax was 1.6 ± 0.2 μmol of sulfate/mg (dry weight) of SRB · h−1 at 1 mM sulfate (0.29 mg [dry weight] of cells/ml). When both electron acceptors were present, sulfate reduction remained zero order for both cultures, while uranium reduction was first order, with rate constants of 0.071 ± 0.003 mg (dry weight) of cells/ml · min−1 for the mixed culture and 0.137 ± 0.016 mg (dry weight) of cells/ml · min−1 (U0 = 1 mM) for the D. desulfuricans culture. Both cultures exhibited a faster rate of uranium reduction in the presence of sulfate and no lag time until the onset of U reduction in contrast to U alone. This kinetics information can be used to design an SRB-dominated biotreatment scheme for the removal of U(VI) from an aqueous source. PMID:10966381

Study of polyethyleneimine- and amidoxime-functionalized hybrid biomass of Spirulina (Arthrospira) platensis for adsorption of uranium (VI) ion.

PubMed

Bayramoglu, Gulay; Akbulut, Aydin; Arica, M Yakup

2015-11-01

This study investigates the potential application of the polyethyleneimine- (PEI) and amidoxime-modified Spirulina (Arthrospira) platensis biomasses for the removal of uranium ion in batch mode using the native biomass as a control system. The uranium ion adsorption was also characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra, zeta potential analysis, and surface area measurement studies. The effects of pH, biomass amount, contact time, initial uranium ion concentration, and ionic strength were evaluated by using native and modified algal biomass preparations. The uranium ion removal was rapid, with more than 70% of total adsorption taking place in 40 min, and equilibrium was established within 60 min. From the experimental data, it was found that the amount of adsorption uranium ion on the algal preparations decreased in the following series: amidoxime-modified algal biomass > PEI-modified algal biomass > native algal biomass. Maximum adsorption capacities of amidoxime- and PEI-modified, and native algal biomasses were found to be 366.8, 279.5, and 194.6 mg/g, respectively, in batchwise studies. The adsorption rate of U(VI) ion by amidoxime-modified algal biomass was higher than those of the native and PEI-modified counterparts. The adsorption processes on all the algal biomass preparations followed by the Dubinin-Radushkevitch (D-R) and Temkin isotherms and pseudo-second-order kinetic models. The thermodynamic parameters were determined at four different temperatures (i.e., 15, 25, 35, and 45 °C) using the thermodynamics constant of the Temkin isotherm model. The ΔH° and ΔG° values of U(VI) ion adsorption on algal preparations show endothermic heat of adsorption; higher temperatures favor the process. The native and modified algal biomass preparations were regenerated using 10 mM HNO3. These results show that amidoxime-modified algal biomass can be a potential candidate for effective removal of U(VI) ion from aqueous solution.

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

Alumino-silicate speciation in aqueous fluids at deep crustal conditions

NASA Astrophysics Data System (ADS)

Mookherjee, M.; Keppler, H.; Manning, C. E.

2014-12-01

Alumina and silica are major oxides in most crustal rocks. While SiO2 is quite soluble in aqueous fluids at metamorphic conditions, behavior of Al2O3 in crustal metamorphic fluids has been poorly understood. It is known that alumina is dramatically less soluble in aqueous fluids and hence it is difficult to explain the common occurrence of quartz with aluminous minerals in metamorphic veins. In order to understand this complex behavior of alumina, we investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 oC. In order to better understand the spectral features of the aqueous fluids, we used first principles simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with KOH solution in equilibrium with Al2O3 show a sharp band at ~620 cm-1 which could be attributed to the [Al(OH)4]1- species. The band grows in intensity with temperature along an isochore. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [Al(OH)4]1- species to dimers [(OH)2-Al-O2-Al(OH)2]2- or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. We are also investigating the effect of SiO2 on the solubility of Al2O3 and the relative energetics of formation of pure alumina dimer [(OH)3-Al-O-Al(OH)3]2- vs. the aluminosilicate dimers, [(OH)3-Al-O-Si(OH)3]2- at deep crustal conditions. Acknowledgement- MM is supported by the US National Science Foundation grant (EAR-1250477).

Grain-Size Based Additivity Models for Scaling Multi-rate Uranyl Surface Complexation in Subsurface Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

The additivity model assumed that field-scale reaction properties in a sediment including surface area, reactive site concentration, and reaction rate can be predicted from field-scale grain-size distribution by linearly adding reaction properties estimated in laboratory for individual grain-size fractions. This study evaluated the additivity model in scaling mass transfer-limited, multi-rate uranyl (U(VI)) surface complexation reactions in a contaminated sediment. Experimental data of rate-limited U(VI) desorption in a stirred flow-cell reactor were used to estimate the statistical properties of the rate constants for individual grain-size fractions, which were then used to predict rate-limited U(VI) desorption in the composite sediment. The resultmore » indicated that the additivity model with respect to the rate of U(VI) desorption provided a good prediction of U(VI) desorption in the composite sediment. However, the rate constants were not directly scalable using the additivity model. An approximate additivity model for directly scaling rate constants was subsequently proposed and evaluated. The result found that the approximate model provided a good prediction of the experimental results within statistical uncertainty. This study also found that a gravel-size fraction (2 to 8 mm), which is often ignored in modeling U(VI) sorption and desorption, is statistically significant to the U(VI) desorption in the sediment.« less

Speciation of Reactive Sulfur Species and their Reactions with Alkylating Agents: Do we have any clue about what is present inside the cell?

PubMed

Bogdándi, Virág; Ida, Tomoaki; Sutton, Thomas R; Bianco, Christopher; Ditrói, Tamás; Koster, Grielof; Henthorn, Hillary A; Minnion, Magda; Toscano, John P; van der Vliet, Albert; Pluth, Michael D; Feelisch, Martin; Fukuto, Jon M; Akaike, Takaaki; Nagy, Péter

2018-06-17

Posttranslational modifications of cysteine (Cys) residues represent a major aspect of redox biology, and their reliable detection is key in providing mechanistic insights. The metastable character of these modifications and cell lysis-induced artifactual oxidation render current state-of-the-art protocols to rely on alkylation-based stabilization of labile Cys derivatives before cell/tissue rupture. An untested assumption in these procedures is that for all Cys derivatives alkylation rates are faster than their dynamic interchange. However, when the interconversion of Cys derivatives is not rate-limiting, then electrophilic labeling is under Curtin-Hammett control and hence the final alkylated mixture may not represent the speciation that prevailed before alkylation. We here present evidence that in the majority of cases, the speciation of alkylated polysulfide/thiol derivatives indeed depends on the experimental conditions. Our results reveal that alkylation perturbs sulfur speciation in both a concentration- and time-dependent manner, and that strong alkylating agents can cleave polysulfur chains. Moreover, we show that labeling of sulfenic acids with dimedone also affects Cys speciation, suggesting that part of the endogenous pool of products previously believed to represent sulfenic acid species may in fact represent polysulfides. These observations were obtained using buffered aqueous solutions of inorganic-, organic-, cysteine-, glutathione- and GAPDH-polysulfide species. Additional experiments in human plasma and serum revealed that monobromobimane can extract sulfide from the endogenous sulfur pool by shifting speciation equilibria, suggesting caution should be exercised when interpreting experimental results using this tool. We highlight methodological caveats potentially arising from these pitfalls and conclude that current derivatization strategies often fail to adequately capture physiologic speciation of sulfur species. This article is protected by copyright. All rights reserved.

Immobilization of uranium into magnetite from aqueous solution by electrodepositing approach.

PubMed

Lu, Bing-Qing; Li, Mi; Zhang, Xiao-Wen; Huang, Chun-Mei; Wu, Xiao-Yan; Fang, Qi

2018-02-05

Immobilization of uranium into magnetite (Fe 3 O 4 ), which was generated from metallic iron by electrochemical method, was proposed to rapidly remove uranium from aqueous solution. The effects of electrochemical parameters such as electrode materials, voltage, electrode gap, reaction time and pH value on the crystallization of Fe 3 O 4 and uranium removal efficiencies were investigated. More than 90% uranium in the solution was precipitated with Fe 3 O 4 under laboratory conditions when uranium concentration range from 0.5mg/L to 10mg/L. The Fe 3 O 4 crystallization mechanism and immobilization of uranium was proved by XPS, XRD, TEM, FTIR and VSM methods. The results indicated that the cationic (including Fe 2+ , Fe 3+ and U(VI)) migrate to cathode side under the electric field and the uranium was incorporated or adsorbed by Fe 3 O 4 which was generated at cathode while the pH ranges between 2-7. The uranium-containing precipitate of Fe 3 O 4 can exist stably at the acid concentration below 60g/L. Furthermore, the precipitate may be used as valuable resources for uranium or iron recycling, which resulted in no secondary pollution in the removal of uranium from aqueous solution. Copyright © 2017. Published by Elsevier B.V.

Characteristics of uranium biosorption from aqueous solutions on fungus Pleurotus ostreatus.

PubMed

Zhao, Changsong; Liu, Jun; Tu, Hong; Li, Feize; Li, Xiyang; Yang, Jijun; Liao, Jiali; Yang, Yuanyou; Liu, Ning; Sun, Qun

2016-12-01

Uranium(VI) biosorption from aqueous solutions was investigated in batch studies by using fungus Pleurotus ostreatus biomass. The optimal biosorption conditions were examined by investigating the reaction time, biomass dosage, pH, temperature, and uranium initial concentration. The interaction between fungus biomass and uranium was confirmed using Fourier transformed infrared (FT-IR), scanning electronic microscopy energy dispersive X-ray (SEM-EDX), and X-ray photoelectron spectroscopy (XPS) analysis. Results exhibited that the maximum biosorption capacity of uranium on P. ostreatus was 19.95 ± 1.17 mg/g at pH 4.0. Carboxylic, amine, as well as hydroxyl groups were involved in uranium biosorption according to FT-IR analysis. The pseudo-second-order model properly evaluated the U(VI) biosorption on fungus P. ostreatus biomass. The Langmuir equation provided better fitting in comparison with Freundlich isotherm models. The obtained thermodynamic parameters suggested that biosorption is feasible, endothermic, and spontaneous. SEM-EDX and XPS were additionally conducted to comprehend the biosorption process that could be described as a complex process involving several mechanisms of physical adsorption, chemisorptions, and ion exchange. Results obtained from this work indicated that fungus P. ostreatus biomass can be used as potential biosorbent to eliminate uranium or other radionuclides from aqueous solutions.

ARSENIC SPECIATION, SEASONAL TRANSFORMATIONS, AND CO-DISTRIBUTION WITH IRON IN A MINE WASTE-INFLUENCED PALUSTRINE EMERGENT WETLAND. (R825399)

EPA Science Inventory

Arsenic is commonly associated with mined ores and thus may be detrimental to naturally occurring wetlands that reside in mine waste-impacted regions. Understanding the relationship between Fe and As in both the aqueous and solid phase is critical for assessing the risk As impose...

Amazon kaolinite functionalized with diethylenetriamine moieties for U(VI) removal: thermodynamic of cation-basic interactions.

PubMed

Guerra, Denis L; Leidens, Victor L; Viana, Rúbia R; Airoldi, Claudio

2010-08-15

The compound N-[3-(trimethoxysilyl)propyl]diethylenetriamine (MPDET) was anchored onto Amazon kaolinite surface (KLT) by heterogeneous route. The modified and natural kaolinite clay samples were characterized by transmission electron microscopy (TEM), scanning electron microscopic (SEM), N(2) adsorption, powder X-ray diffraction, thermal analysis, ion exchange capacities, and nuclear magnetic nuclei of (29)Si and (13)C. The well-defined peaks obtained in the (13)C NMR spectrum in the 5.0-62.1 ppm region confirmed the attachment of organic functional groups as pendant chains bonded into the porous clay. The adsorption of uranyl on natural (KLT) and modified (KLT(MPDET)) kaolinite clays was investigated as a function of the solution pH, metal concentration, temperature, and ionic strength. The ability of these materials to remove U(VI) from aqueous solution was followed by a series of adsorption isotherms adjusted to a Sips equation at room temperature and pH 4.0. The maximum number of moles adsorbed was determined to be 8.37 x 10(-3) and 13.87 x 10(-3) mmol g(-1) for KLT and KLT(MPDET) at 298 K, respectively. The energetic effects (Delta(int)H, Delta(int)G, and Delta(int)S) caused by metal cations adsorption were determined through calorimetric titrations. Copyright 2010. Published by Elsevier B.V.

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Uranium immobilization and nanofilm formation on magnesium-rich minerals

DOE PAGES

van Veelen, Arjen; Bargar, John R.; Law, Gareth T. W.; ...

2016-03-18

Polarization-dependent grazing incidence X-ray absorption spectroscopy (XAS) measurements were completed on oriented single crystals of magnesite [MgCO 3] and brucite [Mg(OH) 2] reacted with aqueous uranyl chloride above and below the solubility boundaries of schoepite (500, 50, and 5 ppm) at pH 8.3 and at ambient (P CO2 = 10 –3.5) or reduced partial pressures of carbon dioxide (P CO2 = 10 –4.5). X-ray absorption near edge structure (XANES) spectra show a striking polarization dependence (χ = 0° and 90° relative to the polarization plane of the incident beam) and consistently demonstrated that the uranyl molecule was preferentially oriented withmore » its O axial = U(VI) = O axial linkage at high angles (60–80°) to both magnesite (101¯4) and brucite (0001). Extended X-ray absorption fine structure (EXAFS) analysis shows that the “effective” number of U(VI) axial oxygens is the most strongly affected fitting parameter as a function of polarization. Furthermore, axial tilt in the surface thin films (thickness ~ 21 Å) is correlated with surface roughness [σ]. Our results show that hydrated uranyl(-carbonate) complexes polymerize on all of our experimental surfaces and that this process is controlled by surface hydroxylation. Lastly, these results provide new insights into the bonding configuration expected for uranyl complexes on the environmentally significant carbonate and hydroxide mineral surfaces.« less

Syntheses and structures of [UO2( L)5](ClO4)2 and [U( L')4(H2O)4](ClO4)4 ( L is dimethylformamide, L' is N,N-dimethylcarbamide)

NASA Astrophysics Data System (ADS)

Serezhkin, V. N.; Vologzhanina, A. V.; Pushkin, D. V.; Astashkina, D. A.; Savchenkov, A. V.; Serezhkina, L. B.

2017-09-01

The reaction of aqueous solutions of uranyl perchlorate with selected organic amides was studied in the dark and under the sunlight. The complexes [UVIO2(C3H7NO)5](ClO4)2 ( I) and [UIV(C3H8N2O)4(H2O)4](ClO4)4 ( II), where C3H7NO is N,N-dimethylformamide ( Dmfa) and C3H8N2O is N,N-dimethylcarbamide ( a-Dmur), were studied by X-ray diffraction. Complex II and the complex UIV( s-Dmur)4(H2O)4(ClO4)4 ( III), where s-Dmur is N,N'-dimethylcarbamide, were studied by IR spectroscopy. Crystals I and II are composed of mononuclear [UO2( Dmfa)5]2+ and [U( Dmur)4(H2O)4]4+ groups as uranium-containing structural units belonging to the crystal-chemical groups AM 7 1 ( A = UVI, M 1 = O2- and Dmfa) and AM 8 1 ( A = UIV, M 1 = Dmur and H2O) of uranium complexes, respectively. The mononuclear uranium- containing complexes in the crystals of U(IV) and U(VI) perchlorates were found to obey the 14 neighbors rule.

Predictions of Actinide Solubilities under Near-Field Conditions Expected in the WIPP

NASA Astrophysics Data System (ADS)

Brush, L. H.; Xiong, Y.

2009-12-01

The Waste Isolation Pilot Plant (WIPP) is a U.S. Department of Energy (DOE) repository in southeast New Mexico for defense-related transuranic (TRU) waste. The repository, which opened in March 1999, is located at a subsurface depth of 655 m (2150 ft) in the Salado Fm., a Permian bedded-salt formation. The repository will eventually contain the equivalent of 844,000 208 L (55 gal) drums of TRU waste. After filling the rooms and access drifts and installing panel closures, creep closure of the salt will crush the steel waste containers in most cases and encapsulate the waste. The WIPP actinide source term model used for long-term performance assessment (PA) of the repository comprises dissolved and suspended submodels (solubilities and colloids). This presentation will describe the solubilities. From the standpoint of long-term PA, the order of importance of the radioelements in the TRU waste to be emplaced in the WIPP is Pu ~ Am >> U > Th >> Np ~ Cm and fission products. The DOE has included all of these actinides, but not fission products, in the WIPP Actinide Source Term Program (ASTP). Anoxic corrosion of Fe- and Al-base metals and microbial consumption of cellulosic, plastic, and rubber materials will produce gas and create strongly reducing conditions in the WIPP after closure. The use of MgO as an engineered barrier to consume microbially produced CO2 will result in low fCO2 and basic pH. Under these conditions, Th, U, Np, Pu, and Am will speciate essentially entirely as Th(IV), U(IV), Np(IV), Pu(III), and Am(III); or Th(IV), U(VI), Np(V), Pu(IV), and Am(III). The DOE has developed thermodynamic speciation-and-solubility models for +III, +IV, and +V actinides in brines. Experimental data for Nd, Am, and Cm species were used to parameterize the +III Pitzer activity-coefficient model; data for Th species were used for the +IV model; and data for Np(V) species were used for the +V model. These models include the effects of the organic ligands acetate, citrate, EDTA, and oxalate in TRU waste. The oxidation-state analogy was then used to extend the +III model to Pu(III), and the +IV model to Pu(IV), U(IV), and Np(IV). The solubility of U(VI) was estimated. For the recent WIPP Compliance Recertification Application PA Baseline Calculations, we calculated actinide solubilities with fCO2 buffered at 3.14 × 10-6 atm by the brucite-hydromagnesite carbonation reaction, with pH maintained at ~9 by the brucite dissolution-precipitation reaction, and with estimated concentrations of the organic ligands in brines from the Salado and the Castile Fm., which underlies the Salado. The calculated +III, +IV, and +V solubilities are 1.56 × 10-6, 5.64 × 10-8, and 4.07 × 10-7 M, respectively, in Salado brine; and 1.51 × 10-6, 6.98 × 10-8, and 8.75 × 10-7 M in Castile brine. The U(VI) solubility estimated for both brines is 1 × 10-3 M. This research is funded by WIPP programs administered by the U.S. Department of Energy. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000.

Solution speciation of plutonium and Americium at an Australian legacy radioactive waste disposal site.

PubMed

Ikeda-Ohno, Atsushi; Harrison, Jennifer J; Thiruvoth, Sangeeth; Wilsher, Kerry; Wong, Henri K Y; Johansen, Mathew P; Waite, T David; Payne, Timothy E

2014-09-02

During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed.

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: the role of Fe(II) and Fe(III).

PubMed

Yan, Sen; Chen, Yongheng; Xiang, Wu; Bao, Zhengyu; Liu, Chongxuan; Deng, Baolin

2014-12-01

The role of Fe(II) and Fe(III) in U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed that U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.9 to 9.0. For instance, at pH 6.9 the observed U(VI) reduction rates decreased by 81% and 82% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) possibly acted as an electron shuttle to ferry the electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 could facilitate U(VI) reductive immobilization in the contaminated groundwater.

WFC3 UVIS Detector Performance

NASA Astrophysics Data System (ADS)

Gunning, Heather C.; Baggett, Sylvia M.; Gosmeyer, Catherine; Bourque, Matthew; MacKenty, John W.; Anderson, Jay; WFC3 Team

2015-01-01

The Wide Field Camera 3 (WFC3) is a fourth-generation imaging instrument installed on the Hubble Space Telescope (HST) during Servicing Mission 4 (SM4) in May 2000. WFC3 has two observational channels, UV/visible (UVIS) and infrared (IR); both have been performing well on-orbit. Since installation, the WFC3 team has been diligent in monitoring the performance of both detectors. The UVIS channel consists of two e2v, backside illuminated, 2Kx4K CCDs arranged in a 2x1 mosaic. We present results from some of the monitoring programs used to check various aspects of the UVIS detector. We discuss the growth trend of hot pixels and the efficacy of regular anneals in controlling the hot pixel population. We detail a pixel population with lowered-sensitivity that evolves during the time between anneals, and is largely reset by each anneal procedure. We discuss the stability of the post-flash LED lamp, used and recommended for CTE mitigation in observations with less than 12 e-/pixel backgrounds. Finally, we summarize long-term photometric trends of the UVIS detector, as well as the absolute gain measurement, used as a proxy for the on-orbit evolution of the UVIS channel.

Uranium(VI) reduction by nanoscale zero-valent iron in anoxic batch systems: The role of Fe(II) and Fe(III)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Sen; Chen, Yongheng; Xiang, Wu

2014-12-01

The role of Fe(II) and Fe(III) on U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.92 to 9.03. For instance, at pH 6.92 the observed U(VI) reduction rates decreased by 80.7% and 82.3% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can bemore » enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) probably acted as an electron shuttle to mediate the transfer of electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 can facilitate the U(VI) reductive immobilization in the contaminated groundwater.« less

Dynamics of microbial community composition and function during in-situ bioremediation of a uranium-contaminated aquifer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nostrand, J.D. Van; Wu, L.; Wu, W.M.

2010-08-15

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter{sup -1}). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed thatmore » Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process.« less

Dynamics of Microbial Community Composition and Function during In Situ Bioremediation of a Uranium-Contaminated Aquifer▿‡

PubMed Central

Van Nostrand, Joy D.; Wu, Liyou; Wu, Wei-Min; Huang, Zhijian; Gentry, Terry J.; Deng, Ye; Carley, Jack; Carroll, Sue; He, Zhili; Gu, Baohua; Luo, Jian; Criddle, Craig S.; Watson, David B.; Jardine, Philip M.; Marsh, Terence L.; Tiedje, James M.; Hazen, Terry C.; Zhou, Jizhong

2011-01-01

A pilot-scale system was established to examine the feasibility of in situ U(VI) immobilization at a highly contaminated aquifer (U.S. DOE Integrated Field Research Challenge site, Oak Ridge, TN). Ethanol was injected intermittently as an electron donor to stimulate microbial U(VI) reduction, and U(VI) concentrations fell to below the Environmental Protection Agency drinking water standard (0.03 mg liter−1). Microbial communities from three monitoring wells were examined during active U(VI) reduction and maintenance phases with GeoChip, a high-density, comprehensive functional gene array. The overall microbial community structure exhibited a considerable shift over the remediation phases examined. GeoChip-based analysis revealed that Fe(III)-reducing bacterial (FeRB), nitrate-reducing bacterial (NRB), and sulfate-reducing bacterial (SRB) functional populations reached their highest levels during the active U(VI) reduction phase (days 137 to 370), in which denitrification and Fe(III) and sulfate reduction occurred sequentially. A gradual decrease in these functional populations occurred when reduction reactions stabilized, suggesting that these functional populations could play an important role in both active U(VI) reduction and maintenance of the stability of reduced U(IV). These results suggest that addition of electron donors stimulated the microbial community to create biogeochemical conditions favorable to U(VI) reduction and prevent the reduced U(IV) from reoxidation and that functional FeRB, SRB, and NRB populations within this system played key roles in this process. PMID:21498771

Attenuation by clouds of UV radiation for low stratospheric ozone conditions

NASA Astrophysics Data System (ADS)

Orte, Facundo; Wolfram, Elian; Salvador, Jacobo; D'Elia, Raúl; Quiroga, Jonathan; Quel, Eduardo; Mizuno, Akira

2017-02-01

Stratospheric poor ozone air masses related to the polar ozone hole overpass subpolar regions in the Southern Hemisphere during spring and summer seasons, resulting in increases of surface Ultraviolet Index (UVI). The impact of these abnormal increases in the ultraviolet radiation could be overestimated if clouds are not taking into account. The aim of this work is to determine the percentage of cases in which cloudiness attenuates the high UV radiation that would reach the surface in low total ozone column situations and in clear sky hypothetical condition for Río Gallegos, Argentina. For this purpose, we analysed UVI data obtained from a multiband filter radiometer GUV-541 (Biospherical Inc.) installed in the Observatorio Atmosférico de la Patagonia Austral (OAPA-UNIDEF (MINDEF - CONICET)) (51 ° 33' S, 69 ° 19' W), Río Gallegos, since 2005. The database used covers the period 2005-2012 for spring seasons. Measured UVI values are compared with UVI calculated using a parametric UV model proposed by Madronich (2007), which is an approximation for the UVI for clear sky, unpolluted atmosphere and low surface albedo condition, using the total ozone column amount, obtained from the OMI database for our case, and the solar zenith angle. It is observed that ˜76% of the total low ozone amount cases, which would result in high and very high UVI categories for a hypothetical (modeled) clear sky condition, are attenuated by clouds, while 91% of hypothetical extremely high UVI category are also attenuated.

A procedure for quantitation of total oxidized uranium for bioremediation studies

USGS Publications Warehouse

Elias, Dwayne A.; Senko, John M.; Krumholz, Lee R.

2003-01-01

A procedure was developed for the quantitation of complexed U(VI) during studies on U(VI) bioremediation. These studies typically involve conversion of soluble or complexed U(VI) (oxidized) to U(IV) (the reduced form which is much less soluble). Since U(VI) freely exchanges between material adsorbed to the solid phase and the dissolved phase, uranium bioremediation experiments require a mass balance of U in both its soluble and adsorbed forms as well as in the reduced sediment bound phase. We set out to optimize a procedure for extraction and quantitation of sediment bound U(VI). Various extractant volumes to sediment ratios were tested and it was found that between 1:1 to 8:1 ratios (v/w) there was a steady increase in U(VI) recovered, but no change with further increases in v/w ratio.Various strengths of NaHCO3, Na-EDTA, and Na-citrate were used to evaluate complexed U(VI) recovery, while the efficiency of a single versus repeated extraction steps was compared with synthesized uranyl-phosphate and uranyl-hydroxide. Total recovery with 1 M NaHCO3 was 95.7% and 97.9% from uranyl-phosphate and uranyl-hydroxide, respectively, compared to 80.7% and 89.9% using 450 mM NaHCO3. Performing the procedure once yielded an efficiency of 81.1% and 92.3% for uranyl-phosphate and uranyl-hydroxide, respectively, as compared to three times. All other extractants yielded 7.9–82.0% in both experiments.

Assessment of total arsenic and arsenic species stability in alga samples and their aqueous extracts.

PubMed

García Salgado, S; Quijano Nieto, M A; Bonilla Simón, M M

2008-05-30

In order to achieve reliable information on speciation analysis, it is necessary to assess previously the species stability in the sample to analyse. Furthermore, in those cases where the sample treatment for species extraction is time-consuming, an assessment of the species integrity in the extracts is of paramount importance. Thus, the present paper reports total arsenic and arsenic species stability in alga samples (Sargassum fulvellum and Hizikia fusiformis), as well as in their aqueous extracts, which were stored in amber glass and polystyrene containers at different temperatures. Total arsenic determination was carried out by inductively coupled plasma atomic emission spectroscopy (ICP-AES), after sample acid digestion in a microwave oven, while arsenic speciation was conducted by anion exchange high performance liquid chromatography on-line coupled to ICP-AES, with and without sample introduction by hydride generation (HPLC-ICP-AES and HPLC-HG-ICP-AES), after aqueous microwave-assisted extraction. The results obtained for solid alga samples showed that total arsenic (for Hijiki alga) and arsenic species present (As(V) for Hijiki and NIES No. 9 Sargasso) are stable for at least 12 months when samples are stored in polystyrene containers at +20 degrees C. On the other hand, a different behaviour was observed in the stability of total arsenic and As(V) species in aqueous extracts for both samples, being the best storage conditions for Sargasso extracts a temperature of -18 degrees C and polystyrene containers, under which they are stable for at least 15 days, while Hijiki extracts must be stored in polystyrene containers at +4 degrees C in order to ensure the stability for 10 days.

Solubility of Aragonite in Subduction Water-Rich Fluids

NASA Astrophysics Data System (ADS)

Daniel, I.; Facq, S.; Petitgirard, S.; Cardon, H.; Sverjensky, D. A.

2017-12-01

Carbonate dissolution in subduction zone fluids is critical to the carbon budget in subduction zones. Depending on the solubility of carbonate minerals in aqueous fluids, the subducting lithosphere may be either strongly depleted and the mantle metasomatized if the solubility is high, as recently suggested by natural samples or transport carbon deeper into the Earth's mantle if the solubility is low enough [1, 2]. Dissolution of carbonate minerals strongly depends on pressure and temperature as well as on the chemistry of the fluid, leading to a highly variable speciation of aqueous carbon. Thanks to recent advances in theoretical aqueous geochemistry [3, 4], combined experimental and theoretical efforts now allow the investigation of speciation and solubility of carbonate minerals in aqueous fluids at PT conditions higher than previously feasible [4, 5]. In this study, we present new in situ X-ray fluorescence measurements of aragonite dissolution up to 5 GPa and 500°C and the subsequent thermodynamic model of aragonite solubility in aqueous fluids thanks to the Deep Earth Water model. The amount of dissolved aragonite in the fluid was calculated from challenging and unprecedented measurements of the Ca fluorescence K-lines at low-energy. Experiments were performed at the ESRF, beamline ID27 using a dedicated design of an externally-heated diamond anvil cell and an incident high-flux and highly focused monochromatic X-Ray beam at 20 keV. The results show a spectacularly high solubility of aragonite at HP-HT in water, further enhanced in presence of NaCl and silica in the solution. [1] Frezzotti, M. L. et al. (2011) doi:10.1038/ngeo1246. [2] Ague, J. J. and Nicolescu, S. (2014) doi:10.1038/ngeo2143. [3] Pan, D. et al. (2013) doi: 10.1073/pnas.1221581110. [4] Sverjensky, D. A et al. (2014) doi: 10.1016/j.gca.2013.12.019. [5] Facq, S. et al. (2014) doi: 10.1016/j.gca.2014.01.030.

Comparing different Ultraviolet Imaging Spectrograph (UVIS) occultation observations using modeling of water vapor jets

NASA Astrophysics Data System (ADS)

Portyankina, Ganna; Esposito, Larry W.; Hansen, Candice; Aye, Klaus-Michael

2016-10-01

Motivation: On March 11, 2016 the Cassini UVIS observed its 6th star occultation by Enceladus' plume. This observation was aimed to determine variability in the total gas flux from the Enceladus' southern polar region. The analysis of the received data suggests that the total gas flux is moderately increased comparing to the average gas flux observed by UVIS from 2005 to 2011 [1]. However, UVIS detected variability in individual jets. In particular, Baghdad 1 is more collimated in 2016 than in 2005, meaning its gas escapes at higher velocity.Model and fits: We use 3D DSMC model for water vapor jets to compare different UVIS occultation observations from 2005 to 2016. The model traces test articles from jets' sources [2] into space and results in coordinates and velocities for a set of test particles. We convert particle positions into the particle number density and integrate along UVIS line of sight (LoS) for each time step of the UVIS observation using precise observational geometry derived from SPICE [3]. We integrate all jets that are crossed by the LoS and perform constrained least-squares fit of resulting modeled opacities to the observed data to solved for relative strengths of jets. The geometry of each occultation is specific, for example, during solar occultation in 2010 UVIS LoS was almost parallel to tiger stripes, which made it possible to distinguish jets venting from different tiger stripes. In 2011 Eps Orionis occultation LoS was perpendicular to tiger stripes and thus many of the jets were geometrically overlapping. Solar occultation provided us with the largest inventory of active jets - our model fit detects at least 43 non-zero jet contributions. Stellar occultations generally have lower temporal resolution and observe only a sub-set of these jets: 2011 Eps Orionis needs minimum 25 non-zero jets to fit UVIS data. We will discuss different occultations and models fits, including the most recent Epsilon Orionis occultation of 2016.[1] Hansen et al., DPS 48, 2016 [2] Porco et al. 2014 The Astronomical Journal 148, 4 [3] Acton, C.H., 1996 PSS 44, 65-70

Kinetic, equilibrium and thermodynamic studies on sorption of uranium and thorium from aqueous solutions by a selective impregnated resin containing carminic acid.

PubMed

Rahmani-Sani, Abolfazl; Hosseini-Bandegharaei, Ahmad; Hosseini, Seyyed-Hossein; Kharghani, Keivan; Zarei, Hossein; Rastegar, Ayoob

2015-04-09

In this work, the removal of uranium and thorium ions from aqueous solutions was studied by solid-liquid extraction using an advantageous extractant-impregnated resin (EIR) prepared by loading carminic acid (CA) onto Amberlite XAD-16 resin beads. Batch sorption experiments using CA/XAD-16 beads for the removal of U(VI) and Th(IV) ions were carried out as a function of several parameters, like equilibration time, metal ion concentration, etc. The equilibrium data obtained from the sorption experiments were adjusted to the Langmuir isotherm model and the calculated maximum sorption capacities in terms of monolayer sorption were in agreement with those obtained from the experiments. The experimental data on the sorption behavior of both metal ions onto the EIR beads fitted well in both Bangham and intra-particle diffusion kinetic models, indicating that the intra-particle diffusion is the rate-controlling step. The thermodynamic studies at different temperatures revealed the feasibility and the spontaneous nature of the sorption process for both uranium and thorium ions. Copyright © 2014 Elsevier B.V. All rights reserved.

Web-phreeq: a WWW instructional tool for modeling the distribution of chemical species in water

NASA Astrophysics Data System (ADS)

Saini-Eidukat, Bernhardt; Yahin, Andrew

1999-05-01

A WWW-based tool, WEB-PHREEQ, was developed for classroom teaching and for routine calculation of low temperature aqueous speciation. Accessible with any computer that has an internet-connected forms-capable WWW-browser, WEB-PHREEQ provides user interface and other support for modeling, creates a properly formatted input file, passes it to the public domain program PHREEQC and returns the output to the WWW browser. Users can calculate the equilibrium speciation of a solution over a range of temperatures or can react solid minerals or gases with a particular water and examine the resulting chemistry. WEB-PHREEQ is one of a number of interactive distributed-computing programs available on the WWW that are of interest to geoscientists.

Redox behavior of uranium at the nanoporous aluminum oxide-water interface: implications for uranium remediation.

PubMed

Jung, Hun Bok; Boyanov, Maxim I; Konishi, Hiromi; Sun, Yubing; Mishra, Bhoopesh; Kemner, Kenneth M; Roden, Eric E; Xu, Huifang

2012-07-03

Sorption-desorption experiments show that the majority (ca. 80-90%) of U(VI) presorbed to mesoporous and nanoporous alumina could not be released by extended (2 week) extraction with 50 mM NaHCO(3) in contrast with non-nanoporous α alumina. The extent of reduction of U(VI) presorbed to aluminum oxides was semiquantitatively estimated by comparing the percentages of uranium desorbed by anoxic sodium bicarbonate between AH(2)DS-reacted and unreacted control samples. X-ray absorption spectroscopy confirmed that U(VI) presorbed to non-nanoporous alumina was rapidly and completely reduced to nanoparticulate uraninite by AH(2)DS, whereas reduction of U(VI) presorbed to nanoporous alumina was slow and incomplete (<5% reduction after 1 week). The observed nanopore size-dependent redox behavior of U has important implications in developing efficient remediation techniques for the subsurface uranium contamination because the efficiency of in situ bioremediation depends on how effectively and rapidly U(VI) bound to sediment or soil can be converted to an immobile phase.

Stochastic simulation of uranium migration at the Hanford 300 Area.

PubMed

Hammond, Glenn E; Lichtner, Peter C; Rockhold, Mark L

2011-03-01

This work focuses on the quantification of groundwater flow and subsequent U(VI) transport uncertainty due to heterogeneity in the sediment permeability at the Hanford 300 Area. U(VI) migration at the site is simulated with multiple realizations of stochastically-generated high resolution permeability fields and comparisons are made of cumulative water and U(VI) flux to the Columbia River. The massively parallel reactive flow and transport code PFLOTRAN is employed utilizing 40,960 processor cores on DOE's petascale Jaguar supercomputer to simultaneously execute 10 transient, variably-saturated groundwater flow and U(VI) transport simulations within 3D heterogeneous permeability fields using the code's multi-realization simulation capability. Simulation results demonstrate that the cumulative U(VI) flux to the Columbia River is less responsive to fine scale heterogeneity in permeability and more sensitive to the distribution of permeability within the river hyporheic zone and mean permeability of larger-scale geologic structures at the site. Copyright © 2010 Elsevier B.V. All rights reserved.

Upscaling of U(VI) Desorption and Transport from Decimeter-Scale Heterogeneity to Plume-Scale Modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Curtis, Gary P.; Kohler, Matthias; Kannappan, Ramakrishnan

2015-02-24

Scientifically defensible predictions of field scale U(VI) transport in groundwater requires an understanding of key processes at multiple scales. These scales range from smaller than the sediment grain scale (less than 10 μm) to as large as the field scale which can extend over several kilometers. The key processes that need to be considered include both geochemical reactions in solution and at sediment surfaces as well as physical transport processes including advection, dispersion, and pore-scale diffusion. The research summarized in this report includes both experimental and modeling results in batch, column and tracer tests. The objectives of this research weremore » to: (1) quantify the rates of U(VI) desorption from sediments acquired from a uranium contaminated aquifer in batch experiments;(2) quantify rates of U(VI) desorption in column experiments with variable chemical conditions, and(3) quantify nonreactive tracer and U(VI) transport in field tests.« less

A gas chromatographic method for the determination of bicarbonate and dissolved gases

USDA-ARS?s Scientific Manuscript database

A gas chromatographic method for the rapid determination of aqueous carbon dioxide and its speciation into solvated carbon dioxide and bicarbonate is presented. One-half mL samples are injected through a rubber septum into 20-mL vials that are filled with 9.5 mL of 0.1 N HCl. A one mL portion of the...

Heavy metal speciation and uptake in crayfish and tadpoles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bundy, K.J.; Berzins, D.; Millet, L.

1996-12-31

Developing valid pollution recording methods is central to assessing environmental damage and remediation. This often is difficult, however, because of speciation and multiphase distribution of contaminants. Polarography, an electroanalytical technique capable of detection and quantification of trace levels of elements and ionic complexes, is a promising method for analyzing environmental samples. Here, polarography has been used to determine lead concentration in water, sediment, bullfrogs, tadpoles, and adsorbed onto kaolin. It has also been used to measure hexavalent chromium concentration in crayfish. This research involves field studies and two laboratory experiments. Studies of a Louisiana swamp have shown lead`s affinity formore » sediment and water particulate phases, rather than being ionically dissolved in the aqueous phase. In swamp bullfrogs, lead was found in greater concentrations in bone compared to muscle. In the first laboratory experiment, lead uptake originating from water and sediment increased in tadpoles as exposure time and concentration increased. Also, this animal`s development was hindered at higher concentrations. The second laboratory experiment exposed crayfish to aqueous hexavalent chromium. Total chromium uptake increased with exposure time and concentration. The chromium tissue abundance was hepatopancreas > gills > muscle. A substantial portion of tissue hexavalent chromium converted to the less toxic trivalent form.« less

Kinetics of Microbial Reduction of Solid Phase U(VI)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Chongxuan; Jeon, Byong Hun; Zachara, John M.

2006-10-01

Sodium boltwoodite (NaUO2SiO3OH ?1.5H2O) was used to assess the kinetics of microbial reduction of solid phase U(VI) by a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. The bioreduction kinetics was studied with Na-boltwoodite in suspension or within alginate beads. Concentrations of U(VI)tot and cell number were varied to evaluate the coupling of U(VI) dissolution, diffusion, and microbial activity. Batch experiments were performed in a non-growth medium with lactate as electron donor at pH 6.8 buffered with PIPES. Microscopic and spectroscopic analyses with transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and laser-induced fluorescence spectroscopy (LIFS) collectively indicated that solidmore » phase U(VI) was first dissolved and diffused out of grain interiors before it was reduced on bacterial surfaces and/or within the periplasm. The kinetics of solid phase U(VI) bioreduction was well described by a coupled model of bicarbonate-promoted dissolution of Na-boltwoodite, intraparticle uranyl diffusion, and Monod type bioreduction kinetics with respect to dissolved U(VI) concentration. The results demonstrated the intimate coupling of biological, chemical, and physical processes in microbial reduction of solid phase U(VI).« less

Surface Complexation Modeling of Eu(III) and U(VI) Interactions with Graphene Oxide.

PubMed

Xie, Yu; Helvenston, Edward M; Shuller-Nickles, Lindsay C; Powell, Brian A

2016-02-16

Graphene oxide (GO) has great potential for actinide removal due to its extremely high sorption capacity, but the mechanism of sorption remains unclear. In this study, the carboxylic functional group and an unexpected sulfonate functional group on GO were characterized as the reactive surface sites and quantified via diffuse layer modeling of the GO acid/base titrations. The presence of sulfonate functional group on GO was confirmed using elemental analysis and X-ray photoelectron spectroscopy. Batch experiments of Eu(III) and U(VI) sorption to GO as the function of pH (1-8) and as the function of analyte concentration (10-100, 000 ppb) at a constant pH ≈ 5 were conducted; the batch sorption results were modeled simultaneously using surface complexation modeling (SCM). The SCM indicated that Eu(III) and U(VI) complexation to carboxylate functional group is the main mechanism for their sorption to GO; their complexation to the sulfonate site occurred at the lower pH range and the complexation of Eu(III) to sulfonate site are more significant than that of U(VI). Eu(III) and U(VI) facilitated GO aggregation was observed with high Eu(III) and U(VI) concentration and may be caused by surface charge neutralization of GO after sorption.

Effect of Subgrid Heterogeneity on Scaling Geochemical and Biogeochemical Reactions: A Case of U(VI) Desorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Chongxuan; Shang, Jianying; Shan, Huimei

2014-02-04

The effect of subgrid heterogeneity in sediment properties on the rate of uranyl[U(VI)] desorption was investigated using a sediment collected from the US Department of Energy Hanford site. The sediment was sieved into 7 grain size fractions that each exhibited different U(VI) desorption properties. Six columns were assembled using the sediment with its grain size fractions arranged in different spatial configurations to mimic subgrid heterogeneity in reactive transport properties. The apparent rate of U(VI) desorption varied significantly in the columns. Those columns with sediment structures leading to preferential transport had much lower rates of U(VI) desorption than those with relativelymore » homogeneous transport. Modeling analysis indicated that the U(VI) desorption model and parameters characterized from well-mixed reactors significantly over-predicted the measured U(VI) desorption in the columns with preferential transport. A dual domain model, which operationally separates reactive transport properties into two subgrid domains improved the predictions significantly. A similar effect of subgrid heterogeneity, albeit at a less degree, was observed for denitrification, which also occurred in the columns. The results imply that subgrid heterogeneity is an important consideration in extrapolating reaction rates from the laboratory to field.« less

Post Audit of a Field Scale Reactive Transport Model of Uranium at a Former Mill Site

NASA Astrophysics Data System (ADS)

Curtis, G. P.

2015-12-01

Reactive transport of hexavalent uranium (U(VI)) in a shallow alluvial aquifer at a former uranium mill tailings site near Naturita CO has been monitored for nearly 30 years by the US Department of Energy and the US Geological Survey. Groundwater at the site has high concentrations of chloride, alkalinity and U(VI) as a owing to ore processing at the site from 1941 to 1974. We previously calibrated a multicomponent reactive transport model to data collected at the site from 1986 to 2001. A two dimensional nonreactive transport model used a uniform hydraulic conductivity which was estimated from observed chloride concentrations and tritium helium age dates. A reactive transport model for the 2km long site was developed by including an equilibrium U(VI) surface complexation model calibrated to laboratory data and calcite equilibrium. The calibrated model reproduced both nonreactive tracers as well as the observed U(VI), pH and alkalinity. Forward simulations for the period 2002-2015 conducted with the calibrated model predict significantly faster natural attenuation of U(VI) concentrations than has been observed by the persistent high U(VI) concentrations at the site. Alternative modeling approaches are being evaluating evaluated using recent data to determine if the persistence can be explained by multirate mass transfer models developed from experimental observations at the column scale(~0.2m), the laboratory tank scale (~2m), the field tracer test scale (~1-4m) or geophysical observation scale (~1-5m). Results of this comparison should provide insight into the persistence of U(VI) plumes and improved management options.

Influence of low ozone episodes on erythemal UV-B radiation in Austria

NASA Astrophysics Data System (ADS)

Schwarz, Matthias; Baumgartner, Dietmar J.; Pietsch, Helga; Blumthaler, Mario; Weihs, Philipp; Rieder, Harald E.

2017-06-01

This study investigates the influence of low ozone episodes on UV-B radiation in Austria during the period 1999 to 2015. To this aim observations of total column ozone (TCO) in the Greater Alpine Region (Arosa, Switzerland; Hohenpeissenberg, Germany; Hradec Kralove, Czech Republic; Sonnblick, Austria), and erythemal UV-B radiation, available from 12 sites of the Austrian UV-B monitoring network, are analyzed. As previous definitions for low ozone episodes are not particularly suited to investigate effects on UV radiation, a novel threshold approach—considering anomalies—is developed to provide a joint framework for the analysis of extremes. TCO and UV extremes are negatively correlated, although modulating effects of sunshine duration impact the robustness of the statistical relationship. Therefore, information on relative sunshine duration (SDrel), available at (or nearby) UV-B monitoring sites, is included as explanatory variable in the analysis. The joint analysis of anomalies of both UV index (UVI) and total ozone (∆UVI, ∆TCO) and SDrel across sites shows that more than 65% of observations with strongly negative ozone anomalies (∆TCO < -1) led to positive UVI anomalies. Considering only days with strongly positive UVI anomaly (∆UVI > 1), we find (across all sites) that about 90% correspond to negative ∆TCO. The remaining 10% of days occurred during fair weather conditions (SDrel ≥ 80%) explaining the appearance of ∆UVI > 1 despite positive TCO anomalies. Further, we introduce an anomaly amplification factor (AAF), which quantifies the expected change of the ∆UVI for a given change in ∆TCO.

Spying on the neighbors' pool

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xantheas, S. S.

2016-12-01

The structure and properties of the aqueous proton is of fundamental interest in many areas of chemistry and biology. Acids and bases are molecules that are able to transfer (donate / accept) a proton according to Brønsted and Lowry, a process that was further explained by Lewis in terms of changes in their electronic structure in an attempt to offer a generalization of the Arrhenius theory. Simple proton transfers or the ones coupled to an electron transfer determine speciation, valence and reactivity in aqueous media and explain electrochemical processes, while voltage-gated proton channels have severe implications to the function ofmore » a number of tissues and species.« less

Chemical controls on uranyl citrate speciation and the self-assembly of nanoscale macrocycles and sandwich complexes in aqueous solutions.

PubMed

Basile, M; Unruh, D K; Gojdas, K; Flores, E; Streicher, L; Forbes, T Z

2015-03-28

Uranyl citrate forms trimeric species at pH > 5.5, but exact structural characteristics of these important oligomers have not previously been reported. Crystallization and structural characterization of the trimers suggests the self-assembly of the 3 : 3 and 3 : 2 U : Cit complexes into larger sandwich and macrocyclic molecules. Raman spectroscopy and ESI-MS have been utilized to investigate the relative abundance of these species in solution under varying pH and citrate concentrations. Additional dynamic light scattering experiments indicate that self-assembly of the larger molecules does occur in aqueous solution.

Ten years of measured UV Index from the Spanish UVB Radiometric Network.

PubMed

Utrillas, M P; Marín, M J; Esteve, A R; Estellés, V; Gandía, S; Núnez, J A; Martínez-Lozano, J A

2013-08-05

An analysis is made of the UV Index (UVI) obtained from the ultraviolet erythemal solar radiation (UVER) data measured by the Spanish UVB Radiometric Network between the years 2000 and 2009. Previously, the daily UVI has been evaluated using two different criteria: (a) the value corresponding to solar noon; and (b) the daily maximum value. The mean percentage of agreement is 92% if we consider the cases for which the difference is zero or one UVI unit. These results are similar to those obtained in a previous work where only 2 years were analyzed. In all the stations the UVI reaches very high values (8-10) in spring-summer, and the very high and extreme (≥ 11) UVI values are more dependent on the continental effect than on the latitude effect. From the UVI values it is possible to classify the stations into four groups: Coastal stations, Continental stations (more than 200 km from the coast), Southern stations (Coastal stations but with similar values of UVI as the Continental ones due to their low latitude) and Canary Islands stations (1400 km southwest from the Iberian Peninsula thus lower latitude). The monthly mean maximum of UVI is reached in July due to the annual evolution of the total ozone column. This value corresponds, for a skin phototype II, to three times the minimal erythemal dose (MED) in an hour in a Coastal station, 3.5 MEDs in an hour measured in a Continental or Southern station and up five MEDs in an hour in the Izaña station (Canary Islands). The cumulative dose on a horizontal plane over an average year has been calculated for each station. More than 40% of the annual dose is received in summer, about 35% in spring, more than 11% in autumn and less than 10% in winter except for the stations in the Canary Islands where the difference between seasons is less significant. Copyright © 2013 Elsevier B.V. All rights reserved.

Formation of stable uranium(VI) colloidal nanoparticles in conditions relevant to radioactive waste disposal.

PubMed

Bots, Pieter; Morris, Katherine; Hibberd, Rosemary; Law, Gareth T W; Mosselmans, J Frederick W; Brown, Andy P; Doutch, James; Smith, Andrew J; Shaw, Samuel

2014-12-09

The favored pathway for disposal of higher activity radioactive wastes is via deep geological disposal. Many geological disposal facility designs include cement in their engineering design. Over the long term, interaction of groundwater with the cement and waste will form a plume of a hyperalkaline leachate (pH 10-13), and the behavior of radionuclides needs to be constrained under these extreme conditions to minimize the environmental hazard from the wastes. For uranium, a key component of many radioactive wastes, thermodynamic modeling predicts that, at high pH, U(VI) solubility will be very low (nM or lower) and controlled by equilibrium with solid phase alkali and alkaline-earth uranates. However, the formation of U(VI) colloids could potentially enhance the mobility of U(VI) under these conditions, and characterizing the potential for formation and medium-term stability of U(VI) colloids is important in underpinning our understanding of U behavior in waste disposal. Reflecting this, we applied conventional geochemical and microscopy techniques combined with synchrotron based in situ and ex situ X-ray techniques (small-angle X-ray scattering and X-ray adsorption spectroscopy (XAS)) to characterize colloidal U(VI) nanoparticles in a synthetic cement leachate (pH > 13) containing 4.2-252 μM U(VI). The results show that in cement leachates with 42 μM U(VI), colloids formed within hours and remained stable for several years. The colloids consisted of 1.5-1.8 nm nanoparticles with a proportion forming 20-60 nm aggregates. Using XAS and electron microscopy, we were able to determine that the colloidal nanoparticles had a clarkeite (sodium-uranate)-type crystallographic structure. The presented results have clear and hitherto unrecognized implications for the mobility of U(VI) in cementitious environments, in particular those associated with the geological disposal of nuclear waste.

Grain-Size Based Additivity Models for Scaling Multi-rate Uranyl Surface Complexation in Subsurface Sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

This study statistically analyzed a grain-size based additivity model that has been proposed to scale reaction rates and parameters from laboratory to field. The additivity model assumed that reaction properties in a sediment including surface area, reactive site concentration, reaction rate, and extent can be predicted from field-scale grain size distribution by linearly adding reaction properties for individual grain size fractions. This study focused on the statistical analysis of the additivity model with respect to reaction rate constants using multi-rate uranyl (U(VI)) surface complexation reactions in a contaminated sediment as an example. Experimental data of rate-limited U(VI) desorption in amore » stirred flow-cell reactor were used to estimate the statistical properties of multi-rate parameters for individual grain size fractions. The statistical properties of the rate constants for the individual grain size fractions were then used to analyze the statistical properties of the additivity model to predict rate-limited U(VI) desorption in the composite sediment, and to evaluate the relative importance of individual grain size fractions to the overall U(VI) desorption. The result indicated that the additivity model provided a good prediction of the U(VI) desorption in the composite sediment. However, the rate constants were not directly scalable using the additivity model, and U(VI) desorption in individual grain size fractions have to be simulated in order to apply the additivity model. An approximate additivity model for directly scaling rate constants was subsequently proposed and evaluated. The result found that the approximate model provided a good prediction of the experimental results within statistical uncertainty. This study also found that a gravel size fraction (2-8mm), which is often ignored in modeling U(VI) sorption and desorption, is statistically significant to the U(VI) desorption in the sediment.« less

Tolerance and bioaccumulation of U(VI) by Bacillus mojavensis and its solid phase preconcentration by Bacillus mojavensis immobilized multiwalled carbon nanotube.

PubMed

Özdemir, Sadin; Oduncu, M Kadir; Kilinc, Ersin; Soylak, Mustafa

2017-02-01

In this study, uranium(VI) tolerance and bioaccumulation were investigated by using thermo -tolerant Bacillus mojavensis. The level of U(VI) was measured by UV-VIS spectrophotometry. The minimum inhibition concentration (MIC) value of U(VI) was experimented. Bacterial growth was not affected in the presence of 1.0 and 2.5 mg/L U(VI) at 36 h and the growth was partially affected in the presence of 5 mg/L U(VI) at 24 h. What was obtained from this study is that there was diversity in the various periods of the growth phases of metal bioaccumulation capacity, which was shown by B. mojavensis. The maximum bioaccumulation capacities were found to be 12.8, 22.7, and 48.2 mg/g dried bacteria, at 24th hours at concentration of 1.0, 2.5 and 5 mg/L U(VI), respectively. In addition to these, U(VI) has been preconcentrated on B. mojavensis immobilized MWCNT. Several factors such as pH, flow rate of solution, amount of biosorbent and support materials, eluent type, concentration and volume, the matrix interference effect on retention have been studied, and extraction conditions were optimized. Preconcentration factor was achieved as 60. Under the optimized conditions, the limit of detection (LOD) and quantification (LOQ) were calculated as 0.74 and 2.47 μg/L. The biosorption capacity of immobilized B. mojavensis was calculated for U(VI) as 25.8 mg/g. The results demonstrated that the immobilized biosorbent column could be reused at least 30 cycles of biosorption and desorption with the higher than 95% recovery. FT-IR and SEM analysis were performed to understand the surface properties of B. mojavensis. Copyright © 2016 Elsevier Ltd. All rights reserved.

An experimental and modeling study of grain-scale uranium desorption from field-contaminated sediments and the potential influence of microporosity on mass-transfer

NASA Astrophysics Data System (ADS)

Stoliker, D.; Liu, C.; Kent, D. B.; Zachara, J. M.

2012-12-01

The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a <8 mm composite of field-contaminated, lower vadose zone sediments. For each size fraction, equilibrium U(VI) sorption/desorption in static batch reactors was well-described by surface complexation models over a range of chemical conditions applicable to the field site. Desorption rates from individual size fractions in flow-through batch reactors, examined under a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions <2 mm. Kinetic U(VI) desorption in flow-through batch reactors was modeled using a multi-rate surface complexation approach, where sorption/desorption rates were assumed to be proportional to the displacement from equilibrium and multiple diffusion domains were described with a two-parameter lognormal distribution of mass-transfer rate coefficients. Parameters describing mass transfer were the same for all size fractions <2 mm but differed for the largest (2-8 mm) size fraction. The evolution of pH, along with dissolved cation and carbonate concentrations, was modeled using equilibrium cation exchange, rate-limited calcite dissolution, aerobic respiration, and silica dissolution. Desorption and chemical reaction models calibrated with individual size fractions predicted U(VI) and chemical composition as a function of time for the bulk sediment sample. Volumes of pores less than 2.4 nm, quantified using nitrogen adsorption-desorption isotherms, were the same for all size fractions < 2 mm, nearly double that of the 2-8 mm size fraction. Similarity in the observed pore volumes and multi-rate mass-transfer parameters across all size fractions <2 mm suggest the importance of pores in this size class in controlling slow grain-scale U(VI) desorption rates. Models like these provide a means for testing the influence of grain-scale mass-transfer on the persistence of U(VI) plume at the site.

Sorption characteristic of uranium(VI) ion onto K-feldspar.

PubMed

Gao, Xiaoqing; Bi, Mingliang; Shi, Keliang; Chai, Zhifang; Wu, Wangsuo

2017-10-01

The effect of pH, contact time, temperature, ionic strength and initial U(VI) concentration on U(VI) sorption onto K-feldspar was investigated using batch techniques. The sorption kinetics was evaluated and the activation energy was obtained based on the rate constants at different temperature. Graphical correlations of sorption isotherm models have been evaluated and applied for U(VI) uptake by K-feldspar. Various thermodynamic parameters, such as, Gibb's free energy, entropy and enthalpy of the on-going sorption process have been calculated and the possible sorption mechanism of U(VI) was deduced. The results are expected to help better understand the migration of uranium in the host materials of granite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Isotopic and geochemical tracers for U(VI) reduction and U mobility at an in situ recovery U mine

DOE PAGES

Basu, Anirban; Brown, Shaun T.; Christensen, John N.; ...

2015-05-19

In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Post-mining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers ²³⁸U/²³⁵U (δ²³⁸U), ²³⁴U/²³⁸U activity ratio, and ³⁴S/³²S (δ³⁴S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility atmore » an ISR mining site at Rosita, TX, USA. The δ²³⁸U in Rosita groundwater varies from 0.61‰ to -2.49‰, with a trend toward lower δ²³⁸U in downgradient wells. The concurrent decrease in U(VI) concentration and δ²³⁸U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic ²³⁴U/²³⁸U activity ratio and δ³⁴S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.« less

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction.

PubMed

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D; Deng, Ye; He, Zhili; Gihring, Thomas; Zhang, Gengxin; Schadt, Chris W; Watson, David; Jardine, Phil; Criddle, Craig S; Brooks, Scott; Marsh, Terence L; Tiedje, James M; Arkin, Adam P; Zhou, Jizhong

2015-06-15

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this study, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using a comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO3 (-), Mn(IV), Fe(III), U(VI), and SO4 (2-) significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO3 (-), Mn(II), Fe(II), U(VI), and SO4 (2-). Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. This study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction

PubMed Central

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D.; Deng, Ye; He, Zhili; Gihring, Thomas; Zhang, Gengxin; Schadt, Chris W.; Watson, David; Jardine, Phil; Criddle, Craig S.; Brooks, Scott; Marsh, Terence L.; Tiedje, James M.; Arkin, Adam P.

2015-01-01

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this study, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using a comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO3−, Mn(IV), Fe(III), U(VI), and SO42− significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO3−, Mn(II), Fe(II), U(VI), and SO42−. Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. This study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction. PMID:25862231

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction

DOE PAGES

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D.; ...

2015-04-10

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this paper, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using amore » comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO 3 -, Mn(IV), Fe(III), U(VI), and SO 4 2- significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO 3 -, Mn(II), Fe(II), U(VI), and SO 4 2-. Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. Finally, this study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction.« less

Dynamic Succession of Groundwater Functional Microbial Communities in Response to Emulsified Vegetable Oil Amendment during Sustained In Situ U(VI) Reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Ping; Wu, Wei-Min; Van Nostrand, Joy D.

A pilot-scale field experiment demonstrated that a one-time amendment of emulsified vegetable oil (EVO) reduced groundwater U(VI) concentrations for 1 year in a fast-flowing aquifer. However, little is known about how EVO amendment stimulates the functional gene composition, structure, and dynamics of groundwater microbial communities toward prolonged U(VI) reduction. In this paper, we hypothesized that EVO amendment would shift the functional gene composition and structure of groundwater microbial communities and stimulate key functional genes/groups involved in EVO biodegradation and reduction of electron acceptors in the aquifer. To test these hypotheses, groundwater microbial communities after EVO amendment were analyzed using amore » comprehensive functional gene microarray. Our results showed that EVO amendment stimulated sequential shifts in the functional composition and structure of groundwater microbial communities. Particularly, the relative abundance of key functional genes/groups involved in EVO biodegradation and the reduction of NO 3 -, Mn(IV), Fe(III), U(VI), and SO 4 2- significantly increased, especially during the active U(VI) reduction period. The relative abundance for some of these key functional genes/groups remained elevated over 9 months. Montel tests suggested that the dynamics in the abundance, composition, and structure of these key functional genes/groups were significantly correlated with groundwater concentrations of acetate, NO 3 -, Mn(II), Fe(II), U(VI), and SO 4 2-. Our results suggest that EVO amendment stimulated dynamic succession of key functional microbial communities. Finally, this study improves our understanding of the composition, structure, and function changes needed for groundwater microbial communities to sustain a long-term U(VI) reduction.« less

Biofilm Shows Spatially Stratified Metabolic Responses to Contaminant Exposure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Bin; Majors, Paul D.; Ahmed, B.

2012-11-01

The objective of this study was to elucidate the spatiotemporal responses of live S. oneidensis MR-1 biofilms to U(VI) (uranyl, UO22+) and Cr(VI) (chromate, CrO42-), important environmental contaminants at DOE contaminated sites. Toward this goal, we applied noninvasive nuclear magnetic resonance (NMR) imaging, diffusion, relaxation and spectroscopy techniques to monitor in situ spatiotemporal responses of S. oneidensis biofilms to U(VI) and Cr(VI) exposure in terms of changes in biofilm structures, diffusion properties, and cellular metabolism. Exposure to U(VI) or Cr(VI) did not appear to change the overall biomass distribution but caused changes in the physicochemical microenvironments inside the biofilm asmore » indicated by diffusion measurements. Changes in the diffusion properties of the biofilms in response to U(VI) and Cr(VI) exposure imply a novel function of the extracellular polymeric substances (EPS) affecting the biotransformation and transport of contaminants in the environment. In the presence of U(VI) or Cr(VI), the anaerobic metabolism of lactate was inhibited significantly, although the biofilms were still capable of reducing U(VI) and Cr(VI). Local concentrations of Cr(III)aq in the biofilm suggested relatively high Cr(VI) reduction activities at the top of the biofilm, near the medium-biofilm interface. The depth-resolved metabolic activities of the biofilm suggested higher diversion effects of gluconeogenesis and C1 metabolism pathways at the bottom of the biofilm and in the presence of U(VI). This study provides a noninvasive means to investigate spatiotemporal responses of biofilms, including surface-associated microbial communities in engineering, natural and medical settings, to various environmental perturbations including exposure to environmental contaminants and antimicrobials.« less

Isotopic and geochemical tracers for U(VI) reduction and U mobility at an in situ recovery U mine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Basu, Anirban; Brown, Shaun T.; Christensen, John N.

In situ recovery (ISR) uranium (U) mining mobilizes U in its oxidized hexavalent form (U(VI)) by oxidative dissolution of U from the roll-front U deposits. Post-mining natural attenuation of residual U(VI) at ISR mines is a potential remediation strategy. Detection and monitoring of naturally occurring reducing subsurface environments are important for successful implementation of this remediation scheme. We used the isotopic tracers ²³⁸U/²³⁵U (δ²³⁸U), ²³⁴U/²³⁸U activity ratio, and ³⁴S/³²S (δ³⁴S), and geochemical measurements of U ore and groundwater collected from 32 wells located within, upgradient, and downgradient of a roll-front U deposit to detect U(VI) reduction and U mobility atmore » an ISR mining site at Rosita, TX, USA. The δ²³⁸U in Rosita groundwater varies from 0.61‰ to -2.49‰, with a trend toward lower δ²³⁸U in downgradient wells. The concurrent decrease in U(VI) concentration and δ²³⁸U with an ε of 0.48‰ ± 0.08‰ is indicative of naturally occurring reducing environments conducive to U(VI) reduction. Additionally, characteristic ²³⁴U/²³⁸U activity ratio and δ³⁴S values may also be used to trace the mobility of the ore zone groundwater after mining has ended. These results support the use of U isotope-based detection of natural attenuation of U(VI) at Rosita and other similar ISR mining sites.« less

Enzymatic iron and uranium reduction by sulfate-reducing bacteria

USGS Publications Warehouse

Lovley, D.R.; Roden, E.E.; Phillips, E.J.P.; Woodward, J.C.

1993-01-01

The potential for sulfate-reducing bacteria (SRB) to enzymatically reduce Fe(III) and U(VI) was investigated. Five species of Desulfovibrio as well as Desulfobacterium autotrophicum and Desulfobulbus propionicus reduced Fe(III) chelated with nitrilotriacetic acid as well as insoluble Fe(III) oxide. Fe(III) oxide reduction resulted in the accumulation of magnetite and siderite. Desulfobacter postgatei reduced the chelated Fe(III) but not Fe(III) oxide. Desulfobacter curvatus, Desulfomonile tiedjei, and Desulfotomaculum acetoxidans did not reduce Fe(III). Only Desulfovibrio species reduced U(VI). U(VI) reduction resulted in the precipitation of uraninite. None of the SRB that reduced Fe(III) or U(VI) appeared to conserve enough energy to support growth from this reaction. However, Desulfovibrio desulfuricans metabolized H2 down to lower concentrations with Fe(III) or U(VI) as the electron acceptor than with sulfate, suggesting that these metals may be preferred electron acceptors at the low H2 concentrations present in most marine sediments. Molybdate did not inhibit Fe(III) reduction by D. desulfuricans. This indicates that the inability of molybdate to inhibit Fe(III) reduction in marine sediments does not rule out the possibility that SRB are important catalysts for Fe(III) reduction. The results demonstrate that although SRB were previously considered to reduce Fe(III) and U(VI) indirectly through the production of sulfide, they may also directly reduce Fe(III) and U(VI) through enzymatic mechanisms. These findings, as well as our recent discovery that the So-reducing microorganism Desulfuromonas acetoxidans can reduce Fe(III), demonstrate that there are close links between the microbial sulfur, iron, and uranium cycles in anaerobic marine sediments. ?? 1993.

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots.

PubMed

Li, Dien; Kaplan, Daniel I; Chang, Hyun-Shik; Seaman, John C; Jaffé, Peter R; Koster van Groos, Paul; Scheckel, Kirk G; Segre, Carlo U; Chen, Ning; Jiang, De-Tong; Newville, Matthew; Lanzirotti, Antonio

2015-03-03

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ∼2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland processes, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.

Oceanographic Research Capacity in the US Virgin Islands

NASA Astrophysics Data System (ADS)

Jobsis, P.; Habtes, S. Y.

2016-02-01

The University of the Virgin Islands (UVI), a small HBCU with campuses on both St Thomas and St Croix, has a growing marine science department that is quickly increasing its capacity for oceanographic monitoring and research due to VI-EPSCoR (National Science Foundation's Experimental Program to Stimulate Competitive Research in the Virgin Islands) and associations with CariCOOS (the Caribbean Coastal Ocean Observing System). CariCOOS is managed through the University of Puerto Rico Mayaguez, with funding from NOAA's Integrated Ocean Observing System (IOOS). Over the past five years two oceanographic data buoys have been deployed increasing the real-time oceanographic data available for the northeastern Caribbean. In addition, researchers at UVI have deployed ADCPs and conducted CTD casts at relevant research sites as part of routine territorial monitoring programs. With VI-EPSCoR funding UVI has developed an Institute for Geocomputational Analysis and Statistic (GeoCAS) to conduct geospatial analysis and to act as a data repository and hosting/serving center for research, environmental and other relevant data. Much of the oceanographic data is available at www.caricoos.org and www.geocas.uvi.edu. As the marine research infrastructure at UVI continues to grow, the oceanographic and marine biology research program at the University's Center for Marine and Environmental Studies will continue to expand. This will benefit not only UVI researchers but also any researcher with interests in this region of the Caribbean.

The Effect of Si and Al Concentration Ratios on the Removal of U(VI) under Hanford Site 200 Area Conditions-12115

DOE Office of Scientific and Technical Information (OSTI.GOV)

Katsenovich, Yelena; Gonzalez, Nathan; Moreno-Pastor, Carol

2012-07-01

Injection of reactive gases, such as NH{sub 3}, is an innovative technique to mitigate uranium contamination in soil for a vadose zone (VZ) contaminated with radionuclides. A series of experiments were conducted to examine the effect of the concentration ratio of silicon to aluminum in the presence of various bicarbonate concentrations on the coprecipitation process of U(VI). The concentration of Al in all tests remained unchanged at 2.8 mM. Experiments showed that the removal efficiency of uranium was not significantly affected by the different bicarbonate and U(VI) concentrations tested. For the lower Si:Al molar ratios of 2:1 and 18:1, themore » removal efficiency of uranium was relatively low (≤ 8%). For the Si:Al molar ratio of 35:1, the removal efficiency of uranium was increased to an average of ∼82% for all bicarbonate concentrations tested. At higher Si:Al molar ratios (53:1 and above), a relatively high removal efficiency of U(VI), approximately 85% and higher, was observed. These results demonstrate that the U(VI) removal efficiency is more affected by the Si:Al molar ratio than by the bicarbonate concentration in solution. The results of this experiment are promising for the potential implementation of NH{sub 3} gas injection for the remediation of U(VI) -contaminated VZ. (authors)« less

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Dien; Kaplan, Daniel I.; Chang, Hyun-Shik

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6–5.8) conditions using U L₃-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U–C bond distance at ~2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulatingmore » the SRS wetland processes, U immobilization on roots was two orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was re-oxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.« less

Spectroscopic evidence of uranium immobilization in acidic wetlands by natural organic matter and plant roots

DOE PAGES

Li, Dien; Kaplan, Daniel I.; Chang, Hyun-Shik; ...

2015-03-03

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6–5.8) conditions using U L₃-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U–C bond distance at ~2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulatingmore » the SRS wetland processes, U immobilization on roots was two orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was re-oxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication for the long-term stewardship of U-contaminated wetlands.« less

U(VI) bioreduction with emulsified vegetable oil as the electron donor--microcosm tests and model development.

PubMed

Tang, Guoping; Wu, Wei-Min; Watson, David B; Parker, Jack C; Schadt, Christopher W; Shi, Xiaoqing; Brooks, Scott C

2013-04-02

We conducted microcosm tests and biogeochemical modeling to study U(VI) reduction in contaminated sediments amended with emulsified vegetable oil (EVO). Indigenous microorganisms in the sediments degraded EVO and stimulated Fe(III), U(VI), and sulfate reduction, and methanogenesis. Acetate concentration peaked in 100-120 days in the EVO microcosms versus 10-20 days in the oleate microcosms, suggesting that triglyceride hydrolysis was a rate-limiting step in EVO degradation and subsequent reactions. Acetate persisted 50 days longer in oleate- and EVO- than in ethanol-amended microcosms, indicating that acetate-utilizing methanogenesis was slower in the oleate and EVO than ethanol microcosms. We developed a comprehensive biogeochemical model to couple EVO hydrolysis, production, and oxidation of long-chain fatty acids (LCFA), glycerol, acetate, and hydrogen, reduction of Fe(III), U(VI) and sulfate, and methanogenesis with growth and decay of multiple functional microbial groups. By estimating EVO, LCFA, and glycerol degradation rate coefficients, and introducing a 100 day lag time for acetoclastic methanogenesis for oleate and EVO microcosms, the model approximately matched observed sulfate, U(VI), and acetate concentrations. Our results confirmed that EVO could stimulate U(VI) bioreduction in sediments and the slow EVO hydrolysis and acetate-utilizing methanogens growth could contribute to longer term bioreduction than simple substrates (e.g., ethanol, acetate, etc.) in the subsurface.

Effects of gamma-sterilization on the physico-chemical properties of natural sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bank, Tracy L.; Kukkadapu, Ravi K.; Madden, Andrew S.

2008-06-30

A series of experiments were completed to determine the effects of soil sterilization on various soil chemical properties including U(VI) sorption, soil pH, natural organic matter (NOM), cation exchange capacity (CEC), and iron oxidation state. Soils under investigation were a saprolitic sequence of interbedded weathered shale and limestone collected from the Oak Ridge Reservation (ORR). Sediments were sterilized by either steam sterilization at 121oC or by γ-irradiation using a cobalt-60 source. Subsamples of sediments were pretreated with dithionate-citrate-bicarbonate (DCB) and/or H2O2 to remove reducible Fe(III) oxides and NOM. Results from aerobic U(VI) sorption experiments indicated that γ-sterilized sediments sorbed moremore » U(VI) compared to non-sterile sediments. Results from sorption experiments completed using DCB and H2O2-treated samples indicated that the iron oxide and NOM fractions of the sediment accounted for the majority of U(VI) sorption and that γ-irradiation of these phases resulted in increased sorption of U(VI). Mössbauer spectra of γ-sterilized sedimentsdisplayed a decrease in the amount of ferric iron associated with goethite and a small increase in the amount of reduced iron in silicate minerals compared to spectra from non-sterile samples. Our results suggest that sterilization by γ-irradiation induced iron reduction that may have increased sorption of U(VI) on these sediments.« less

Variably Saturated Flow and Multicomponent Biogeochemical Reactive Transport Modeling of a Uranium Bioremediation Field Experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yabusaki, Steven B.; Fang, Yilin; Williams, Kenneth H.

2011-11-01

Field experiments at a former uranium mill tailings site have identified the potential for stimulating indigenous bacteria to catalyze the conversion of aqueous uranium in the +6 oxidation state to immobile solid-associated uranium in the +4 oxidation state. This effectively removes uranium from solution resulting in groundwater concentrations below actionable standards. Three-dimensional, coupled variably-saturated flow and biogeochemical reactive transport modeling of a 2008 in situ uranium bioremediation field experiment is used to better understand the interplay of transport rates and biogeochemical reaction rates that determine the location and magnitude of key reaction products. A comprehensive reaction network, developed largely throughmore » previous 1-D modeling studies, was used to simulate the impacts on uranium behavior of pulsed acetate amendment, seasonal water table variation, spatially-variable physical (hydraulic conductivity, porosity) and geochemical (reactive surface area) material properties. A principal challenge is the mechanistic representation of biologically-mediated terminal electron acceptor process (TEAP) reactions whose products significantly alter geochemical controls on uranium mobility through increases in pH, alkalinity, exchangeable cations, and highly reactive reduction products. In general, these simulations of the 2008 Big Rusty acetate biostimulation field experiment in Rifle, Colorado confirmed previously identified behaviors including (1) initial dominance by iron reducing bacteria that concomitantly reduce aqueous U(VI), (2) sulfate reducing bacteria that become dominant after {approx}30 days and outcompete iron reducers for the acetate electron donor, (3) continuing iron-reducer activity and U(VI) bioreduction during dominantly sulfate reducing conditions, and (4) lower apparent U(VI) removal from groundwater during dominantly sulfate reducing conditions. New knowledge on simultaneously active metal and sulfate reducers has been incorporated into the modeling. In this case, an initially small population of slow growing sulfate reducers is active from the initiation of biostimulation. Three-dimensional, variably saturated flow modeling was used to address impacts of a falling water table during acetate injection. These impacts included a significant reduction in aquifer saturated thickness and isolation of residual reactants and products, as well as unmitigated uranium, in the newly unsaturated vadose zone. High permeability sandy gravel structures resulted in locally high flow rates in the vicinity of injection wells that increased acetate dilution. In downgradient locations, these structures created preferential flow paths for acetate delivery that enhanced local zones of TEAP reactivity and subsidiary reactions. Conversely, smaller transport rates associated with the lower permeability lithofacies (e.g., fine) and vadose zone were shown to limit acetate access and reaction. Once accessed by acetate, however, these same zones limited subsequent acetate dilution and provided longer residence times that resulted in higher concentrations of TEAP products when terminal electron donors and acceptors were not limiting. Finally, facies-based porosity and reactive surface area variations were shown to affect aqueous uranium concentration distributions; however, the ranges were sufficiently small to preserve general trends. Large computer memory and high computational performance were required to simulate the detailed coupled process models for multiple biogeochemical components in highly resolved heterogeneous materials for the 110-day field experiment and 50 days of post-biostimulation behavior. In this case, a highly-scalable subsurface simulator operating on 128 processor cores for 12 hours was used to simulate each realization. An equivalent simulation without parallel processing would have taken 60 days, assuming sufficient memory was available.« less

Net alkalinity and net acidity 1: Theoretical considerations

USGS Publications Warehouse

Kirby, C.S.; Cravotta, C.A.

2005-01-01

Net acidity and net alkalinity are widely used, poorly defined, and commonly misunderstood parameters for the characterization of mine drainage. The authors explain theoretical expressions of 3 types of alkalinity (caustic, phenolphthalein, and total) and acidity (mineral, CO2, and total). Except for rarely-invoked negative alkalinity, theoretically defined total alkalinity is closely analogous to measured alkalinity and presents few practical interpretation problems. Theoretically defined "CO 2-acidity" is closely related to most standard titration methods with an endpoint pH of 8.3 used for determining acidity in mine drainage, but it is unfortunately named because CO2 is intentionally driven off during titration of mine-drainage samples. Using the proton condition/mass- action approach and employing graphs to illustrate speciation with changes in pH, the authors explore the concept of principal components and how to assign acidity contributions to aqueous species commonly present in mine drainage. Acidity is defined in mine drainage based on aqueous speciation at the sample pH and on the capacity of these species to undergo hydrolysis to pH 8.3. Application of this definition shows that the computed acidity in mg L -1 as CaCO3 (based on pH and analytical concentrations of dissolved FeII, FeIII, Mn, and Al in mg L -1):aciditycalculated=50{1000(10-pH)+[2(FeII)+3(FeIII)]/56+2(Mn)/ 55+3(Al)/27}underestimates contributions from HSO4- and H+, but overestimates the acidity due to Fe3+ and Al3+. However, these errors tend to approximately cancel each other. It is demonstrated that "net alkalinity" is a valid mathematical construction based on theoretical definitions of alkalinity and acidity. Further, it is shown that, for most mine-drainage solutions, a useful net alkalinity value can be derived from: (1) alkalinity and acidity values based on aqueous speciation, (2) measured alkalinity minus calculated acidity, or (3) taking the negative of the value obtained in a standard method "hot peroxide" acidity titration, provided that labs report negative values. The authors recommend the third approach; i.e., net alkalinity = -Hot Acidity. ?? 2005 Elsevier Ltd. All rights reserved.

Photometric Repeatability of Scanned Imagery: UVIS

NASA Astrophysics Data System (ADS)

Shanahan, Clare E.; McCullough, Peter; Baggett, Sylvia

2017-08-01

We provide the preliminary results of a study on the photometric repeatability of spatial scans of bright, isolated white dwarf stars with the UVIS channel of the Wide Field Camera 3 (WFC3) on the Hubble Space Telescope (HST). We analyze straight-line scans from the first pair of identical orbits of HST program 14878 to assess if sub 0.1% repeatability can be attained with WFC3/UVIS. This study is motivated by the desire to achieve better signal-to-noise in the UVIS contamination and stability monitor, in which observations of standard stars in staring mode have been taken from the installation of WFC3 in 2009 to the present to assess temporal photometric stability. Higher signal to noise in this program would greatly benefit the sensitivity to detect contamination, and to better characterize the observed small throughput drifts over time. We find excellent repeatability between identical visits of program 14878, with sub 0.1% repeatability achieved in most filters. These! results support the initiative to transition the staring mode UVIS contamination and photometric stability monitor from staring mode images to spatial scans.

Comparison between UV index measurements performed by research-grade and consumer-products instruments.

PubMed

Corrêa, Marcelo de Paula; Godin-Beekmann, Sophie; Haeffelin, Martial; Brogniez, Colette; Verschaeve, Franck; Saiag, Philippe; Pazmiño, Andrea; Mahé, Emmanuel

2010-04-01

Ultraviolet radiation (UVR) exposure, skin cancer and other related diseases are not just subjects of scientific literature. Nowadays, these themes are also discussed on television, newspapers and magazines for the general public. Consequently, the interest in prevention of sun overexposure is increasing, as the knowledge of photoprotection methods and UVR levels. The ultraviolet index (UVI) is a well-known tool recommended by the World Health Organization to avoid harmful effects of UV sunlight. UVI forecasts are provided by many national meteorological services, but local UVI measurements can provide a more realistic and appropriate evaluation of UVR levels. Indeed, as scientific instruments are very expensive and difficult to manipulate, several manufacturers and retail shops offer cheap and simple non-scientific instruments for UVI measurements, sometimes included in objects of everyday life, such as watches, outfits and hand-held instruments. In this work, we compare measurements provided by several commercial non-scientific instruments with data provided by a Bentham spectrometer, a very accurate sensor used for UV measurements. Results show that only a few of the instruments analyzed provide trustworthy UVI measurements.

Adsorption of uranium(VI) to manganese oxides: X-ray absorption spectroscopy and surface complexation modeling.

PubMed

Wang, Zimeng; Lee, Sung-Woo; Catalano, Jeffrey G; Lezama-Pacheco, Juan S; Bargar, John R; Tebo, Bradley M; Giammar, Daniel E

2013-01-15

The mobility of hexavalent uranium in soil and groundwater is strongly governed by adsorption to mineral surfaces. As strong naturally occurring adsorbents, manganese oxides may significantly influence the fate and transport of uranium. Models for U(VI) adsorption over a broad range of chemical conditions can improve predictive capabilities for uranium transport in the subsurface. This study integrated batch experiments of U(VI) adsorption to synthetic and biogenic MnO(2), surface complexation modeling, ζ-potential analysis, and molecular-scale characterization of adsorbed U(VI) with extended X-ray absorption fine structure (EXAFS) spectroscopy. The surface complexation model included inner-sphere monodentate and bidentate surface complexes and a ternary uranyl-carbonato surface complex, which was consistent with the EXAFS analysis. The model could successfully simulate adsorption results over a broad range of pH and dissolved inorganic carbon concentrations. U(VI) adsorption to synthetic δ-MnO(2) appears to be stronger than to biogenic MnO(2), and the differences in adsorption affinity and capacity are not associated with any substantial difference in U(VI) coordination.

In situ Raman study of dissolved CaCO3 minerals under subduction zone conditions

NASA Astrophysics Data System (ADS)

Facq, S.; Daniel, I.; Sverjensky, D. A.

2012-12-01

The fate and the characteristics of the Earth's deep carbon reservoirs are still not well understood [1]. The connection between the surficial and the deep-Earth carbon cycles occurs at subduction zones where carbon is transported into the mantle and where hydrous silicates and carbonate minerals break down releasing H2O and C-species in fluids associated with mantle metasomatism and the generation of arc volcanism [2]. In order to obtain mass balance between recycling and burial in the deep mantle, the study of the dissolution of CaCO3 minerals in equilibrium with aqueous fluids under mantle conditions is crucial. We report a novel integrated experimental and theoretical study of the equilibration of CaCO3 minerals with aqueous solutions (pure water or NaCl solutions) at high pressures and temperatures (0.5 to 8 GPa and 250 to 500 °C). The fluid speciation was studied using in situ Raman spectroscopy coupled to an externally heated membrane type DAC equipped with 500 μm pure synthetic diamond anvils. In a typical experiment, the aqueous fluid and a calcite crystal [3] were loaded in a rhenium gasket. The pressure was determined from the calibrated shift of the carbonate υ1 symmetric stretching mode of aragonite and the temperature measured with a K-type thermocouple. Raman spectra were recorded using a Labram HR800 Raman spectrometer (Horiba Jobin-Yvon) coupled to a Spectra Physics Ar+ laser. At equilibrium with an aragonite crystal, the Raman data show that bicarbonate is the most abundant species in low-pressure fluids (below 4 GPa) whereas carbonate becomes progressively dominant at higher pressure. After correction from their Raman cross-sections [4], the relative amounts of dissolved carbonate and bicarbonate were estimated from the areas of the Raman bands of the carbonate and bicarbonate ions (υ1 and υ5 symmetric stretching modes, respectively). The presence of sodium chloride influences the speciation by extending the pressure field where the bicarbonate species is dominant in the fluid. The Raman data were also used to constrain a theoretical thermodynamic model of the fluid speciation in equilibrium with CaCO3. Building on published calcite solubility data from 400 - 700 °C and 2 - 16 kb [3, 5], revised thermodynamic properties of aqueous CO2 and HCO3-, data for the aqueous CaHCO3+ complex from 4 to 90 °C [6], and estimated dielectric constants of water, enabled an equation of state characterization of the standard Gibbs free energy of CaHCO3+ at the conditions of the Raman study. At 300 - 400 °C, the Raman speciation results were used to constrain equilibrium constants involving the carbonate ion. The results indicate that CO2 is a minor species in fluids in equilibrium with aragonite at 300 - 500 °C and P > 1.0 GPa. Instead, the CaHCO3+ species becomes important at high pressures until carbonate ion becomes the dominant C-species. [1] Marty, B. and Tolstikhin, I.N., Chemical Geology 145, 233 (1998) [2] Schmidt, M.W. and Poli, S., Earth and Planetary Science Letters 163, 163 (1998) [3] Caciagli, N.C. and Manning, C.E., Contributions to Mineralogy and Petrology 146, 275 (2003) [4] Frantz, J., Chemical Geology 152, 211 (1998) [5] Fein, J.B. and Walther, J.V., Contributions to Mineralogy and Petrology 103, 317 (1989) [6] Plummer, L.N. and Busenberg, E., Geochimica et Cosmochimica Acta 46, 1011 (1982)

Highly Efficient Interception and Precipitation of Uranium(VI) from Aqueous Solution by Iron-Electrocoagulation Combined with Cooperative Chelation by Organic Ligands.

PubMed

Li, Peng; Zhun, Bao; Wang, Xuegang; Liao, PingPing; Wang, Guanghui; Wang, Lizhang; Guo, Yadan; Zhang, Weimin

2017-12-19

A new strategy combining iron-electrocoagulation and organic ligands (OGLs) cooperative chelation was proposed to screen and precipitate low concentrations (0-18.52 μmol/L) of uranium contaminant in aqueous solution. We hypothesized that OGLs with amino, hydroxyl, and carboxyl groups hydrophobically/hydrophilically would realize precuring of uranyl ion at pH < 3.0, and the following iron-electrocoagulation would achieve faster and more efficient uranium precipitation. Experimentally, the strategy demonstrated highly efficient uranium(VI) precipitation efficiency, especially with hydrophilic macromolecular OGLs. The uranium removal efficiency at optimized experimental condition reached 99.65%. The decrease of zeta potential and the lattice enwrapping between U-OGLs chelates and flocculation precursor were ascribed to the enhanced uranium precipitation activity. Uranium was precipitated as oxides of U(VI) or higher valences that were easily captured in aggregated micelles under low operation current potential. The actual uranium tailing wastewater was treated, and a satisfied uranium removal efficiency of 99.02% was discovered. After elution of the precipitated flocs, a concentrated uranium solution (up to 106.52 μmol/L) with very few other metallic impurities was obtained. Therefore, the proposed strategy could remove uranium and concentrate it concurrently. This work could provide new insights into the purification and recovery of uranium from aqueous solutions in a cost-effective and environmentally friendly process.

Uranium redox transition pathways in acetate-amended sediments

USGS Publications Warehouse

Bargar, John R.; Williams, Kenneth H.; Campbell, Kate M.; Long, Philip E.; Stubbs, Joanne E.; Suvorova, Elenal I.; Lezama-Pacheco, Juan S.; Alessi, Daniel S.; Stylo, Malgorzata; Webb, Samuel M.; Davis, James A.; Giammar, Daniel E.; Blue, Lisa Y.; Bernier-Latmani, Rizlan

2013-01-01

Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

Thermodynamic Characterization of Iron Oxide-Aqueous Fe(2+) Redox Couples.

PubMed

Gorski, Christopher A; Edwards, Rebecca; Sander, Michael; Hofstetter, Thomas B; Stewart, Sydney M

2016-08-16

Iron is present in virtually all terrestrial and aquatic environments, where it participates in redox reactions with surrounding metals, organic compounds, contaminants, and microorganisms. The rates and extent of these redox reactions strongly depend on the speciation of the Fe2+ and Fe3+ phases, although the underlying reasons remain unclear. In particular, numerous studies have observed that Fe2+ associated with iron oxide surfaces (i.e., oxide-associated Fe2+) often reduces oxidized contaminants much faster than aqueous Fe2+ alone. Here, we tested two hypotheses related to this observation by determining if solutions containing two commonly studied iron oxides—hematite and goethite—and aqueous Fe2+ reached thermodynamic equilibrium over the course of a day. We measured reduction potential (EH) values in solutions containing these oxides at different pH values and aqueous Fe2+ concentrations using mediated potentiometry. This analysis yielded standard reduction potential (EH0) values of 768 ± 1 mV for the aqueous Fe2+–goethite redox couple and 769 ± 2 mV for the aqueous Fe2+–hematite redox couple. These values were in excellent agreement with those calculated from existing thermodynamic data, and the data could be explained by the presence of an iron oxide lowering EH values of aqueous Fe3+/Fe2+ redox couples.

pH-specific hydrothermal assembly of binary and ternary Pb(II)-(O,N-carboxylic acid) metal organic framework compounds: correlation of aqueous solution speciation with variable dimensionality solid-state lattice architecture and spectroscopic signatures.

PubMed

Gabriel, C; Perikli, M; Raptopoulou, C P; Terzis, A; Psycharis, V; Mateescu, C; Jakusch, T; Kiss, T; Bertmer, M; Salifoglou, A

2012-09-03

Hydrothermal pH-specific reactivity in the binary/ternary systems of Pb(II) with the carboxylic acids N-hydroxyethyl-iminodiacetic acid (Heida), 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid (Dpot), and 1,10-phenanthroline (Phen) afforded the new well-defined crystalline compounds [Pb(Heida)](n)·nH(2)O(1), [Pb(Phen)(Heida)]·4H(2)O(2), and [Pb(3)(NO(3))(Dpot)](n)(3). All compounds were characterized by elemental analysis, FT-IR, solution or/and solid-state NMR, and single-crystal X-ray diffraction. The structures in 1-2 reveal the presence of a Pb(II) center coordinated to one Heida ligand, with 1 exhibiting a two-dimensional (2D) lattice extending to a three-dimensional (3D) one through H-bonding interactions. The concurrent aqueous speciation study of the binary Pb(II)-Heida system projects species complementing the synthetic efforts, thereby lending credence to a global structural speciation strategy in investigating binary/ternary Pb(II)-Heida/Phen systems. The involvement of Phen in 2 projects the significance of nature and reactivity potential of N-aromatic chelators, disrupting the binary lattice in 1 and influencing the nature of the ultimately arising ternary 3D lattice. 3 is a ternary coordination polymer, where Pb(II)-Dpot coordination leads to a 2D metal-organic-framework material with unique architecture. The collective physicochemical properties of 1-3 formulate the salient features of variable dimensionality metal-organic-framework lattices in binary/ternary Pb(II)-(hydroxy-carboxylate) structures, based on which new Pb(II) materials with distinct architecture and spectroscopic signature can be rationally designed and pursued synthetically.

Deviation between the chemistry of Ce(IV) and Pu(IV) and routes to ordered and disordered heterobimetallic 4f/5f and 5f/5f phosphonates.

PubMed

Diwu, Juan; Wang, Shuao; Good, Justin J; DiStefano, Victoria H; Albrecht-Schmitt, Thomas E

2011-06-06

The heterobimetallic actinide compound UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O was prepared via the hydrothermal reaction of U(VI) and Ce(IV) in the presence of 1,2-phenylenediphosphonic acid. We demonstrate that this is a kinetic product that is not stable with respect to decomposition to the monometallic compounds. Similar reactions have been explored with U(VI) and Ce(III), resulting in the oxidation of Ce(III) to Ce(IV) and the formation of the Ce(IV) phosphonate, Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O, UO(2)Ce(H(2)O)[C(6)H(4)(PO(3)H)(2)](2)·H(2)O, and UO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O. In comparison, the reaction of U(VI) with Np(VI) only yields Np[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O and aqueous U(VI), whereas the reaction of U(VI) with Pu(VI) yields the disordered U(VI)/Pu(VI) compound, (U(0.9)Pu(0.1))O(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·H(2)O, and the Pu(IV) phosphonate, Pu[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. The reactions of Ce(IV) with Np(VI) yield disordered heterobimetallic phosphonates with both M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Np) and M[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Ce, Np) structures, as well as the Ce(IV) phosphonate Ce[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O. Ce(IV) reacts with Pu(IV) to yield the Pu(VI) compound, PuO(2)[C(6)H(4)(PO(3)H)(2)](H(2)O)·3H(2)O, and a disordered heterobimetallic Pu(IV)/Ce(IV) compound with the M[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Ce, Pu) structure. Mixtures of Np(VI) and Pu(VI) yield disordered heterobimetallic Np(IV)/Pu(IV) phosphonates with both the An[C(6)H(4)(PO(3)H)(PO(3)H(2))][C(6)H(4)(PO(3)H)(PO(3))]·2H(2)O (M = Np, Pu) and An[C(6)H(4)(PO(3)H)(2)](2)·2H(2)O (M = Np, Pu) formulas. © 2011 American Chemical Society

Self-Assembled Mercaptan on Mesoporous Silica (SAMMS) technology of mercury removal and stabilization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Xiangdong; Liu, Jun; Fryxell, G.E.

1997-09-01

This paper explains the technology developed to produce Self-Assembled Mercaptan on Mesoporous Silica (SAMMS) for mercury removal from aqueous wastewater and from organic wastes. The characteristics of SAMMS materials, including physical characteristics and mercury loading, and its application for mercury removal and stabilization are discussed. Binding kinetics and binding speciations are reported. Preliminary cost estimates are provided for producing SAMMS materials and for mercury removal from wastewater. The characteristics of SAMMS in mercury separation were studied at PNNL using simulated aqueous tank wastes and actual tritiated pump oil wastes from Savannah River Site; preliminary results are outlined. 47 refs., 16more » figs., 16 tabs.« less

Heat-assisted aqueous extraction of rice flour for arsenic speciation analysis.

PubMed

Narukawa, Tomohiro; Chiba, Koichi

2010-07-28

A versatile heat-assisted pretreatment aqueous extraction method for the analysis of arsenic species in rice was developed. Rice flour certified reference materials NIST SRM1568a and NMIJ CRM 7503-a and a flour made from polished rice were used as samples, and HPLC-ICP-MS was employed for the determination of arsenic species. Arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) were detected in NIST SRM, and As(III), As(V) and DMAA were found in NMIJ CRM and the prepared polished rice flour. The sums of the concentrations of all species in each rice flour sample were 97-102% of the total arsenic concentration in each sample.

Aqueous and solid phase speciation of arsenic in a Bengali aquifer using IC-ICP-MS and EXAFS

NASA Astrophysics Data System (ADS)

Gault, A. G.; Davidson, L. E.; Lythgoe, P. R.; Charnock, J. M.; Chatterjee, D.; Abou-Shakra, F. R.; Walker, H. J.; Polya, D. A.

2003-04-01

Contamination of groundwater and drinking water supplies with arsenic has been reported in many parts of the world and constitutes a serious public health threat. Nowhere is this more apparent than in West Bengal and Bangladesh where arsenic concentrations exceed both World Health Organisation (WHO) and national limits in drinking water supplies leading to what has been described as the worst mass poisoning of a human population in history. Knowledge of both aqueous and solid phase speciation of arsenic in such hazardous arsenic-rich groundwaters is crucial to understanding the processes controlling arsenic release. We report here preliminary work involving the determination of dissolved arsenic speciation in West Bengali groundwaters and extended X-ray absorption fine structure (EXAFS) analysis of the associated sediment. Groundwater samples collected from Nadia district, West Bengal were analysed for arsenic speciation by ion chromatography-inductively coupled plasma-mass spectrometry (IC-ICP-MS) within 14 days of collection. Total arsenic concentrations exceeding 850 ug/L were determined; inorganic arsenic constituted the bulk of the dissolved arsenic burden with As(III) as the dominant form. Minor amounts of methylated arsenicals were also detected, however, their concentration did not exceed 5 ug/L. The local coordination environment of arsenic in sediment associated with such groundwaters was probed using K-edge As EXAFS. This revealed that arsenic exists predominantly in its oxidised form, As(V), most likely adsorbed as bidentate arsenate tetrahedra on metal (Fe and/or Al) oxide/hydroxide surfaces, although incorporation of arsenic into a metal oxide structure cannot be unequivocally ruled out. Arsenic was found to occur in several different coordination environments and this, together with the low concentration (< 5 ug/g) of arsenic in the sediment, prevented the unambiguous assignment of the second coordination sphere. The analysis of the trends of key groundwater constituents in our data suggest that arsenic is released due to the reductive dissolution of arsenic laden-hydrous ferric oxides, however, further work is required to fully evaluate the mode of arsenic release.

Spectroscopic Evidence of Uranium Immobilization in Acidic ...

EPA Pesticide Factsheets

Biogeochemistry of uranium in wetlands plays important roles in U immobilization in storage ponds of U mining and processing facilities but has not been well understood. The objective of this work was to study molecular mechanisms responsible for high U retention by Savannah River Site (SRS) wetland sediments under varying redox and acidic (pH = 2.6-5.8) conditions using U L3-edge X-ray absorption spectroscopy. Uranium in the SRS wetland sediments existed primarily as U(VI) bonded as a bidentate to carboxylic sites (U-C bond distance at ~2.88 Å), rather than phenolic or other sites of natural organic matter (NOM). In microcosms simulating the SRS wetland process, U immobilization on roots was 2 orders of magnitude higher than on the adjacent brown or more distant white sands in which U was U(VI). Uranium on the roots were both U(IV) and U(VI), which were bonded as a bidentate to carbon, but the U(VI) may also form a U phosphate mineral. After 140 days of air exposure, all U(IV) was reoxidized to U(VI) but remained as a bidentate bonding to carbon. This study demonstrated NOM and plant roots can highly immobilize U(VI) in the SRS acidic sediments, which has significant implication on the long-term stewardship of U-contaminated wetlands. There were several former U processing facilities at the Savannah River Site (SRS), Aiken, SC. As a result of their operations, uranium has entered the surrounding environments. For example, approximately 45,000 kg o

Influence of Bicarbonate, Sulfate, and Electron Donors on Biological reduction of Uranium and Microbial Community Composition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Wensui; Zhou, Jizhong; Wu, Weimin

2007-01-01

A microcosm study was performed to investigate the effect of ethanol and acetate on uranium(VI) biological reduction and microbial community changes under various geochemical conditions. Each microcosm contained an uranium-contaminated sediment (up to 2.8 g U/kg) suspended in buffer with bicarbonate at concentrations of either 1 mM or 40 mM and sulfate at either 1.1 or 3.2 mM. Ethanol or acetate was used as an electron donor. Results indicate that ethanol yielded in significantly higher U(VI) reduction rates than acetate. A low bicarbonate concentration (1 mM) was favored for U(VI) bioreduction to occur in sediments, but high concentrations of bicarbonatemore » (40 mM) and sulfate (3.2 mM) decreased the reduction rates of U(VI). Microbial communities were dominated by species from the Geothrix genus and Proteobacteria phylum in all microcosms. However, species in the Geobacteraceae family capable of reducing U(VI) were significantly enriched by ethanol and acetate in low bicarbonate buffer. Ethanol increased the population of unclassified Desulfuromonales, while acetate increased the population of Desulfovibrio. Additionally, species in the Geobacteraceae family were not enriched in high bicarbonate buffer, but the Geothrix and the unclassified Betaproteobacteria species were enriched. This study concludes that ethanol could be a better electron donor than acetate for reducing U(VI) under given experimental conditions, and electron donor and geoundwater geochemistry alter microbial communities responsible for U(VI) reduction.« less

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

PubMed Central

Wills, Lindsay A.; Qu, Xiaohui; Chang, I-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-01-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions. PMID:28643782

Chapter A6. Section 6.5. Reduction-Oxidation Potential (Electrode Method)

USGS Publications Warehouse

Nordstrom, D. Kirk; Wilde, Franceska D.

2005-01-01

Reduction-oxidation (redox) potential--also referred to as Eh--is a measure of the equilibrium potential, relative to the standard hydrogen electrode, developed at the interface between a noble metal electrode and an aqueous solution containing electroactive chemical species. Measurements of Eh are used to evaluate geochemical speciation models, and Eh data can provide insights on the evolution and status of water chemistry in an aqueous system. Nevertheless, the measurement is fraught with inherent interferences and limitations that must be understood and considered to determine applicability to the aqueous system being studied. For this reason, Eh determination is not one of the field parameters routinely measured by the U.S. Geological Survey (USGS). This section of the National Field Manual (NFM) describes the equipment and procedures needed to measure Eh in water using a platinum electrode. Guidance as to the limitations and interpretation of Eh measurement also is included.

Group additivity-Pourbaix diagrams advocate thermodynamically stable nanoscale clusters in aqueous environments

NASA Astrophysics Data System (ADS)

Wills, Lindsay A.; Qu, Xiaohui; Chang, I.-Ya; Mustard, Thomas J. L.; Keszler, Douglas A.; Persson, Kristin A.; Cheong, Paul Ha-Yeon

2017-06-01

The characterization of water-based corrosion, geochemical, environmental and catalytic processes rely on the accurate depiction of stable phases in a water environment. The process is aided by Pourbaix diagrams, which map the equilibrium solid and solution phases under varying conditions of pH and electrochemical potential. Recently, metastable or possibly stable nanometric aqueous clusters have been proposed as intermediate species in non-classical nucleation processes. Herein, we describe a Group Additivity approach to obtain Pourbaix diagrams with full consideration of multimeric cluster speciation from computations. Comparisons with existing titration results from experiments yield excellent agreement. Applying this Group Additivity-Pourbaix approach to Group 13 elements, we arrive at a quantitative evaluation of cluster stability, as a function of pH and concentration, and present compelling support for not only metastable but also thermodynamically stable multimeric clusters in aqueous solutions.

Measured solubilities and speciations from oversaturation experiments of neptunium, plutonium, and americium in UE-25p No. 1 well water from the Yucca Mountain region: Milestone report 3329-WBS1.2.3.4.1.3.1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nitsche, H.; Roberts, K.; Prussin, T.

1994-04-01

Solubility and speciation are important in understanding aqueous radionuclide transport through the geosphere. They define the source term for transport retardation processes such as sorption and colloid formation. Solubility and speciation data are useful in verifying the validity of geochemical codes that are a part of predictive transport models. Results are presented from solubility and speciation experiments of {sup 237}NpO{sub 2}{sup +}, {sup 239}Pu{sup 4+}, and {sup 241}Am{sup 3+}/Nd{sup 3+} in a modified UE-25p No. 1 groundwater (from the Yucca Mountain region, Nevada, which is being investigated as a potential high-level nuclear waste disposal site) at two different temperatures (25{degree}more » and 60{degree}C) and three pH values (6.0, 7.0, 8.5). The solubility-controlling steady-state solids were identified and the speciation and/or oxidation states present in the supernatant solutions were determined. The neptunium solubility decreased with increasing temperature and pH. Plutonium concentrations significantly decreased with increasing temperature at pH 6 and 7. The concentration at pH 8.5 hardly decreased at all with increasing temperature. At both temperatures the concentrations were highest at pH 8.5, lowest at pH 7, and in between at pH 6. For the americium/neodymium solutions, the solubility decreased significantly with increasing temperature and increased somewhat with increasing pH.« less

User's guide to PHREEQC, a computer program for speciation, reaction-path, advective-transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, D.L.

1995-01-01

PHREEQC is a computer program written in the C pwgranuning language that is designed to perform a wide variety of aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations, (2) reaction-path and advective-transport calculations involving specified irreversible reactions, mixing of solutions, mineral and gas equilibria surface-complex-ation reactions, and ion-exchange reactions, and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for composition differences between waters, within specified compositional uncertainties. PHREEQC is derived from the Fortran program PHREEQE, but it has been completely rewritten in C with the addition many new capabilities. New features include the capabilities to use redox couples to distribute redox elements among their valence states in speciation calculations; to model ion-exchange and surface-compiexation reactions; to model reactions with a fixed-pressure, multicomponent gas phase (that is, a gas bubble); to calculate the mass of water in the aqueous phase during reaction and transport calculations; to keep track of the moles of minerals present in the solid phases and determine antomaticaHy the thermodynamically stable phase assemblage; to simulate advective transport in combination with PHREEQC's reaction-modeling capability; and to make inverse modeling calculations that allow for uncertainties in the analytical data. The user interface is improved through the use of a simplified approach to redox reactions, which includes explicit mole-balance equations for hydrogen and oxygen; the use of a revised input that is modular and completely free format; and the use of mineral names and standard chemical symbolism rather than index numbers. The use of (2 eliminates nearly all limitations on army sizes, including numbers of elements, aqueous species, solutions, phases, and lengths of character strings. A new equation solver that optimizes a set of equalities subject to both equality and inequality constraints is used to determine the thermodynamically stable set of phases in equilibrium with a solution. A more complete Newton-Raphson formulation, master-species switching, and scaling of the algebraic equations reduce the number of failures of the nunmrical method in PHREEQC relative to PHREEQE. This report presents the equations that are the basis for chemical equilibrium and inverse-modeling calculations in PHREEQC, describes the input for the program, and presents twelve examples that demonstrate most of the program's capabilities.

Mechanisms and Rates of U(VI) Reduction by Fe(II) in Homogeneous Aqueous Solution and the Role of U(V) Disproportionation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, Richard N.; Rosso, Kevin M.

Molecular-level pathways in the aqueous redox transformation of uranium by iron remain unclear, despite the importance of this knowledge for predicting uranium transport and distribution in natural and engineered environments. As the relative importance of homogeneous versus heterogeneous pathways is difficult to probe experimentally, here we apply computational molecular simulation to isolate rates of key one electron transfer reactions in the homogeneous pathway. By comparison to experimental observations the role of the heterogeneous pathway also becomes clear. Density functional theory (DFT) and Marcus theory calculations for all primary monomeric species at pH values ≤7 show for UO22+ and its hydrolysismore » species UO2OH+ and UO2(OH)20 that reduction by Fe2+ is thermodynamically favorable, though kinetically limited for UO22+. An inner-sphere encounter complex between UO2OH+ and Fe2+ was the most stable for the first hydrolysis species and displayed an electron transfer rate constant ket = 4.3 × 103 s-1. Three stable inner- and outer-sphere encounter complexes between UO2(OH)20 and Fe2+ were found, with electron transfer rate constants ranging from ket = 7.6 × 102 to 7.2 × 104 s-1. Homogeneous reduction of these U(VI) hydrolysis species to U(V) is, therefore, predicted to be facile. In contrast, homogeneous reduction of UO2+ by Fe2+ was found to be thermodynamically unfavorable, suggesting the possible importance of U(V)-U(V) disproportionation as a route to U(IV). Calculations on homogeneous disproportionation, however, while yielding a stable outer-sphere U(V)-U(V) encounter complex, indicate that this electron transfer reaction is not feasible at circumneutral pH. Protonation of both axial O atoms of acceptor U(V) (i.e., by H3O+) was found to be a prerequisite to stabilize U(IV), consistent with the experimental observation that the rate of this reaction is inversely correlated with pH. Thus, despite prevailing notions that U(V) is rapidly eliminated by homogeneous disproportionation, this pathway is irrelevant at environmental conditions.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Casella, Amanda J.; Hylden, Laura R.; Campbell, Emily L.

Knowledge of real-time solution properties and composition is a necessity for any spent nuclear fuel reprocessing method. Metal-ligand speciation in aqueous solutions derived from the dissolved commercial spent fuel is highly dependent upon the acid concentration/pH, which influences extraction efficiency and the resulting speciation in the organic phase. Spectroscopic process monitoring capabilities, incorporated in a counter current centrifugal contactor bank, provide a pathway for on-line real-time measurement of solution pH. The spectroscopic techniques are process-friendly and can be easily configured for on-line applications, while classic potentiometric pH measurements require frequent calibration/maintenance and have poor long-term stability in aggressive chemical andmore » radiation environments. Our research is focused on developing a general method for on-line determination of pH of aqueous solutions through chemometric analysis of Raman spectra. Interpretive quantitative models have been developed and validated under the range of chemical composition and pH using a lactic acid/lactate buffer system. The developed model was applied to spectra obtained on-line during solvent extractions performed in a centrifugal contactor bank. The model predicted the pH within 11% for pH > 2, thus demonstrating that this technique could provide the capability of monitoring pH on-line in applications such as nuclear fuel reprocessing.« less

REE controls in ultramafic hosted MOR hydrothermal systems: An experimental study at elevated temperature and pressure

NASA Astrophysics Data System (ADS)

Allen, Douglas E.; Seyfried, W. E.

2005-02-01

A hydrothermal experiment involving peridotite and a coexisting aqueous fluid was conducted to assess the role of dissolved Cl - and redox on REE mobility at 400°C, 500 bars. Data show that the onset of reducing conditions enhances the stability of soluble Eu +2 species. Moreover, Eu +2 forms strong aqueous complexes with dissolved Cl - at virtually all redox conditions. Thus, high Cl - concentrations and reducing conditions can combine to reinforce Eu mobility. Except for La, trivalent REE are not greatly affected by fluid speciation under the chemical and physical condition considered, suggesting control by secondary mineral-fluid partitioning. LREE enrichment and positive Eu anomalies observed in fluids from the experiment are remarkably similar to patterns of REE mobility in vent fluids issuing from basalt- and peridotite-hosted hydrothermal systems. This suggests that the chondrite normalized REE patterns are influenced greatly by fluid speciation effects and secondary mineral formation processes. Accordingly, caution must be exercised when using REE in hydrothermal vent fluids to infer REE sources in subseafloor reaction zones from which the fluids are derived. Although vent fluid patterns having LREE enrichment and positive Eu anomalies are typically interpreted to suggest plagioclase recrystallization reactions, this need not always be the case.

Batch versus column modes for the adsorption of radioactive metal onto rice husk waste: conditions optimization through response surface methodology.

PubMed

Kausar, Abida; Bhatti, Haq Nawaz; Iqbal, Munawar; Ashraf, Aisha

2017-09-01

Batch and column adsorption modes were compared for the adsorption of U(VI) ions using rice husk waste biomass (RHWB). Response surface methodology was employed for the optimization of process variables, i.e., (pH (A), adsorbent dose (B), initial ion concentration (C)) in batch mode. The B, C and C 2 affected the U(VI) adsorption significantly in batch mode. The developed quadratic model was found to be validated on the basis of regression coefficient as well as analysis of variance. The predicted and actual values were found to be correlated well, with negligible residual value, and B, C and C 2 were significant terms. The column study was performed considering bed height, flow rate and initial metal ion concentration, and adsorption efficiency was evaluated through breakthrough curves and bed depth service time and Thomas models. Adsorption was found to be dependent on bed height and initial U(VI) ion concentration, and flow rate decreased the adsorption capacity. Thomas models fitted well to the U(VI) adsorption onto RHWB. Results revealed that RHWB has potential to remove U(VI) ions and batch adsorption was found to be efficient versus column mode.

Site-specific incorporation of uranyl carbonate species at the calcite surface

NASA Astrophysics Data System (ADS)

Reeder, Richard J.; Elzinga, Evert J.; Tait, C. Drew; Rector, K. D.; Donohoe, Robert J.; Morris, David E.

2004-12-01

Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101¯4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the "-" vicinal regions and featureless, weak luminescence at the "+" vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the "-" vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite. The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at "-" steps, as observed in experiments.

Aluminum speciation in aqueous fluids at deep crustal pressure and temperature

NASA Astrophysics Data System (ADS)

Mookherjee, Mainak; Keppler, Hans; Manning, Craig E.

2014-05-01

We investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 °C. We have studied aluminum species in (a) pure H2O, (b) 5.3 m KOH solution, and (c) 1 m KOH solution. In order to better understand the spectral features of the aqueous fluids, we used ab initio simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with 5.3 m and 1 m KOH solution in equilibrium with Al2O3 show a sharp band at ˜620 cm-1 which could be attributed to the [ species. The band grows in intensity with temperature along an isochore. A shoulder on the high-frequency side of this band may be due to a hydrated, charge neutral Al(OH)3·H2O species. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [ species to dimers [(OH)2-Al-(OH)2-Al(OH)2] or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. Upon cooling of Al-bearing solutions to room temperatures, Raman bands indicating the precipitation of diaspore (AlOOH) were observed in some experiments. The Raman spectra of the KOH solutions (with or without dissolved alumina) showed a sharp OH stretching band at ˜3614 cm-1 and an in-plane OH bending vibration at ˜1068 cm-1, likely related to an OH- ion with the oxygen atom attached to a water molecule by hydrogen bonding. A weak feature at ˜935 cm-1 may be related to the out-of-plane bending vibration of the same species or to an OH species with a different environment.

Clear-Sky UV-B trends over Northern Midlatitudes derived from TOMS Low-Reflectivity Footprint Measurements

NASA Technical Reports Server (NTRS)

Ziemke, Jerry; Chandra, Sushil; Varotsos, C.

1998-01-01

This study investigates the distribution of clear-sky ultraviolet-B (UV-B, wavelengths 290-320 nm) trends in northern midlatitudes using 1979-1991 Nimbus 7 total ozone mapping spectrometer (TOMS) version 7 low-reflectivity (R<0.2) total ozone footprint measurements. The incorporation of essentially cloud-free ozone data from TOMS provides a direct method for separating transient cloud effects from anthropogenic and other dynamical factors present in UV-B. This study has also included both National Oceanic and Atmospheric Administration (NOAA) microwave sounding unit channel 4 (MSU4) and National Centers for Environmental Prediction (NCEP) 500 hPa temperature (T500) fields in our trend models to improve UV-Index (UVI) trend statistics and to investigate the effects of interannual changes in UVI caused by synoptic-scale (horizontal wavelengths 4000-8000 km) and planetary-scale (horizontal wavelengths greater than 8000 km) dynamical events. Clear-sky UVI trends in the northern midlatitudes show large increases (exceeding 10 % per decade) and distinct regional variability especially during winter-spring months which can be attributed to topography and dynamical forcing effects. In the UV-important summer-autumn months, these trends are more uniformly distributed and still statistically significant, although smaller at around +2 to +3 % per decade. Specifically, during April largest increases in midlatitude UVI are seen to extend from near the dateline eastward across North America. In June months largest UVI increases occur over the east Asian continent with values around +5 to +6 % per decade. These increases in UVI over both the Pacific and Asian continent regions persist through summer into Autumn. In the the European sector, statistically significant increases in clear-sky UVI are found over central Europe with values around +2 to +3 % per decade and +8 to +9 % per decade during summer and winter-spring months, respectively. Over the nearby Mediterranean region these seasonal trends are around +2 to +3 and +5 to +6 % per decade.

Evaluation of the impact of atmospheric ozone and aerosols on the horizontal global/diffuse UV Index at Livorno (Italy)

NASA Astrophysics Data System (ADS)

Scaglione, Daniele; Giulietti, Danilo; Morelli, Marco

2016-08-01

A study was conducted at Livorno (Italy) to evaluate the impact of atmospheric aerosols and ozone on the solar UV radiation and its diffuse component at ground in clear sky conditions. Solar UV radiation has been quantified in terms of UV Index (UVI), following the ISO 17166:1999/CIE S007/E-1998 international standard. UVI has been calculated by exploiting the libRadtran radiative transfer modelling software as a function of both the Aerosols Optical Depth (AOD) and the Total Ozone Column (TOC). In particular AOD and TOC values have been remotely sensed by the Ozone Monitoring Instrument (OMI) on board the NASA's EOS (Earth Observing System) satellites constellation. An experimental confirmation was also obtained by exploiting global UVI ground-based measurements from the 26/9/14 to 12/8/15 and diffuse UVI ground-based measurements from the 17/5/15 to 12/8/15. For every considered value of Solar Zenith Angle (SZA) and atmospheric condition, estimates and measurements confirm that the diffuse component contributes for more than 50% on the global UV radiation. Therefore an exposure of human skin also to diffuse solar UV radiation can be potentially harmful for health and need to be accurately monitored, e.g. by exploiting innovative applications such as a mobile app with a satellite-based UV dosimeter that has been developed. Global and diffuse UVI variations due to the atmosphere are primarily caused by the TOC variations (typically cyclic): the maximum TOC variation detected by OMI in the area under study leads to a corresponding variation in global and diffuse UVI of about 50%. Aerosols in the area concerned, mainly of maritime nature, have instead weaker effects causing a maximum variation of the global and diffuse UVI respectively of 9% and 35% with an SZA of 20° and respectively of 13% and 10% with an SZA of 60°.

Combined EXAFS Spectroscopic and Quantum Chemical Study on the Complex Formation of Am(III) with Formate.

PubMed

Fröhlich, Daniel R; Kremleva, Alena; Rossberg, André; Skerencak-Frech, Andrej; Koke, Carsten; Krüger, Sven; Rösch, Notker; Panak, Petra J

2017-06-19

The complexation of Am(III) with formate in aqueous solution is studied as a function of the pH value using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy, iterative transformation factor analysis (ITFA), and quantum chemical calculations. The Am L III -edge EXAFS spectra are analyzed to determine the molecular structure (coordination numbers; Am-O and Am-C distances) of the formed Am(III)-formate species and to track the shift of the Am(III) speciation with increasing pH. The experimental data are compared to predictions from density functional calculations. The results indicate that formate binds to Am(III) in a monodentate fashion, in agreement with crystal structures of lanthanide formates. Furthermore, the investigations are complemented by thermodynamic speciation calculations to verify further the results obtained.

Ultra-Sensitive Elemental Analysis Using Plasmas 5.Speciation of Arsenic Compounds in Biological Samples by High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry System

NASA Astrophysics Data System (ADS)

Kaise, Toshikazu

Arsenic originating from the lithosphere is widely distributed in the environment. Many arsenicals in the environment are in organic and methylated species. These arsenic compounds in drinking water or food products of marine origin are absorbed in human digestive tracts, metabolized in the human body, and excreted viatheurine. Because arsenic shows varying biological a spects depending on its chemical species, the biological characteristics of arsenic must be determined. It is thought that some metabolic pathways for arsenic and some arsenic circulation exist in aqueous ecosystems. In this paper, the current status of the speciation analysis of arsenic by HPLC/ICP-MS (High Performance Liquid Chromatography-Inductively Coupled Plasma Mass spectrometry) in environmental and biological samples is summarized using recent data.

Remediation of uranium contaminated soils with bicarbonate extraction and microbial U(VI) reduction

USGS Publications Warehouse

Philips , Elizabeth J.P.; Landa, Edward R.; Lovely, Derek R.

1995-01-01

A process for concentrating uranium from contaminated soils in which the uranium is first extracted with bicarbonate and then the extracted uranium is precipitated with U(VI)-reducing microorganisms was evaluated for a variety of uranuum-contaminated soils. Bicarbonate (100 mM) extracted 20–94% of the uranium that was extracted with nitric acid. The U(VI)-reducing microorganism,Desulfovibrio desulfuricans reduced the U(VI) to U(IV) in the bicarbonate extracts. In some instances unidentified dissolved extracted components, presumably organics, gave the extract a yellow color and inhibited U(VI) reduction and/or the precipitation of U(IV). Removal of the dissolved yellow material with the addition of hydrogen peroxide alleviated this inhibition. These results demonstrate that bicarbonate extraction of uranium from soil followed by microbial U(VI) reduction might be an effective mechanism for concentrating uranium from some contaminated soils.

Upscaling of U (VI) desorption and transport from decimeter‐scale heterogeneity to plume‐scale modeling

USGS Publications Warehouse

Curtis, Gary P.; Kohler, Matthias; Kannappan, Ramakrishnan; Briggs, Martin A.; Day-Lewis, Frederick D.

2015-01-01

Scientifically defensible predictions of field scale U(VI) transport in groundwater requires an understanding of key processes at multiple scales. These scales range from smaller than the sediment grain scale (less than 10 μm) to as large as the field scale which can extend over several kilometers. The key processes that need to be considered include both geochemical reactions in solution and at sediment surfaces as well as physical transport processes including advection, dispersion, and pore-scale diffusion. The research summarized in this report includes both experimental and modeling results in batch, column and tracer tests. The objectives of this research were to: (1) quantify the rates of U(VI) desorption from sediments acquired from a uranium contaminated aquifer in batch experiments;(2) quantify rates of U(VI) desorption in column experiments with variable chemical conditions, and(3) quantify nonreactive tracer and U(VI) transport in field tests.

Composition of COH fluids at 1 GPa: an experimental study on speciation and solubility

NASA Astrophysics Data System (ADS)

Tiraboschi, Carla; Tumiati, Simone; Recchia, Sandro; Ulmer, Peter; Pettke, Thomas; Fumagalli, Patrizia; Poli, Stefano

2014-05-01

COH fluids play a fundamental role in many geological processes, controlling the location of melting in subduction zones and promoting mass transfer from the subducting litosphere to the overlying mantle wedge. The properties of COH fluids are strictly dependent on the composition of the fluid in subduction systems, i.e., the speciation of the volatile components of the fluid itself and the presence of solutes deriving from the dissolution of rock-forming minerals. In the scientific literature, the speciation of COH fluids has been generally determined through thermodynamic calculations using equations of state of simple H2O-non-polar gas systems (e.g., H2O-CO2-CH4), equations that do not consider the complexity related to dissolution processes, which are substantially unexplored in COH fluids and limited so far to aqueous fluids (Newton & Manning, 2002). The aim of this work is to investigate experimentally the speciation and the dissolution of mantle minerals in carbon-saturated COH fluids at buffered fO2 conditions. Our experimental approach relies on two different techniques: 1) analysis by means of quadrupole mass spectrometer (QMS) of the fluids from pierced run capsules to retrieve speciation of volatile components and 2) analysis of frozen COH fluid with laser-ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) to measure the amount of solutes. Experiments were conducted at pressure of 1 GPa and temperatures from 800 to 900° C using a rocking piston cylinder apparatus. Mantle minerals in equilibrium with COH fluid are represented by synthetic forsterite. fO2 conditions were controlled using the double capsule technique and NNO buffer (ΔFMQ=-0.61 at 800° C; ΔFMQ =-0.98 at 900° C). For the speciation experiments, oxalic acid dihydrate and graphite have been used to generate carbon-saturated COH fluid. The speciation was determined by analyzing the quenched COH fluid, retrieved by piercing the capsule in a gas-tight vessel at T =80° C and convoying evolved gases to a QMS through a heated line to avoid the condensation of water. This type of analyzer ensures superior performances in terms of selectivity of molecules to be detected, high acquisition rates and extended linear response range. The influence of dissolved solutes on fluid speciation has been evaluated by comparing experiments in the pure COH system and in the COH+forsterite system. To determine the solubility of forsterite in COH fluids we performed a second set of experiments at the same P , T and fO2 conditions above. Fluids trapped in a diamond layer were analysed by the cryogenic LA-ICP-MS technique described by Aerts et al. (2010). With this method the aqueous part of the COH fluid is frozen prior the opening and maintained frozen during the analysis to avoid any precipitation of solutes. The results will highlight the importance of fluids for the mass transport in subduction zones. Comparison between experimental data and thermodynamic calculation will also be shown. References: Aerts, M., Hack, A.C., Reusser, E., Ulmer, P. (2010) Am. Mineral. 95, 1523-1526. Newton, R.C., Manning, C.E. (2002) Geochim. Cosmochim. Ac. 66, 4165-4176.

Assessing the concentration, speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine, Vermont, USA

USGS Publications Warehouse

Balistrieri, L.S.; Seal, R.R.; Piatak, N.M.; Paul, B.

2007-01-01

The authors determine the composition of a river that is impacted by acid-mine drainage, evaluate dominant physical and geochemical processes controlling the composition, and assess dissolved metal speciation and toxicity using a combination of laboratory, field and modeling studies. Values of pH increase from 3.3 to 7.6 and the sum of dissolved base metal (Cd + Co + Cu + Ni + Pb + Zn) concentrations decreases from 6270 to 100 ??g/L in the dynamic mixing and reaction zone that is downstream of the river's confluence with acid-mine drainage. Mixing diagrams and PHREEQC calculations indicate that mixing and dilution affect the concentrations of all dissolved elements in the reach, and are the dominant processes controlling dissolved Ca, K, Li, Mn and SO4 concentrations. Additionally, dissolved Al and Fe concentrations decrease due to mineral precipitation (gibbsite, schwertmannite and ferrihydrite), whereas dissolved concentrations of Cd, Co, Cu, Ni, Pb and Zn decrease due to adsorption onto newly formed Fe precipitates. The uptake of dissolved metals by aquatic organisms is dependent on the aqueous speciation of the metals and kinetics of complexation reactions between metals, ligands and solid surfaces. Dissolved speciation of Cd, Cu, Ni and Zn in the mixing and reaction zone is assessed using the diffusive gradients in thin films (DGT) technique and results of speciation calculations using the Biotic Ligand Model (BLM). Data from open and restricted pore DGT units indicate that almost all dissolved metal species are inorganic and that aqueous labile or DGT available metal concentrations are generally equal to total dissolved concentrations in the mixing zone. Exceptions occur when labile metal concentrations are underestimated due to competition between H+ and metal ions for Chelex-100 binding sites in the DGT units at low pH values. Calculations using the BLM indicate that dissolved Cd and Zn species in the mixing and reaction zone are predominantly inorganic, which is consistent with the DGT results. Although the DGT method indicates that the majority of aqueous Cu species are inorganic, BLM calculations indicate that dissolved Cu is inorganic at pH 5.5. Integrated dissolved labile concentrations of Cd, Cu and Zn in the mixing and reaction zone are compared to calculated acute toxicity concentrations (LC50 values) for fathead minnows (Pimephales promelas) (Cd, Cu and Zn) and water fleas (Ceriodaphnia dubia) (Cd and Cu) using the BLM, and to national recommended water quality criteria [i.e., criteria maximum concentration (CMC) and criterion continuous concentration (CCC)]. Observed labile concentrations of Cd and Zn are below LC50 values and CMC for Cd, but above CCC and CMC for Zn at sites <30 m downstream of the confluence. In contrast, labile Cu concentrations exceed LC50 values for the organisms as well as CCC and CMC at sites <30 m downstream of the confluence. These results suggest that environmental conditions at sites closest to the confluence of the river and acid-mine drainage should not support healthy aquatic organisms. ?? 2007 Elsevier Ltd. All rights reserved.

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

USGS Publications Warehouse

Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

2009-01-01

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10-3 to 6.0 ?? 10 -3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

Removal of phosphate from aqueous solutions and sewage using natural and surface modified coir pith.

PubMed

Krishnan, K Anoop; Haridas, Ajit

2008-04-01

Iron impregnated coir pith (CP-Fe-I) can be effectively used for the removal of phosphate from aqueous streams and sewage. Iron impregnation on natural coir pith was carried out by drop by drop addition method. The effect of various factors such as pH, initial concentration of phosphate, contact time and adsorbent dose on phosphate adsorption was studied by batch technique. The pH at 3.0 favored the maximum adsorption of phosphate from aqueous solutions. The effect of pH on phosphate adsorption was explained by pH(zpc), phosphate speciation in solution and affinity of anions towards the adsorbent sites. A comparative study of the adsorption of phosphate using CP-Fe-I and CP (coir pith) was made and results show that the former one is five to six times more effective than the latter. Kinetic studies revealed that the adsorption process followed a pseudo-second order kinetic model. Adsorption followed Langmuir isotherm model. Column studies were conducted to examine the utility of the investigated adsorbent for the removal of phosphate from continuously flowing aqueous solutions.

Equilibrium of molybdenum in selected extraction systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tkac, Peter; Paulenova, Alena

2007-07-01

The concentration of molybdenum(VI) in dissolved irradiated nuclear fuel is comparable with the concentrations of Tc, Am and Np. Therefore it is of big interest to understand its behavior under conditions related to the UREX/TRUEX process. The effect of the poly-speciation of molybdenum in aqueous solution on its extraction by neutral solvents TBP and CMPO/TBP was studied. Extraction yields of molybdenum decreased significantly when AHA was added to aqueous phase. Our investigation confirmed a strong ability of the aceto-hydroxamic acid to form complexes with Mo in high acidic solutions. Spectroscopic data (UV-Vis) confirmed that a fraction of the Mo(VI)-AHA complexmore » is present in the organic phase after extraction. (authors)« less

Unique reversibility in extraction mechanism of U compared to solvent extraction for sorption of U(VI) and Pu(IV) by a novel solvent impregnated resin containing trialkyl phosphine oxide functionalized ionic liquid.

PubMed

Paramanik, M; Panja, S; Dhami, P S; Yadav, J S; Kaushik, C P; Ghosh, S K

2018-07-15

Novel Solvent Impregnated Resin (SIR) material was prepared by impregnating a trialkyl phosphine oxide functionalized ionic liquid (IL) into an inert polymeric material XAD-7. A series of SIR materials were prepared by varying the IL quantity. Sorption of both U(VI) and Pu(IV) were found to increase with increasing IL concentration in SIR up to an optimum IL concentration of 435 mg g -1 of SIR beyond which no effect of IL concentration was observed. A change of mechanism of sorption for U(VI) by SIR was observed in comparison to solvent extraction. The dependency of U(VI) sorption with nitric acid concentration showed a reverse trend compared to solvent extraction studies while for Pu(IV) the trend remained same as observed with solvent extraction. Sorption of both the radionuclides was found to follow pseudo second order mechanism and Langmuir adsorption isotherm. Distribution co-efficient measurements on IL impregnated SIR showed highly selective sorption of U(VI) and Pu(IV) over other trivalent f-elements and fission products from nitric acid medium. Copyright © 2018 Elsevier B.V. All rights reserved.

Uranium reduction and microbial community development in response to stimulation with different electron donors.

PubMed

Barlett, Melissa; Moon, Hee Sun; Peacock, Aaron A; Hedrick, David B; Williams, Kenneth H; Long, Philip E; Lovley, Derek; Jaffe, Peter R

2012-07-01

Stimulating microbial reduction of soluble U(VI) to less soluble U(IV) shows promise as an in situ bioremediation strategy for uranium contaminated groundwater, but the optimal electron donors for promoting this process have yet to be identified. The purpose of this study was to better understand how the addition of various electron donors to uranium-contaminated subsurface sediments affected U(VI) reduction and the composition of the microbial community. The simple electron donors, acetate or lactate, or the more complex donors, hydrogen-release compound (HRC) or vegetable oil, were added to the sediments incubated in flow-through columns. The composition of the microbial communities was evaluated with quantitative PCR probing specific 16S rRNA genes and functional genes, phospholipid fatty acid analysis, and clone libraries. All the electron donors promoted U(VI) removal, even though the composition of the microbial communities was different with each donor. In general, the overall biomass, rather than the specific bacterial species, was the factor most related to U(VI) removal. Vegetable oil and HRC were more effective in stimulating U(VI) removal than acetate. These results suggest that the addition of more complex organic electron donors could be an excellent option for in situ bioremediation of uranium-contaminated groundwater.

Size of Self-Gravity Wakes from Cassini UVIS Tracking Occultations and Ring Transparency Statistics

NASA Astrophysics Data System (ADS)

Esposito, Larry W.; Rehnberg, Morgan; Colwell, Joshua E.; Sremcevic, Miodrag

2017-10-01

We compare two methods for determining the size of self-gravity wakes in Saturn’s rings. Analysis of gaps seen in UVIS occultations gives a power law distribution from 10-100m (Rehnberg etal 2017). Excess variance from UVIS occultations can be related to characteristic clump widths, a method which extends the work of Showalter and Nicholson (1990) to more arbitrary shadow distributions. In the middle A ring, we use results from Colwell etal (2017) for the variance and results from Jerousek etal (2016) for the relative size of gaps and wakes to estimate the wake width consistent with the excess variance observed there. Our method gives:W= sqrt (A) * E/T2 * (1+ S/W)Where A is the area observed by UVIS in an integration period, E is the measured excess variance above Poisson statistics, T is the mean transparency, and S and W are the separation and width of self-gravity wakes in the granola bar model of Colwell etal (2006). We find:W ~ 10m and infer the wavelength of the fastest growing instabilityLambda(TOOMRE) = S + W ~ 30m.This is consistent with the calculation of the Toomre wavelength from the surface mass density of the A ring, and with the highest resolution UVIS star occultations.

Size of Self-Gravity Wakes from Cassini UVIS Tracking Occultations and Ring Transparency Statistics

NASA Astrophysics Data System (ADS)

Esposito, L. W.; Rehnberg, M.; Colwell, J. E.; Sremcevic, M.

2017-12-01

We compare two methods for determining the size of self-gravity wakes in Saturn's rings. Analysis of gaps seen in UVIS occultations gives a power law distribution from 10-100m (Rehnberg etal 2017). Excess variance from UVIS occultations can be related to characteristic clump widths, a method which extends the work of Showalter and Nicholson (1990) to more arbitrary shadow distributions. In the middle A ring, we use results from Colwell etal (2017) for the variance and results from Jerousek etal (2016) for the relative size of gaps and wakes to estimate the wake width consistent with the excess variance observed there. Our method gives: W= sqrt (A) * E/T2 * (1+ S/W)Where A is the area observed by UVIS in an integration period, E is the measured excess variance above Poisson statistics, T is the mean transparency, and S and W are the separation and width of self-gravity wakes in the granola bar model of Colwell etal (2006). We find: W 10m and infer the wavelength of the fastest growing instability lamdaT = S + W 30m. This is consistent with the calculation of the Toomre wavelength from the surface mass density of the A ring, and with the highest resolution UVIS star occultations.

Cassini UVIS Observations of Saturn during the Grand Finale Orbits

NASA Astrophysics Data System (ADS)

Pryor, W. R.; Esposito, L. W.; West, R. A.; Jouchoux, A.; Radioti, A.; Grodent, D. C.; Gerard, J. C. M. C.; Gustin, J.; Lamy, L.; Badman, S. V.

2017-12-01

In 2016 and 2017, the Cassini Saturn orbiter executed a final series of high inclination, low-periapsis orbits ideal for studies of Saturn's polar regions. The Cassini Ultraviolet Imaging Spectrograph (UVIS) obtained an extensive set of auroral images, some at the highest spatial resolution obtained during Cassini's long orbital mission (2004-2017). In some cases, two or three spacecraft slews at right angles to the long slit of the spectrograph were required to cover the entire auroral region to form auroral images. We will present selected images from this set showing narrow arcs of emission, more diffuse auroral emissions, multiple auroral arcs in a single image, discrete spots of emission, small scale vortices, large-scale spiral forms, and parallel linear features that appear to cross in places like twisted wires. Some shorter features are transverse to the main auroral arcs, like barbs on a wire. UVIS observations were in some cases simultaneous with auroral observations from the Hubble Space Telescope Space Telescope Imaging Spectrograph (STIS) that will also be presented. UVIS polar images also contain spectral information suitable for studies of the auroral electron energy distribution. The long wavelength part of the UVIS polar images contains a signal from reflected sunlight containing absorption signatures of acetylene and other Saturn hydrocarbons. The hydrocarbon spatial distribution will also be examined.

Two Methods for Retrieving UV Index for All Cloud Conditions from Sky Imager Products or Total SW Radiation Measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Badosa, Jordi; Calbo, J.; McKenzie, R. L.

2014-07-01

In the present study, we assess the cloud effects on UV Index (UVI) and total solar radiation (TR) as a function of cloud cover estimations and sunny conditions (from sky imaging products) as well as of solar zenith angle (SZA). These analyses are undertaken for a southern-hemisphere mid-latitude site where a 10-years dataset is available. It is confirmed that clouds reduce TR more than UV, in particular for obscured Sun conditions, low cloud fraction (< 60%) and large SZA (> 60º). Similarly, clouds enhance TR more than UV, mainly for visible Sun conditions, large cloud fraction and large SZA. Twomore » methods to estimate UVI are developed: 1) from sky imaging cloud cover and sunny conditions, and 2) from TR measurements. Both methods may be used in practical operational applications, although Method 2 shows overall the best performance, since TR allows accounting for cloud optical properties. The mean absolute differences of Method 2 estimations with respect to measured values are 0.17 UVI units (for 1-minute data) and 0.79 Standard Erythemal Dose (SED) units (for daily integrations). Method 1 shows less accurate results but it is still suitable to estimate UVI: mean absolute differences are 0.37 UVI units and 1.6 SED.« less

Adding to the Mercury Speciation Toolbox

NASA Astrophysics Data System (ADS)

Fitts, J. P.; Northrup, P. A.; Chidambaram, D.; Kalb, P. D.

2007-12-01

Mercury was used to separate lithium-6 isotope for weapons production at the Y-12 Plant in Oak Ridge, TN in the 1950s and 1960s. A large portion of the waste Hg entered the environment and continues to move throughout the sub-surface and surface waters in the area. Environmental management of Hg contamination within this complex hydrologic system, where Hg speciation and the mobile fraction have been found to vary widely, will require ongoing characterization and predictive modeling of Hg speciation. State-of-the-art spectroscopic tools that can directly probe Hg speciation in preserved aqueous and sediment samples with greater sensitivity, however, are required to determine rates and mechanisms of biogeochemical reactions. We will present the first results demonstrating the use of x-ray absorption spectroscopy (XAS) at the Hg M5 edge (2295 eV) to fingerprint Hg species. Heavy-metal M5 absorption edges can have very sharp features due to local electron transitions, and therefore, we are developing this edge as a tool for quantitative measurement of Hg species. In addition, sulfur speciation using the sulfur K absorption edge, which is at a similar energy (2472 eV), can be measured in the same scan as the Hg M5 edge. Potentially important organic and inorganic sulfur species (sulfide, disulfide, elemental sulfur, sulfite and sulfate) are readily differentiated, and thereby, provides an independent method for monitoring the redox state of the system along with changes in S-Hg bonding. We will also present x-ray microprobe 2-D concentration maps of Hg and other elements at the grain and pore scales to identify its microscopic distribution and chemical associations. When used in combination with established sequential extraction and direct spectroscopic methods, the addition of XAS at the Hg M5 edge should provide a significant advancement in the determination of Hg speciation in complex biogeochemical environments.

Phytoextraction of cadmium by Ipomoea aquatica (water spinach) in hydroponic solution: effects of cadmium speciation.

PubMed

Wang, Kai-Sung; Huang, Lung-Chiu; Lee, Hong-Shen; Chen, Pai-Ye; Chang, Shih-Hsien

2008-06-01

Phytoextraction is a promising technique to remediate heavy metals from contaminated wastewater. However, the interactions of multi-contaminants are not fully clear. This study employed cadmium, Triton X-100 (TX-100), and EDTA to investigate their interactions on phytotoxicity and Cd phytoextraction of Ipomoea aquatica (water spinach) in simulated wastewater. The Cd speciation was estimated by a chemical equilibrium model and MINEQL+. Statistic regression was applied to evaluate Cd speciation on Cd uptake in shoots and stems of I. aquatica. Results indicated that the root length was a more sensitive parameter than root weight and shoot weight. Root elongation was affected by Cd in the Cd-EDTA solution and TX-100 in the Cd-TX-100 solution. Both the root length and the root biomass were negatively correlated with the total soluble Cd ions. In contrast, Cd phytoextraction of I. aquatic was correlated with the aqueous Cd ions in the free and complex forms rather than in the chelating form. Additionally, the high Cd bioconcentration factors of I. aquatica (375-2227 l kg(-1) for roots, 45-144 l kg(-1) for shoots) imply that I. aquatica is a potential aquatic plant to remediate Cd-contaminated wastewater.

Effects of sorbate speciation on sorption of selected sulfonamides in three loamy soils

USGS Publications Warehouse

Kurwadkar , Sudarshan T.; Adams, Craig D.; Meyer, Michael T.; Kolpin, Dana W.

2007-01-01

Sorption of sulfamethazine (SMN) and sulfathiazole (STZ) was investigated in three soils, a North Carolina loamy sand, an Iowa sandy loam, and a Missouri loam, under various pH conditions. A significant increase in the sorption coefficient (KD) was observed in all three soils, as the sulfonamides converted from an anionic form at higher pH to a neutral/cationic form at lower pH. Above pH 7.5, sulfonamides exist primarily in anionic form and have higher aqueous solubility and no cationic character, thereby consequently leading to lower sorption to soils. The effect of speciation on sorption is not the same for all sulfonamides; it is a function of the pH of the soil and the pKa of the sulfonamides. The results indicate that, for the soils under investigation, SMN has comparatively lower KD values than STZ. The pH-dependent sorption of sulfonamides was observed to be consistent in all three soils investigated. The KD values for each speciated formcationic, neutral, and anionicwere calculated using an empirical model in which the species-specific sorption coefficients (KD0, KD1, and KD2) were weighted with their respective fractions present at any given pH.

The potential leaching and mobilization of trace elements from FGD-gypsum of a coal-fired power plant under water re-circulation conditions.

PubMed

Córdoba, Patricia; Castro, Iria; Maroto-Valer, Mercedes; Querol, Xavier

2015-06-01

Experimental and geochemical modelling studies were carried out to identify mineral and solid phases containing major, minor, and trace elements and the mechanism of the retention of these elements in Flue Gas Desulphurisation (FGD)-gypsum samples from a coal-fired power plant under filtered water recirculation to the scrubber and forced oxidation conditions. The role of the pH and related environmental factors on the mobility of Li, Ni, Zn, As, Se, Mo, and U from FGD-gypsums for a comprehensive assessment of element leaching behaviour were also carried out. Results show that the extraction rate of the studied elements generally increases with decreasing the pH value of the FGD-gypsum leachates. The increase of the mobility of elements such as U, Se, and As in the FGD-gypsum entails the modification of their aqueous speciation in the leachates; UO2SO4, H2Se, and HAsO2 are the aqueous complexes with the highest activities under acidic conditions. The speciation of Zn, Li, and Ni is not affected in spite of pH changes; these elements occur as free cations and associated to SO4(2) in the FGD-gypsum leachates. The mobility of Cu and Mo decreases by decreasing the pH of the FGD-gypsum leachates, which might be associated to the precipitation of CuSe2 and MoSe2, respectively. Time-of-Flight mass spectrometry of the solid phase combined with geochemical modelling of the aqueous phase has proved useful in understanding the mobility and geochemical behaviour of elements and their partitioning into FGD-gypsum samples. Copyright © 2015. Published by Elsevier B.V.

User's guide to PHREEQC (Version 2) : a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations

USGS Publications Warehouse

Parkhurst, David L.; Appelo, C.A.J.

1999-01-01

PHREEQC version 2 is a computer program written in the C programming language that is designed to perform a wide variety of low-temperature aqueous geochemical calculations. PHREEQC is based on an ion-association aqueous model and has capabilities for (1) speciation and saturation-index calculations; (2) batch-reaction and one-dimensional (1D) transport calculations involving reversible reactions, which include aqueous, mineral, gas, solid-solution, surface-complexation, and ion-exchange equilibria, and irreversible reactions, which include specified mole transfers of reactants, kinetically controlled reactions, mixing of solutions, and temperature changes; and (3) inverse modeling, which finds sets of mineral and gas mole transfers that account for differences in composition between waters, within specified compositional uncertainty limits.New features in PHREEQC version 2 relative to version 1 include capabilities to simulate dispersion (or diffusion) and stagnant zones in 1D-transport calculations, to model kinetic reactions with user-defined rate expressions, to model the formation or dissolution of ideal, multicomponent or nonideal, binary solid solutions, to model fixed-volume gas phases in addition to fixed-pressure gas phases, to allow the number of surface or exchange sites to vary with the dissolution or precipitation of minerals or kinetic reactants, to include isotope mole balances in inverse modeling calculations, to automatically use multiple sets of convergence parameters, to print user-defined quantities to the primary output file and (or) to a file suitable for importation into a spreadsheet, and to define solution compositions in a format more compatible with spreadsheet programs. This report presents the equations that are the basis for chemical equilibrium, kinetic, transport, and inverse-modeling calculations in PHREEQC; describes the input for the program; and presents examples that demonstrate most of the program's capabilities.

Chemical speciation and recovery of gold(I, III) from wastewater and silver by liquid-liquid extraction with the ion-pair reagent amiloride mono hydrochloride and AAS determination.

PubMed

El-Shahawi, M S; Bashammakh, A S; Bahaffi, S O

2007-06-15

A novel and low cost liquid-liquid extraction procedure for the separation of gold(III) at trace level from aqueous medium of pH 5-9 has been developed. The method has been based upon the formation of a yellow colored ternary complex ion associate of tetrachloro gold(III) complex anion, AuCl(4)(-) with the ion-pair reagent 1-(3,5-diamino-6-chloropyrazinecarboxyl) guanidine hydrochloride monohydrate, namely amiloride, DPG(+).Cl(-). The effect of various parameters, e.g. pH, organic solvent, shaking time, etc. on the preconcentration of gold(III) from the aqueous media by the DPG(+).Cl(-) reagent has been investigated. The colored gold species was quantitatively extracted into 4-methyl pentan-2-one. The chemical composition of the ion associate of DPG(+).Cl(-) with AuCl(4)(-) in the organic solvent has been determined by the Job's method. The molar absorptivity (2.19x10(4)Lmol(-1)cm(-1)) of the associate DPG(+).AuCl(4)(-) at 362nm enabled a convenient application of the developed extraction procedure for the separation and AAS determination of traces of aurate ions. Mono-valence gold ions after oxidation to gold(III) with bromine water in HCl (1.0molL(-1)) media have been also extracted quantitatively from the aqueous media by the developed procedure. The chemical speciation of mono- and/or tri-valence gold species spiked to fresh and industrial wastewater samples has been achieved. The method has been also applied successfully from the separation of gold(I) and gold(III) species from metallic ions and silver. The developed method has also the advantage of freedom from most diverse ions.

Occurrence and Speciation of Polymeric Chromium(III), Monomeric Chromium(III) and Chromium(VI) in Environmental Samples

PubMed Central

HU, LIGANG; CAI, YONG; JIANG, GUIBIN

2016-01-01

Laboratory experiments suggest that polymeric Cr(III) could exist in aqueous solution for a relative long period of time. However, the occurrence of polymeric Cr(III) has not been reported in environmental media due partially to the lack of method for speciating polymeric Cr. We observed an unknown Cr species during the course of study on speciation of Cr in the leachates of chromated-copper-arsenate (CCA)-treated wood. Efforts were made to identify structure of the unknown Cr species. Considering the forms of Cr existed in the CCA-treated woods, we mainly focused our efforts to determine if the unknown species were polymeric Cr(III), complex of Cr/As or complex of Cr with dissolved organic matter (DOM). In order to evaluate whether polymeric Cr(III) largely exist in wood leachates, high performance liquid chromatography coupled with inductively coupled mass spectrometry (HPLC-ICPMS was used) for simultaneous speciation of monomeric Cr(III), polymeric Cr(III), and Cr(VI). In addition to wood leachates where polymeric Cr (III) ranged from 39.1 to 67.4 %, occurrence of the unknown Cr species in other environmental matrices, including surface waters, tap and waste waters, was also investigated. It was found that polymeric Cr(III) could exist in environmental samples containing μg/L level of Cr, at a level up to 60% of total Cr, suggesting that polymeric Cr(III) could significantly exist in natural environments. Failure in quantifying polymeric Cr(III) would lead to the underestimation of total Cr and bias in Cr speciation. The environmental implication of the presence of polymeric Cr(III) species in the environment deserves further study. PMID:27156211

Including the spatial variability of metal speciation in the effect factor in life cycle impact assessment: Limits of the equilibrium partitioning method.

PubMed

Tromson, Clara; Bulle, Cécile; Deschênes, Louise

2017-03-01

In life cycle assessment (LCA), the potential terrestrial ecotoxicity effect of metals, calculated as the effect factor (EF), is usually extrapolated from aquatic ecotoxicological data using the equilibrium partitioning method (EqP) as it is more readily available than terrestrial data. However, when following the AMI recommendations (i.e. with at least enough species that represents three different phyla), there are not enough terrestrial data for which soil properties or metal speciation during ecotoxicological testing are specified to account for the influence of soil property variations on metal speciation when using this approach. Alternatively, the TBLM (Terrestrial Biotic Ligand Model) has been used to determine an EF that accounts for speciation, but is not available for metals; hence it cannot be consistently applied to metals in an LCA context. This paper proposes an approach to include metal speciation by regionalizing the EqP method for Cu, Ni and Zn with a geochemical speciation model (the Windermere Humic Aqueous Model 7.0), for 5213 soils selected from the Harmonized World Soil Database. Results obtained by this approach (EF EqP regionalized ) are compared to the EFs calculated with the conventional EqP method, to the EFs based on available terrestrial data and to the EFs calculated with the TBLM (EF TBLM regionalized ) when available. The spatial variability contribution of the EF to the overall spatial variability of the characterization factor (CF) has been analyzed. It was found that the EFs EqP regionalized show a significant spatial variability. The EFs calculated with the two non-regionalized methods (EqP and terrestrial data) fall within the range of the EFs EqP regionalized . The EFs TBLM regionalized cover a larger range of values than the EFs EqP regionalized but the two methods are not correlated. This paper highlights the importance of including speciation into the terrestrial EF and shows that using the regionalized EqP approach is not an acceptable proxy for terrestrial ecotoxicological data even if it can be applied to all metals. Copyright © 2016. Published by Elsevier B.V.

Na, Mg, Ni and Cs distribution and speciation after long-term alteration of a simulated nuclear waste glass: A micro-XAS/XRF/XRD and wet chemical study

NASA Astrophysics Data System (ADS)

Curti, Enzo; Dähn, Rainer; Farges, François; Vespa, Marika

2009-04-01

Microscopic distribution and speciation of Na, Mg, Ni and Cs in a simulated (inactive) nuclear waste glass were studied using micro X-ray fluorescence (μ-XRF) and micro X-ray absorption spectroscopy (μ-XAS), after aqueous leaching during 12 years at 90 °C. Na and Mg are major constituents of the glass that can be used to determine the progress of the glass corrosion process and the nature of secondary alteration phases. Ni and Cs represent dose determining long-lived radionuclides ( 59Ni, 135Cs) in vitrified nuclear waste. The Na-Mg μ-XRF maps revealed that the core regions of the glass fragments are apparently unaltered and compositionally homogeneous, whereas rims and interstitial spaces are enriched with Mg-rich smectite formed during the leaching process. The micro X-ray absorption near edge structure (μ-XANES) spectra collected at the Mg K-edge in the altered zones show three sharp resonances typical for crystalline Mg-silicates. These resonances are distinctive of Mg occupying undistorted octahedral positions. In contrast, the μ-XANES spectra collected in the core zones of the glass fragments lack this resonance pattern and are identical to the spectra measured on the pristine (unleached) MW glass. Micro extended X-ray absorption fine structure (μ-EXAFS) and μ-XANES analyses at the Ni K-edge revealed three distinct Ni(II) species: (a) Ni uniformly distributed in the glass matrix, (b) micro-inclusions with high Ni concentrations and (c) Ni associated to the Mg-clay. The comparison with reference spectra of unleached MW and other Ni-bearing silicate glasses indicated that species (a) represents the original coordinative environment of Ni in the glass. The μ-EXAFS analyses revealed that species (b) is structural Ni in trevorite (NiFe 2O 4), which probably formed through unmixing processes during the cooling of the glass melt. The μ-EXAFS of species (c) could be successfully modeled assuming specific adsorption or incorporation of Ni into the lattice of trioctahedral Mg-clay minerals. Alternative models assuming other elements (Ni, Al, Fe) in addition to Mg in the second shell could not be fitted successfully. Aqueous concentration data were used to calculate the speciation of the leaching solutions. Saturation index (SI) calculations indicate undersaturation with respect to NiCO 3 and NiSO 4·7H 2O, but oversaturation with respect to β-Ni(OH) 2. The latter result is probably due to the omission of Ni borate and Ni silicate complexes in the speciation calculations, for which formation constants are not available. With the help of estimation techniques, we could infer that such complexes would dominate the Ni speciation and consequently reduce the SI below the saturation of β-Ni(OH) 2. The μ-XRF maps show that Cs is uniformly distributed in the MW glass, since no region with high Cs concentration could be detected. The Cs L III-edge μ-XAS spectra were all very similar independently of the degree of alteration, indicating similar coordination environments of Cs in the core regions of the glass as well as in the secondary clays. These spectra largely differ from that measured for pollucite (a potential secondary Cs-phase in altered glasses) implying that the coordination environments of Cs in the MW glass and in pollucite are fundamentally different. The present study shows that μ-XRF and μ-XAS are essential tools in determining the fate and the retention mechanisms of radionuclides released from nuclear waste during aqueous alteration. Our spectroscopic analyses allowed us to exclude formation of specific Ni and Cs secondary solids (e.g. nepouite, β-Ni(OH) 2, pollucite) during the aqueous alteration. Ni and Cs are instead distributed as trace elements in the alteration phases formed by major elements during the leaching process. Our results imply that solid solution and/or adsorption equilibria, rather than pure phase solubility equilibria, are the adequate chemical models to determine Ni and Cs aqueous concentrations in performance assessments for radioactive waste repositories.

Anaerobic bioremediation of hexavalent uranium in groundwater by reductive precipitation with methanogenic granular sludge.

PubMed

Tapia-Rodriguez, Aida; Luna-Velasco, Antonia; Field, Jim A; Sierra-Alvarez, Reyes

2010-04-01

Uranium has been responsible for extensive contamination of groundwater due to releases from mill tailings and other uranium processing waste. Past evidence has confirmed that certain bacteria can enzymatically reduce soluble hexavalent uranium (U(VI)) to insoluble tetravalent uranium (U(IV)) under anaerobic conditions in the presence of appropriate electron donors. This paper focuses on the evaluation of anaerobic granular sludge as a source of inoculum for the bioremediation of uranium in water. Batch experiments were performed with several methanogenic anaerobic granular sludge samples and different electron donors. Abiotic controls consisting of heat-killed inoculum and non-inoculated treatments confirmed the biological removal process. In this study, unadapted anaerobic granular sludge immediately reduced U(VI), suggesting an intrinsic capacity of the sludge to support this process. The high biodiversity of anaerobic granular sludge most likely accounts for the presence of specific microorganisms capable of reducing U(VI). Oxidation by O(2) was shown to resolubilize the uranium. This observation combined with X-ray diffraction evidence of uraninite confirmed that the removal during anaerobic treatment was due to reductive precipitation. The anaerobic removal activity could be sustained after several respikes of U(VI). The U(VI) removal was feasible without addition of electron donors, indicating that the decay of endogenous biomass substrates was contributing electron equivalents to the process. Addition of electron donors, such as H(2) stimulated the removal of U(VI) to varying degrees. The stimulation was greater in sludge samples with lower endogenous substrate levels. The present work reveals the potential application of anaerobic granular sludge for continuous bioremediation schemes to treat uranium-contaminated water. Copyright (c) 2009 Elsevier Ltd. All rights reserved.

Optimization of a bioremediation system of soluble uranium based on the biostimulation of an indigenous bacterial community.

PubMed

Maleke, Maleke; Williams, Peter; Castillo, Julio; Botes, Elsabe; Ojo, Abidemi; DeFlaun, Mary; van Heerden, Esta

2015-06-01

High concentrations of uranium(VI) in the Witwatersrand Basin, South Africa from mining leachate is a serious environmental concern. Treatment systems are often ineffective. Therefore, optimization of a bioremediation system that facilitates the bioreduction of U(VI) based on biostimulation of indigenous bacterial communities can be a viable alternative. Tolerance of the indigenous bacteria to high concentrations of U and the amount of citric acid required for U removal was optimized. Two bioreactor studies which showed effective U(VI) removal more than 99 % from low (0.0037 mg L(-1)) and high (10 mg L(-1)) concentrations of U to below the limit allowed by South African National Standards for drinking water (0.0015 mg L(-1)). The second bioreactor was able to successfully adapt even with increasing levels of U(VI) feed water up to 10 mg L(-1), provided that enough electron donor was available. Molecular biology analyses identified Desulfovibrio sp. and Geobacter sp. among known species, which are known to reduce U(VI). The mineralogical analysis determined that part of the uranium precipitated intracellularly, which meant that the remaining U(VI) was precipitated as U(IV) oxides and TEM-EDS also confirmed this analysis. This was predicted with the geochemical model from the chemical data, which demonstrated that the treated drainage was supersaturated with respect to uraninite > U4O9 > U3O8 > UO2(am). Therefore, the tolerance of the indigenous bacterial community could be optimized to remediate up to 10 mg L(-1), and the system can thus be upscaled and employed for remediation of U(VI) impacted sites.

Advective removal of intraparticle uranium from contaminated vadose zone sediments, Hanford, U.S.

PubMed

Ilton, Eugene S; Qafoku, Nikolla P; Liu, Chongxuan; Moore, Dean A; Zachara, John M

2008-03-01

A column study on U(VI)-contaminated vadose zone sediments from the Hanford Site, WA, was performed to investigate U(VI) release kinetics with water advection and variable geochemical conditions. The sediments were collected from an area adjacent to and below tank BX-102 that was contaminated as a result of a radioactive tank waste overfill event. The primary reservoir for U(VI) in the sediments are micrometer-size precipitates composed of nanocrystallite aggregates of a Na-U-Silicate phase, most likely Na-boltwoodite, that nucleated and grew within microfractures of the plagioclase component of sand-sized granitic clasts. Two sediment samples, with different U(VI) concentrations and intraparticle mass transfer properties, were leached with advective flows of three different solutions. The influent solutions were all calcite-saturated and in equilibrium with atmospheric CO2. One solution was prepared from DI water, the second was a synthetic groundwater (SGW) with elevated Na that mimicked groundwater at the Hanford site, and the third was the same SGW but with both elevated Na and Si. The latter two solutions were employed, in part, to test the effect of saturation state on U(VI) release. For both sediments, and all three electrolytes, there was an initial rapid release of U(VI) to the advecting solution followed by slower near steady-state release. U(VI)aq concentrations increased during subsequent stop-flow events. The electrolytes with elevated Na and Si depressed U(VL)aq concentrations in effluent solutions. Effluent U(VI)aq concentrations for both sediments and all three electrolytes were simulated reasonably well by a three domain model (the advecting fluid, fractures, and matrix) that coupled U(VI) dissolution, intraparticle U(VI)aq diffusion, and interparticle advection, where diffusion and dissolution properties were parameterized in a previous batch study.

Zinc fractionation in contaminated soils by sequential and single extractions: influence of soil properties and zinc content.

PubMed

Voegelin, Andreas; Tokpa, Gerome; Jacquat, Olivier; Barmettler, Kurt; Kretzschmar, Ruben

2008-01-01

We studied the fractionation of zinc (Zn) in 49 contaminated soils as influenced by Zn content and soil properties using a seven-step sequential extraction procedure (F1: NH4NO3; F2: NH4-acetate, pH 6; F3: NH3OHCl, pH 6; F4: NH4-EDTA, pH 4.6; F5: NH4-oxalate, pH 3; F6: NH4-oxalate/ascorbic acid, pH 3; F7: residual). The soils had developed from different geologic materials and covered a wide range in soil pH (4.0-7.3), organic C content (9.3-102 g kg(-1)), and clay content (38-451 g kg(-1)). Input of aqueous Zn with runoff water from electricity towers during 26 to 74 yr resulted in total soil Zn contents of 3.8 to 460 mmol kg(-1). In acidic soils (n = 24; pH <6.0), Zn was mainly found in the mobile fraction (F1) and the last two fractions (F6 and F7). In neutral soils (n = 25; pH > or =6.0), most Zn was extracted in the mobilizable fraction (F2) and the intermediate fractions (F4 and F5). The extractability of Zn increased with increasing Zn contamination of the soils. The sum of mobile (F1) and mobilizable (F2) Zn was independent of soil pH, the ratio of Zn in F1 over F1+F2 plotted against soil pH, exhibited the typical shape of a pH sorption edge and markedly increased from pH 6 to pH 5, reflecting the increasing lability of mobilizable Zn with decreasing soil pH. In conclusion, the extractability of Zn from soils contaminated with aqueous Zn after decades of aging under field conditions systematically varied with soil pH and Zn content. The same trends are expected to apply to aqueous Zn released from decomposing Zn-bearing contaminants, such as sewage sludge or smelter slag. The systematic trends in Zn fractionation with varying soil pH and Zn content indicate the paramount effect of these two factors on molecular scale Zn speciation. Further research is required to characterize the link between the fractionation and speciation of Zn and to determine how Zn loading and soil physicochemical properties affect Zn speciation in soils.

Investigation of uranium binding forms in selected German mineral waters.

PubMed

Osman, Alfatih A A; Geipel, Gerhard; Bernhard, Gert; Worch, Eckhard

2013-12-01

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 μg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca2UO2(CO3)3 in all investigated waters, while other uranyl-carbonate complexes, viz, UO2CO3(aq) and UO2(CO3)2 (2-), only existed as minor species. The pH value, alkalinity (CO3 (2-)), and the main water inorganic constituents, specifically the Ca(2+) concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.

Speciation of volatile arsenic at geothermal features in Yellowstone National Park

USGS Publications Warehouse

Planer-Friedrich, B.; Lehr, C.; Matschullat, J.; Merkel, B.J.; Nordstrom, D. Kirk; Sandstrom, M.W.

2006-01-01

Geothermal features in the Yellowstone National Park contain up to several milligram per liter of aqueous arsenic. Part of this arsenic is volatilized and released into the atmosphere. Total volatile arsenic concentrations of 0.5-200 mg/m3 at the surface of the hot springs were found to exceed the previously assumed nanogram per cubic meter range of background concentrations by orders of magnitude. Speciation of the volatile arsenic was performed using solid-phase micro-extraction fibers with analysis by GC-MS. The arsenic species most frequently identified in the samples is (CH3)2AsCl, followed by (CH3)3As, (CH3)2AsSCH3, and CH3AsCl2 in decreasing order of frequency. This report contains the first documented occurrence of chloro- and thioarsines in a natural environment. Toxicity, mobility, and degradation products are unknown. ?? 2006 Elsevier Inc. All rights reserved.

A spectroscopic study for understanding the speciation of Cr on palm shell based adsorbents and their application for the remediation of chrome plating effluents.

PubMed

Kushwaha, Shilpi; Sreedhar, B; Sudhakar, Padmaja P

2012-07-01

Palm shell based adsorbents prepared under five different thermochemical conditions have been shown to be quite effective for removal of chromium (III and VI) from aqueous solutions. X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FT-IR) have been used to determine information about the speciation and binding of chromium on the adsorbents under study. X-ray photoelectron spectroscopy (XPS) studies indicate that oxidation of lignin moieties takes place concurrently to Cr(VI) reduction and leads to the formation of hydroxyl and carboxyl functions. The maximum adsorption capacity for hexavalent chromium was found to be about 313 mg/g in an acidic medium using PAPSP. This is comparable to other natural substrates and ordinary adsorbents. The efficacy of the adsorbents under study to remove chromium from plating waste water has been demonstrated. Copyright © 2012 Elsevier Ltd. All rights reserved.

Role of U(VI) Adsorption in U(VI) Reduction by Geobacter Species.

DOE Office of Scientific and Technical Information (OSTI.GOV)

None, None

2009-03-09

Previous work had suggested that Acholeplasma palmae has a higher capacity for uranium sorption than other bacteria studied. Sorption studies were performed with cells in suspension in various solutions containing uranium and results were used to generate uranium-biosorption isotherms.

Biomineralization of Uranium by PhoY Phosphatase Activity Aids Cell Survival in Caulobacter crescentus

PubMed Central

Yung, Mimi C.

2014-01-01

Caulobacter crescentus is known to tolerate high levels of uranium [U(VI)], but its detoxification mechanism is poorly understood. Here we show that C. crescentus is able to facilitate U(VI) biomineralization through the formation of U-Pi precipitates via its native alkaline phosphatase activity. The U-Pi precipitates, deposited on the cell surface in the form of meta-autunite structures, have a lower U/Pi ratio than do chemically produced precipitates. The enzyme that is responsible for the phosphatase activity and thus the biomineralization process is identified as PhoY, a periplasmic alkaline phosphatase with broad substrate specificity. Furthermore, PhoY is shown to confer a survival advantage on C. crescentus toward U(VI) under both growth and nongrowth conditions. Results obtained in this study thus highlight U(VI) biomineralization as a resistance mechanism in microbes, which not only improves our understanding of bacterium-mineral interactions but also aids in defining potential ecological niches for metal-resistant bacteria. PMID:24878600

Biomineralization of Uranium by PhoY Phosphatase Activity Aids Cell Survival in Caulobacter crescentus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yung, M C; Jiao, Y

2014-07-22

Caulobacter crescentus is known to tolerate high levels of uranium [U(VI)], but its detoxification mechanism is poorly understood. Here we show that C. crescentus is able to facilitate U(VI) biomineralization through the formation of U-P i precipitates via its native alkaline phosphatase activity. The U-P i precipitates, deposited on the cell surface in the form of meta-autunite structures, have a lower U/P i ratio than do chemically produced precipitates. The enzyme that is responsible for the phosphatase activity and thus the biomineralization process is identified as PhoY, a periplasmic alkaline phosphatase with broad substrate specificity. Furthermore, PhoY is shown tomore » confer a survival advantage on C. crescentus toward U(VI) under both growth and nongrowth conditions. Results obtained in this study thus highlight U(VI) biomineralization as a resistance mechanism in microbes, which not only improves our understanding of bacterium-mineral interactions but also aids in defining potential ecological niches for metal-resistant bacteria.« less

Issues in Quantitative Analysis of Ultraviolet Imager (UV) Data: Airglow

NASA Technical Reports Server (NTRS)

Germany, G. A.; Richards, P. G.; Spann, J. F.; Brittnacher, M. J.; Parks, G. K.

1999-01-01

The GGS Ultraviolet Imager (UVI) has proven to be especially valuable in correlative substorm, auroral morphology, and extended statistical studies of the auroral regions. Such studies are based on knowledge of the location, spatial, and temporal behavior of auroral emissions. More quantitative studies, based on absolute radiometric intensities from UVI images, require a more intimate knowledge of the instrument behavior and data processing requirements and are inherently more difficult than studies based on relative knowledge of the oval location. In this study, UVI airglow observations are analyzed and compared with model predictions to illustrate issues that arise in quantitative analysis of UVI images. These issues include instrument calibration, long term changes in sensitivity, and imager flat field response as well as proper background correction. Airglow emissions are chosen for this study because of their relatively straightforward modeling requirements and because of their implications for thermospheric compositional studies. The analysis issues discussed here, however, are identical to those faced in quantitative auroral studies.

Réduction des nitrates et de l'uranium par les bactéries indigènes

NASA Astrophysics Data System (ADS)

Abdelouas, Abdesselam; Lutze, Werner; Nuttall, Eric

1998-07-01

A bioremediation concept has been developed to clean up ground water contaminated with nitrate (1200 mg·L -1) and uranium (0.25 mg·L -1). We studied the Tuba City mill tailings site, Arizona, USA. Indigenous bacteria capable of catalyzing the reduction of NO 3- and U(VI) were identified in the ground water and in the host rock, the Navajo sandstone. After complete reduction of O 2 and NO 3- within one week, U(VI) was reduced and precipitated as uraninite. Final uranium concentrations < 15 μg·L -1 were reached after a few weeks at 24 °C. Iron sulfide also precipitated as a result of reduction of Fe(III) on the sand surface and sulfate in the ground water. U(VI) was not reduced by sulfide. It was found that enzymatic reduction of U(VI) is faster than abiotic reduction under the conditions given by the composition of the ground water.

Applications of time-resolved laser fluorescence spectroscopy to the environmental biogeochemistry of actinides.

PubMed

Collins, Richard N; Saito, Takumi; Aoyagi, Noboru; Payne, Timothy E; Kimura, Takaumi; Waite, T David

2011-01-01

Time-resolved laser fluorescence spectroscopy (TRLFS) is a useful means of identifying certain actinide species resulting from various biogeochemical processes. In general, TRLFS differentiates chemical species of a fluorescent metal ion through analysis of different excitation and emission spectra and decay lifetimes. Although this spectroscopic technique has largely been applied to the analysis of actinide and lanthanide ions having fluorescence decay lifetimes on the order of microseconds, such as UO , Cm, and Eu, continuing development of ultra-fast and cryogenic TRLFS systems offers the possibility to obtain speciation information on metal ions having room-temperature fluorescence decay lifetimes on the order of nanoseconds to picoseconds. The main advantage of TRLFS over other advanced spectroscopic techniques is the ability to determine in situ metal speciation at environmentally relevant micromolar to picomolar concentrations. In the context of environmental biogeochemistry, TRLFS has principally been applied to studies of (i) metal speciation in aqueous and solid phases and (ii) the coordination environment of metal ions sorbed to mineral and bacterial surfaces. In this review, the principles of TRLFS are described, and the literature reporting the application of this methodology to the speciation of actinides in systems of biogeochemical interest is assessed. Significant developments in TRLFS methodology and advanced data analysis are highlighted, and we outline how these developments have the potential to further our mechanistic understanding of actinide biogeochemistry. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

The (biological) speciation of vanadate(V) as revealed by (51)V NMR: A tribute on Lage Pettersson and his work.

PubMed

Rehder, Dieter

2015-06-01

Four decades of research carried out by Lage Pettersson, his group and his coworkers are reviewed, research that has been directed predominantly towards the speciation of vanadate and systems containing, along with vanadate and co-reactants such as phosphate and peroxide, biologically relevant organics. In particular, those organics have been addressed that either are (potential) ligands for vanadate-derived coordination compounds generated at physiological conditions and/or function as constituents in medicinally interesting oxidovanadium compounds. Examples for molecules introduced in the context of the physiological vanadate-ligand interaction include the dipeptides Pro-Ala, Ala-Gly, Ala-His and Ala-Ser, the serum constituents lactate and citrate, and the nucleobases adenosine and uridine. The speciation in the vanadate-picolinate and vanadate-maltol systems is geared towards insulin-enhancing vanadium drugs. The speciation as a function of pH, ionic strength and the concentration of vanadate and the ligand(s) is based on potentiometric and (51)V NMR investigations, a methodical combination that allows reliable access to composition, formation constants and, to some extent, also structural details for the manifold of species present in aqueous media at physiological pH and beyond. The time frame 1971 to 2014 is reviewed, emphasizing the interval 1985 to 2006, and thus focusing on biologically interesting vanadium systems. Figurative representations from the original literature have been included. Copyright © 2015 Elsevier Inc. All rights reserved.

Soil-solution speciation of Cd as affected by soil characteristics in unpolluted and polluted soils.

PubMed

Meers, Erik; Unamuno, Virginia; Vandegehuchte, Michiel; Vanbroekhoven, Karolien; Geebelen, Wouter; Samson, Roeland; Vangronsveld, Jaco; Diels, Ludo; Ruttens, Ann; Du Laing, Gijs; Tack, Filip

2005-03-01

Total metal content by itself is insufficient as a measure to indicate actual environmental risk. Understanding the mobility of heavy metals in the soil and their speciation in the soil solution is of great importance for accurately assessing environmental risks posed by these metals. In a first explorative study, the effects of general soil characteristics on Cd mobility were evaluated and expressed in the form of empirical formulations. The most important factors influencing mobility of Cd proved to be pH and total soil content. This may indicate that current legislation expressing the requirement for soil sanitation in Flanders (Belgium) as a function of total soil content, organic matter, and clay does not successfully reflect actual risks. Current legal frameworks focusing on total content, therefore, should be amended with criteria that are indicative of metal mobility and availability and are based on physicochemical soil properties. In addition, soil-solution speciation was performed using two independent software packages (Visual Minteq 2.23 and Windermere Humic Aqueous model VI [WHAM VI]). Both programs largely were in agreement in concern to Cd speciation in all 29 soils under study. Depending on soil type, free ion and the organically complexed forms were the most abundant species. Additional inorganic soluble species were sulfates and chlorides. Minor species in solution were in the form of nitrates, hydroxides, and carbonates, the relative importance of which was deemed insignificant in comparison to the four major species.

Arsenic speciation and fucoxanthin analysis from seaweed dietary supplements using LC-MS.

PubMed

Avula, Bharathi; Wang, Yan-Hong; Khan, Ikhlas A

2015-01-01

The study involves the analysis of total arsenic (As) in metallic form, and organic and inorganic As species from seaweeds and dietary supplements. The analysis provides data for dietary exposure estimates of inorganic species that are considered more toxic to humans than organic and total As. Total As was determined by acid digestion followed by inductively coupled plasma (ICP)-MS. To characterize the As species, solvent extraction with sonication and microwave extraction using various aqueous and aqueous/organic solvent mixtures were initially evaluated. The optimum As speciation method was determined to be water extraction followed by anion exchange HPLC coupled with ICP-MS. Optimization of chromatographic conditions led to baseline separation for six As species, including As acid, arsenous acid, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine, in approximately 8 min using gradient elution. Detection limits for all six compounds were in the range of 10-15 ng/mL. The data presented here will be valuable for the QA of analytical method development and surveys of total As and As species in dietary supplements. The most abundant As species found were arsenite [As(III)] and arsenate [As(V)]. The sum of inorganic As species present in the dietary supplements ranged from 1.2 to 31 μg/day. In addition, the dietary supplements purported to contain fucoxanthin, a carotenoid having pharmacological activities, were analyzed using ultra-performance LC-UV/MS.

Determination of the total concentration and speciation of metal ions in river, estuarine and seawater samples.

PubMed

Alberti, Giancarla; Biesuz, Raffaela; Pesavento, Maria

2008-12-01

Different natural water samples were investigated to determine the total concentration and the distribution of species for Cu(II), Pb(II), Al(III) and U(VI). The proposed method, named resin titration (RT), was developed in our laboratory to investigate the distribution of species for metal ions in complex matrices. It is a competition method, in which a complexing resin competes with natural ligands present in the sample to combine with the metal ions. In the present paper, river, estuarine and seawater samples, collected during a cruise in Adriatic Sea, were investigated. For each sample, two RTs were performed, using different complexing resins: the iminodiacetic Chelex 100 and the carboxylic Amberlite CG50. In this way, it was possible to detect different class of ligands. Satisfactory results have been obtained and are commented on critically. They were summarized by principal component analysis (PCA) and the correlations with physicochemical parameters allowed one to follow the evolution of the metals along the considered transect. It should be pointed out that, according to our findings, the ligands responsible for metal ions complexation are not the major components of the water system, since they form considerably weaker complexes.

DOE/SC0001389 Final technical report: Investigation of uranium attenuation and release at column and pore scales in response to advective geochemical gradients

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savage, Kaye S.; Zhu, Wenyi; Barnett, Mark O.

2013-05-13

Experimental approach Column experiments were devised to investigate the role of changing fluid composition on mobility of uranium through a sequence of geologic media. Fluids and media were chosen to be relevant to the ground water plume emanating from the former S-3 ponds at the Oak Ridge Integrated Field Research Challenge (ORIFC) site. Synthetic ground waters were pumped upwards at 0.05 mL/minute for 21 days through layers of quartz sand alternating with layers of uncontaminated soil, quartz sand mixed with illite, quartz sand coated with iron oxides, and another soil layer. Increases in pH or concentration of phosphate, bicarbonate, ormore » acetate were imposed on the influent solutions after each 7 pore volumes while uranium (as uranyl) remained constant at 0.1mM. A control column maintained the original synthetic groundwater composition with 0.1mM U. Pore water solutions were extracted to assess U retention and release in relation to the advective ligand or pH gradients. Following the column experiments, subsamples from each layer were characterized using microbeam X-ray absorption spectroscopy (XANES) in conjunction with X-ray fluorescence mapping and compared to sediment core samples from the ORIFC, at SSRL Beam Line 2-3. Results U retention of 55-67mg occurred in phosphate >pH >control >acetate >carbonate columns. The mass of U retained in the first-encountered quartz layer in all columns was highest and increased throughout the experiment. The rate of increase in acetate- and bicarbonate-bearing columns declined after ligand concentrations were raised. U also accumulated in the first soil layer; the pH-varied column retained most, followed by the increasing-bicarbonate column. The mass of U retained in the upper layers was far lower. Speciation of U, interpreted from microbeam XANES spectra and XRF maps, varied within and among the columns. Evidence of minor reduction to U(IV) was observed in the first-encountered quartz layer in the phosphate, bicarbonate, and pH columns while only U(VI) was observed in the control and acetate columns. In the soil layer, the acetate and bicarbonate columns both indicate minor reduction to U(IV), but U(VI) predominated in all columns. In the ORIFC soils, U was consistently present as U(VI); sorption appears to be the main mechanism of association for U present with Fe and/or Mn, while U occurring with P appears in discrete particles consistent with a U mineral phase. U in soil locations with no other elemental associations shown by XRF are likely uranium oxide phases.« less

Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay.

PubMed

Dong, Wenming; Xie, Guibo; Miller, Todd R; Franklin, Mark P; Oxenberg, Tanya Palmateer; Bouwer, Edward J; Ball, William P; Halden, Rolf U

2006-07-01

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).

Preparation and characterization of porous reduced graphene oxide based inverse spinel nickel ferrite nanocomposite for adsorption removal of radionuclides.

PubMed

Lingamdinne, Lakshmi Prasanna; Choi, Yu-Lim; Kim, Im-Soon; Yang, Jae-Kyu; Koduru, Janardhan Reddy; Chang, Yoon-Young

2017-03-15

For the removal of uranium(VI) (U(VI)) and thorium(IV) (Th(IV)), graphene oxide based inverse spinel nickel ferrite (GONF) nanocomposite and reduced graphene oxide based inverse spinel nickel ferrite (rGONF) nanocomposite were prepared by co-precipitation of GO with nickel and iron salts in one pot. The spectral characterization analyses revealed that GONF and rGONF have a porous surface morphology with an average particle size of 41.41nm and 32.16nm, respectively. The magnetic property measurement system (MPMS) studies confirmed the formation of ferromagnetic GONF and superparamagnetic rGONF. The adsorption kinetics studies found that the pseudo-second-order kinetics was well tune to the U(VI) and Th(IV) adsorption. The results of adsorption isotherms showed that the adsorption of U(VI) and Th(IV) were due to the monolayer on homogeneous surface of the GONF and rGONF. The adsorptions of both U(VI) and Th(IV) were increased with increasing system temperature from 293 to 333±2K. The thermodynamic studies reveal that the U(VI) and Th(IV) adsorption onto GONF and rGONF was endothermic. GONF and rGONF, which could be separated by external magnetic field, were recycled and re-used for up to five cycles without any significant loss of adsorption capacity. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of a low cost UV index datalogger and comparison between UV index sensors

NASA Astrophysics Data System (ADS)

Gomes, L. M.; Ventura, L.

2018-02-01

Ultraviolet radiation (UVR) is the part of radiation emitted by the Sun, with range between 280 nm and 400 nm, and that reaches the Earth's surface. The UV rays are essential to the human because it stimulates the production of vitamin D but this radiation may be related to several health problems, including skin cancer and ocular diseases like pterygium, photokeratitis, cataract and more. To inform people about UV radiation, it is adopted the Ultraviolet Index (UVI). This UVI consists in a measure of solar UV radiation level, which contributes to cause sunburn on skin, also known as Erythema, and is indicated as an integer number between 1 and 14, associated to categories from low to extreme respectively. The aim of this work was to develop a low cost UVI datalogger capable of measuring three different UVI sensors simultaneously, record their data with timestamp and serve the measures online through a dedicated server, so general public can access their data and see the current UV radiation conditions. We also compared three different UVI sensors (SGlux UV cosine, Skye SKU440 and SiLabs SI1145) between them and with meteorological models during a period of months to verify their compliance. With five months data, we could verify the sensors working characteristics and decide which among them are the most suitable for research purposes.

Extreme ultraviolet index due to broken clouds at a midlatitude site, Granada (southeastern Spain)

NASA Astrophysics Data System (ADS)

Antón, M.; Piedehierro, A. A.; Alados-Arboledas, L.; Wolfran, E.; Olmo, F. J.

2012-11-01

Cloud cover usually attenuates the ultraviolet (UV) solar radiation but, under certain sky conditions, the clouds may produce an enhancement effect increasing the UV levels at surface. The main objective of this paper is to analyze an extreme UV enhancement episode recorded on 16 June 2009 at Granada (southeastern Spain). This phenomenon was characterized by a quick and intense increase in surface UV radiation under broken cloud fields (5-7 oktas) in which the Sun was surrounded by cumulus clouds (confirmed with sky images). Thus, the UV index (UVI) showed an enhancement of a factor 4 in the course of only 30 min around midday, varying from 2.6 to 10.4 (higher than the corresponding clear-sky UVI value). Additionally, the UVI presented values higher than 10 (extreme erythemal risk) for about 20 min running, with a maximum value around 11.5. The use of an empirical model and the total ozone column (TOC) derived from the Global Ozone Monitoring Experiment (GOME) for the period 1995-2011 showed that the value of UVI ~ 11.5 is substantially larger than the highest index that could origin the natural TOC variations over Granada. Finally, the UV erythemal dose accumulated during the period of 20 min with the extreme UVI values under broken cloud fields was 350 J/m2 which surpass the energy required to produce sunburn of the most human skin types.

Chemical trapping and characterization of small oxoacids of sulfur (SOS) generated in aqueous oxidations of H2S.

PubMed

Kumar, Murugaeson R; Farmer, Patrick J

2018-04-01

Small oxoacids of sulfur (SOS) are elusive molecules like sulfenic acid, HSOH, and sulfinic acid, HS(O)OH, generated during the oxidation of hydrogen sulfide, H 2 S, in aqueous solution. Unlike their alkyl homologs, there is a little data on their generation and speciation during H 2 S oxidation. These SOS may exhibit both nucleophilic and electrophilic reactivity, which we attribute to interconversion between S(II) and S(IV) tautomers. We find that SOS may be trapped in situ by derivatization with nucleophilic and electrophilic trapping agents and then characterized by high resolution LC MS. In this report, we compare SOS formation from H 2 S oxidation by a variety of biologically relevant oxidants. These SOS appear relatively long lived in aqueous solution, and thus may be involved in the observed physiological effects of H 2 S. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

Dolomite surface speciation and reactivity in aquatic systems

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques; Thomas, Fabien

1999-10-01

The surface charge of dolomite (CaMg(CO3)2) was measured as a function of pH (6.5-11.5), pCO2 (10-3.5, 0.01, and 0.96 atm) and ionic strength (0.01, 0.1, and 0.5 M NaCl) using potentiometric titrations in a limited residence time reactor. Dolomite zeta potential (ζ) was determined using streaming potential and electrophoresis techniques at pH 2 to 12 in solutions having ionic strengths from 0.001 to 0.1 M NaCl as a function of aqueous Ca2+, Mg2+, and CO32- concentrations. The point of zero charge (PZC) and isoelectric point (IEP) of dolomite are the same (pH ∼8 at pCO2 ∼10-3.5 atm) and very close to those of calcite and magnesite. On the basis of these results, a surface complexation model (SCM) is proposed that postulates the presence of three distinct primary hydration sites: >CO3H°, >CaOH°, and >MgOH°. The intrinsic stability constants of dolomite surface reactions were determined by fitting the pH dependence of the surface charge and taking into account the isoelectric points and ζ-potential values for a wide range of solution compositions. In most natural aquatic environments, dolomite surface speciation can be modeled using the following species: >CO3-, >CO3Me+, >MeOH2+, >MeHCO3o, and >MeCO3-, where Me = Ca, Mg. The speciation model presented in this study allows description of metal and ligand adsorption onto dolomite surface and provides new insights on the mechanisms that control dolomite dissolution/crystallization in aqueous solutions. In particular, it is shown that dolomite dissolution is controlled by the protonation of >CO3H° surface complexes at pH < 6 and by hydrolysis of >MeOH2+ groups at higher pH.

Thermodynamic Modeling of Poorly Complexing Metals in Concentrated Electrolyte Solutions: An X-Ray Absorption and UV-Vis Spectroscopic Study of Ni(II) in the NiCl2-MgCl2-H2O System

PubMed Central

Zhang, Ning; Brugger, Joël; Etschmann, Barbara; Ngothai, Yung; Zeng, Dewen

2015-01-01

Knowledge of the structure and speciation of aqueous Ni(II)-chloride complexes is important for understanding Ni behavior in hydrometallurgical extraction. The effect of concentration on the first-shell structure of Ni(II) in aqueous NiCl2 and NiCl2-MgCl2 solutions was investigated by Ni K edge X-ray absorption (XAS) and UV-Vis spectroscopy at ambient conditions. Both techniques show that no large structural change (e.g., transition from octahedral to tetrahedral-like configuration) occurs. Both methods confirm that the Ni(II) aqua ion (with six coordinated water molecules at R Ni-O = 2.07(2) Å) is the dominant species over the whole NiCl2 concentration range. However, XANES, EXAFS and UV-Vis data show subtle changes at high salinity (> 2 mol∙kg-1 NiCl2), which are consistent with the formation of small amounts of the NiCl+ complex (up to 0.44(23) Cl at a Ni-Cl distance of 2.35(2) Å in 5.05 mol∙kg-1 NiCl2) in the pure NiCl2 solutions. At high Cl:Ni ratio in the NiCl2-MgCl2-H2O solutions, small amounts of [NiCl2]0 are also present. We developed a speciation-based mixed-solvent electrolyte (MSE) model to describe activity-composition relationships in NiCl2-MgCl2-H2O solutions, and at the same time predict Ni(II) speciation that is consistent with our XAS and UV-Vis data and with existing literature data up to the solubility limit, resolving a long-standing uncertainty about the role of chloride complexing in this system. PMID:25885410

A first principles investigation of electron transfer between Fe(II) and U(VI) on insulating Al- vs. semiconducting Fe-oxide surfaces via the proximity effect

NASA Astrophysics Data System (ADS)

Taylor, S. D.; Marcano, M. C.; Becker, U.

2017-01-01

This study investigates how the intrinsic chemical and electronic properties of mineral surfaces and their associated electron transfer (ET) pathways influence the reduction of U(VI) by surface-associated Fe(II). Density functional theory (DFT), including the Hubbard U correction to the exchange-correlation functional, was used to investigate sorption/redox reactions and ET mechanisms between Fe(II) and U(VI) coadsorbed on isostructural, periodic (0 0 1) surfaces of the insulator corundum (α-Al2O3) vs. the semiconductor hematite (α-Fe2O3). Furthermore, the coadsorbed Fe(II) and U(VI) ions are spatially separated from one another on the surfaces (⩾5.9 Å) to observe whether electronic-coupling through the semiconducting hematite surface facilitates ET between the adsorbates, a phenomenon known as the proximity effect. The calculations show that the different chemical and electronic properties between the isostructural corundum and hematite (0 0 1) surfaces lead to considerably different ET mechanisms between Fe(II) and U(VI). ET on the insulating corundum (0 0 1) surface is limited by the adsorbates' structural configuration. When Fe(II) and U(VI) are spatially separated and do not directly interact with one another (e.g. via an inner-sphere complex), U(VI) reduction by Fe(II) cannot occur as there is no physical pathway enabling ET between the adsorbates. In contrast to the insulating corundum (0 0 1) surface, the hematite (0 0 1) surface can potentially participate in ET reactions due to the high number of electron acceptor sites from the Fe d-states near the Fermi level at the hematite surface. The adsorption of Fe(II) also introduces d-states near the Fermi level as well as shifts unoccupied d-states of the Fe cations at the hematite surface to lower energies, making the surface more conductive. In turn, electronic coupling through the surface can link the spatially separated adsorbates to one another and provide distinct ET pathways for an electron from Fe(II) to travel through the hematite surface and reach U(VI). The progression and extent of ET occurring on the semiconducting hematite (0 0 1) surface via the proximity effect depends on the electronic properties of the surface. ET between the spatially separated U(VI) and Fe(II) occurs most readily when orbitals between the Fe and U adsorbates overlap with those of neighboring O and Fe ions at the hematite surface, as shown by calculations without the Hubbard U correction. Analyses of the spins densities confirm that the U and Fe adsorbates were reduced and oxidized, respectively, (acquiring 0.33 μB and 0.11-0.20 μB, respectively), while Fe cations at the hematite surface were reduced (losing ⩽0.6 μB). If electrons are highly localized, the amount of orbital mixing and electronic coupling through the hematite surface decreases and in turn leads to a lower degree of spin transfer, as predicted by calculations with the Hubbard U correction. Thus, the proximity effect is a potential mechanism on semiconducting surfaces facilitating surface-mediated redox reactions, although its significance varies depending on the electronic properties and subsequent charge-carrying ability of the surface. These results provide insight into ET pathways and mechanisms on insulating Al- and semiconducting Fe oxide surfaces influencing the reduction U(VI) by Fe(II) that may subsequently limit uranium's transport in the subsurface.

Uranium Isotope Fractionation during Oxidation of Dissolved U(iv) and Synthetic Solid UO2

NASA Astrophysics Data System (ADS)

Wang, X.; Johnson, T. M.; Lundstrom, C. C.

2013-12-01

U isotopes (238U/235U) show promise as a tool for environmental monitoring of U contamination as well as a proxy for paleo-redox conditions. However, the isotopic fractionation mechanisms of U are still poorly understood. In groundwater systems, U(VI), a mobile contaminant, can be reduced to immobile U(IV) and thus remediated. Previous work shows that 238U/235U of the remaining U(VI) changes with the extent of reduction. Therefore, U(VI) isotope composition in groundwater can potentially be used to detect and perhaps quantify the extent of reduction. However, knowing if isotopic fractionation occurs during U(IV) oxidation is equally important. First, the reduced U(IV) (either solid or as dissolved organic complexes) potentially can be reoxidized to U(VI). If isotope fractionation occurs during oxidation, it would complicate the use of U isotope composition as a monitoring technique. Further, in natural weathering processes, U(IV) minerals are oxidized to form dissolved U(VI), which is carried to rivers and eventually to the ocean and deposited in marine sediments. The weathering cycle is thus sensitive to redox conditions, meaning the sedimentary U isotope record may serve as a paleoredox indicator, provided U isotope fractionation during oxidation and reduction are well known. We conducted experiments oxidizing 2 different U(IV) species by O2 and measuring isotopic fractionation factors. In one experiment, dissolved U(IV) in 0.1 N HCl (pH 1) was oxidized by entrained air. As oxidation proceeds at pH 1, the remaining dissolved U(IV) becomes progressively enriched in 238U in a linear trend, while the product U(VI) paralleled, but was offset to 1.0‰ lighter in 238U/235U. This linear progression of both remaining reactant and product suggests equilibrium fractionation during oxidation of dissolved U(IV) by O2. A second experiment oxidized synthetic, solid UO2 (in 20 mM NaHCO3, pH 7) with entrained air. The oxidative fractionation is very weak in this case with product U(VI) ~0.1‰ heavier than the remaining UO2. We attribute the lack of strong fractionation during oxidation of solid UO2 to a 'rind effect', where the surface layer must be completely oxidized before the next layer is exposed to oxidant. Hence, nearly complete, congruent conversion of each layer of U(IV) to U(VI) results in minimal isotope fractionation. A small amount of transient fractionation probably occurs initially, but this is quickly negated as the surface becomes isotopically fractionated. Interestingly, our measured ~0.1‰ U isotope fractionation during oxidation of solid U(IV) agrees with the natural observation that 238U/235U ratios in river water (mainly U(VI)) are ~0.1‰ greater than those in fresh continental rocks (primarily U(IV) minerals). Application of these results to natural settings should be done with caution, however. Oxidation of natural uraninite in continental rocks is a much slower process. If the U(VI) product and the U(IV) reactant remain in contact for long periods of time (e.g., months), they may evolve toward isotopic equilibrium. Measurements of 238U/235U in various natural weathering environments should be undertaken to examine this idea.

Coordination and structure of Ca(II)-acetate complexes in aqueous solution studied by a combination of Raman and XAFS spectroscopies

NASA Astrophysics Data System (ADS)

Muñoz Noval, Álvaro; Nishio, Daisuke; Kuruma, Takuya; Hayakawa, Shinjiro

2018-06-01

The determination of the structure of Ca(II)-acetate in aqueous solution has been addressed by combining Raman and X-ray absorption fine structure spectroscopies. The pH-dependent speciation of the acetate/Ca(II) system has been studied observing modifications in specific Raman bands of the carboxyl group. The current results evidence the Ca(II)-acetate above acetate pKa forms a bidentate complex and presents a coordination 6, in which the Ca-O shell radius decrease of about 0.1 Å with respect the hydrated Ca2+ with coordination 8. The experimental results show the OCO angle of the carboxyl in the complex is close to 124°, being the OCaO angle about 60°.

Spectroscopic confirmation of uranium(VI)-carbonato adsorption complexes on hematite

USGS Publications Warehouse

Bargar, John R.; Reitmeyer, Rebecca; Davis, James A.

1999-01-01

Evaluating societal risks posed by uranium contamination from waste management facilities, mining sites, and heavy industry requires knowledge about uranium transport in groundwater, often the most significant pathway of exposure to humans. It has been proposed that uranium mobility in aquifers may be controlled by adsorption of U(VI)−carbonato complexes on oxide minerals. The existence of such complexes has not been demonstrated, and little is known about their compositions and reaction stoichiometries. We have used attenuated total reflectance Fourier transform infrared (ATR-FTIR) and extended X-ray absorption fine structure (EXAFS) spectroscopies to probe the existence, structures, and compositions of ≡FeOsurface−U(VI)−carbonato complexes on hematite throughout the pH range of uranyl uptake under conditions relevant to aquifers. U(VI)−carbonato complexes were found to be the predominant adsorbed U(VI) species at all pH values examined, a much wider pH range than previously postulated based on analogy to aqueous U(VI)−carbonato complexes, which are trace constituents at pH < 6. This result indicates the inadequacy of the common modeling assumption that the compositions and predominance of adsorbed species can be inferred from aqueous species. By extension, adsorbed carbonato complexes may be of major importance to the groundwater transport of similar actinide contaminants such as neptunium and plutonium.

Diagnostic modeling of trace metal partitioning in south San Francisco Bay

USGS Publications Warehouse

Wood, T. W.; Baptista, A. M.; Kuwabara, J.S.; Flegal, A.R.

1995-01-01

The numerical results indicate that aqueous speciation will control basin-scale spatial variations in the apparent distribution coefficient, Kda, if the system is close to equilibrium. However, basin-scale spatial variations in Kda are determined by the location of the sources of metal and the suspended solids concentration of the receiving water if the system is far from equilibrium. The overall spatial variability in Kda also increases as the system moves away from equilibrium.

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

NASA Astrophysics Data System (ADS)

Bhattacharyya, Amrita; Campbell, Kate M.; Kelly, Shelly D.; Roebbert, Yvonne; Weyer, Stefan; Bernier-Latmani, Rizlan; Borch, Thomas

2017-06-01

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (~58-89%) of U is bound as U(IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Constraints on atmospheric structure and helium abundance of Saturn from Cassini/UVIS and CIRS

NASA Astrophysics Data System (ADS)

Koskinen, Tommi; Guerlet, Sandrine

2017-10-01

We combine results from stellar occultations observed by Cassini/UVIS and infrared emissions observed by Cassini/CIRS to create empirical models of atmospheric structure on Saturn corresponding to the locations probed by the UVIS stellar occultations. These models span multiple occultation locations at different latitudes from 2005 to the end of 2015. In summary, we connect the temperature-pressure profiles retrieved from the CIRS data to the temperature-pressure profiles in the thermosphere retrieved from the occultations. A corresponding altitude scale is calculated and matched to the altitude scale of the density profiles that are retrieved directly from the occultations. In addition to the temperature structure, our ability to match the altitudes in the occultation light curves depends on the mean molecular weight of the atmosphere. We use the UVIS occultations to constrain the abundance of methane near the homopause, allowing us to constrain the eddy mixing rate of the atmosphere. In addition, our preliminary results are consistent with a mixing ratio of about 11% for helium in the lower atmosphere. Our results provide an important reference for future models of Saturn’s upper atmosphere.

An experimental study of Au removal from solution by non-metabolizing bacterial cells and their exudates

NASA Astrophysics Data System (ADS)

Kenney, Janice P. L.; Song, Zhen; Bunker, Bruce A.; Fein, Jeremy B.

2012-06-01

In this study, we examine the initial interactions between aqueous Au(III)-hydroxide-chloride aqueous complexes and bacteria by measuring the effects of non-metabolizing cells on the speciation and distribution of Au. We conducted batch Au(III) removal experiments, measuring the kinetics and pH dependence of Au removal, and tracking valence state transformations and binding environments using XANES spectroscopy. These experiments were conducted using non-metabolizing cells of Bacillus subtilis or Pseudomonas putida suspended in a 5 ppm Au(III)-(hydroxide)-chloride starting solution of 0.1 M NaClO4 to buffer ionic strength. Both bacterial species removed greater than 85% of the Au from solution after 2 h of exposure time below approximately pH 5. Above pH 5, the extent of Au removed from solution decreased with increasing pH, with less than approximately 10% removal of Au from solution above pH 7.5. Kinetics experiments indicated that the Au removal with both bacterial species was rapid at pH 3, and slowed with increasing pH. Reversibility experiments demonstrated that (1) once the Au was removed from solution, adjusting 35 the pH alone did not remobilize the Au into solution and (2) the presence of cysteine in solution in the reversibility experiments caused Au to desorb, suggesting that the Au was not internalized within the bacterial cells. Our results suggest that Au removal occurs as a two-step pH-dependent adsorption reduction process. The speciation of the aqueous Au and the bacterial surface appears to control the rate of Au removal from solution. Under low pH conditions, the cell walls are only weakly negatively charged and aqueous Au complexes adsorb readily and rapidly. With increasing pH, the cell wall becomes more negatively charged, slowing adsorption significantly. The XANES data demonstrate that the reduction of Au(III) by bacterial exudates is slower and less extensive than the reduction observed in the bacteria-bearing systems, and we conclude that Au reduction occurs most rapidly and extensively upon interaction with cell wall functional groups.

Sediment phosphorus speciation and mobility under dynamic redox conditions

NASA Astrophysics Data System (ADS)

Parsons, Chris T.; Rezanezhad, Fereidoun; O'Connell, David W.; Van Cappellen, Philippe

2017-07-01

Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ˜ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h-1 kg-1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the activity of phosphomonoesterases was 37 % higher than under N2 sparging. The results emphasize that the magnitude and timing of internal P loading during periods of anoxia are dependent on both P redistribution within sediments and bottom-water nitrate concentrations.

GeoChip-based analysis of functional microbial communities in a bioreduced uranium-contaminated aquifer during reoxidation by oxygen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Nostrand, J.D.; Wu, W.-M.; Wu, L.

2009-07-15

A pilot-scale system was established for in situ biostimulation of U(VI) reduction by ethanol addition at the US Department of Energy's (DOE's) Field Research Center (Oak Ridge, TN). After achieving U(VI) reduction, stability of the bioreduced U(IV) was evaluated under conditions of (i) resting (no ethanol injection), (ii) reoxidation by introducing dissolved oxygen (DO), and (iii) reinjection of ethanol. GeoChip, a functional gene array with probes for N, S and C cycling, metal resistance and contaminant degradation genes, was used for monitoring groundwater microbial communities. High diversity of all major functional groups was observed during all experimental phases. The microbialmore » community was extremely responsive to ethanol, showing a substantial change in community structure with increased gene number and diversity after ethanol injections resumed. While gene numbers showed considerable variations, the relative abundance (i.e. percentage of each gene category) of most gene groups changed little. During the reoxidation period, U(VI) increased, suggesting reoxidation of reduced U(IV). However, when introduction of DO was stopped, U(VI) reduction resumed and returned to pre-reoxidation levels. These findings suggest that the community in this system can be stimulated and that the ability to reduce U(VI) can be maintained by the addition of electron donors. This biostimulation approach may potentially offer an effective means for the bioremediation of U(VI)-contaminated sites.« less

Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

USGS Publications Warehouse

Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

2006-01-01

Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

The use of halloysite functionalized with isothiouronium salts as an organic/inorganic hybrid adsorbent for uranium(VI) ions removal.

PubMed

Gładysz-Płaska, A; Majdan, M; Tarasiuk, B; Sternik, D; Grabias, E

2018-07-15

Elimination of U(VI) from nuclear wastes and from the underground water near the uranium mines is the serious problem. Therefore search for new sorbents for U(VI) is still a big challenge for the scientists. This paper investigates of U(VI) ions sorption on halloysite modified with the isothiouronium salts: S-dodecaneisothiouronium bromide (ligand 1), S,S'-dodecane-1,12-diylbis(isothiouronium bromide) (ligand 2), S-hexadecaneisothiouronium chloride (ligand 3), S,S'-naphthalene-1,4-diylbis(methylisothiouronium) dichloride (ligand 4), and S,S'-2,5-dimethylbenzene-1,4-diylbis(methylisothiouronium) dichloride (ligand 5). It was established that halloysite modified by the ligands with four nitrogen atoms in their structure (ligand-5, 2 and 4) was characterized by higher sorption capacity compared with that modified by the ligands with two donor nitrogens (ligand-1 and 3). The maximum sorption capacity of halloysite-5 toward U(VI) was 157 mg U/g and this places the modified mineral among the most effective sorbents for U(VI) removal from wastes. As follows from ATR, XPS and thermal degradation spectra of the sorption products [R-S-C(NH)(NH 2 )] n = 1-2 (UO 2 2+ ) complexes are formed on the external surface of the halloysite whereas oligomeric hydroxy complexes (UO 2 ) 3 (OH) 5 + and (UO 2 ) 4 (OH) 7 + are present in the interior of halloysite structure and interact predominantly with aluminols. Copyright © 2018 Elsevier B.V. All rights reserved.

Burning daylight: balancing vitamin D requirements with sensible sun exposure.

PubMed

Stalgis-Bilinski, Kellie L; Boyages, John; Salisbury, Elizabeth L; Dunstan, Colin R; Henderson, Stuart I; Talbot, Peter L

2011-04-04

To examine the feasibility of balancing sunlight exposure to meet vitamin D requirements with sun protection guidelines. We used standard erythemal dose and Ultraviolet Index (UVI) data for 1 June 1996 to 30 December 2005 for seven Australian cities to estimate duration of sun exposure required for fair-skinned individuals to synthesise 1000 IU (25 µg) of vitamin D, with 11% and 17% body exposure, for each season and hour of the day. Periods were classified according to whether the UVI was < 3 or ≥ 3 (when sun protection measures are recommended), and whether required duration of exposure was ≤ 30 min, 31-60 min, or > 60 min. Duration of sunlight exposure required to achieve 1000 IU of vitamin D synthesis. Duration of sunlight exposure required to synthesise 1000 IU of vitamin D varied by time of day, season and city. Although peak UVI periods are typically promoted as between 10 am and 3 pm, UVI was often ≥ 3 before 10 am or after 3 pm. When the UVI was < 3, there were few opportunities to synthesise 1000 IU of vitamin D within 30 min, with either 11% or 17% body exposure. There is a delicate line between balancing the beneficial effects of sunlight exposure while avoiding its damaging effects. Physiological and geographical factors may reduce vitamin D synthesis, and supplementation may be necessary to achieve adequate vitamin D status for individuals at risk of deficiency. ©The Medical Journal of Australia 2011

Speciation of inorganic tellurium from seawater by ICP-MS following magnetic SPE separation and preconcentration.

PubMed

Huang, Chaozhang; Hu, Bin

2008-03-01

A new method was developed for the speciation of inorganic tellurium species in seawater by inductively coupled plasma-MS (ICP-MS) following selective magnetic SPE (MSPE) separation. Within the pH range of 2-9, tellurite (Te(IV)) could be quantitatively adsorbed on gamma-mercaptopropyltrimethoxysilane (gamma-MPTMS) modified silica-coated magnetic nanoparticles (MNPs), while the tellurate (Te(VI)) was not retained and remained in solution. Without filtration or centrifugation, these tellurite-loaded MNPs could be separated easily from the aqueous solution by simply applying external magnetic field. The Te(IV) adsorbed on the MNPs could be recovered quantitatively using a solution containing 2 mol/L HCl and 0.03 mol/L K2Cr2O7. Te(VI) was reduced to Te(IV) by L-cysteine prior to the determination of total tellurium, and its assay was based on subtracting Te(IV) from total tellurium. The parameters affecting the separation were investigated systematically and the optimal separation conditions were established. Under the optimal conditions, the LOD obtained for Te(IV) was 0.079 ng/L, while the precision was 7.0% (C = 10 ng/L, n = 7). The proposed method was successfully applied to the speciation of inorganic tellurium in seawater.

Microbial Sulfate Reduction Enhances Arsenic Mobility Downstream of Zerovalent-Iron-Based Permeable Reactive Barrier.

PubMed

Kumar, Naresh; Couture, Raoul-Marie; Millot, Romain; Battaglia-Brunet, Fabienne; Rose, Jérôme

2016-07-19

We assessed the potential of zerovalent-iron- (Fe(0)) based permeable reactive barrier (PRB) systems for arsenic (As) remediation in the presence or absence of microbial sulfate reduction. We conducted long-term (200 day) flow-through column experiments to investigate the mechanisms of As transformation and mobility in aquifer sediment (in particular, the PRB downstream linkage). Changes in As speciation in the aqueous phase were monitored continuously. Speciation in the solid phase was determined at the end of the experiment using X-ray absorption near-edge structure (XANES) spectroscopy analysis. We identified thio-As species in solution and AsS in solid phase, which suggests that the As(V) was reduced to As(III) and precipitated as AsS under sulfate-reducing conditions and remained as As(V) under abiotic conditions, even with low redox potential and high Fe(II) content (4.5 mM). Our results suggest that the microbial sulfate reduction plays a key role in the mobilization of As from Fe-rich aquifer sediment under anoxic conditions. Furthermore, they illustrate that the upstream-downstream linkage of PRB affects the speciation and mobility of As in downstream aquifer sediment, where up to 47% of total As initially present in the sediment was leached out in the form of mobile thio-As species.

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

DOE PAGES

Balboni, Enrica; Spano, T; Cook, N; ...

2017-10-20

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.« less

Rare-earth element fractionation in uranium ore and its U(VI) alteration minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balboni, Enrica; Spano, T; Cook, N

We developed a cation exchange chromatography method employing sulfonated polysterene cation resin (DOWEX AG50-X8) in order to separate rare-earth elements (REEs) from uranium-rich materials. The chemical separation scheme is designed to reduce matrix effects and consequently yield enhanced ionization efficiencies for concentration determinations of REEs without significant fractionation using solution mode-inductively coupled plasma mass spectrometry (ICP-MS) analysis. This method was then applied to determine REE abundances in four uraninite (ideally UO 2) samples and their associated U(VI) alteration minerals. In three of the samples analyzed, the concentration of REEs for primary uraninite are higher than those for their corresponding secondarymore » uranium alteration phases. The results for U(VI) alteration minerals of two samples indicate enrichment of the light REEs (LREEs) over the heavy REEs (HREEs). This differential mobilization is attributed to differences in the mineralogical composition of the U(VI) alteration. There is a lack of fractionation of the LREEs in the uraninite alteration rind that is composed of U(VI) minerals containing Ca 2+ as the interlayer cation (uranophane and bequerelite); contrarily, U(VI) alteration minerals containing K + and Pb 2+ as interlayer cations (fourmarierite, dumontite) indicate fractionation (enrichment) of the LREEs. Our results have implications for nuclear forensic analyses since a comparison is reported between the REE abundances for the CUP-2 (processed uranium ore) certified reference material and previously determined values for uranium ore concentrate (UOC) produced from the same U deposit (Blind River/Elliott Lake, Canada). UOCs represent the most common form of interdicted nuclear material and consequently is material frequently targeted for forensic analysis. The comparison reveals similar chondrite normalized REE signatures but variable absolute abundances. Based on the results reported here, the latter may be attributed to the differing REE abundances between primary ore and associated alteration phases, and/or is related to varying fabrication processes adopted during production of UOC.« less

In-situ evidence for uranium immobilization and remobilization

USGS Publications Warehouse

Senko, John M.; Istok, Jonathan D.; Suflita, Joseph M.; Krumholz, Lee R.

2002-01-01

The in-situ microbial reduction and immobilization of uranium was assessed as a means of preventing the migration of this element in the terrestrial subsurface. Uranium immobilization (putatively identified as reduction) and microbial respiratory activities were evaluated in the presence of exogenous electron donors and acceptors with field push−pull tests using wells installed in an anoxic aquifer contaminated with landfill leachate. Uranium(VI) amended at 1.5 μM was reduced to less than 1 nM in groundwater in less than 8 d during all field experiments. Amendments of 0.5 mM sulfate or 5 mM nitrate slowed U(VI) immobilization and allowed for the recovery of 10% and 54% of the injected element, respectively, as compared to 4% in the unamended treatment. Laboratory incubations confirmed the field tests and showed that the majority of the U(VI) immobilized was due to microbial reduction. In these tests, nitrate treatment (7.5 mM) inhibited U(VI) reduction, and nitrite was transiently produced. Further push−pull tests were performed in which either 1 or 5 mM nitrate was added with 1.0 μM U(VI) to sediments that already contained immobilized uranium. After an initial loss of the amendments, the concentration of soluble U(VI) increased and eventually exceeded the injected concentration, indicating that previously immobilized uranium was remobilized as nitrate was reduced. Laboratory experiments using heat-inactivated sediment slurries suggested that the intermediates of dissimilatory nitrate reduction (denitrification or dissimilatory nitrate reduction to ammonia), nitrite, nitrous oxide, and nitric oxide were all capable of oxidizing and mobilizing U(IV). These findings indicate that in-situ subsurface U(VI) immobilization can be expected to take place under anaerobic conditions, but the permanence of the approach can be impaired by disimilatory nitrate reduction intermediates that can mobilize previously reduced uranium.

Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface.

PubMed

Wu, Wei-Min; Carley, Jack; Green, Stefan J; Luo, Jian; Kelly, Shelly D; Van Nostrand, Joy; Lowe, Kenneth; Mehlhorn, Tonia; Carroll, Sue; Boonchayanant, Benjaporn; Löfller, Frank E; Watson, David; Kemner, Kenneth M; Zhou, Jizhong; Kitanidis, Peter K; Kostka, Joel E; Jardine, Philip M; Criddle, Craig S

2010-07-01

The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H(2)S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 microM.

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride.

PubMed

Grossmann, Kay; Arnold, Thuro; Steudtner, Robin; Weiss, Stefan; Bernhard, Gert

2009-08-01

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO(2)) and uranium tetrachloride (UCl(4)) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415-475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480-560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature.

Surface Complexation Modeling of U(VI) Adsorption onto Savannah River Site Sediments

NASA Astrophysics Data System (ADS)

Dong, W.; Wan, J.; Tokunaga, T. K.; Denham, M.; Davis, J.; Hubbard, S. S.

2011-12-01

The Savannah River Site (SRS) was a U.S. Department of Energy facility for plutonium production during the Cold War. Waste plumes containing low-level radioactivity and acidic waste solutions were discharged to a series of unlined seepage basins in the F-Area of the SRS from 1955 to 1988. Although the site has undergone many years of active remediation, the groundwater remains acidic, and the concentrations of U and other radionuclides are still significantly higher than their Maximum Contaminant Levels (MCLs). The objective of this effort is to understand and predict U(VI) mobility in acidic waste plumes through developing surface complexation models (SCMs). Laboratory batch experiments were conducted to evaluate U adsorption behavior over the pH range of 3.0 to 9.5. Ten sorbent samples were selected including six contaminated sediment samples from three boreholes drilled within the plume and along the groundwater flow direction, two uncontaminated (pristine) sediment samples from a borehole outside of the plume, and two reference minerals, goethite and kaolinite (identified as the dominant minerals in the clay size fraction of the F-Area sediments). The results show that goethite and kaolinite largely control U partitioning behavior. In comparison with the pristine sediment, U(VI) adsorption onto contaminated sediments exhibits adsorption edges shifted toward lower pH by about 1.0 unit (e.g., from pH≈4.5 to pH≈3.5). We developed a SCMs based component additivity (CA) approach, which can successfully predict U(VI) adsorption onto uncontaminated SRS sediments. However, application of the same SCMs based CA approach to contaminated sediments resulted in underestimates of U(VI) adsorption at acidic pH conditions. The model sensitivity analyses indicate that both goethite and kaolinite surfaces co-contributed to U(VI) adsorption under acidic pH conditions. In particular, the exchange sites of clay minerals might play an important role in adsorption of U(VI) at pH < 5.0. These results suggested that the contaminated sediments might either contain other more reactive clay minerals such as smectite, or that the long-term acid-leaching process might have altered the surface reactivity of the original sediments. Further studies are needed to identify more reactive mineral facies and understand the effects of acid leaching on the surface reactivity of the sediments.

Umbilical vein injection for management of retained placenta.

PubMed

Nardin, Juan Manuel; Weeks, Andrew; Carroli, Guillermo

2011-05-11

If a retained placenta is left untreated, there is a high risk of maternal death. However, manual removal of the placenta is an invasive procedure with serious complications of haemorrhage, infection or genital tract trauma. To assess the use of umbilical vein injection (UVI) of saline solution alone or with oxytocin in comparison either with expectant management or with an alternative solution or other uterotonic agent for retained placenta. We searched the Cochrane Pregnancy and Childbirth Group's Trials Register (28 February 2011). Randomized trials comparing UVI of saline or other fluids, with or without oxytocics, either with expectant management or with an alternative solution or other uterotonic agent, in the management of retained placenta. Two review authors assessed the methodological quality of the studies and extracted the data. We included 15 trials (1704 women). The trials were of variable quality. Compared with expectant management, UVI of saline solution alone did not show any significant difference in the incidence of manual removal of the placenta (risk ratio (RR) 0.99; 95% confidence interval (CI) 0.84 to 1.16). UVI of oxytocin solution compared with expectant management showed no reduction in the need for manual removal (RR 0.87; 95% CI 0.74 to 1.03).Oxytocin solution compared with saline solution alone showed a reduction in manual removal of the placenta, but this was not statistically significant (RR 0.91; 95% CI 0.82 to 1.00). When only high-quality studies were assessed, there was no statistical difference (RR 0.92; 95% CI 0.83 to 1.01). We detected no differences in any of the other outcomes.UVI of oxytocin solution compared with UVI of plasma expander showed no statistically significant difference in the outcomes assessed by the only one small trial included. Prostaglandin solution compared with saline solution alone was associated with a statistically significant lower incidence in manual removal of placenta (RR 0.42; 95% CI 0.22 to 0.82) but we observed no difference in the other outcomes evaluated. Prostaglandin plus saline solution showed a statistically significant reduction in manual removal of placenta when compared with oxytocin plus saline solution (RR 0.43; 95% CI 0.25 to 0.75), and we also observed a small reduction in time from injection to placental delivery (mean difference -6.00; 95% CI -8.78 to -3.22). However, there were only two small trials contributing to this meta-analysis. UVI of oxytocin solution is an inexpensive and simple intervention that could be performed while placental delivery is awaited. However, high-quality randomized trials show that the use of oxytocin has little or no effect. Further research into the optimal timing of manual removal and into UVI of prostaglandins or plasma expander is warranted.

Recent studies on UV radiation in Brazil

NASA Astrophysics Data System (ADS)

Correa, M. P.; Ceballos, J. C.; Moregula, A.; Okuno, E.; Fausto, A.; Mol, A.; Santos, J. C.

2009-04-01

This presentation shows a summary of UV index measurements performed in the last years in Southeastern (SE) and Northeastern (NE) Brazilian regions. Brazil has an area of 8.5 million km2 distributed between latitudes 5˚ N and 35˚ S and longitudes 5˚ W and 75˚ W. SE is the most important economic pole of South America and the NE coast is an important tourist region. This large area has a great diversity of climatic, atmospheric and geographical conditions in addition to very diverse social and cultural habits. Non-melanoma skin cancer (NMSC) is an epidemiological health problem with more than 120,000 new cases each year. The most of these cases are found in the South and Southeast regions, with about 70 new NMSC per 100,000 inhabitants. Solar Light UV501 biometers are installed in the SE cities of São Paulo (23.6˚ S, 46.7˚ W, 865 m ASL), Itajubá/Minas Gerais (22.4˚ S; 45.5˚ W, 846 m ASL) and the NE city of Ilhéus/Bahia (14.8˚ S; 39.3˚ W; 54 m ASL). First measurements began in 2005 in São Paulo city, while Itajubá and Ilhéus have regular measurements from the beginning of 2008. Other studies related to the UV radiation modeling and interactions with atmosphere components, as ozone, aerosols and clouds, have also been performed. For example: a) UVI modelling calculations performed by a multiple-scattering spectral models; b) studies on the aerosol radiative properties based on satellite (MODIS/Terra-Aqua) and ground-based (Aeronet) observation; c) ozone content variability from satellite (OMI/Aura) and ground-based (Microtops ozonometer) measurements; d) behavioral profile of the population, as regarding habits of solar exposure and sun protection measures. Results show that more than 75% of the measurements conducted in the summer (outside noon) can be classified as upper than high UVI according to World Health Organization (WHO) recommended categories: Low (UVI < 2), Medium (3 ? UVI < 6), High (6 ? UVI < 8), Very High (8 ? UVI < 11) and Extreme (UVI ≥ 11). Under clear-sky conditions it has been constantly high in all the Brazilian territories. Maximum UVI recorded: São Paulo (2005-2008): 17.2; Itajubá: 15.5; and Ilhéus: 13.6. Even during winter, measurements constantly reach values around UVI = 6. São Paulo is appreciably touched for these high UV radiation levels to have a population very exposed during its quotidian. In the popular culture, an urban site is not popularly considered as a sunny place. In other words, for a large part of the Brazilian population, São Paulo or Itajubá are perceived as places where the risk to the sun overexposure is relatively low. These recent results are being used as basis for educational programs to teach the population about precautions to be taken during sun exposure. Acknowledgments: This study was supported by FAPEMIG (Minas Gerais, Brazil), FAPESP (São Paulo, Brazil) and CNPq (Brasília, Brazil).

Platinum recovery from industrial process streams by halophilic bacteria: Influence of salt species and platinum speciation.

PubMed

Maes, Synthia; Claus, Mathias; Verbeken, Kim; Wallaert, Elien; De Smet, Rebecca; Vanhaecke, Frank; Boon, Nico; Hennebel, Tom

2016-11-15

The increased use and criticality of platinum asks for the development of effective low-cost strategies for metal recovery from process and waste streams. Although biotechnological processes can be applied for the valorization of diluted aqueous industrial streams, investigations considering real stream conditions (e.g., high salt levels, acidic pH, metal speciation) are lacking. This study investigated the recovery of platinum by a halophilic microbial community in the presence of increased salt concentrations (10-80 g L -1 ), different salt matrices (phosphate salts, sea salts and NH 4 Cl) and a refinery process stream. The halophiles were able to recover 79-99% of the Pt at 10-80 g L -1 salts and at pH 2.3. Transmission electron microscopy suggested a positive correlation between intracellular Pt cluster size and elevated salt concentrations. Furthermore, the halophiles recovered 46-95% of the Pt-amine complex Pt[NH 3 ] 4 2+ from a process stream after the addition of an alternative Pt source (K 2 PtCl 4 , 0.1-1.0 g L -1 Pt). Repeated Pt-tetraamine recovery (from an industrial process stream) was obtained after concomitant addition of fresh biomass and harvesting of Pt saturated biomass. This study demonstrates how aqueous Pt streams can be transformed into Pt rich biomass, which would be an interesting feed of a precious metals refinery. Copyright © 2016 Elsevier Ltd. All rights reserved.

Method optimization and quality assurance in speciation analysis using high performance liquid chromatography with detection by inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Larsen, Erik H.

1998-02-01

Achievement of optimum selectivity, sensitivity and robustness in speciation analysis using high performance liquid chromatography (HPLC) with inductively coupled mass spectrometry (ICP-MS) detection requires that each instrumental component is selected and optimized with a view to the ideal operating characteristics of the entire hyphenated system. An isocratic HPLC system, which employs an aqueous mobile phase with organic buffer constituents, is well suited for introduction into the ICP-MS because of the stability of the detector response and high degree of analyte sensitivity attained. Anion and cation exchange HPLC systems, which meet these requirements, were used for the seperation of selenium and arsenic species in crude extracts of biological samples. Furthermore, the signal-to-noise ratios obtained for these incompletely ionized elements in the argon ICP were further enhanced by a factor of four by continously introducing carbon as methanol via the mobile phase into the ICP. Sources of error in the HPLC system (column overload), in the sample introduction system (memory by organic solvents) and in the ICP-MS (spectroscopic interferences) and their prevention are also discussed. The optimized anion and cation exchange HPLC-ICP-MS systems were used for arsenic speciation in contaminated ground water and in an in-house shrimp reference sample. For the purpose of verification, HPLC coupled with tandem mass spectrometry with electrospray ionization was additionally used for arsenic speciation in the shrimp sample. With this analytical technique the HPLC retention time in combination with mass analysis of the molecular ions and their collision-induced fragments provide almost conclusive evidence of the identity of the analyte species. The speciation methods are validated by establishing a mass balance of the analytes in each fraction of the extraction procedure, by recovery of spikes and by employing and comparing independent techniques. The urgent need for reference materials certified for elemental species is stressed.

The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

PubMed

Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

2012-11-01

The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

Towards a More Complete Picture: Dissimilatory Metal Reduction by Anaeromyxobacter Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loeffler, Frank E.

2004-06-01

We investigate the physiological requirements of available Anaeromyxobacter isolates, and assess their distribution and abundance in the environment, including DOE sites. The performers on this project include Frank Loeffler (PI), Robert Sanford (Co-PI), Qingzhong Wu (postdoc), Sara Henry (graduate student) and Cornell Gayle (undergraduate student). Year-1 efforts focused on method and tool development to address the research objectives. First, we compared different analytical assays (based on fluorescent light emission and calorimetric methods) to quantify U(VI) in cultures of Anaeromyxobacter dehalogenans strain 2CP-C. The assays were optimized to reflect specific culture conditions, and we found that a laser-excited spectrofluorescence assay providedmore » reproducible and accurate information on the amount of U(VI) reduced in bacterial cultures. To demonstrate the ability of Anaeromyxobacter dehalogenans strain 2CP-C to reduce U(VI), washed suspensions of fumarate-grown cells were prepared. These experiments confirmed that the rapid reduction of U(VI) to U(IV) depended on the presence of live cells, and no U(VI) reduction occurred in cell-free controls. Additional experiments explored the ability of three different Anaeromyxobacter strains to grow with the mineral hematite, an insoluble form of ferric iron, as electron acceptor. All strain grew equally well with soluble ferric iron (provided as ferric citrate) but distinct differences were observed between strains when grown with hematite. All strains tested shared a 16S rRNA gene similarity of >99.5%, suggesting that closely related strains may differ in their ability to access insoluble forms of ferric iron.« less

Ce, Ti modified MCM-48 mesoporous photocatalysts: Effect of the synthesis route on support and metal ion properties

NASA Astrophysics Data System (ADS)

Mureseanu, Mihaela; Filip, Mihaela; Somacescu, Simona; Baran, Adriana; Carja, Gabriela; Parvulescu, Viorica

2018-06-01

New Ti-MCM-48 and CeTi-MCM-48 photocatalysts were obtained by impregnation of the MCM-48 silica support synthesized by a hydrothermal process with aqueous solution of Ti and Ce precursors. The immobilization of metal cations presented a low effect on the porosity, morphology and structure of MCM-48 mesoporous silica support as was evidenced by N2 adsorption-desorption, X-ray diffraction, SEM and TEM electron microscopy. EDAX analysis and X-ray photoelectron microscopy (XPS) indicated that titanium cations were present on the mesoporous silica surface only as Ti4+ species and the effect of ceria on titanium speciation was different, compared to the CeTi-MCM-48 sample, previously obtained by direct synthesis. The photocatalytic properties of mono- and bimetallic catalysts were evaluated in degradation of phenol from water and correlated with the active metallic species concentration, distribution, speciation and their interaction with the support or each other. An advanced oxidation mechanism for phenol degradation by radical species was proposed.

Abundance and Speciation of Water and Sulfate at Gusev Crater and Meridiani Planum

NASA Technical Reports Server (NTRS)

Ming, D. W.; Clark, B. C.; Klingelhoefer, G.; Gellert, R.; Rodionov, D.; Schroeder, C.; deSouza, P.; Yen, A.

2005-01-01

A major science goal of the Mars Exploration Rover (MER) mission is to search for evidence of water activity, and direct mineralogical evidence for aqueous activity has been reported for Meridiani Planum in the form of the iron sulfate hydroxide mineral jarosite and at Gusev crater in the form of goethite. The Spirit and Opportunity rovers have each collected 110+ Moessbauer (MB) and 75+ Alpha Particle X-Ray Spectrometer (APXS) spectra from Gusev crater and Meridiani Planum [1 - 4]. In this abstract, we use mineralogical and elemental data, primarily from the Moessbauer and APXS instruments, to infer the speciation and estimate the abundance of sulfate and water (as either the H2O molecule or the hydroxyl anion) at Gusev crater and Meridiani Planum. Throughout the abstract, we adopt a format for mineral formulas that shows water explicitly rather than the usual practice of structure-based formulas (e.g., for goethite we write Fe2O3xH2O instead of FeOOH).

Microbial reduction of uranium (VI) by Bacillus sp. dwc-2: A macroscopic and spectroscopic study.

PubMed

Li, Xiaolong; Ding, Congcong; Liao, Jiali; Du, Liang; Sun, Qun; Yang, Jijun; Yang, Yuanyou; Zhang, Dong; Tang, Jun; Liu, Ning

2017-03-01

The microbial reduction of U(VI) by Bacillus sp. dwc-2, isolated from soil in Southwest China, was explored using transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). Our studies indicated that approximately 16.0% of U(VI) at an initial concentration of 100mg/L uranium nitrate could be reduced by Bacillus sp. dwc-2 at pH8.2 under anaerobic conditions at room temperature. Additionally, natural organic matter (NOM) played an important role in enhancing the bioreduction of U(VI) by Bacillus sp. dwc-2. XPS results demonstrated that the uranium presented mixed valence states (U(VI) and U(IV)) after bioreduction, which was subsequently confirmed by XANES. Furthermore, the TEM and high resolution transmission electron microscopy (HRTEM) analysis suggested that the reduced uranium was bioaccumulated mainly within the cell and as a crystalline structure on the cell wall. These observations implied that the reduction of uranium may have a significant effect on its fate in the soil environment in which these bacterial strains occur. Copyright © 2016. Published by Elsevier B.V.

Simultaneous reduction of arsenic(V) and uranium(VI) by mackinawite: role of uranyl arsenate precipitate formation.

PubMed

Troyer, Lyndsay D; Tang, Yuanzhi; Borch, Thomas

2014-12-16

Uranium (U) and arsenic (As) often occur together naturally and, as a result, can be co-contaminants at sites of uranium mining and processing, yet few studies have examined the simultaneous redox dynamics of U and As. This study examines the influence of arsenate (As(V)) on the reduction of uranyl (U(VI)) by the redox-active mineral mackinawite (FeS). As(V) was added to systems containing 47 or 470 μM U(VI) at concentrations ranging from 0 to 640 μM. In the absence of As(V), U was completely removed from solution and fully reduced to nano-uraninite (nano-UO2). While the addition of As(V) did not reduce U uptake, at As(V) concentrations above 320 μM, the reduction of U(VI) was limited due to the formation of a trögerite-like uranyl arsenate precipitate. The presence of U also significantly inhibited As(V) reduction. While less U(VI) reduction to nano-UO2 may take place in systems with high As(V) concentrations, formation of trögerite-like mineral phases may be an acceptable reclamation end point due to their high stability under oxic conditions.

Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques

DOE PAGES

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald; ...

2016-12-27

The interactions of two extremely halophilic archaea with uranium were investigated in this paper at high ionic strength as a function of time, pH and uranium concentration. Halobacterium noricense DSM-15987 and Halobacterium sp. putatively noricense, isolated from the Waste Isolation Pilot Plant repository, were used for these investigations. The kinetics of U(VI) bioassociation with both strains showed an atypical multistage behavior, meaning that after an initial phase of U(VI) sorption, an unexpected interim period of U(VI) release was observed, followed by a slow reassociation of uranium with the cells. By applying in situ attenuated total reflection Fourier-transform infrared spectroscopy, themore » involvement of phosphoryl and carboxylate groups in U(VI) complexation during the first biosorption phase was shown. Differences in cell morphology and uranium localization become visible at different stages of the bioassociation process, as shown with scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Finally, our results demonstrate for the first time that association of uranium with the extremely halophilic archaeon is a multistage process, beginning with sorption and followed by another process, probably biomineralization.« less

Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald

The interactions of two extremely halophilic archaea with uranium were investigated in this paper at high ionic strength as a function of time, pH and uranium concentration. Halobacterium noricense DSM-15987 and Halobacterium sp. putatively noricense, isolated from the Waste Isolation Pilot Plant repository, were used for these investigations. The kinetics of U(VI) bioassociation with both strains showed an atypical multistage behavior, meaning that after an initial phase of U(VI) sorption, an unexpected interim period of U(VI) release was observed, followed by a slow reassociation of uranium with the cells. By applying in situ attenuated total reflection Fourier-transform infrared spectroscopy, themore » involvement of phosphoryl and carboxylate groups in U(VI) complexation during the first biosorption phase was shown. Differences in cell morphology and uranium localization become visible at different stages of the bioassociation process, as shown with scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Finally, our results demonstrate for the first time that association of uranium with the extremely halophilic archaeon is a multistage process, beginning with sorption and followed by another process, probably biomineralization.« less

Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques.

PubMed

Bader, Miriam; Müller, Katharina; Foerstendorf, Harald; Drobot, Björn; Schmidt, Matthias; Musat, Niculina; Swanson, Juliet S; Reed, Donald T; Stumpf, Thorsten; Cherkouk, Andrea

2017-04-05

The interactions of two extremely halophilic archaea with uranium were investigated at high ionic strength as a function of time, pH and uranium concentration. Halobacterium noricense DSM-15987 and Halobacterium sp. putatively noricense, isolated from the Waste Isolation Pilot Plant repository, were used for these investigations. The kinetics of U(VI) bioassociation with both strains showed an atypical multistage behavior, meaning that after an initial phase of U(VI) sorption, an unexpected interim period of U(VI) release was observed, followed by a slow reassociation of uranium with the cells. By applying in situ attenuated total reflection Fourier-transform infrared spectroscopy, the involvement of phosphoryl and carboxylate groups in U(VI) complexation during the first biosorption phase was shown. Differences in cell morphology and uranium localization become visible at different stages of the bioassociation process, as shown with scanning electron microscopy in combination with energy dispersive X-ray spectroscopy. Our results demonstrate for the first time that association of uranium with the extremely halophilic archaeon is a multistage process, beginning with sorption and followed by another process, probably biomineralization. Copyright © 2016. Published by Elsevier B.V.

Solar ultraviolet radiation measurements in one of the most populous cities of the world: aspects related to skin cancer cases and vitamin D availability.

PubMed

de Paula Corrêa, Marcelo; Ceballos, Juan Carlos

2010-01-01

A number of studies published in the scientific literature have shown the relationship between sun exposure and nonmelanoma skin cancer (NMSC) and vitamin D synthesis. However, the paucity of medical data, particularly in developing countries, hampers a global assessment of the impact of sun exposure on NMSC and vitamin D. To improve knowledge on this subject, this paper presents UV index (UVI) measurements performed in São Paulo City (SPC) in the period 2005-2008. It was found that 65% of the UVI measured 2 h around local noon during the summer show very high (8 < UVI < 10) and extreme (UVI > 11) levels according to the World Health Organization (WHO) classification. During the winter, 40% of the measurements around noontime show high or very high levels. In spite of worrisome recent statistics from SPC, showing that NMSCs make up about 28% of over a million of new cases of cancer in 2008, sun protection is not considered a real problem in these urban areas. UV measurements also show that every month of the year UV levels are high enough to ensure vitamin D production in human skin from incidental sun exposure.

Chemistry of transuranium elements in salt-base repository

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borkowski, Marian; Reed, Donald T; Lucchini, Jean - Francois

2010-12-02

The mobility and potential release of actinides into the accessible environment continues to be the key performance assessment concern of nuclear repositories. Actinide, in particular plutonium speciation under the wide range of conditions that can exist in the subsurface is complex and depends strongly on the coupled effects of redox conditions, inorganic/organic complexation, and the extent/nature of aggregation. Understanding the key factors that define the potential for actinide migration is, in this context, an essential and critical part of making and sustaining a licensing case for a nuclear repository. Herein we report on recent progress in a concurrent modeling andmore » experimental study to determine the speciation of plutonium, uranium and americium in high ionic strength Na-CI-Mg brines. This is being done as part of the ongomg recertification effort m the Waste Isolation Pilot Plant (WIPP). The oxidation-state specific solubility of actinides were established in brine as function of pC{sub H+}, brine composition and the presence and absence of organic chelating agents and carbonate. An oxidation-state invariant analog approach using Nd{sup 3+} and Th{sup 4+} was used for An{sup 3+} and An{sup 4+} respectively. These results show that organic ligands and hydrolysis are key factors for An(III) solubility, hydrolysis at pC{sub H+} above 8 is predominate for An(IV) and carbonates are the key factor for U(VI) solubility. The effect of high ionic strength and brine components measured in absence of carbonates leads to measurable increased in overall solubility over analogous low ionic strength groundwater. Less is known about the bioreduction of actinides by halo-tolerant microorganisms, but there is now evidence that bioreduction does occur and is analogous, in many ways, to what occurs with soil bacteria. Results of solubility studies that focus on Pitzer parameter corrections, new species (e.g. borate complexation), and the thermodynamic parameters for modeling are discussed.« less

Kinetic concepts to quantify the role of oxidants and photooxidants in natural waters and water treatment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoigne, J.

1995-12-31

Research performed during the last two decades has led to a significant evolution of reaction kinetic concepts to estimate the role of reactive oxidants and photooxidants in natural waters and for water treatment. Although many reaction-rate data for oxidants such as OH and HO{sub 2}/O{sub 2}{sup -} radicals, O{sub 2} and O{sub 3} or ClO{sub 2} had been compiled before, these were rather selected to elucidate other areas of research and applications. Their critical applications for describing reactions of interest for aqueous chemistry has then required to extend the compilations of rate data: (1) to include more reactions of relevancemore » in aqueous media, (2) to critically account for the aqueous speciations, (3) to experimentally characterise the environmental factors controlling the steady-state concentration of different oxidants, (4) to formulate models useful for computing predictions and allowing for critical experimental tests, and (5) to allow for a unified concept for teaching environmental chemistry that better approaches the concepts of classical chemistry.« less

DOE workshop: Sedimentary systems, aqueous and organic geochemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1993-07-01

A DOE workshop on sedimentary systems, aqueous and organic geochemistry was held July 15-16, 1993 at Lawrence Berkeley Laboratory. Papers were organized into several sections: Fundamental Properties, containing papers on the thermodynamics of brines, minerals and aqueous electrolyte solutions; Geochemical Transport, covering 3-D imaging of drill core samples, hydrothermal geochemistry, chemical interactions in hydrocarbon reservoirs, fluid flow model application, among others; Rock-Water Interactions, with presentations on stable isotope systematics of fluid/rock interaction, fluid flow and petotectonic evolution, grain boundary transport, sulfur incorporation, tracers in geologic reservoirs, geothermal controls on oil-reservoir evolution, and mineral hydrolysis kinetics; Organic Geochemistry covered new methodsmore » for constraining time of hydrocarbon migration, kinetic models of petroleum formation, mudstones in burial diagenesis, compound-specific carbon isotope analysis of petroleums, stability of natural gas, sulfur in sedimentary organic matter, organic geochemistry of deep ocean sediments, direct speciation of metal by optical spectroscopies; and lastly, Sedimentary Systems, covering sequence stratigraphy, seismic reflectors and diagenetic changes in carbonates, geochemistry and origin of regional dolomites, and evidence of large comet or asteroid impacts at extinction boundaries.« less

Very short-term reactive forecasting of the solar ultraviolet index using an extreme learning machine integrated with the solar zenith angle.

PubMed

Deo, Ravinesh C; Downs, Nathan; Parisi, Alfio V; Adamowski, Jan F; Quilty, John M

2017-05-01

Exposure to erythemally-effective solar ultraviolet radiation (UVR) that contributes to malignant keratinocyte cancers and associated health-risk is best mitigated through innovative decision-support systems, with global solar UV index (UVI) forecast necessary to inform real-time sun-protection behaviour recommendations. It follows that the UVI forecasting models are useful tools for such decision-making. In this study, a model for computationally-efficient data-driven forecasting of diffuse and global very short-term reactive (VSTR) (10-min lead-time) UVI, enhanced by drawing on the solar zenith angle (θ s ) data, was developed using an extreme learning machine (ELM) algorithm. An ELM algorithm typically serves to address complex and ill-defined forecasting problems. UV spectroradiometer situated in Toowoomba, Australia measured daily cycles (0500-1700h) of UVI over the austral summer period. After trialling activations functions based on sine, hard limit, logarithmic and tangent sigmoid and triangular and radial basis networks for best results, an optimal ELM architecture utilising logarithmic sigmoid equation in hidden layer, with lagged combinations of θ s as the predictor data was developed. ELM's performance was evaluated using statistical metrics: correlation coefficient (r), Willmott's Index (WI), Nash-Sutcliffe efficiency coefficient (E NS ), root mean square error (RMSE), and mean absolute error (MAE) between observed and forecasted UVI. Using these metrics, the ELM model's performance was compared to that of existing methods: multivariate adaptive regression spline (MARS), M5 Model Tree, and a semi-empirical (Pro6UV) clear sky model. Based on RMSE and MAE values, the ELM model (0.255, 0.346, respectively) outperformed the MARS (0.310, 0.438) and M5 Model Tree (0.346, 0.466) models. Concurring with these metrics, the Willmott's Index for the ELM, MARS and M5 Model Tree models were 0.966, 0.942 and 0.934, respectively. About 57% of the ELM model's absolute errors were small in magnitude (±0.25), whereas the MARS and M5 Model Tree models generated 53% and 48% of such errors, respectively, indicating the latter models' errors to be distributed in larger magnitude error range. In terms of peak global UVI forecasting, with half the level of error, the ELM model outperformed MARS and M5 Model Tree. A comparison of the magnitude of hourly-cumulated errors of 10-min lead time forecasts for diffuse and global UVI highlighted ELM model's greater accuracy compared to MARS, M5 Model Tree or Pro6UV models. This confirmed the versatility of an ELM model drawing on θ s data for VSTR forecasting of UVI at near real-time horizon. When applied to the goal of enhancing expert systems, ELM-based accurate forecasts capable of reacting quickly to measured conditions can enhance real-time exposure advice for the public, mitigating the potential for solar UV-exposure-related disease. Crown Copyright © 2017. Published by Elsevier Inc. All rights reserved.

Predicting equilibrium uranium isotope fractionation in crystals and solution

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2015-12-01

Despite the rapidly growing interest in using 238U/235U measurements as a proxy for changes in oxygen abundance in surface and near-surface environments, the present theoretical understanding of uranium isotope fractionation is limited to a few simple gas-phase molecules and analogues of dissolved species (e.g., 1,2,3). Understanding uranium isotope fractionation behavior in more complicated species, such as crystals and adsorption complexes, will help in the design and interpretation of experiments and field studies, and may suggest other uses for 38U/235U measurements. In this study, a recently developed first-principles method for estimating the nuclear volume component of field shift fractionation in crystals and complex molecular species (4) is combined with mass-dependent fractionation theory to predict equilibrium 38U/235U fractionations in aqueous and crystalline uranium compounds, including uraninite (UO2). The nuclear field shift effect, caused by the interaction of electrons with the finite volume of the positive charge distribution in uranium nuclei, is estimated using Density Functional Theory and the Projector Augmented Wave method (DFT-PAW). Tests against relativistic electronic structure calculations and Mössbauer isomer shift data indicate that the DFT-PAW method is reasonably accurate, while being much better suited to models of complex and crystalline species. Initial results confirm previous predictions that the nuclear volume effect overwhelms mass depdendent fractionation in U(VI)-U(IV) exchange reactions, leading to higher 238U/235U in U(IV) species (i.e., for UO2 xtal vs. UO22+aq, ln αNV ≈ +1.8‰ , ln αMD ≈ -0.8‰, ln αTotal ≈ +1.0‰ at 25ºC). UO2 and U(H2O)94+, are within ~0.4‰ of each other, while U(VI) species appear to be more variable. This suggests that speciation is likely to significantly affect natural uranium isotope fractionations, in addition to oxidation state. Tentatively, it appears that uranyl-type (UO22+-bearing) structures will tend to have higher 238U/235U than uranate-type structures that lack strong U=O bonds. References: 1. Bigeleisen (1996) JACS 118:3676; 2. Schauble (2006) Eos 87:V21B-0570; 3. Abe et al. (2008) J Chem Phys 128:144309, 129:164309, & Abe et al. (2010) J Chem Phys 133:044309; 4. Schauble (2013) PNAS 110:17714.

Persistence of uranium groundwater plumes: contrasting mechanisms at two DOE sites in the groundwater-river interaction zone.

PubMed

Zachara, John M; Long, Philip E; Bargar, John; Davis, James A; Fox, Patricia; Fredrickson, Jim K; Freshley, Mark D; Konopka, Allan E; Liu, Chongxuan; McKinley, James P; Rockhold, Mark L; Williams, Kenneth H; Yabusaki, Steve B

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (

Persistence of uranium groundwater plumes: Contrasting mechanisms at two DOE sites in the groundwater-river interaction zone

NASA Astrophysics Data System (ADS)

Zachara, John M.; Long, Philip E.; Bargar, John; Davis, James A.; Fox, Patricia; Fredrickson, Jim K.; Freshley, Mark D.; Konopka, Allan E.; Liu, Chongxuan; McKinley, James P.; Rockhold, Mark L.; Williams, Kenneth H.; Yabusaki, Steve B.

2013-04-01

We examine subsurface uranium (U) plumes at two U.S. Department of Energy sites that are located near large river systems and are influenced by groundwater-river hydrologic interaction. Following surface excavation of contaminated materials, both sites were projected to naturally flush remnant uranium contamination to levels below regulatory limits (e.g., 30 μg/L or 0.126 μmol/L; U.S. EPA drinking water standard), with 10 years projected for the Hanford 300 Area (Columbia River) and 12 years for the Rifle site (Colorado River). The rate of observed uranium decrease was much lower than expected at both sites. While uncertainty remains, a comparison of current understanding suggests that the two sites have common, but also different mechanisms controlling plume persistence. At the Hanford 300 A, the persistent source is adsorbed U(VI) in the vadose zone that is released to the aquifer during spring water table excursions. The release of U(VI) from the vadose zone and its transport within the oxic, coarse-textured aquifer sediments is dominated by kinetically-limited surface complexation. Modeling implies that annual plume discharge volumes to the Columbia River are small (< one pore volume). At the Rifle site, slow oxidation of naturally reduced, contaminant U(IV) in the saturated zone and a continuous influx of U(VI) from natural, up-gradient sources influence plume persistence. Rate-limited mass transfer and surface complexation also control U(VI) migration velocity in the sub-oxic Rifle groundwater. Flux of U(VI) from the vadose zone at the Rifle site may be locally important, but it is not the dominant process that sustains the plume. A wide range in microbiologic functional diversity exists at both sites. Strains of Geobacter and other metal reducing bacteria are present at low natural abundance that are capable of enzymatic U(VI) reduction in localized zones of accumulated detrital organic carbon or after organic carbon amendment. Major differences between the sites include the geochemical nature of residual, contaminant U; the rates of current kinetic processes (both biotic and abiotic) influencing U(VI) solid-liquid distribution; the presence of detrital organic matter and the resulting spatial heterogeneity in microbially-driven redox properties; and the magnitude of groundwater hydrologic dynamics controlled by river-stage fluctuations, geologic structures, and aquifer hydraulic properties. The comparative analysis of these sites provides important guidance to the characterization, understanding, modeling, and remediation of groundwater contaminant plumes influenced by surface water interaction that are common world-wide.

Effect of Reaction Pathway on the Extent and Mechanism of Uranium(VI) Immobilization with Calcium and Phosphate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehta, Vrajesh S.; Maillot, Fabien; Wang, Zheming

Phosphate addition to subsurface environments contaminated with uranium can be used as an in situ remediation approach. Batch experiments were conducted to evaluate the dependence of the extent and mechanism of uranium uptake on the pathway for reaction with calcium phosphates. At pH 4.0 and 6.0 uranium uptake occurred via autunite (Ca(UO2)(PO4)3) precipitation irrespective of the starting forms of calcium and phosphate. At pH 7.5, the uptake mechanism depended on the nature of the calcium and phosphate. When dissolved uranium, calcium, and phosphate were added simultaneously, uranium was structurally incorporated into a newly formed amorphous calcium phosphate solid. Adsorption wasmore » the dominant removal mechanism for uranium contacted with pre-formed amorphous calcium phosphate solids,. When U(VI) was added to a suspension containing amorphous calcium phosphate solids as well as dissolved calcium and phosphate, then removal occurred through precipitation (57±4 %) of autunite and adsorption (43±4 %) onto calcium phosphate. The solid phase speciation of the uranium was determined using X-ray absorption spectroscopy and laser induced fluorescence spectroscopy. Dissolved uranium, calcium, and phosphate concentrations with saturation index calculations helped identify removal mechanisms and determine thermodynamically favorable solid phases.« less

Is the Global Solar UV Index an Effective Instrument for Promoting Sun Protection? A Systematic Review

ERIC Educational Resources Information Center

Italia, Nadia; Rehfuess, Eva A.

2012-01-01

Exposure to ultraviolet radiation is an important risk factor for skin cancer. The Global Solar Ultraviolet Index (UVI) was developed as a tool to visualize the amount of harmful radiation and to encourage people to use sun protection. We conducted a systematic review of the effectiveness of the UVI. We employed a comprehensive search strategy to…

Activation of Persulfate by Nanosized Zero-Valent Iron (NZVI): Mechanisms and Transformation Products of NZVI.

PubMed

Kim, Cheolyong; Ahn, Jun-Young; Kim, Tae Yoo; Shin, Won Sik; Hwang, Inseong

2018-03-20

The mechanisms involved in the activation of persulfate by nanosized zero-valent iron (NZVI) were elucidated and the NZVI transformation products identified. Two distinct reaction stages, in terms of the kinetics and radical formation mechanism, were found when phenol was oxidized by the persulfate/NZVI system. In the initial stage, lasting 10 min, Fe 0 (s) was consumed rapidly and sulfate radicals were produced through activation by aqueous Fe 2+ . The second stage was governed by Fe catalyzed activation in the presence of aqueous Fe 3+ and iron (oxyhydr)oxides in the NZVI shells. The second stage was 3 orders of magnitude slower than the initial stage. An electron balance showed that the sulfate radical yield per mole of persulfate was more than two times higher in the persulfate/NZVI system than in the persulfate/Fe 2+ system. Radicals were believed to be produced more efficiently in the persulfate/NZVI system because aqueous Fe 2+ was supplied slowly, preventing sulfate radicals being scavenged by excess aqueous Fe 2+ . In the second stage, the multilayered shell conducted electrons, and magnetite in the shell provided electrons for the activation of persulfate. Iron speciation analysis (including X-ray absorption spectroscopy) results indicated that a shrinking core/growing shell model explained NZVI transformation during the persulfate/NZVI process.

Magnetospheric particle precipitation at Titan

NASA Astrophysics Data System (ADS)

Royer, Emilie; Esposito, Larry; Crary, Frank; Wahlund, Jan-Erik

2017-04-01

Although solar XUV radiation is known to be the main source of ionization in Titan's upper atmosphere around 1100 km of altitude, magnetospheric particle precipitation can also account for about 10% of the ionization process. Magnetospheric particle precipitation is expected to be the most intense on the nightside of the satelllite and when Titan's orbital position around Saturn is the closest to Noon Saturn Local Time (SLT). In addition, on several occasion throughout the Cassini mission, Titan has been observed while in the magnetosheath. We are reporting here Ultraviolet (UV) observations of Titan airglow enhancements correlated to these magnetospheric changing conditions occurring while the spacecraft, and thus Titan, are known to have crossed Saturn's magnetopause and have been exposed to the magnetosheath environnment. Using Cassini-Ultraviolet Imaging Spectrograph (UVIS) observations of Titan around 12PM SLT as our primary set of data, we present evidence of Titan's upper atmosphere response to a fluctuating magnetospheric environment. Pattern recognition software based on 2D UVIS detector images has been used to retrieve observations of interest, looking for airglow enhancement of a factor of 2. A 2D UVIS detector image, created for each UVIS observation of Titan, displays the spatial dimension of the UVIS slit on the x-axis and the time on the y-axis. In addition, data from the T32 flyby and from April 17, 2005 from in-situ Cassini instruments are used. Correlations with data from simultaneous observations of in-situ Cassini instruments (CAPS, RPWS and MIMI) has been possible on few occasions and events such as electron burst and reconnections can be associated with unusual behaviors of the Titan airglow. CAPS in-situ measurements acquired during the T32 flyby are consistent with an electron burst observed at the spacecraft as the cause of the UV emission. Moreover, on April 17, 2005 the UVIS observation displays feature similar to what could be aTitan aurora on the north pole, linked to a very fluctuating magnetospheric environment. CAPS data taken this same day indicates that the spacecraft crossed the magnetopause and provide evidence for possible reconnection events.

Periphyton and abiotic factors influencing arsenic speciation in aquatic environments: Periphyton alters arsenic speciation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lopez, Adeline R.; Silva, Silmara Costa; Webb, Samuel M.

Benthic periphytic biofilms are important food sources at the base of aquatic ecosystems. These biofilms also sit at the interface of oxic waters and hypoxic sediments, and can be influenced by or influence trace element speciation. In the present study, we compared arsenic (As) enrichment in periphyton exposed to arsenate (As[V]) or arsenite (As[III]) (20 μg/L, static renewal, 7 d), and we found similar accumulation patterns of total As (101 ± 27 and 88 ± 22mgkg -1 dry wt, respectively). Periphyton As was 6281- and 6684-fold higher than their aqueous exposures and occurred primarily as As(V). When these biofilms weremore » fed to larval mayflies, similar total As tissue concentrations (13.9 and 14.6mgkg -1 dry wt, respectively) were observed, revealing significant biodilution (~10% of their dietary concentrations). Finally, we investigated the influence of aeration and periphyton presence on As speciation in solutions and solid phases treated with As(III). Predominantly As(III) solutions were slowly oxidized over a 7-d time period, in the absence of periphyton, and aeration did not strongly affect oxidation rates. However, in the presence of periphyton, solution and solid-phase analyses (by microscale x-ray absorption spectroscopy) showed rapid As(III) oxidation to As(V) and an increasing proportion of organo-As forming over time. Thus periphyton plays several roles in As environmental behavior: 1) decreasing total dissolved As concentrations via abiotic and biotic accumulation, 2) rapidly oxidizing As(III) to As(V), 3) effluxing organo-As forms into solution, and 4) limiting trophic transfer to aquatic grazers.« less

Periphyton and abiotic factors influencing arsenic speciation in aquatic environments: Periphyton alters arsenic speciation

DOE PAGES

Lopez, Adeline R.; Silva, Silmara Costa; Webb, Samuel M.; ...

2017-11-02

Benthic periphytic biofilms are important food sources at the base of aquatic ecosystems. These biofilms also sit at the interface of oxic waters and hypoxic sediments, and can be influenced by or influence trace element speciation. In the present study, we compared arsenic (As) enrichment in periphyton exposed to arsenate (As[V]) or arsenite (As[III]) (20 μg/L, static renewal, 7 d), and we found similar accumulation patterns of total As (101 ± 27 and 88 ± 22mgkg -1 dry wt, respectively). Periphyton As was 6281- and 6684-fold higher than their aqueous exposures and occurred primarily as As(V). When these biofilms weremore » fed to larval mayflies, similar total As tissue concentrations (13.9 and 14.6mgkg -1 dry wt, respectively) were observed, revealing significant biodilution (~10% of their dietary concentrations). Finally, we investigated the influence of aeration and periphyton presence on As speciation in solutions and solid phases treated with As(III). Predominantly As(III) solutions were slowly oxidized over a 7-d time period, in the absence of periphyton, and aeration did not strongly affect oxidation rates. However, in the presence of periphyton, solution and solid-phase analyses (by microscale x-ray absorption spectroscopy) showed rapid As(III) oxidation to As(V) and an increasing proportion of organo-As forming over time. Thus periphyton plays several roles in As environmental behavior: 1) decreasing total dissolved As concentrations via abiotic and biotic accumulation, 2) rapidly oxidizing As(III) to As(V), 3) effluxing organo-As forms into solution, and 4) limiting trophic transfer to aquatic grazers.« less

Chromium speciation in environmental samples using a solid phase spectrophotometric method

NASA Astrophysics Data System (ADS)

Amin, Alaa S.; Kassem, Mohammed A.

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H2SO4 and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11 × 107 and 3.90 × 107 L mol-1 cm-1 for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L-1 with RSD of <1.85% (n = 8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L-1 for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L-1, respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested.

A systematic investigation of aluminium ion speciation at high temperature. Part 1. Solution studies.

PubMed

Shafran, Kirill L; Perry, Carole C

2005-06-21

Speciation diagrams of aluminium ions in aqueous solution (0.2 M) at high temperature (90 degrees C) have been obtained from 48 h time-resolved multi-batch titration experiments monitored by 27Al NMR spectroscopy, potentiometry and dynamic light scattering. The quantitative speciation patterns and kinetic data obtained offer a dynamic picture of the distribution of soluble and insoluble Al species as a function of hydrolysis ratio h(h=[OH-]/[Al3+]) over a very broad range of conditions (-1.0 < or =h < or = 4.0). Monomeric, small oligomeric, tridecameric (the 'Al13-mer') and the recently characterised 30-meric aluminium species (the 'Al30-mer') as well as aluminium hydroxide have been identified and quantified. The Al13-mer species dominates over a relatively broad range of hydrolysis ratios (1.5 < or =h< or = 2.7) during the first 6 h of experiment, but are gradually replaced by Al30-mers at longer reaction times. Kinetic profiles indicate that the formation of the Al30-mer is limited by the disappearance of the Al13 species at mildly acidic conditions. The estimated rate constants of both hydrolytic processes show good internal correlation at h> or = 1.5. The effect of local perturbations leading to the formation of aluminium hydroxide below the electroneutrality point (h= 3.0) has been estimated quantitatively.

Speciation analysis of aluminium in plant parts of Betula pendula and in soil.

PubMed

Zioła-Frankowska, Anetta; Frankowski, Marcin

2018-03-01

The research presents the first results of aluminium speciation analysis in aqueous extracts of individual plant parts of Betula pendula and soil samples, using High Performance Ion Chromatography with Diode Array Detection (HPIC-DAD). The applied method allowed us to carry out a full speciation analysis of aluminium in the form of predominant aluminium-fluoride complexes: AlF (x=2,3,4) (3-x) (first analytical signal), AlF 2+ (second analytical signal) and Al 3+ (third analytical signal) in samples of lateral roots, tap roots, twigs, stem, leaf and soil collected under roots of B. pendula. Concentrations of aluminium and its complexes were determined for two types of environment characterised by different degree of human impact: contaminated site of the Chemical Plant in Luboń and protected area of the Wielkopolski National Park. For all the analysed samples of B. pendula and soil, AlF (x=2,3,4) (3-x) had the largest contribution, followed by Al 3+ and AlF 2+ . Significant differences in concentration and contribution of Al-F complexes and Al 3+ form, depending on the place of sampling (different anthropogenic pressure) and plant part of B. pendula were observed. Based on the obtained results, it was found that transport of aluminium is "blocked" by lateral roots, and is closely related to Al content of soil. Copyright © 2017. Published by Elsevier B.V.

Determination of the distribution and speciation of selenium in an argillaceous sample using chemical extractions and post-extractions analyses: application to the hydrogeological experimental site of Poitiers.

PubMed

Bassil, Joseph; Naveau, Aude; Bueno, Maïté; Di Tullo, Pamela; Grasset, Laurent; Kazpard, Véronique; Razack, Moumtaz

2016-05-01

To better understand selenium's dynamics in environmental systems, the present study aims to investigate selenium speciation and distribution in black argillaceous sediments, partially fulfilling karstic cavities into the Hydrogeological Experimental Site of Poitiers. These sediments are suspected to be responsible for selenium concentrations exceeding the European Framework Directive's drinking water limit value (10 μg L(-1)) in some specific wells. A combination of a sequential extractions scheme and single parallel extractions was thus applied on a representative argillaceous sample. Impacts of the extractions on mineral dissolution and organic matter mobilization were followed by quantifying major cations and total organic carbon (TOC) in the aqueous extracts. The nature of the released organic matter was characterized using thermochemolysis coupled with gas chromatography-mass spectrometry (GC-MS). About 10 % of selenium from the black argillaceous studied matrix could be defined as 'easily mobilizable' when the majority (around 70 %) revealed associated with the aliphatic and alkaline-soluble organic matter's fraction (about 20 %). In these fractions, selenium speciation was moreover dominated by oxidized species including a mixture of Se(VI) (20-30 %) and Se(IV) (70-80 %) in the 'easily mobilizable' fraction, while only Se(IV) was detected in alkaline-soluble organic matter fraction.

The effect of bicarbonate on the microbial dissolution of autunite mineral in the presence of gram-positive bacteria.

PubMed

Sepulveda-Medina, Paola M; Katsenovich, Yelena P; Wellman, Dawn M; Lagos, Leonel E

2015-06-01

Bacteria are key players in the processes that govern fate and transport of contaminants. The uranium release from Na and Ca-autunite by Arthrobacter oxydans strain G968 was evaluated in the presence of bicarbonate ions. This bacterium was previously isolated from Hanford Site soil and in earlier prescreening tests demonstrated low tolerance to U(VI) toxicity compared to other A. oxydans isolates. Experiments were conducted using glass serum bottles as mixed bioreactors and sterile 6-well cell culture plates with inserts separating bacteria cells from mineral solids. Reactors containing phosphorus-limiting media were amended with bicarbonate ranging between 0 and 10 mM and meta-autunite solids to provide a U(VI) concentration of 4.4 mmol/L. Results showed that in the presence of bicarbonate, A. oxydans G968 was able to enhance the release of U(VI) from Na and Ca autunite at the same capacity as other A. oxydans isolates with relatively high tolerance to U(VI). The effect of bacterial strains on autunite dissolution decreases as the concentration of bicarbonate increases. The results illustrate that direct interaction between the bacteria and the mineral is not necessary to result in U(VI) biorelease from autunite. The formation of secondary calcium-phosphate mineral phases on the surface of the mineral during the dissolution can ultimately reduce the natural autunite mineral contact area, which bacterial cells can access. This thereby reduces the concentration of uranium released into the solution. This study provides a better understanding of the interactions between meta-autunite and microbes in conditions mimicking arid and semiarid subsurface environments of western U.S. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluation of tourists' UV exposure in Paris.

PubMed

Mahé, E; Corrêa, M P; Godin-Beekmann, S; Haeffelin, M; Jégou, F; Saiag, P; Beauchet, A

2013-03-01

Ultraviolet (UV) exposure is one of the most important risk factor for skin cancers. If UV hazard has been evaluated in tropical countries or in some population - children, outdoor activities - little information is available about UV hazard in high latitude towns like Paris, considered as the most 'charismatic city' in the world. To evaluate UV exposure in Paris in spring, in sun and shade, in real life conditions. We evaluated erythemal UV exposure, during four sunny days in May-June in eight Paris touristic sites during peak hours (2 days), and during two walks in touristic downtown of Paris. Measures were performed in sun and shade. UV radiation exposure was evaluated with UV index performed with a 'Solarmeter ultraviolet index (UVI)' and UV dose with 'standard erythema dose' (SED) and 'minimal erythema dose' (MED) calculations. Despite 'average' UVI in sunny conditions, a 4-h sun exposure reaches 13-20 SED and 3-10 MED according to phototype. Clouds were inefficient to protect against UV. Shade of places reduces moderately UVI (50-60%) in forecourts. Exposure during 1-h walk reach at least one MED in real life conditions for skin phototypes I-IV. UV risk for tourist is quite high in spring in Paris. UVI remains high despite high cloud fraction. Shade reduces UVI, but UV protection factor is only 2-3 in large places such as Place Notre Dame and Place Charles de Gaulle. So sun protection campaigns should be proposed, and sun protective strategies could be integrated in urban planning. © 2012 The Authors. Journal of the European Academy of Dermatology and Venereology © 2012 European Academy of Dermatology and Venereology.

Sexual violence, condom negotiation, and condom use in the context of sex work: results from two West African countries.

PubMed

Wirtz, Andrea L; Schwartz, Sheree; Ketende, Sosthenes; Anato, Simplice; Nadedjo, Felicity D; Ouedraogo, Henri G; Ky-Zerbo, Odette; Pitche, Vincent; Grosso, Ashley; Papworth, Erin; Baral, Stefan

2015-03-01

Female sex workers (FSWs) are vulnerable to violence within and beyond the workplace. Violence is associated with increased burden of HIV, possibly explained through physiologic or behavioral causal pathways. These analyses sought to determine the relationship between lifetime sexual violence with unprotected, condomless vaginal intercourse (UVI) among FSWs in West Africa. FSWs (aged ≥18 years) were recruited into a cross-sectional study through respondent-driven sampling in two West African countries, Togo and Burkina Faso. A total of 1380 participants were enrolled from January to July 2013, and completed a sociobehavioral questionnaire and HIV testing. Measures included sex work history, lifetime experiences of violence victimization, sexual practices, and UVI (past month). Crude and adjusted robust log binomial regression was conducted to estimate prevalence ratios (PrR) as a measure of association between UVI with clients and the primary exposure, forced sex. Self-reported lifetime physical abuse (47.3%), forced sex (33.0%), and any violence (57.9%) were common. Almost one-quarter (23.9%) reported recent UVI with clients. History of forced sex was independently associated with recent UVI with clients [vs. none, adjusted PrR: 1.49; 95% confidence interval (CI): 1.18 to 1.88], with evidence of partial mediation by difficult condom negotiation with regular (aPrR: 1.83; 95% CI: 1.43 to 2.34) and new clients (aPrR: 1.60; 95% CI: 1.13 to 2.29). These data demonstrate the significant relationship between sexual violence experienced by FSWs and unprotected sex with clients. Comprehensive interventions reducing vulnerabilities to violence combined with improved condom negotiation are needed to address the complex influences of condom use during sex work as a means of ultimately lowering HIV acquisition and transmission.

Simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate in welding fume alkaline extracts by HPLC-ICP-MS.

PubMed

Ščančar, Janez; Berlinger, Balázs; Thomassen, Yngvar; Milačič, Radmila

2015-09-01

A novel analytical procedure was developed for the simultaneous speciation analysis of chromate, molybdate, tungstate and vanadate by anion-exchange high performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Linear gradient elution from 100% water to 100% 0.7 M NaCl was applied for chromatographic separation of metal species. In standard aqueous solution at neutral pH molybdate, tungstate and vanadate exist in several aqueous species, while chromate is present as a single CrO4(2-) species. Consequently, only chromate can be separated from this solution in a sharp chromatographic peak. For obtaining sharp chromatographic peaks for molybdate, tungstate and vanadate, the pH of aqueous standard solutions was raised to 12. At highly alkaline conditions single CrO4(2-), MoO4(2-) and WO4(2-) are present and were eluted in sharp chromatographic peaks, while VO4(3-) species, which predominates at pH 12 was eluted in slightly broaden peak. In a mixture of aqueous standard solutions (pH 12) chromate, molybdate, tungstate and vanadate were eluted at retention times from 380 to 420 s, 320 to 370 s, 300 to 350 s and 240 to 360 s, respectively. Eluted species were simultaneously detected on-line by ICP-MS recording m/z 52, 95, 182 and 51. The developed procedure was successfully applied to the analysis of leachable concentrations of chromate, molybdate, tungstate and vanadate in alkaline extracts (2% NaOH+3% Na2CO3) of manual metal arc (MMA) welding fumes loaded on filters. Good repeatability and reproducibility of measurement (RSD±3.0%) for the investigated species were obtained in both aqueous standard solutions (pH 12) and in alkaline extracts of welding fumes. Low limits of detection (LODs) were found for chromate (0.02 ng Cr mL(-1)), molybdate (0.1 ng Mo mL(-1)), tungstate (0.1 ng W mL(-1)) and vanadate (0.2 ng V mL(-1)). The accuracy of analytical procedure for the determination of chromate was checked by analysis of CRM 545, Cr(VI) in welding dust loaded on a filter. Good agreement between determined and reported certified values was obtained. For molybdate, tungstate and vanadate the assessment of accuracy was performed by spiking welding fume filters. Good recoveries for all investigated species (98-101%) confirmed the accuracy of the analytical procedure. Copyright © 2015 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Fan; Parker, Jack C.; Watson, David B

This study investigates uranium and technetium sorption onto aluminum and iron hydroxides during titration of acidic groundwater. The contaminated groundwater exhibits oxic conditions with high concentrations of NO{sub 3}{sup -}, SO{sub 4}{sup 2-}, U, Tc, and various metal cations. More than 90% of U and Tc was removed from the aqueous phase as Al and Fe precipitated above pH 5.5, but was partially resolublized at higher pH values. An equilibrium hydrolysis and precipitation reaction model adequately described variations in aqueous concentrations of metal cations. An anion exchange reaction model was incorporated to simulate sulfate, U and Tc sorption onto variablymore » charged (pH-dependent) Al and Fe hydroxides. Modeling results indicate that competitive sorption/desorption on mixed mineral phases needs to be considered to adequately predict U and Tc mobility. The model could be useful for future studies of the speciation of U, Tc and co-existing ions during pre- and post-groundwater treatment practices.« less

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

NASA Astrophysics Data System (ADS)

Morgan, G. B., VI; Chou, I.-Ming; Pasteris, J. D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H 2C 2O 4 · 2H 2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750°C, with bulk fluid densities in the range 0.01-0.53 g/cm 3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350°C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3 H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H 2O-CO 2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of SAXENA and FEI (1988). Such disagreement suggests that the formations of CH 4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650°C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H 2O-CO 2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions.

Speciation in experimental C-O-H fluids produced by the thermal dissociation of oxalic acid dihydrate

USGS Publications Warehouse

Morgan, G.B.; Chou, I.-Ming; Pasteris, J.D.

1992-01-01

Fluid speciations and their related reaction pathways were studied in C-O-H-system fluids produced by the thermal dissociation of oxalic acid dihydrate (OAD: H2C2O4 ?? 2H2O) sealed in silica glass capsules. Experiments were conducted in the temperature range 230-750??C, with bulk fluid densities in the range 0.01-0.53 g/cm3. Pressure was controlled by temperature and density in the isochoric systems. The quenched products of dissociation experiments were an aqueous liquid and one (supercritical fluid) or, rarely, two (vapor plus liquid) carbonic phase (s). In-situ Raman microanalyses were performed on the quenched carbonic phases at room temperature, at which fluid pressures ranged from about 50 to 340 bars. Bulk fluid speciations were reconstructed from the Raman analyses via mass balance constraints, and appear to monitor the true fluid speciations at run conditions. In experiments from the lowtemperature range (230-350??C), fluid speciations record the dissociation of OAD according to the reaction OAD = CO2 + CO + 3H2O. A process of the form CO + H2O = CO2 + H2 is driven to the right with increasing temperature. The hydrogen gas produced tends to escape from the sample systems via diffusion into/through the silica glass capsules, shifting bulk compositions toward equimolar binary H2O-CO2 mixtures. The speciations of fluids in experiments with minimal hydrogen loss show poor agreement with speciations calculated for equilibrium fluids by the corresponding-states model of Saxena and Fei (1988). Such disagreement suggests that the formations of CH4 and graphite are metastably inhibited in the current experiments, which correlates with their absence or trivial abundances in experimental products. Moreover, calculations in which the stabilities of methane and graphite are suppressed suggest that such metastable equilibrium is approached only in experiments at temperatures greater than about 600-650??C. These results have applications to fluid processes in geological environments, in addition to considerations of using oxalate compounds as volatile sources in experimental studies. It is possible that disequilibrium or metastable fluids may be entrapped as inclusions; re-speciation (toward metastable or stable equilibrium) during P-T evolution of a given terrain would place the fluid inclusion on a new isochore that would not project through the original conditions of entrapment. Moreover, the disequilibrium to metastable nature of dissociation reactions, coupled with the diffusional mobility of hydrogen gas observed in the current experiments, suggests that the predominance of binary H2O-CO2 fluid mixtures in natural inclusions from medium- to high-grade metamorphic terrains may be more than a coincidence of similar initial bulk compositions. ?? 1992.

Removal of Radioactive Materials from Groundwater Using Porous Iron Composite Media

NASA Astrophysics Data System (ADS)

Dorward, E.; Thomas, R.; Cochran, J. P.; Chang, H. S.; Tandukar, M.; Coutelot, F.; Seaman, J. C.

2017-12-01

Uranium (U) is a concern in aqueous environments because of its toxicity. Reducing the mobile U(VI) to the relatively immobile U(IV) can decrease soluble U concentrations. Zero valent iron (ZVI) has been demonstrated as an effective reducing agent for U(VI) as well as other frequently occurring co-contaminants, such as nitrate (NO3-). However, the ability of ZVI to chemically reduce and immobilize U and other associated contaminants in more complex systems containing many alternate electron acceptors and non-ideal chemical conditions remains a concern. Porous iron composite (PIC) materials were evaluated for their ability to address these concerns in both batch and column experiments. We created an artificial groundwater surrogate containing ≈ 100 mg L-1 NO3-, 200 mg L-1 alkalinity, 100 µg L-1 U(VI) as uranyl (UO2+2), 100 µg L-1 rhenium (Re) as perrhenate (ReO4-), and 50 µg L-1 arsenic (As). In batch, we reacted 5 grams of PIC material with 200 mL groundwater surrogate under two different atmospheric conditions to evaluate the impact of O2. At specific time intervals, 5 mL aliquots from each batch treatment were removed for chemical analysis (i.e., U, Re, As, Fe, NO3, etc.) and the pH and ORP of the remaining suspension was measured. The PIC was effective at fully reducing NO3- levels over the extended reaction time despite rapid pH increase (> 8) during equilibration. Soluble levels of U and Re, a chemical surrogate for 99Tc, decreased in a similar fashion to NO3- in both the presence and absence of O2. Soluble As levels decreased more rapidly than other contaminants, but remained at ≈ 1 µg L-1. Very little nitrite (NO2-) was detected in the batch tests, with NH4+ levels consistent with the amount of NO3- reduced. Similar rates of immobilization for U, Re, and As were observed in the presence and absence of NO3-. Subsequent leaching tests corresponding to residence times ranging from 120 to 7.5 minutes demonstrated the ability of the PIC to reduce NO3- to NH4+, with no persistence of NO2-. Uranium and As were readily immobilized regardless of flow velocity. A strong kinetic component was observed for Re leaching behavior in the column tests. These results indicate the strong ability of PIC material to reduce U, NO3-, and other species under conditions that frequently inhibit conventional ZVI effectiveness.

HST/WFC3: Evolution of the UVIS Channel's Charge Transfer Efficiency

NASA Astrophysics Data System (ADS)

Gosmeyer, Catherine; Baggett, Sylvia M.; Anderson, Jay; WFC3 Team

2016-06-01

The Wide Field Camera 3 (WFC3) on the Hubble Space Telescope (HST) contains both an IR and a UVIS channel. After more than six years on orbit, the UVIS channel performance remains stable; however, on-orbit radiation damage has caused the charge transfer efficiency (CTE) of UVIS's two CCDs to degrade. This degradation is seen as vertical charge 'bleeding' from sources during readout and its effect evolves as the CCDs age. The WFC3 team has developed software to perform corrections that push the charge back to the sources, although it cannot recover faint sources that have been bled out entirely. Observers can mitigate this effect in various ways such as by placing sources near the amplifiers, observing bright targets, and by increasing the total background to at least 12 electrons, either by using a broader filter, lengthening exposure time, or post-flashing. We present results from six years of calibration data to re-evaluate the best level of total background for mitigating CTE loss and to re-verify that the pixel-based CTE correction software is performing optimally over various background levels. In addition, we alert observers that CTE-corrected products are now available for retrieval from MAST as part of the CALWF3 v3.3 pipeline upgrade.

Simultaneous determination of uranium carbide dissolution products by capillary zone electrophoresis.

PubMed

Sladkov, Vladimir; Fourest, Blandine

2009-03-20

Separation and simultaneous determination of a number of organic acid anions (oxalate, mellitate, trimellitate and benzoate) and U(VI) with direct UV detection is developed for analysis of uranium carbide (UC) dissolution products by capillary zone electrophoresis (CZE). Reverse polarity mode is used. It is found that complex formation of U(VI) with carbonate, used as a carrier electrolyte, allows U(VI) to be determined, as negatively charged species, in a single run with organic acid anions. Some parameters such as pH value, composition of electrolyte and detection wavelength are optimized. Under the chosen conditions (carbonate buffer (ionic strength of 100 mM), pH 9.8, 0.15 mM tetradecyltrimethylammonium bromide (TTAB)) a complete separation is achieved. Calibration plots are linear in two ranges of concentration for U(VI) ( approximately 1 x 10(-5) to 1 x 10(-3)), mellitate and trimellitate ( approximately 5 x 10(-6) to 5 x 10(-4)), and about one range ( approximately 1 x 10(-4) to 5 x 10(-3)) for oxalate and benzoate. Accuracy of the procedure is checked by the "added-found" method in standard mixture solutions. Relative standard deviation is within the range of 2-10% and the recovery is in the range of 90-110%. This method is applied for the analysis of real UC dissolution samples.

Arsenite and Ferrous Iron Oxidation Linked to Chemolithotrophic Denitrification for the Immobilization of Arsenic in Anoxic Environments

PubMed Central

Sun, Wenjie; Sierra-Alvarez, Reyes; Milner, Lily; Oremland, Ron; Field, Jim A.

2014-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3− to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flow sand filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (SF1) or absence (SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 µg l−1 was reduced to 10.6 (±9.6) µg l−1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5–10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns was close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by XRD and XPS. The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxides coated sands with adsorbed As(V). PMID:19764221

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

NASA Astrophysics Data System (ADS)

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

2016-09-01

Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

Speciation and isotopic exchangeability of nickel in soil solution.

PubMed

Nolan, Annette L; Ma, Yibing; Lombi, Enzo; McLaughlin, Mike J

2009-01-01

Knowledge of trace metal speciation in soil pore waters is important in addressing metal bioavailability and risk assessment of contaminated soils. In this study, free Ni(2+) activities were determined in pore waters of long-term Ni-contaminated soils using a Donnan dialysis membrane technique. The pore water free Ni(2+) concentration as a percentage of total soluble Ni ranged from 21 to 80% (average 53%), and the average amount of Ni bound to dissolved organic matter estimated by Windermere Humic Aqueous Model VI was < or = 17%. These data indicate that complexed forms of Ni can constitute a significant fraction of total Ni in solution. Windermere Humic Aqueous Model VI provided reasonable estimates of free Ni(2+) fractions in comparison to the measured fractions (R(2) = 0.83 with a slope of 1.0). Also, the isotopically exchangeable pools (E value) of soil Ni were measured by an isotope dilution technique using water extraction, with and without resin purification, and 0.1 mol L(-1) CaCl(2) extraction, and the isotopic exchangeability of Ni species in soil water extracts was investigated. The concentrations of isotopically non-exchangeable Ni in water extracts were <9% of total water soluble Ni concentrations for all soils. The resin E values expressed as a percentage of the total Ni concentrations in soil showed that the labile Ni pool ranged from 0.9 to 32.4% (average 12.4%) of total soil Ni. Therefore the labile Ni pool in these well-equilibrated contaminated soils appears to be relatively small in relation to total Ni concentrations.

Recrystallization of Manganite (γ-MnOOH) and Implications for Trace Element Cycling.

PubMed

Hens, Tobias; Brugger, Joël; Cumberland, Susan A; Etschmann, Barbara; Frierdich, Andrew J

2018-02-06

The recrystallization of Mn(III,IV) oxides is catalyzed by aqueous Mn(II) (Mn(II) aq ) during (bio)geochemical Mn redox cycling. It is poorly understood how trace metals associated with Mn oxides (e.g., Ni) are cycled during such recrystallization. Here, we use X-ray absorption spectroscopy (XAS) to examine the speciation of Ni associated with Manganite (γ-Mn(III)OOH) suspensions in the presence or absence of Mn(II) aq under variable pH conditions (pH 5.5 and 7.5). In a second set of experiments, we used a 62 Ni isotope tracer to quantify the amount of dissolved Ni that exchanges with Ni incorporated in the Manganite crystal structure during reactions in 1 mM Mn(II) aq and in Mn(II)-free solutions. XAS spectra show that Ni is initially sorbed on the Manganite mineral surface and is progressively incorporated into the mineral structure over time (13% after 51 days) even in the absence of dissolved Mn(II). The amount of Ni incorporation significantly increases to about 40% over a period of 51 days when Mn(II) aq is present in solution. Similarly, Mn(II) aq promotes Ni exchange between Ni-substituted Manganite and dissolved Ni(II), with around 30% of Ni exchanged at pH 7.5 over the duration of the experiment. No new mineral phases are detected following recrystallization as determined by X-ray diffraction and XAS. Our results reveal that Mn(II)-catalyzed mineral recrystallization partitions Ni between Mn oxides and aqueous fluids and can therefore affect Ni speciation and mobility in the environment.

A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

NASA Astrophysics Data System (ADS)

Usher, Al; McPhail, D. C.; Brugger, Joël

2009-06-01

The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0.05. The results of our study increase the understanding of gold aqueous geochemistry, with the potential to lead to new methods for mineral exploration, hydrometallurgy and medicine.

Uranium removal from a contaminated effluent using a combined microbial and nanoparticle system.

PubMed

Baiget, Mar; Constantí, Magda; López, M Teresa; Medina, Francesc

2013-09-25

Reduction of soluble uranium(VI) to insoluble uranium(IV) for remediating a uranium-contaminated effluent (EF-03) was examined using a biotic and abiotic integrated system. Shewanella putrefaciens was first used and reduced U(VI) in a synthetic medium but not in the EF-03 effluent sample. Subsequently the growth of autochthonous microorganisms was stimulated with lactate. When lactate was supported on active carbon 77% U(VI) was removed in 4 days. Separately, iron nanoparticles that were 50 nm in diameter reduced U(VI) by 60% in 4 hours. The efficiency of uranium(VI) removal was improved to 96% in 30 min by using a system consisting of lactate and iron nanoparticles immobilized on active carbon. Lactate also stimulated the growth of potential uranium-reducing microorganisms in the EF-03 sample. This system can be efficiently used for the bioremediation of uranium-contaminated effluents. Copyright © 2013 Elsevier B.V. All rights reserved.

HST/WFC3 Characteristics: gain, post-flash stability, UVIS low-sensitivity pixels, persistence, IR flats and bad pixel table

NASA Astrophysics Data System (ADS)

Gunning, Heather C.; Baggett, Sylvia; Gosmeyer, Catherine M.; Long, Knox S.; Ryan, Russell E.; MacKenty, John W.; Durbin, Meredith

2015-08-01

The Wide Field Camera 3 (WFC3) is a fourth-generation imaging instrument on the Hubble Space Telescope (HST). Installed in May 2009, WFC3 is comprised of two observational channels covering wavelengths from UV/Visible (UVIS) to infrared (IR); both have been performing well on-orbit. We discuss the gain stability of both WFC3 channel detectors from ground testing through present day. For UVIS, we detail a low-sensitivity pixel population that evolves during the time between anneals, but is largely reset by the annealing procedure. We characterize the post-flash LED lamp stability, used and recommended to mitigate CTE effects for observations with less than 12e-/pixel backgrounds. We present mitigation options for IR persistence during and after observations. Finally, we give an overview on the construction of the IR flats and provide updates on the bad pixel table.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Joel E. Kostka

This project represented a joint effort between Oak Ridge National Laboratory (ORNL), the University of Tennessee (UT), and Florida State University (FSU). ORNL served as the lead in-stitution with Dr. A.V. Palumbo responsible for project coordination, integration, and deliver-ables. In situ uranium bioremediation is focused on biostimulating indigenous microorganisms through a combination of pH neutralization and the addition of large amounts of electron donor. Successful biostimulation of U(VI) reduction has been demonstrated in the field and in the laboratory. However, little data is available on the dynamics of microbial populations capable of U(VI) reduction, and the differences in the microbialmore » community dynamics between proposed electron donors have not been explored. In order to elucidate the potential mechanisms of U(VI) reduction for optimization of bioremediation strategies, structure-function relationships of microbial populations were investigated in microcosms of subsurface materials cocontaminated with radionuclides and nitrate from the Oak Ridge Field Research Center (ORFRC), Oak Ridge, Tennessee.« less

Measuring the accelerating effect of the planetary-scale waves on Venus observed with UVI/AKATSUKI and ground-based telescopes

NASA Astrophysics Data System (ADS)

Imai, M.; Kouyama, T.; Takahashi, Y.; Watanabe, S.; Yamazaki, A.; Yamada, M.; Nakamura, M.; Satoh, T.; Imamura, T.; Nakaoka, T.; Kawabata, M.; Yamanaka, M.; Kawabata, K. S.

2017-12-01

Venus has a global cloud layer, and the atmosphere rotates with the speed over 100 m/s. The scattering of solar radiance and absorber in clouds cause the strong dark and bright contrast in 365 nm unknown absorption bands. The Japanese Venus orbiter AKATSUKI and the onboard instrument UVI capture 100 km mesoscale cloud features over the entire visible dayside area. In contrast, planetary-scale features are observed when the orbiter is at the moderate distance from Venus and when the Sun-Venus-orbiter phase angle is smaller than 45 deg. Cloud top wind velocity was measured with the mesoscale cloud tracking technique, however, observations of the propagation velocity and its variation of the planetary-scale feature are not well conducted because of the limitation of the observable area. The purpose of the study is measuring the effect of wind acceleration by planetary-scale waves. Each cloud motion can be represented as the wind and phase velocity of the planetary-scale waves, respectively. We conducted simultaneous observations of the zonal motion of both mesoscale and planetary-scale feature using UVI/AKATSUKI and ground-based Pirka and Kanata telescopes in Japan. Our previous ground-based observation revealed the periodicity change of planetary-scale waves with a time scale of a couple of months. For the initial analysis of UVI images, we used the time-consecutive images taken in the orbit #32. During this orbit (from Nov. 13 to 20, 2016), 7 images were obtained with 2 hr time-interval in a day whose spatial resolution ranged from 10-35 km. To investigate the typical mesoscale cloud motion, the Gaussian-filters with sigma = 3 deg. were used to smooth geometrically mapped images with 0.25 deg. resolution. Then the amount of zonal shift for each 5 deg. latitudinal bands between the pairs of two time-consecutive images were estimated by searching the 2D cross-correlation maximum. The final wind velocity (or rotation period) for mesoscale features were determined with a small error about +/- 0.1-day period in equatorial region (Figure 2). The same method will be applied for planetary-scale features captured by UVI, and ground-based observations compensate the discontinuity in UVI data. At the presentation, the variability in winds and wave propagation velocity with the time scale of a couple of months will be shown.

The complete set of Cassini's UVIS occultation observations of Enceladus plume: model fits

NASA Astrophysics Data System (ADS)

Portyankina, G.; Esposito, L. W.; Hansen, C. J.

2017-12-01

Since the discovery in 2005, plume of Enceladus was observed by most of the instruments onboard Cassini spacecraft. Ultraviolet Imaging Spectrograph (UVIS) have observed Enceladus plume and collimated jets embedded in it in occultational geometry on 6 different occasions. We have constructed a 3D direct simulation Monte Carlo (DSMC) model for Enceladus jets and apply it to the analysis of the full set of UVIS occultation observations conducted during Cassini's mission from 2005 to 2017. The Monte Carlo model tracks test particles from their source at the surface into space. The initial positions of all test particles for a single jet are fixed to one of 100 jets sources identified by Porco et al. (2014). The initial three-dimensional velocity of each particle contains two components: a velocity Vz which is perpendicular to the surface, and a thermal velocity which is isotropic in the upward hemisphere. The direction and speed of the thermal velocity of each particle is chosen randomly but the ensemble moves isotropically at a speed which satisfies a Boltzmann distribution for a given temperature Tth. A range for reasonable Vz is then determined by requiring that modeled jet widths match the observed ones. Each model run results in a set of coordinates and velocities of a given set of test particles. These are converted to the test particle number densities and then integrated along LoS for each time step of the occultation observation. The geometry of the observation is calculated using SPICE. The overarching result of the simulation run is a test particle number density along LoS for each time point during the occultation observation for each of the jets separately. To fit the model to the data, we integrate all jets that are crossed by the LoS at each point during an observation. The relative strength of the jets must be determined to fit the observed UVIS curves. The results of the fits are sets of active jets for each occultation. Each UVIS occultation observation was done under a unique observational geometry. Consequently, the model fits produce different sets of active jets and different minimum Vz. We discuss and compare the results of fitting all UVIS occultation observations.

[Sun exposure at school: Evaluation of risk (erythema dose), benefits (vitamin-D synthesis) and behaviour among children in France].

PubMed

Mahé, E; de Paula Corrêa, M; Vouldoukis, I; Godin-Beekmann, S; Sigal, M-L; Beauchet, A

2016-01-01

To better understand the potential risk associated with sun exposure during the school year, we decided to evaluate behaviour, risk [UV index (UVI), minimal erythema dose (MED)] and benefits (vitamin-D synthesis) of sun exposure in primary schoolchildren in France, as well as the various sun protection methods used for children. We performed the study on a sunny day (July 24) in a school in Antony (France). Evaluation of UVI (with calculation of MED) and the amount of vitamin D synthesized according to exposed body surface area and phototype were performed every 15minutes from 9 a.m. to 5 p.m. The effects of albedo and shade on UVI were assessed in 8 different locations at the school. The sun-protection measures used by the children were systematically evaluated. Fifty-seven children were evaluated; the maximum UVI was 7.2 and the maximum temperature was 30.7°C. Irrespective of phototype and clothing, 1 MED was reached and an adequate level of vitamin D was synthesized in the skin before midday. Albedo had little impact on irradiation. The amount of protection afforded by shadow varied greatly, with the highest level occurring in the covered courtyard (99.5% reduction of UVI) and the lowest in the shadow of buildings (53.7% reduction of UVI). With strict sun protection measures concerning dress, children reached 1 MED before synthesizing 1000IU of vitamin D, but with clothing "suited to high temperatures", 1000IU of vitamin D were synthetized before 1 MED was reached. Compliance with photoprotection measures was poor. Regardless of duration of exposure during the day (minimal model: two play breaks+lunchtime break) and of skin phototype, at least 1.5 MED was reached during the day. This was an experimental study ignoring children's actual behaviour (movement, sweating, application of sun protection products, etc.). Moreover, due to weather conditions, the study was performed at a recreation centre in July and not during the "standard" school year. Sun protection campaigns should naturally be directed chiefly towards children for several reasons relating to solar risk and learning. This study shows the complex link between UV, MED, vitamin D as well as the difficulties of implementing solar protection measures in schools in France. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

The ecology of arsenic

USGS Publications Warehouse

Oremland, Ronald S.; Stolz, John F.

2003-01-01

Arsenic is a metalloid whose name conjures up images of murder. Nonetheless, certain prokaryotes use arsenic oxyanions for energy generation, either by oxidizing arsenite or by respiring arsenate. These microbes are phylogenetically diverse and occur in a wide range of habitats. Arsenic cycling may take place in the absence of oxygen and can contribute to organic matter oxidation. In aquifers, these microbial reactions may mobilize arsenic from the solid to the aqueous phase, resulting in contaminated drinking water. Here we review what is known about arsenic-metabolizing bacteria and their potential impact on speciation and mobilization of arsenic in nature.

Electrically induced fluorescence Fe3+ sensing behavior of nanostructured Tiron doped polypyrrole.

PubMed

Tavoli, Farnaz; Alizadeh, Naader

2016-11-23

Nanostructured polypyrrole (PPy) film doped with Tiron was electrodeposited from aqueous solution on the surface of transparent electrode and used for sensitive, selective and rapid electrically controlled fluorescence detection of Fe 3+ in aqueous media. The fluorescence intensity of PPy-Tiron film decreases linearly in the presence of Fe 3+ by applying negative potential over a concentration range from 5.0 × 10 -8 to 1.0 × 10 -6  mol L -1 , with a relatively fast response time of less than 30 s at pH 7.4. The detection is not affected by the coexistence of other competitive metal ions such as Al 3+ , Ce 3+ , Tl 3+ , La 3+ , Bi 3+ , Cr 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Cd 2+ , Hg 2+ , Pb 2+ , Na + , K + , Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ . The proposed electro-fluorescence sensor has a potential application to the determination of Fe 3+ in environmental and biological systems. The fluorescent thin film sensor was also used as a novel probe for Fe 3+ /Fe 2+ speciation in aqueous solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Structure and spectroscopic study of aqueous Fe(III)-As(V) complexes using UV-Vis, XAS and DFT-TDDFT.

PubMed

Chai, Liyuan; Yang, Jinqin; Zhang, Ning; Wu, Pin-Jiun; Li, Qingzhu; Wang, Qingwei; Liu, Hui; Yi, Haibo

2017-09-01

Aqueous complexes between ferric (Fe(III)) and arsenate (As(V)) are indispensable for understanding the mobility of arsenic (As) in Fe(III)-As(V)-rich systems. In this study, aqueous Fe(III)-As(V) complexes, FeH 2 AsO 4 2+ and FeHAsO 4 + , were postulated based on the qualitative analysis of UV-Vis spectra in both Fe(III)-As(V)-HClO 4 and Fe(III)-As(V)-H 2 SO 4 systems. Subsequently, monodentate structures were evidenced by Fe K-edge EXAFS and modeled as [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + by DFT. The feature band at ∼280 nm was verified as electron excitation chiefly from Fe-As-bridged O atoms to d-orbital of Fe in [FeH 2 AsO 4 (H 2 O) 5 ] 2+ and [FeHAsO 4 (H 2 O) 5 ] + . The structural and spectral information of Fe(III)-As(V) complexes will enable future speciation analysis in Fe(III)-As(V)-rich system. Copyright © 2017. Published by Elsevier Ltd.

Mercury speciation by differential photochemical vapor generation at UV-B vs. UV-C wavelength

NASA Astrophysics Data System (ADS)

Chen, Guoying; Lai, Bunhong; Mei, Ni; Liu, Jixin; Mao, Xuefei

2017-11-01

Photochemical vapor generation (PVG) is an effective sample introduction scheme for volatile mercury (Hg). Speciation of Hg++ and MeHg+ was fulfilled for the first time by differential PVG under UV-B vs. UV-C wavelength and applied to fish oil supplements. After liquid-liquid extraction, the aqueous extract was mixed with 0.4% anthranilic acid (AA)-20% formic acid (FA) in a quartz coil, and exposed sequentially to 311 nm or 254 nm UV light. The resulting Hg0 vapor was detected by atomic fluorescence spectrometry (AFS). At each wavelength, the AFS intensity was a linear function of Hg++ and MeHg+ concentrations, which were solvable from a set of two equations. This method achieved ultrahigh sensitivity with 0.50 and 0.63 ng mL- 1 limits of detection for Hg++ and MeHg+, respectively, and 73% recovery for MeHg+ at 10 ng mL- 1. Validation was performed by ICP-MS on total Hg. Obviation of chemical or chromatographic separation rendered this method rapid, green, and cost-effective.

Investigation of lead bioimmobilization and transformation by Penicillium oxalicum SL2.

PubMed

Ye, Binhui; Luo, Yating; He, Junyu; Sun, Lijuan; Long, Bibo; Liu, Qinglin; Yuan, Xiaofeng; Dai, Peibin; Shi, Jiyan

2018-05-18

Fungi Penicillium oxalicum SL2 was applied for Pb 2+ bioremediation in aqueous solution in this study. After 7 days of incubation at different initial concentrations of Pb 2+ (0, 100, 500 and 2500 mg L -1 ), most of Pb 2+ were removed (90, 98.3, and 86.2%), the maximum Pb content in mycelium reached about 155.6 mg g -1  dw. Meanwhile, the formation of extracellular secondary minerals and intracellular Pb-complex were observed and identified, the speciation of Pb in mycelium was also detected by X-ray absorption near-edge structure (XANES) spectroscopy, i.e., Pb-oxalate, Pb-citrate, Pb-hydrogen phosphate and Pb-glutathione analogues. In addition, content of glutathione and oxidized glutathione was increased under the exposure of Pb 2+ , which implied that glutathione might play a key role in Pb immobilization and detoxification in P. oxalicum SL2. This study elucidated partial mechanisms of Pb immobilization and speciation transformation of this strain, providing an alternative biomaterial in the bioremediation of Pb-contaminated wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments.

PubMed

Stoliker, Deborah L; Campbell, Kate M; Fox, Patricia M; Singer, David M; Kaviani, Nazila; Carey, Minna; Peck, Nicole E; Bargar, John R; Kent, Douglas B; Davis, James A

2013-08-20

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

Behavior of Colorado Plateau uranium minerals during oxidation

USGS Publications Warehouse

Garrels, Robert Minard; Christ, C.L.

1956-01-01

Uranium occurs as U(VI) and U(IV) in minerals of the Colorado Plateau ores. The number of species containing U(VI) is large, but only two U(IV) minerals are known from the Plateau: uraninite, and oxide, and coffinite, a hydroxy-silicate. These oxidize to yield U(VI) before reacting significantly with other mineral constituents. Crystal-structure analysis has shown that U(VI) invariable occurs as uranyl ion, UO2+2. Uranyl ion may form complex carbonate or sulfate ions with resulting soluble compounds, but only in the absence of quinquevalent vanadium, arsenic, or phosphorous. In the presence of these elements in the +5 valence state, the uranyl ion is fixed in insoluble layer compounds formed by union of uranyl ion with orthovanadate, orthophosphate, or orthoarsenate. Under favorable conditions UO2+2 may react to form the relatively insoluble rutherfordine, UO2CO3, or hydrated uranyl hydroxides. These are rarely found on the Colorado Plateau as opposed to their excellent development in other uraniferous areas, a condition which is apparently related to the semiarid climate and low water table of the Plateau. Uranium may also be fixed as uranyl silicate, but little is known about minerals of this kind. In the present study emphasis has been placed on a detailing of the chemical and crystal structural changes which occur in the oxidation paragenetic sequence.

Uncertainty analysis of multi-rate kinetics of uranium desorption from sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xiaoying; Liu, Chongxuan; Hu, Bill X.

2014-01-01

A multi-rate expression for uranyl [U(VI)] surface complexation reactions has been proposed to describe diffusion-limited U(VI) sorption/desorption in heterogeneous subsurface sediments. An important assumption in the rate expression is that its rate constants follow a certain type probability distribution. In this paper, a Bayes-based, Differential Evolution Markov Chain method was used to assess the distribution assumption and to analyze parameter and model structure uncertainties. U(VI) desorption from a contaminated sediment at the US Hanford 300 Area, Washington was used as an example for detail analysis. The results indicated that: 1) the rate constants in the multi-rate expression contain uneven uncertaintiesmore » with slower rate constants having relative larger uncertainties; 2) the lognormal distribution is an effective assumption for the rate constants in the multi-rate model to simualte U(VI) desorption; 3) however, long-term prediction and its uncertainty may be significantly biased by the lognormal assumption for the smaller rate constants; and 4) both parameter and model structure uncertainties can affect the extrapolation of the multi-rate model with a larger uncertainty from the model structure. The results provide important insights into the factors contributing to the uncertainties of the multi-rate expression commonly used to describe the diffusion or mixing-limited sorption/desorption of both organic and inorganic contaminants in subsurface sediments.« less

Global Dynamics of Dayside Auroral Precipitation in Conjunction with Solar Wind Pressure Pulses

NASA Technical Reports Server (NTRS)

Brittnacher, M.; Chua, D.; Fillingim, M.; Parks, G. K.; Spann, James F., Jr.; Germany, G. A.; Carlson, C. W.; Greenwald, R. A.

1999-01-01

Global observation of the dayside auroral region by the Ultraviolet Imager (UVI) during transient solar wind pressure pulse events on October 1, 1997 has revealed unusual features in the auroral precipitation. The auroral arc structure on the dayside, possibly connected with the LLBL, split into 2 arc structures; one moving poleward and fading over a 5 min period, and the other stationary or slightly shifted equatorward (by changes in the x component). The y component was large and positive, and the z component was small and negative. The splitting of the arc structure extended from 9 to 15 MLT and was concurrent with an enhancement of the convection in the cusp region identified by SuperDARN observations. The convection reversal on the morningside was adjacent to and poleward of the weak lower latitude band of precipitation. The sensitivity of the UVI instrument enabled observation of arc structures down to about 0.2 erg electron energy flux, as confirmed by comparison with particle measurements from the FAST satellite for other dayside events. Removal of the spacecraft wobble by PIXON image reconstruction restored the original resolution of the UVI of about 40 km from apogee. This event is being analyzed in connection with a larger study of global dynamics of dayside energy and momentum transfer related to changes in IMF conditions using UVI images in conjunction with observations from FAST and SuperDARN.

Functionalized Sugarcane Bagasse for U(VI) Adsorption from Acid and Alkaline Conditions.

PubMed

Su, Shouzheng; Liu, Qi; Liu, Jingyuan; Zhang, Hongsen; Li, Rumin; Jing, Xiaoyan; Wang, Jun

2018-01-15

The highly efficient removal of uranium from mine tailings effluent, radioactive wastewater and enrichment from seawater is of great significance for the development of nuclear industry. In this work, we prepared an efficient U(VI) adsorbent by EDTA modified sugarcane bagasse (MESB) with a simple process. The prepared adsorbent preserves high adsorptive capacity for UO 2 2+ (pH 3.0) and uranyl complexes, such as UO 2 (OH) + , (UO 2 ) 2 (OH) 2 2+ and (UO 2 ) 3 (OH) 5 + (pH 4.0 and pH 5.0) and good repeatability in acidic environment. The maximum adsorption capacity for U(VI) at pH 3.0, 4.0 and 5.0 is 578.0, 925.9 and 1394.1 mg/g and the adsorption capacity loss is only 7% after five cycles. With the pH from 3.0 to 5.0, the inhibitive effects of Na + and K + decreased but increased of Mg 2+ and Ca 2+ . MESB also exhibits good adsorption for [UO 2 (CO 3 ) 3 ] 4- at pH 8.3 from 10 mg/L to 3.3 μg/L. Moreover, MESB could effectively extract U(VI) from simulated seawater in the presence of other metals ions. This work provided a general and efficient uranyl enriched material for nuclear industry.

Evaluating chemical extraction techniques for the determination of uranium oxidation state in reduced aquifer sediments

USGS Publications Warehouse

Stoliker, Deborah L.; Campbell, Kate M.; Fox, Patricia M.; Singer, David M.; Kaviani, Nazila; Carey, Minna; Peck, Nicole E.; Barger, John R.; Kent, Douglas B.; Davis, James A.

2013-01-01

Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2012-09-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (<2%) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

NASA Astrophysics Data System (ADS)

Mouchel-Vallon, C.; Bräuer, P.; Camredon, M.; Valorso, R.; Madronich, S.; Herrmann, H.; Aumont, B.

2013-01-01

The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere) is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene) is investigated for various NOx conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis) under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation) to 70% (octane oxidation) of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NOx conditions. For high NOx conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively). Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Nickel (II) Preconcentration and Speciation Analysis During Transport from Aqueous Solutions Using a Hollow-fiber Permeation Liquid Membrane (HFPLM) Device.

PubMed

Bautista-Flores, Ana Nelly; De San Miguel, Eduardo Rodríguez; Gyves, Josefina de; Jönsson, Jan Åke

2011-08-18

Nickel (II) preconcentration and speciation analysis using a hollow fiber supported liquid membrane (HFSLM) device was studied. A counterflow of protons coupled to complexation with formate provided the driving force of the process, while Kelex 100 was employed as carrier. The influence of variables related to module configuration (acceptor pH and carrier concentration) and to the sample properties (donor pH) on the preconcentration factor, E, was simultaneously studied and optimized using a 3 factor Doehlert matrix response surface methodology. The effect of metal concentration was studied as well. Preconcentration factors as high as 4240 were observed  depending on the values of the different variables. The effects of the presence of inorganic anions (NO2-, SO42-, Cl-, NO3-, CO32-, CN-) and dissolved organic matter (DOM) in the form of humic acids were additionally considered in order to carry out a speciation analysis study. Nickel preconcentration was observed to be independent of both effects, except when cyanide was present in the donor phase. A characterization of the transport regime was performed through the analysis of the dependence of E on the temperature. E increases with the increase in temperature according to the equation E(K) = -8617.3 + 30.5T with an activation energy of 56.7 kJ mol-1 suggesting a kinetic-controlled regime. Sample depletion ranged from 12 to 1.2% depending on the volume of the donor phase (100 to 1000 mL, respectively).

Speciation of inorganic arsenic in drinking water by wavelength-dispersive X-ray fluorescence spectrometry after in situ preconcentration with miniature solid-phase extraction disks.

PubMed

Hagiwara, Kenta; Inui, Tetsuo; Koike, Yuya; Aizawa, Mamoru; Nakamura, Toshihiro

2015-03-01

A rapid and simple method using wavelength-dispersive X-ray fluorescence (WDXRF) spectrometry after in situ solid-phase extraction (SPE) was developed for the speciation and evaluation of the concentration of inorganic arsenic (As) in drinking water. The method involves the simultaneous collection of As(III) and As(V) using 13 mm ϕ SPE miniature disks. The removal of Pb(2+) from the sample water was first conducted to avoid the overlapping PbLα and AsKα spectra on the XRF spectrum. To this end, a 50 mL aqueous sample (pH 5-9) was passed through an iminodiacetate chelating disk. The filtrate was adjusted to pH 2-3 with HCl, and then ammonium pyrrolidine dithiocarbamate solution was added. The solution was passed through a hydrophilic polytetrafluoroethylene filter placed on a Zr and Ca loaded cation-exchange disk at a flow rate of 12.5 mL min(-1) to separate As(III)-pyrrolidine dithiocarbamate complex and As(V). Each SPE disk was affixed to an acrylic plate using adhesive cellophane tape, and then examined by WDXRF spectrometry. The detection limits of As(III) and As(V) were 0.8 and 0.6 μg L(-1), respectively. The proposed method was successfully applied to screening for As speciation and concentration evaluation in spring water and well water. Copyright © 2014 Elsevier B.V. All rights reserved.

A new turn-on fluorimetric method for the rapid speciation of Cr(III)/Cr(VI) species in tea samples with rhodamine-based fluorescent reagent

NASA Astrophysics Data System (ADS)

Özyol, Esra; Saçmacı, Şerife; Saçmacı, Mustafa; Ülgen, Ahmet

2018-02-01

A new fluorimetric method with rhodamine-based fluorescent agent was developed for the rapid speciation of Cr(III)/Cr(VI) in tea, soil and water samples. The system, which utilizes a fluorescent reagent, was used for the first time after synthesis/characterization of 3‧,6‧-bis(diethylamino)-2-{[(1E)-(2,4-dimethoxyphenyl)methylene] amino}spiro[isoindole-1,9‧-xanthen]-3(2H)-one (BDAS). The reagent responds instantaneously at room temperature in a 1:1 stoichiometric manner to the amount of Cr(III). The selectivity of this system for Cr(III) over other metal ions is remarkably high, and its sensitivity is below 0.01 mg L- 1 in aqueous solutions which enables a simplification without any pretreatment of the real sample. The method has a wide linear range of 0.1-10 mg L- 1 and a detection limit of 0.15 μg L- 1 for Cr(III) while the relative standard deviation was 0.1% for 0.1 mg L- 1 Cr(III) concentration. The results of detection and recovery experiments for Cr(III) in tea, soil and water were satisfactory, indicating that the method has better feasibility and application potential in the routine determination and speciation of Cr(III)/Cr(VI). The results of analysis of the certified reference material (INCT-TL-1 tea sample and CWW-TM-D waste water) are in good agreement with the certified value.

Assessing natural attenuation potential at a uranium (U) in situ recovery site (Rosita, TX, USA) using multiple redox-sensitive isotope systems

NASA Astrophysics Data System (ADS)

Basu, A.; Brown, S. T.; Christensen, J. N.; DePaolo, D. J.; Reimus, P. W.; Heikoop, J. M.; Simmons, A. M.; House, B.; Schilling, K.; Johnson, T. M.; Pelizza, M.

2013-12-01

The In Situ Recovery (ISR) U mining operation at Rosita, TX, USA, involved oxidative dissolution of U from roll front U deposits. This process mobilized U along with other characteristic elements (e.g., Se) from the roll fronts in their soluble and toxic oxidized forms (e.g., U(VI), Se(VI)). The dissolved U(VI) in groundwater poses significant ecological risk due to its chemical toxicity and must be restored below the existing regulatory limit to minimize the environmental impact of ISR mining. However, the undisturbed sediments downgradient to the roll front deposits are expected to remain reduced. Naturally occurring Fe-minerals (e.g., FeS, siderite, magnetite) and microorganisms in the sediments downgradient to ISR activity can reduce dissolved U(VI) to less toxic and insoluble U(IV) and promote natural attenuation. The reduction of oxyanions of U or Se induces measurable isotopic fractionation that can be used to monitor the natural attenuation by downgradient sediments. Here, we used multiple redox-sensitive isotope systems (U, Se, and S) to detect reducing conditions and natural attenuation of U(VI) at the ISR site. We collected groundwater samples from 26 wells located in the ore body, upgradient and downgradient to the ore body. The δ238U values measured in groundwater samples from 23 wells range from 0.48‰ to -1.66‰ (×0.12‰). A preliminary investigation of 6 groundwater samples shows a variation of δ82Se values from -1.44‰ to 5.24‰ (×0.15‰). The δ34SO4 measurements in groundwater vary from 11.8‰ to -19.9‰. The reduction of Se(VI) and SO42- fractionates the lighter isotopes (i.e., 32S and 76Se) in the reduced product phase rendering the remaining reactants in the groundwater enriched in heavier isotopes. Therefore, the high δ82Se and δ34SO4 values may suggest reduction of Se(VI) and SO42-, respectively. The highest δ238U values are observed in the wells located in the ore body or upgradient to the ore body whereas the downgradient wells show significantly lower δ238U values. High δ238U values in most of the wells located in the ore-zone may be attributed to the dissolution of the U ore enriched in 238U. The low δ238U values are generally observed in the wells with low U(VI) concentrations. Since U(VI) reduction fractionates 238U to the solid U(IV) phase, the depletion of 238U in the groundwater samples in the downgradient monitoring wells suggest U(VI) reduction by the downgradient sediments. The δ238U values in the groundwater samples conform to a Rayleigh distillation model with an isotopic fractionation factor α = 1.00013 × 0.00010. Future investigations include characterization of the U ore bearing sediments collected from boreholes in the ore body and downgradient of the ore body, measurement of the δ238U and δ82Se values in the ore and in remaining groundwater samples. The U(VI) reducing capacity and concomitant U isotopic fractionation factors for the sediments from downgradient boreholes will be determined from the batch incubation experiments and flow through column experiments.

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Perspectives of UV nowcasting to monitor personal pro-health outdoor activities.

PubMed

Krzyścin, Janusz W; Lesiak, Aleksandra; Narbutt, Joanna; Sobolewski, Piotr; Guzikowski, Jakub

2018-07-01

Nowcasting model for online monitoring of personal outdoor behaviour is proposed. It is envisaged that it will provide an effective e-tool used by smartphone users. The model could estimate maximum duration of safe (without erythema risk) outdoor activity. Moreover, there are options to estimate duration of sunbathing to get adequate amount of vitamin D 3 and doses necessary for the antipsoriatic heliotherapy. The application requires information of starting time of sunbathing and the user's phototype. At the beginning the user will be informed of the approximate duration of sunbathing required to get the minimum erythemal dose, adequate amount of vitamin D 3 , and the dose necessary for the antipsoriatic heliotherapy. After every 20-min the application will recalculate the remaining duration of sunbathing based on the UVI measured in the preceding 20 min. If the estimate of remaining duration is <20 min the user will be informed that the deadline of sunbathing is approaching. Finally, a warning signal will be sent to stop sunbathing if the measured dose reaches the required dose. The proposed model is verified using the data collected at two measuring sites for the warm period of 2017 (1st April-30th September) in large Polish cities (Warsaw and Lodz). First instrument represents the UVI monitoring station. The information concerning sunbathing duration, which is sent to a remote user, is evaluated on the basis of the UVI measurements collected by the second measuring unit in a distance of ~7 km and 10 km for Warsaw and Lodz, respectively. The statistical analysis of the differences between sunbathing duration by nowcasting model and observation shows that the model provides reliable doses received by the users during outdoor activities in proximity (~10 km) to the UVI source site. Standard 24 h UVI forecast based on prognostic values of total ozone and cloudiness appears to only be valid for sunny days. Copyright © 2018 Elsevier B.V. All rights reserved.

Engineering support for an ultraviolet imager for the ISTP mission

NASA Technical Reports Server (NTRS)

Torr, Douglas G.

1991-01-01

Design and development activities were carried out for the Ultraviolet Imager (UVI) to be flown on the Polar Spacecraft of the INternational Solar Terrestrial Physics (ISTP) Mission. The following tasks were performed: (1) design and fabrication of prototype/engineering model of the UVI imager; (2) preliminary design review; (3) vacuum ultraviolet filter design; (4) auroral energy deposition code; (5) model of LBH vehicle glow; (6) laboratory measurement program of collision cross-sections; and (7) support of ISTP meetings.

Bioremediation of Uranium-Contaminated Groundwater using Engineered Injection and Extraction

NASA Astrophysics Data System (ADS)

Greene, J. A.; Neupauer, R.; Ye, M.; Kasprzyk, J. R.; Mays, D. C.; Curtis, G. P.

2017-12-01

During in-situ remediation of contaminated groundwater, a treatment chemical is injected into the contaminated groundwater to react with and degrade the contaminant, with reactions occurring where the treatment chemical contacts the contaminant. Traditional in-situ groundwater remediation relies on background groundwater flow for spreading of treatment chemicals into contaminant plumes. Engineered Injection and Extraction (EIE), in which time-varying induced flow fields are used to actively spread the treatment chemical into the contaminant plume, has been developed to increase contact between the contaminant and treatment chemical, thereby enhancing contaminant degradation. EIE has been investigated for contaminants that degrade through irreversible bimolecular reaction with a treatment chemical, but has not been investigated for a contaminant governed by reversible reactions. Uranium primarily occurs in its aqueous, mobile form, U(VI), in the environment but can be bioreduced to its sparingly soluble, immobile form, U(IV), by iron reducing bacteria stimulated by an acetate amendment. In this study, we investigate the ability of EIE to facilitate and sustain favorable conditions to immobilize uranium during remediation, and to prevent re-mobilization of uranium into the aqueous phase after active remediation has ended. Simulations in this investigation are conducted using a semi-synthetic model based on physical and chemical conditions at the Naturita Uranium Mill Tailings Remedial Action (UMTRA) site in southwestern Colorado and the Old Rifle UMTRA site in western Colorado. The EIE design is optimized for the synthetic model using the Borg multi-objective evolutionary algorithm.

Effect of temperature on the protonation of N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid in aqueous solutions: Potentiometric and calorimetric studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xingliang; Zhang, Zhicheng; Endrizzi, Francesco

2015-06-01

The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) has been demonstrated in several pilot-scale operations to be effective at separating trivalent actinides (An 3+) from trivalent lanthanides (Ln 3+). However, fundamental studies have revealed undesired aspects of TALSPEAK, such as the significant partitioning of Na +, lactic acid, and water into the organic phase, thermodynamically unpredictable pH dependence, and the slow extraction kinetics. In the modified TALSPEAK process, the combination of the aqueous holdback complexant HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid) with the extractant HEH[EHP] (2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester) in the organic phase has been found tomore » exhibit a nearly flat pH dependence between 2.5 and 4.5 and more rapid phase transfer kinetics for the heavier lanthanides. To help understand the speciation of Ln 3+ and An 3+ in the modified TALSPEAK, systematic studies are underway on the thermodynamics of major reactions in the HEDTA system under conditions relevant to the process (e.g., higher temperatures). Thermodynamics of the protonation and complexation of HEDTA with Ln 3+ were studied at variable temperatures. Equilibrium constants and enthalpies were determined by a combination of techniques including potentiometry and calorimetry. This paper presents the protonation constants of HEDTA at T = (25 to 70) °C. The potentiometric titrations have demonstrated that, stepwise, the first two protonation constants decrease and the third one slightly increases with the increase of temperature. This trend is in good agreement with the enthalpy of protonation directly determined by calorimetry. The results of NMR analysis further confirm that the first two protonation reactions occur on the diamine nitrogen atoms, while the third protonation reaction occurs on the oxygen of a carboxylate group. These data, in conjunction with the thermodynamic parameters of Ln 3+/An 3+ complexes with HEDTA at different temperatures, will help to predict the speciation and temperature-dependent behavior of Ln 3+/An 3+ in the modified TALSPEAK process.« less

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

USGS Publications Warehouse

Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

2003-01-01

In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Identifying key controls on the behavior of an acidic-U(VI) plume in the Savannah River Site using reactive transport modeling.

PubMed

Bea, Sergio A; Wainwright, Haruko; Spycher, Nicolas; Faybishenko, Boris; Hubbard, Susan S; Denham, Miles E

2013-08-01

Acidic low-level waste radioactive waste solutions were discharged to three unlined seepage basins at the F-Area of the Department of Energy (DOE) Savannah River Site (SRS), South Carolina, USA, from 1955 through 1989. Despite many years of active remediation, the groundwater remains acidic and contaminated with significant levels of U(VI) and other radionuclides. Monitored Natural Attenuation (MNA) is a desired closure strategy for the site, based on the premise that regional flow of clean background groundwater will eventually neutralize the groundwater acidity, immobilizing U(VI) through adsorption. An in situ treatment system is currently in place to accelerate this in the downgradient portion of the plume and similar measures could be taken upgradient if necessary. Understanding the long-term pH and U(VI) adsorption behavior at the site is critical to assess feasibility of MNA along with the in-situ remediation treatments. This paper presents a reactive transport (RT) model and uncertainty quantification (UQ) analyses to explore key controls on the U(VI)-plume evolution and long-term mobility at this site. Two-dimensional numerical RT simulations are run including the saturated and unsaturated (vadose) zones, U(VI) and H(+) adsorption (surface complexation) onto sediments, dissolution and precipitation of Al and Fe minerals, and key hydrodynamic processes are considered. UQ techniques are applied using a new open-source tool that is part of the developing ASCEM reactive transport modeling and analysis framework to: (1) identify the complex physical and geochemical processes that control the U(VI) plume migration in the pH range where the plume is highly mobile, (2) evaluate those physical and geochemical parameters that are most controlling, and (3) predict the future plume evolution constrained by historical, chemical and hydrological data. The RT simulation results show a good agreement with the observed historical pH and concentrations of U(VI), nitrates and Al concentrations at multiple locations. Mineral dissolution and precipitation combined with adsorption reactions on goethite and kaolinite (the main minerals present with quartz) could buffer pH at the site for long periods of time. UQ analysis using the Morris one-at-a-time (OAT) method indicates that the model/parameter is most sensitive to the pH of the waste solution, discharge rates, and the reactive surface area available for adsorption. However, as a key finding, UQ analysis also indicates that this model (and parameters) sensitivity evolves in space and time, and its understanding could be crucial to assess the temporal efficiency of a remediation strategy in contaminated sites. Results also indicate that residual U(VI) and H(+) adsorbed in the vadose zone, as well as aquifer permeability, could have a significant impact on the acidic plume long-term mobility. Copyright © 2013 Elsevier B.V. All rights reserved.

Organic and Aqueous Redox Speciation of Cu(III) Periodate Oxidized Transuranium Actinides

DOE Office of Scientific and Technical Information (OSTI.GOV)

McCann, Kevin; Sinkov, Sergey I.; Lumetta, Gregg J.

A hexavalent group actinide separation process could streamline used nuclear fuel recycle and waste management. The limiting factor to such a process compatible with current fuel dissolution practices is obtaining and maintaining hexavalent Am, in molar nitric acid due to the high reduction potential of the Am(VI)/Am(III) couple (1.68 V vs SCE). Two strong oxidants, sodium bismuthate and Cu(III) periodate, have demonstrated quantitative oxidation of Am under molar acid conditions and better than 50% recovery by diamyl amylphosphonate (DAAP) is possible under these same conditions. This work considers the use of Cu(III) periodate to oxidize Np(V) to Np(VI) and Pu(IV)more » to Pu(VI) and recover these elements by extraction with DAAP. A metal:oxidant ratio of 1:1.2 and 1:3 was necessary to quantitatively oxidize Np(V) and Pu(IV), respectively, to the hexavalent state. Extraction of hexavalent Np, Pu, and Am by 1 M DAAP in n-dodecane was measured using UV-Vis [Pu(VI), Am (VI)] and NIR [Np(VI)]. Distribution values of Am(VI) were found to match previous tracer level studies. The organic phase spectra of Np, Pu, and Am are presented and molar absorptivities are calculated for characteristic peaks. Hexavalent Pu was found to be stable in the organic phase while Np(VI) showed some reduction to Np(V) and Am was present as Am(III), Am(V), and Am(VI) species in aqueous and organic phases during the extraction experiments. These results demonstrate, for the first time, the ability to recover macroscopic amounts of americium that would be present during fuel reprocessing and are the first characterization of Am organic phase oxidation state speciation relevant to a hexavalent group actinide separation process under acidic conditions.« less

Revision of iron(III)-citrate speciation in aqueous solution. Voltammetric and spectrophotometric studies.

PubMed

Vukosav, Petra; Mlakar, Marina; Tomišić, Vladislav

2012-10-01

A detailed study of iron (III)-citrate speciation in aqueous solution (θ=25°C, I(c)=0.7 mol L(-1)) was carried out by voltammetric and UV-vis spectrophotometric measurements and the obtained data were used for reconciled characterization of iron (III)-citrate complexes. Four different redox processes were registered in the voltammograms: at 0.1 V (pH=5.5) which corresponded to the reduction of iron(III)-monocitrate species (Fe:cit=1:1), at about -0.1 V (pH=5.5) that was related to the reduction of FeL(2)(5-), FeL(2)H(4-) and FeL(2)H(2)(3-) complexes, at -0.28 V (pH=5.5) which corresponded to the reduction of polynuclear iron(III)-citrate complex(es), and at -0.4V (pH=7.5) which was probably a consequence of Fe(cit)(2)(OH)(x) species reduction. Reversible redox process at -0.1 V allowed for the determination of iron(III)-citrate species and their stability constants by analyzing E(p) vs. pH and E(p) vs. [L(4-)] dependence. The UV-vis spectra recorded at varied pH revealed four different spectrally active species: FeLH (logβ=25.69), FeL(2)H(2)(3-) (log β=48.06), FeL(2)H(4-) (log β=44.60), and FeL(2)(5-) (log β=38.85). The stability constants obtained by spectrophotometry were in agreement with those determined electrochemically. The UV-vis spectra recorded at various citrate concentrations (pH=2.0) supported the results of spectrophotometric-potentiometric titration. Copyright © 2012 Elsevier B.V. All rights reserved.

Thermodynamic and spectroscopic study of Al3+ interaction with glycine, l-cysteine and tranexamic acid in aqueous solution.

PubMed

Cardiano, Paola; Giacobello, Fausta; Giuffrè, Ottavia; Sammartano, Silvio

2017-11-01

In this paper a thermodynamic and spectroscopic study on the interaction between Al 3+ and glycine (Gly), l-cysteine (Cys), tranexamic acid (Tranex) is reported. Speciation models have been obtained by processing potentiometric titration data to determine stability constants of the species formed in aqueous solution at T=298.15K, 0.15≤I/molL -1 ≤1 in NaCl. Thermodynamic formation parameters have been obtained from calorimetric titration data, at T=298.15K, I=0.15molL -1 using NaCl as ionic medium. Al 3+ -Cys system was also investigated by spectrophotometric and 1 H NMR measurements. 1 H NMR experiments were performed on Al 3+ -Tranex system as well. Different speciation models have been observed for the three systems. The results showed the formation of MLH, ML and M 2 L 2 (OH) 2 species for Gly, ML, M 2 L and MLOH for Cys, MLH and MLOH for Tranex. The formed species are quite stable, i.e. for ML, logβ=7.18, 11.91 for Gly and Cys, respectively, at I=0.15molL -1 and T=298.15K. For all the systems the dependence of formation constants on ionic strength over the range 0.1-1molL -1 is reported. The sequestering ability of the ligands under study was also evaluated by pL 0.5 empiric parameter. For Gly, Cys and Tranex, pL 0.5 =2.51, 3.74, 3.91 respectively, at pH=5, I=0.15molL -1 and T=298.15K. Copyright © 2017 Elsevier B.V. All rights reserved.

Arsenite and ferrous iron oxidation linked to chemolithotrophic denitrification for the immobilization of arsenic in anoxic environments

USGS Publications Warehouse

Sun, W.; Sierra-Alvarez, R.; Milner, L.; Oremland, R.; Field, J.A.

2009-01-01

The objective of this study was to explore a bioremediation strategy based on injecting NO3- to support the anoxic oxidation of ferrous iron (Fe(II)) and arsenite (As(III)) in the subsurface as a means to immobilize As in the form of arsenate (As(V)) adsorbed onto biogenic ferric (Fe(III)) (hydr)oxides. Continuous flows and filled columns were used to simulate a natural anaerobic groundwater and sediment system with co-occurring As(III) and Fe(II) in the presence (column SF1) or absence (column SF2) of nitrate, respectively. During operation for 250 days, the average influent arsenic concentration of 567 ??g L-1 was reduced to 10.6 (??9.6) ??g L-1 in the effluent of column SF1. The cumulative removal of Fe(II) and As(III) in SF1 was 6.5 to 10-fold higher than that in SF2. Extraction and measurement of the mass of iron and arsenic immobilized on the sand packing of the columns were close to the iron and arsenic removed from the aqueous phase during column operation. The dominant speciation of the immobilized iron and arsenic was Fe(III) and As(V) in SF1, compared with Fe(II) and As(III) in SF2. The speciation was confirmed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicate that microbial oxidation of As(III) and Fe(II) linked to denitrification resulted in the enhanced immobilization of aqueous arsenic in anaerobic environments by forming Fe(III) (hydr)oxide coated sands with adsorbed As(V). ?? 2009 American Chemical Society.

Biogeochemical modeling of CO 2 and CH 4 production in anoxic Arctic soil microcosms

DOE PAGES

Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; ...

2016-09-12

Soil organic carbon turnover to CO 2 and CH 4 is sensitive to soil redox potential and pH conditions. But, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximatelymore » describe the observed pH evolution without additional parameterization. Though Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. Furthermore, the equilibrium speciation predicts a substantial increase in CO 2 solubility as pH increases, and taking into account CO 2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO 2 production from closed microcosms can be substantially underestimated based on headspace CO 2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

Mercury methylation dynamics in estuarine and coastal marine environments — A critical review

NASA Astrophysics Data System (ADS)

Merritt, Karen A.; Amirbahman, Aria

2009-09-01

Considerable recent research has focused on methylmercury (MeHg) cycling within estuarine and coastal marine environments. Because MeHg represents a potent neurotoxin that may magnify in marine foodwebs, it is important to understand the mechanisms and environmental variables that drive or constrain methylation dynamics in these environments. This critical review article explores the mechanisms hypothesized to influence aqueous phase and sediment solid phase MeHg concentrations and depth-specific inorganic Hg (II) (Hg i) methylation rates (MMR) within estuarine and coastal marine environments, and discusses issues of terminology or methodology that complicate mechanism-oriented interpretation of field and laboratory data. Mechanisms discussed in this review article include: 1) the metabolic activity of sulfate reducing bacteria (SRB), the microbial group thought to dominate mercury methylation in these environments; 2) the role that Hg i concentration and/or speciation play in defining depth-specific Hg i methylation rates; and 3) the depth-dependent balance between MeHg production and consumption within the sedimentary environment. As discussed in this critical review article, the hypothesis of SRB community control on the Hg i methylation rate in estuarine and coastal marine environments is broadly supported by the literature. Although Hg i speciation, as a function of porewater inorganic sulfide and/or dissolved organic matter concentration and/or pH, may also play a role in observed variations in MMR, the nature and function of the controlling ligand(s) has not yet been adequately defined. Furthermore, although it is generally recognized that the processes responsible for MeHg production and consumption overlap spatially and/or kinetically in the sedimentary environment, and likely dictate the extent to which MeHg accumulates in the aqueous and/or sediment solid phase, this conceptual interpretation requires refinement, and would benefit greatly from the application of kinetic modeling.

Base-catalyzed hydrolysis and speciation-dependent photolysis of two cephalosporin antibiotics, ceftiofur and cefapirin.

PubMed

Ribeiro, Alyson R; Lutze, Holger V; Schmidt, Torsten C

2018-05-01

Lately, special attention has been given to veterinary cephalosporin antibiotics due to their broad activity spectrum and significant consumption. Indeed, the determination of hydrolytic and photolytic kinetics provides a better comprehension of the undesired persistence of cephalosporins in aqueous matrices. In this work, the two widely used veterinary antibiotics ceftiofur (CEF) and cefapirin (CEPA) showed high instability under alkaline conditions, degrading in few minutes at pH > 11. In buffered solutions at neutral pH and natural temperature (T = 22 ± 1 °C), both drugs presented moderate stability (t½ = 3 d, CEPA and 1.4 d, CEF). Our study also demonstrated that CEPA and CEF speciation did not significantly influence the direct photolysis rates. Using a simulated water disinfection set-up (λ = 254 nm), all ionic species of CEF and CEPA presented fast and similar pseudo-first order degradation rates, k app 0.0095 ± 0.0004 and 0.0092 ± 0.001 cm 2 mJ -1 , respectively. Furthermore, using surface water in hydrolysis experiments, CEF demonstrated significant matrix-dependent stability with a half-life (t½ = 14.7 d) tenfold higher than in buffered solutions. In contrast, CEPA presented a very similar hydrolysis rate in river water (t½ = 4.2 d) and a subtle faster photo-degradation rate in this same matrix (k app 0.0128 ± 0.001 cm 2 mJ -1 ), highlighting the importance of disinfection radiation for cephalosporin depletion in aqueous environments. Copyright © 2017 Elsevier Ltd. All rights reserved.

Microbial mobilization of plutonium and other actinides from contaminated soil

DOE PAGES

Francis, A. J.; Dodge, C. J.

2015-12-01

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Microbial mobilization of plutonium and other actinides from contaminated soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Francis, A. J.; Dodge, C. J.

Here we examined the dissolution of Pu, U, and Am in contaminated soil from the Nevada Test Site (NTS) due to indigenous microbial activity. Scanning transmission x-ray microscopy (STXM) analysis of the soil showed that Pu was present in its polymeric form and associated with Fe- and Mn- oxides and aluminosilicates. Uranium analysis by x-ray diffraction (μ-XRD) revealed discrete U-containing mineral phases, viz., schoepite, sharpite, and liebigite; synchrotron x-ray fluorescence (μ-XRF) mapping showed its association with Fe- and Ca-phases; and μ-x-ray absorption near edge structure (μ-XANES) confirmed U(IV) and U(VI) oxidation states. Addition of citric acid or glucose to themore » soil and incubated under aerobic or anaerobic conditions enhanced indigenous microbial activity and the dissolution of Pu. Detectable amount of Am and no U was observed in solution. In the citric acid-amended sample, Pu concentration increased with time and decreased to below detection levels when the citric acid was completely consumed. In contrast, with glucose amendment, Pu remained in solution. Pu speciation studies suggest that it exists in mixed oxidation states (III/IV) in a polymeric form as colloids. Although Pu(IV) is the most prevalent and generally considered to be more stable chemical form in the environment, our findings suggest that under the appropriate conditions, microbial activity could affect its solubility and long-term stability in contaminated environments.« less

Fabrication of hierarchical core-shell polydopamine@MgAl-LDHs composites for the efficient enrichment of radionuclides

NASA Astrophysics Data System (ADS)

Zhu, Kairuo; Lu, Songhua; Gao, Yang; Zhang, Rui; Tan, Xiaoli; Chen, Changlun

2017-02-01

Novel hierarchical core/shell structured polydopamine@MgAl-layered double hydroxides (PDA@MgAl-LDHs) composites involving MgAl-layered double hydroxide shells and PDA cores were fabricated thought one-pot coprecipitation assembly and methodically characterized by X-ray diffraction, Fourier transformed infrared spectroscopy, scanning/transmission electron microscopy, selected area electron diffraction, elemental mapping, thermogravimetric analysis and X-ray photoelectron spectroscopy technologies. U(VI) and Eu(III) sorption experiments showed that the PDA@MgAl-LDHs exhibited higher sorption ability with a maximum sorption capacity of 142.86 and 76.02 mg/g at 298 K and pH 4.5, respectively. More importantly, according to XPS analyses, U(VI) and Eu(III) were sorbed on PDA@MgAl-LDHs via oxygen-containing functional groups, and the chemical affinity of U(VI) by oxygen-containing functional groups is higher than that of Eu(III). These observations show great expectations in the enrichment of radionuclides from aquatic environments by PDA@MgAl-LDHs.

Martian atmospheric O3 retrieval development for the NOMAD-UVIS spectrometer

NASA Astrophysics Data System (ADS)

Hewson, W.; Mason, J. P.; Leese, M.; Hathi, B.; Holmes, J.; Lewis, S. R.; Iriwin, P. G. J.; Patel, M. R.

2017-09-01

The composition of atmospheric trace gases and aerosols is a highly variable and poorly constrained component of the martian atmosphere, and by affecting martian climate and UV surface dose, represents a key parameter in the assessment of suitability for martian habitability. The ExoMars Trace Gas Orbiter (TGO) carries the Open University (OU) designed Ultraviolet and VIsible Spectrometer (UVIS) instrument as part of the Belgian-led Nadir and Occultation for MArs Discovery (NOMAD) spectrometer suite. NOMAD will begin transmitting science observations of martian surface and atmosphere back-scattered UltraViolet (UV) and visible radiation in Spring 2018, which will be processed to derive spatially and temporally averaged atmospheric trace gas and aerosol concentrations, intended to provide a better understanding of martian atmospheric photo-chemistry and dynamics, and will also improve models of martian atmospheric chemistry, climate and habitability. Work presented here illustrates initial development and testing of the OU's new retrieval algorithm for determining O3 and aerosol concentrations from the UVIS instrument.

Incorporation of Uranium into Hematite during Crystallization from Ferrihydrite

PubMed Central

2014-01-01

Ferrihydrite was exposed to U(VI)-containing cement leachate (pH 10.5) and aged to induce crystallization of hematite. A combination of chemical extractions, TEM, and XAS techniques provided the first evidence that adsorbed U(VI) (≈3000 ppm) was incorporated into hematite during ferrihydrite aggregation and the early stages of crystallization, with continued uptake occurring during hematite ripening. Analysis of EXAFS and XANES data indicated that the U(VI) was incorporated into a distorted, octahedrally coordinated site replacing Fe(III). Fitting of the EXAFS showed the uranyl bonds lengthened from 1.81 to 1.87 Å, in contrast to previous studies that have suggested that the uranyl bond is lost altogether upon incorporation into hematite. The results of this study both provide a new mechanistic understanding of uranium incorporation into hematite and define the nature of the bonding environment of uranium within the mineral structure. Immobilization of U(VI) by incorporation into hematite has clear and important implications for limiting uranium migration in natural and engineered environments. PMID:24580024

Ultraviolet Views of Enceladus, Tethys, and Dione

NASA Technical Reports Server (NTRS)

Hansen, C. J.; Hendrix, A. R.

2005-01-01

The Cassini Ultraviolet Imaging Spectrograph (UVIS) has collected ultraviolet observations of many of Saturn's icy moons since Cassini's insertion into orbit around Saturn. We will report on results from Enceladus, Tethys and Dione, orbiting in the Saturn system at distances of 3.95, 4.88 and 6.26 Saturn radii, respectively. Icy satellite science objectives of the UVIS include investigations of surface age and evolution, surface composition and chemistry, and tenuous exospheres. We address these objectives by producing albedo maps, and reflection and emission spectra, and observing stellar occultations. UVIS has four channels: EUV: Extreme Ultraviolet (55 nm to 110 nm), FUV: Far Ultraviolet (110 to 190 nm), HSP: High Speed Photometer, and HDAC: Hydrogen-Deuterium Absorption Cell. The EUV and FUV spectrographs image onto a 2-dimensional detector, with 64 spatial rows by 1024 spectral columns. To-date we have focused primarily on the far ultraviolet data acquired with the low resolution slit width (4.8 angstrom spectral resolution). Additional information is included in the original extended abstract.

Hydrothermal synthesis of (C6N2H14)2(UVI2UIVO4F12), a mixed-valent one-dimensional uranium oxyfluoride.

PubMed

Allen, S; Barlow, S; Halasyamani, P S; Mosselmans, J F; O'Hare, D; Walker, S M; Walton, R I

2000-08-21

A new hybrid organic-inorganic mixed-valent uranium oxyfluoride, (C6N2H14)2(U3O4F12), UFO-17, has been synthesized under hydrothermal conditions using uranium dioxide as the uranium source, hydrofluoric acid as mineralizer, and 1,4-diazabicyclo[2.2.2]octane as template. The single-crystal X-ray structure was determined. Crystals of UFO-17 belonged to the orthorhombic space group Cmcm (no. 63), with a = 14.2660(15) A, b = 24.5130(10) A, c = 7.201(2) A, and Z = 4. The structure reveals parallel uranium-containing chains of two types: one type is composed of edge-sharing UO2F5 units; the other has a backbone of edge-sharing UF8 units, each sharing an edge with a pendant UO2F5 unit. Bond-valence calculations suggest the UF8 groups contain UIV, while the UO2F5 groups contain UVI. EXAFS data give results consistent with the single-crystal X-ray structure determination, while comparison of the uranium LIII-edge XANES of UFO-17 with that of related UIV and UVI compounds supports the oxidation-state assignment. Variable-temperature magnetic susceptibility measurements on UFO-17 and a range of related hybrid organic-inorganic uranium(IV) and uranium(VI) fluorides and oxyfluorides further support the formulation of UFO-17 as a mixed-valent UIV/UVI compound.

Uranium(VI) Scavenging by Amorphous Iron Phosphate Encrusting Sphaerotilus natans Filaments.

PubMed

Seder-Colomina, Marina; Morin, Guillaume; Brest, Jessica; Ona-Nguema, Georges; Gordien, Nilka; Pernelle, Jean-Jacques; Banerjee, Dipanjan; Mathon, Olivier; Esposito, Giovanni; van Hullebusch, Eric D

2015-12-15

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.

Model-based Analysis of Mixed Uranium(VI) Reduction by Biotic and Abiotic Pathways During in Situ Bioremediation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Jiao; Scheibe, Timothy D.; Mahadevan, Radhakrishnan

2013-10-24

Uranium bioremediation has emerged as a potential strategy of cleanup of radionuclear contamination worldwide. An integrated geochemical & microbial community model is a promising approach to predict and provide insights into the bioremediation of a complicated natural subsurface. In this study, an integrated column-scale model of uranium bioremediation was developed, taking into account long-term interactions between biotic and abiotic processes. It is also combined with a comprehensive thermodynamic analysis to track the fate and cycling of biogenic species. As compared with other bioremediation models, the model increases the resolution of the connection of microbial community to geochemistry and establishes directmore » quantitative correlation between overall community evolution and geochemical variation, thereby accurately predicting the community dynamics under different sedimentary conditions. The thermodynamic analysis examined a recently identified homogeneous reduction of U(VI) by Fe(II) under dynamic sedimentary conditions across time and space. It shows that the biogenic Fe(II) from Geobacter metabolism can be removed rapidly by the biogenic sulphide from sulfate reducer metabolism, hence constituting one of the reasons that make the abiotic U(VI) reduction thermodynamically infeasible in the subsurface. Further analysis indicates that much higher influent concentrations of both Fe(II) and U(VI) than normal are required to for abiotic U(VI) reduction to be thermodynamically feasible, suggesting that the abiotic reduction cannot be an alternative to the biotic reduction in the remediation of uranium contaminated groundwater.« less

Modeling the effectiveness of U(VI) biomineralization in dual-porosity porous media

NASA Astrophysics Data System (ADS)

Rotter, B. E.; Barry, D. A.; Gerhard, J. I.; Small, J. S.

2011-05-01

SummaryUranium contamination is a serious environmental concern worldwide. Recent attention has focused on the in situ immobilization of uranium by stimulation of dissimilatory metal-reducing bacteria (DMRB). The objective of this work was to investigate the effectiveness of this approach in heterogeneous and structured porous media, since such media may significantly affect the geochemical and microbial processes taking place in contaminated sites, impacting remediation efficiency during biostimulation. A biogeochemical reactive transport model was developed for uranium remediation by immobile-region-resident DMRB in two-region porous media. Simulations were used to investigate the parameter sensitivities of the system over wide-ranging geochemical, microbial and groundwater transport conditions. The results suggest that optimal biomineralization is generally likely to occur when the regional mass transfer timescale is less than one-thirtieth the value of the volumetric flux timescale, and/or the organic carbon fermentation timescale is less than one-thirtieth the value of the advective timescale, and/or the mobile region porosity ranges between equal to and four times the immobile region porosity. Simulations including U(VI) surface complexation to Fe oxides additionally suggest that, while systems exhibiting U(VI) surface complexation may be successfully remediated, they are likely to display different degrees of remediation efficiency over varying microbial efficiency, mobile-immobile mass transfer, and porosity ratios. Such information may aid experimental and field designs, allowing for optimized remediation in dual-porosity (two-region) biostimulated DMRB U(VI) remediation schemes.

Development of a mercury speciation, fate, and biotic uptake (BIOTRANSPEC) model: Application to Lahontan Reservoir (Nevada, USA)

USGS Publications Warehouse

Gandhi, N.; Bhavsar, S.P.; Diamond, M.L.; Kuwabara, J.S.; Marvin-DiPasquale, M.; Krabbenhoft, D.P.

2007-01-01

A mathematically linked mercury transport, speciation, kinetic, and simple biotic uptake (BIOTRANSPEC) model has been developed. An extension of the metal transport and speciation (TRANSPEC) model, BIOTRANSPEC estimates the fate and biotic uptake of inorganic (Hg(II)), elemental (Hg(0)) and organic (MeHg) forms of mercury and their species in the dissolved, colloidal (e.g., dissolved organic matter [DOM]), and particulate phases of surface aquatic systems. A pseudo-steady state version of the model was used to describe mercury dynamics in Lahontan Reservoir (near Carson City, NV, USA), where internal loading of the historically deposited mercury is remobilized, thereby maintaining elevated water concentrations. The Carson River is the main source of total mercury (THg), of which more than 90% is tightly bound in a gold-silver-mercury amalgam, to the system through loadings in the spring, with negligible input from the atmospheric deposition. The speciation results suggest that aqueous species are dominated by Hg-DOM, Hg(OH)2, and HgClOH. Sediment-to-water diffusion of MeHg and Hg-DOM accounts for approximately 10% of total loadings to the water column. The water column acts as a net sink for MeHg by reducing its levels through two competitive processes: Uptake by fish, and net MeHg demethylation. Although reservoir sediments produce significant amounts of MeHg (4 g/d), its transport from sediment to water is limited (1.6 g/d), possibly because of its adsorption on metal oxides of iron and manganese at the sediment-water interface. Fish accumulate approximately 45% of the total MeHg mass in the water column, and 9% of total MeHg uptake by fish leaves the system because of fishing. Results from this new model reiterate the previous conclusion that more than 90% of THg input is retained in sediment, which perpetuates elevated water concentrations. ?? 2007 SETAC.

Micronutrient metal speciation is controlled by competitive organic chelation in grassland soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boiteau, Rene M.; Shaw, Jared B.; Pasa-Tolic, Ljiljana

Many elements are scarcely soluble in aqueous conditions found in high pH environments, such as calcareous grassland soils, unless complexed to strong binding organic ligands. To overcome this limitation, some plants and microbes produce chelators that solubilize micronutrient metals such as Fe, Ni, Cu, and Zn from mineral phases. These complexes are taken up by organisms via specific membrane receptors, thereby differentially impacting the bioavailability of these metals to the plant and microbial community. Although the importance of these chelation strategies for individual organisms has been well established, little is known about which pathways coexist within rhizosphere microbiomes or howmore » they interact and compete for metal binding. Identifying these metallo-organic species within natural ecosystems has remained a formidable analytical challenge due to the vast diversity of compounds and poorly defined metabolic processes in complex soil matrix. Herein, we employed recently developed liquid chromatography (LC) mass spectrometry (MS) methods to characterize the speciation of water-soluble dissolved trace elements (Fe, Ni, Cu, and Zn) from Kansas Prairie soil. Both plant and fungal chelators were identified, revealing compound-specific patterns of chelation to biologically essential metals. Numerous metabolites typically implicated in plant iron acquisition and homeostasis, including mugineic acids, deoxymugineic acid, nicotianamine, and hydroxynicotianamine, dominated the speciation of divalent metals such as Ni, Cu, and Zn (2-57 pmol / g soil). In contrast, the fungal siderophore ferricrocine bound comparatively more trivalent Fe (9pmol / g soil). These results define biochemical pathways that underpin the regulation of metals in the grassland rhizosphere. They also raise new questions about the competition of these compounds for metal binding and their bioavailability to different members of the rhizosphere population. Even small structural differences result in significant differences in their environmental metal speciation, and likely impact metal uptake within the rhizosphere of calcareous soils.« less

Miscibility and Speciation in the Water/carbon Dioxide System

NASA Astrophysics Data System (ADS)

Abramson, E.; Bollengier, O.; Brown, J. M.

2017-12-01

We have been exploring fluid-fluid solubilities and speciation in mixed systems of CO2-H2O. Fluid-fluid immiscibility extends to the highest pressures and temperatures yet explored (7 GPa, 700K). In this region, commonly used COH fluid models agree neither with the data nor among themselves. The range of immiscibility is extended by addition of NaCl, but miscibility limits determined in preliminary experiments are not as expected from extrapolation of lower pressure (<0.2 GPa) results. For majority-water systems (XCO2<0.5) an abrupt increase of solubility with pressure is linked to an observed change in speciation as CO2(aq) reacts with water. The identity of the newly formed species is, as of the writing of this abstract, unknown, but presumed to be either H2CO3 or HCO3-. A reasonable match between the observed equilibria and an application of HKF theory suggests that the new species is, indeed, HCO3-, but with a Raman frequency shifted from that found in the dilute aqueous solution. Application of HKF theory to the CO2(f)-CO2(aq) equilibrium suffers from an incompatibility of the usual formulation of the theory with known molar volumes of CO2(f) at higher pressures. On the basis of these studies we conclude that models of CO2-H2O fluids must take into account major changes in speciation, and that simple equations-of-state, of a few fitted parameters, will not afford an adequate description of such fluids. "First principles" models, tested against real data, seem more likely to yield the desired results. This statement extends as well to the calculation of the dielectric constants of these mixed fluids, the basis of ionic solution chemistry. Further, semi-empirical formulations of solution thermodynamics, which function well at pressures of kbars, ought to be re-worked for use over larger pressure ranges.

Chromium speciation in environmental samples using a solid phase spectrophotometric method.

PubMed

Amin, Alaa S; Kassem, Mohammed A

2012-10-01

A solid phase extraction technique is proposed for preconcentration and speciation of chromium in natural waters using spectrophotometric analysis. The procedure is based on sorption of chromium(III) as 4-(2-benzothiazolylazo)2,2'-biphenyldiol complex on dextran-type anion-exchange gel (Sephadex DEAE A-25). After reduction of Cr(VI) by 0.5 ml of 96% concentrated H(2)SO(4) and ethanol, the system was applied to the total chromium. The concentration of Cr(VI) was calculated as the difference between the total Cr and the Cr(III) content. The influences of some analytical parameters such as: pH of the aqueous solution, amounts of 4-(2-benzothiazolylazo)2,2'-biphenyldiol (BTABD), and sample volumes were investigated. The absorbance of the gel, at 628 and 750 nm, packed in a 1.0 mm cell, is measured directly. The molar absorptivities were found to be 2.11×10(7) and 3.90×10(7) L mol(-1)cm(-1) for 500 and 1000 ml, respectively. Calibration is linear over the range 0.05-1.45 μg L(-1) with RSD of <1.85% (n=8.0). Using 35 mg exchanger, the detection and quantification limits were 13 and 44 ng L(-1) for 500 ml sample, whereas for 1000 ml sample were 8.0 and 27 ng L(-1), respectively. Increasing the sample volume can enhance the sensitivity. No considerable interferences have been observed from other investigated anions and cations on the chromium speciation. The proposed method was applied to the speciation of chromium in natural waters and total chromium preconcentration in microwave digested tobacco, coffee, tea, and soil samples. The results were simultaneously compared with those obtained using an ET AAS method, whereby the validity of the method has been tested. Copyright © 2012 Elsevier B.V. All rights reserved.

The variations of aluminium species in mountainous forest soils and its implications to soil acidification.

PubMed

Bradová, Monika; Tejnecký, Václav; Borůvka, Luboš; Němeček, Karel; Ash, Christopher; Šebek, Ondřej; Svoboda, Miroslav; Zenáhlíková, Jitka; Drábek, Ondřej

2015-11-01

Aluminium (Al) speciation is a characteristic that can be used as a tool for describing the soil acidification process. The question that was answered is how tree species (beech vs spruce) and type of soil horizon affect Al speciation. Our hypotesis is that spruce and beech forest vegetation are able to modify the chemical characteristics of organic horizon, hence the content of Al species. Moreover, these characteristics are seasonally dependent. To answer these questions, a detailed chromatographic speciation of Al in forest soils under contrasting tree species was performed. The Jizera Mountains area (Czech Republic) was chosen as a representative mountainous soil ecosystem. A basic forestry survey was performed on the investigated area. Soil and precipitation samples (throughfall, stemflow) were collected under both beech and spruce stands at monthly intervals from April to November during the years 2008-2011. Total aluminium content and Al speciation, pH, and dissolved organic carbon were determined in aqueous soil extracts and in precipitation samples. We found that the most important factors affecting the chemistry of soils, hence content of the Al species, are soil horizons and vegetation cover. pH strongly affects the amount of Al species under both forests. Fermentation (F) and humified (H) organic horizons contain a higher content of water extractable Al and Al(3+) compared to organo-mineral (A) and mineral horizons (B). With increasing soil profile depth, the amount of water extractable Al, Al(3+) and moisture decreases. The prevailing water-extractable species of Al in all studied soils and profiles under both spruce and beech forests were organically bound monovalent Al species. Distinct seasonal variations in organic and mineral soil horizons were found under both spruce and beech forests. Maximum concentrations of water-extractable Al and Al(3+) were determined in the summer, and the lowest in spring.

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

NASA Astrophysics Data System (ADS)

Pokrovsky, Oleg S.; Schott, Jacques

2004-01-01

Dissolution and precipitation rates of brucite (Mg(OH) 2) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10 -4 to 3 M), saturation index (-12 < log Ω < 0.4) and aqueous magnesium concentrations (10 -6 to 5·10 -4 M). Brucite surface charge and isoelectric point (pH IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m 2) and lack of dependence on ionic strength predicts the dominance of >MgOH 2+ species at pH < 8 and their progressive replacement by >MgOH° and >MgO - as pH increases to 10-12. Rates are proportional to the square of >MgOH 2+ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH 2+ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity: R=k Mg+ · {>MgOH 2+} 2 · (1-Ω 2) where kMg+ is the dissolution rate constant, {> i} is surface species concentration (mol/m 2), and Ω is the solution saturation index with respect to brucite. Measurements of nonsteady state brucite dissolution rates, in response to cycling the pH from 12 to 2 (pH-jump experiments), indicate the important role of surface hydroxylation — that leads to the formation of Mg oxo or -hydroxo complexes — in the formation of dissolution-active sites. Replacement of water molecules by these oxygen donor complexes in the Mg coordination sphere has a labilizing effect on the dynamics of the remaining water molecules and thus increases reaction rates.

Actinide geochemistry: from the molecular level to the real system.

PubMed

Geckeis, Horst; Rabung, Thomas

2008-12-12

Geochemical processes leading to either mobilization or retention of radionuclides in an aquifer system are significantly influenced by their interaction with rock, sediment and colloid surfaces. Therefore, a sound safety assessment of nuclear waste disposal requires the elucidation and quantification of those processes. State-of-the-art analytical techniques as e.g. laser- and X-ray spectroscopy are increasingly applied to study solid-liquid interface reactions to obtain molecular level speciation insight. We have studied the sorption of trivalent lanthanides and actinides onto aluminium oxides, hydroxides and purified clay minerals by the time-resolved laser fluorescence spectroscopy and X-ray-absorption spectroscopy. Chemical constitution and structure of surface bound actinides are proposed based on spectroscopic information. Open questions still remain with regard to the exact nature of mineral surface ligands and the mineral/water interface. Similarities of spectroscopic data obtained for M(III) sorbed onto gamma-alumina, and clay minerals suggest the formation of very comparable inner-sphere surface complexes such as S-O-An(III)(OH)x(2-x)(H2O)5-x at pH > 5. Those speciation data are found consistent with those predicted by surface complexation modelling. The applicability of data obtained for pure mineral phases to actinide sorption onto heterogeneously composed natural clay rock is examined by experiments and by geochemical modelling. Good agreement of experiment and model calculations is found for U(VI) and trivalent actinide/lanthanide sorption to natural clay rock. The agreement of spectroscopy, geochemical modelling and batch experiments with natural rock samples and purified minerals increases the reliability in model predictions. The assessment of colloid borne actinide migration observed in various laboratory and field studies calls for detailed information on actinide-colloid interaction. Kinetic stabilization of colloid bound actinides can be due to inclusion into inorganic colloid matrix or by macromolecular rearrangement in case of organic, humic/fulvic like colloids. Only a combination of spectroscopy, microscopy and classical batch sorption experiments can help to elucidate the actinide-colloid interaction mechanisms and thus contribute to the assessment of colloids for radionuclide migration.