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Redox-reactive, biogeochemical phases generated by reductive microbial activity in hyporheic zone sediments from a dynamic groundwater–river interaction zone were evaluated for their ability to reduce soluble pertechnetate [ 99 Tc(VII)O 4 − ] to less soluble Tc(IV). The sediments were bioreduced by indigenous microorganisms that were stimulated by organic substrate addition in synthetic groundwater with or without sulfate. In most treatments, 20 μmol L −1 initial aqueous Tc(VII) was reduced to near or below detection (3.82 × 10 −9 mol L −1 ) over periods of days to months in suspensions of variable solids concentrations. Native sediments containing significant lithogenic Fe(II) in various phases were, in contrast, unreactive with Tc(VII). The reduction rates in the bioreduced sediments increased with increases in sediment mass, in proportion to weak acid-extractable Fe(II) and sediment-associated sulfide (AVS). The rate of Tc(VII) reduction was first order with respect to both aqueous Tc(VII) concentration and sediment mass, but correlations between specific reductant concentrations and reaction rate were not found. X-ray microprobe measurements revealed a strong correlation between Tc hot spots and Fe-containing mineral particles in the sediment. However, only a portion of Fe-containing particles were Tc-hosts. The Tc-hot spots displayed a chemical signature (by EDXRF) similar to pyroxene. The application of autoradiography and electron microprobe allowed further isolation of Tc-containing particles that were invariably found to be ca 100 μm aggregates of primary mineral material embedded within a fine-grained phyllosilicate matrix. EXAFS spectroscopy revealed that the Tc(IV) within these were a combination of a Tc(IV)O 2 -like phase and Tc(IV)–Fe surface clusters, with a significant fraction of a TcS x -like phase in sediments incubated with SO 4 2− . AVS was implicated as a more selective reductant at low solids concentration even though its concentration was below that required for stoichiometric reduction of Tc(VII). These results demonstrate that composite mineral aggregates may be redox reaction centers in coarse-textured hyporheic zone sediments regardless of the dominant anoxic biogeochemical processes.

Technetium is an important environmental contaminant introduced by the processing and disposal of irradiated nuclear fuel and atmospheric nuclear tests. Under oxic conditions technetium is soluble and exists as pertechnatate anion (TcO4−), while under anoxic conditions Tc is usually insoluble and exists as precipitated Tc(IV). Here we investigated abiotic Tc(VII) reduction in mineralogically heterogeneous, Fe(II)-containing sediments. The sediments were collected from a 55 m borehole that sampled a semi-confined aquifer at the Hanford Site, USA that contained a dramatic redox transition zone. One oxic facies (18.0–18.3 m) and five anoxic facies (18.3–18.6 m, 30.8–31.1 m, 39.0–39.3 m, 47.2–47.5 m and 51.5–51.8 m) were selected for this study. Chemical extractions, X-ray diffraction, electron microscopy, and Mossbauer spectroscopy were applied to characterize the Fe(II) mineral suite that included Fe(II)-phyllosilicates, pyrite, magnetite and siderite. The Fe(II) mineral phase distribution differed between the sediments. Sediment suspensions were adjusted to the same 0.5 M HCl extractable Fe(II) concentration (0.6 mM) for Tc(VII) reduction experiments. Total aqueous Fe was below the Feaq detection limit (

Bioreduced anthraquinone-2,6-disulfonate (AH2DS; dihydro-anthraquinone) was reacted with a 2-line, Si-substituted ferrihydrite under anoxic conditions at neutral pH in PIPES buffer. Phosphate (P) and bicarbonate (C); common adsorptive oxyanions and media/buffer components known to effect ferrihydrite mineralization; and Fe(II)aq (as a catalytic mineralization agent) were used in comparative experiments. Heterogeneous AH2DS oxidation coupled with Fe(III) reduction occurred within 0.13–1 day, with mineralogic transformation occurring thereafter. The product suite included lepidocrocite, goethite, and/or magnetite, with proportions varing with reductant:oxidant ratio (r:o) and the presence of P or C. Lepidocrocite was the primary product at low r:o in the absence of P or C, with evidence for multiple formation pathways. Phosphate inhibited reductive recrystallization, while C promoted goethite formation. Stoichiometric magnetite was the sole product at higher r:o in the absence and presence of P. Lepidocrocite was the primary mineralization product in the Fe(II)aq system, with magnetite observed at near equal amounts when Fe(II) was high [Fe(II)/Fe(III)] = 0.5 and P was absent. P had a greater effect on reductive mineralization in the Fe(II)aq system, while AQDS was more effective than Fe(II)aq in promoting magnetite formation. The mineral products of the direct AH2DS-driven reductive reaction are different from those observed in AH2DS-ferrihydite systems with metal reducing bacteria, particularly in presence of P.

The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized Kd values were measured at U(VI) concentrations of 5 × 10−7 and 5 × 10−6 mol L−1 that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > quartz ≈ Michigan chlorite > illite > montmorillonite. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparison with literature data suggested that U(VI) exist primarily as inner-sphere complexes with surface silanol groups on quartz and as surface U(VI) tricarbonate complexes on phyllosilicates.

Contaminated capillary fringe sediments are believed to function as long-term source of U(VI) to Hanford’s 300 Area groundwater uranium plume that discharges to the Columbia River. The deep vadose zone at this site experiences seasonal water table elevation and water compositional changes in response to Columbia River stage. Batch and column desorption experiments of U(VI) were performed on two mildly contaminated sediments from this system that vary in hydrologic position to ascertain their U(VI) release behavior and factors controlling it. Solid phase characterization of the sediments was performed to identify mineralogic and chemical factors controlling U(VI) desorption. Low adsorbed U(VI) concentrations prevented spectroscopic analysis. The desorption behavior of U(VI) was different for the two sediments in spite of similar chemical and textural characteristics, and non-carbonate mineralogy. Adsorption strength and sorbed U(VI) lability was higher in the near-river sediment. The inland sediment displayed low sorbed U(VI) lability (∼10%) and measurable solid-phase carbonate content. Kinetic desorption was observed that was attributed to regeneration of labile U(VI) in the near river sediment, and carbonate mineral dissolution in the inland sediment. The desorption reaction was best described as an equilibrium surface complexation reaction. The noted differences in desorption behavior appear to result from U(VI) contamination and hydrologic history, as well as sediment carbonate content. Insights are provided on the dynamic adsorption/desorption behavior of contaminants in linked groundwater–river systems.

Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite–citrate–bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of Fe 2 + (aq) adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added Fe 2 + (aq) that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) ∼ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ≪ structural Fe(II) in phyllosilicates ≪ Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO2 monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mossbauer spectroscopy applied to an experiment with 56Fe-goethite with adsorbed 57Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxide-adsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.

The subsurface behaviour of 99Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)(aq) in pH 6–8 solutions was investigated under strictly anoxic conditions using an oxygen trap (

Uranyl silicates such as uranophane and Na-boltwoodite appear to control the solubility of uranium in certain contaminated sediments at the US Department of Energy Hanford site [Liu, C., Zachara, J.M., Qafoku, O., McKinley, J.P., Heald, S.M., Wang, Z. 2004. Dissolution of uranyl microprecipitates in subsurface sediments at Hanford Site, USA. Geochim. Cosmochim. Acta 68, 4519–4537.]. Consequently, the solubility of synthetic Na-boltwoodite, Na(UO2)(SiO3OH) · 1.5H2O, was determined over a wide range of bicarbonate concentrations, from circumneutral to alkaline pH, that are representative of porewater and groundwater compositions at the Hanford site and calcareous environments generally. Experiments were open to air. Results show that Na-boltwoodite dissolution was nearly congruent and its solubility and dissolution kinetics increased with increasing bicarbonate concentration and pH. A consistent set of solubility constants were determined from circumneutral pH (0 added bicarbonate) to alkaline pH (50 mM added bicarbonate). Average log K sp o = 5.86 ± 0.24 or 5.85 ± 0.0.26; using the Pitzer ion-interaction model or Davies equation, respectively. These values are close to the one determined by [Nguyen, S.N., Silva, R.J., Weed, H.C., Andrews, Jr., J.E., 1992. Standard Gibbs free energies of formation at the temperature 303.15 K of four uranyl silicates: soddyite, uranophane, sodium boltwoodite, and sodium weeksite. J. Chem. Thermodynamics 24, 359–376.] under very different conditions (pH 4.5, Ar atmosphere).

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am (soil) solid [Am (soil) + H + ⇌ Am (aq complex) + ] was found to be −4.12. The predictions based upon thermodynamic data suggest that Am (aq complex) + is likely to be Am(OH) 2 + . Although the chemical formula of Am (soil) was not determined, it does not appear to be Am(OH) 3 (a). Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am (soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.

There is presented the abbreviated clinical record of a patient who suffered from compound fracture of the ankle with subsequent invasion of the blood stream by hemolytic streptococci and staphylococci with eventual recovery after prolonged illness. Various therapeutic measures contributed to this favorable outcome but one may mention especially the repeated transfusions, use of the anti-streptococcus serum and the use of bacteriophage.