The influence of Fe(II) on the dissimilatory bacterial reduction of an Fe(III) aqueous complex (Fe(III)-citrate(aq)) was investigated using Shewanella putrefaciens strain CN32. The sorption of Fe(II) on CN32 followed a Langmuir isotherm. Least-squares fitting gave a maximum sorption capacity of Qmax = 4.19 x 10(-3) mol/10(12) cells (1.19 mmol/m2 of cell surface area) and an affinity coefficient of log K = 3.29. The growth yield of CN32 with respect to Fe(III)aq reduction showed a linear trend with an average value of 5.24 (+/-0.12) x 10(9) cells/mmol of Fe(III). The reduction of Fe(III)aq by CN32 was described by Monod kinetics with respect to the electron acceptor concentration, Fe(III)aq, with a half-saturation constant (Ks) of 29 (+/-3) mM and maximum growth rate (micromax) of 0.32 (+/-0.02) h(-1). However, the pretreatment of CN32 with Fe(II)aq significantly inhibited the reduction of Fe(III)aq, resulting in a lag phase of about 3-30 h depending on initial cell concentrations. Lower initial cell concentration led to longer lag phase duration, and higher cell concentration led to a shorter one. Transmission electron microscopy and energy dispersive spectroscopy revealed that many cells carried surface precipitates of Fe mineral phases (valence unspecified) during the lag phase. These precipitates disappeared after the cells recovered from the lag phase. The cell inhibition and recovery mechanisms from Fe(II)-induced mineral precipitation were not identified by this study, but several alternatives were discussed. A modified Monod model incorporating a lag phase, Fe(II) adsorption, and aqueous complexation reactions was able to describe the experimental results of microbial Fe(III)aq reduction and cell growth when cells were pretreated with Fe(II)aq.

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Radioactive core samples containing elevated concentrations of Cr from a high level nuclear waste plume in the Hanford vadose zone were studied to asses the future mobility of Cr. Cr(VI) is an important subsurface contaminant at the Hanford Site. The plume originated in 1969 by leakage of self-boiling supernate from a tank containing REDOX process waste. The supernate contained high concentrations of alkali (NaOH Ϸ 5.25 mol/L), salt (NaNO 3 /NaNO 2 Ͼ10 mol/L), aluminate [Al(OH) 4 Ϫ ϭ 3.36 mol/L], Cr(VI) (0.413 mol/L), and 137 Cs ϩ (6.51 ϫ 10 Ϫ5 mol/L). Water and acid extraction of the oxidized subsurface sediments indicated that a significant portion of the total Cr was associated with the solid phase. Mineralogic analyses, Cr valence speciation measurements by X-ray adsorption near edge structure (XANES) spectroscopy, and small column leaching studies were performed to identify the chemical retardation mechanism and leachability of Cr. While X-ray diffraction detected little mineralogic change to the sediments from waste reaction, scanning electron microscopy (SEM) showed that mineral particles within 5 m of the point of tank failure were coated with secondary, sodium aluminosilicate precipitates. The density of these precipitates decreased with distance from the source (e.g., beyond 10 m). The XANES and column studies demonstrated the reduction of 29-75% of the total Cr to insoluble Cr(III), and the apparent precipitation of up to 43% of the Cr(VI) as an unidentified, non-leachable phase. Both Cr(VI) reduction and Cr(VI) precipitation were greater in sediments closer to the leak source where significant mineral alteration was noted by SEM. These and other observations imply that basic mineral hydrolysis driven by large concentrations of OH Ϫ in the waste stream liberated Fe(II) from the otherwise oxidizing sediments that served as a reductant for CrO 4 2Ϫ. The coarse-textured Hanford sediments contain silt-sized mineral phases (biotite, clinochlore, magnetite, and ilmenite) that are sources of Fe(II). Other dissolution products (e.g., Ba 2ϩ) or Al(OH) 4 Ϫ present in the waste stream may have induced Cr(VI) precipitation as pH moderated through mineral reaction. The results demonstrate that a minimum of 42% of the total Cr inventory in all of the samples was immobilized as Cr(III) and Cr(VI) precipitates that are unlikely to dissolve and migrate to groundwater under the low recharge conditions of the Hanford vadose zone.

The time-variant chemical behavior of CoIIEDTA (and other metal-EDTA complexes) was investigated in suspensions of iron oxide-coated sand to identify equilibrium and kinetic reactions that control the mobility of MeII-EDTA complexes in subsurface environments. Batch experiments were conducted to evaluate the adsorption as a function of pH, concentration, and time and to quantify the rate-controlling step@) of dissolution of the iron oxide by EDTA complexes. Ionic Co2+ exhibited typical cation-like adsorption, whereas MeIIEDTA adsorption was ligand-like, increasing with decreasing pH. Adsorption isotherms for all reactive species exhibited Langmuir behavior, with site saturation occurring at molar values of <0.5% of FetOt. The adsorption of MeIIEDTA enhanced the apparent solubility of the iron oxide phase, which destabilized the CoIIEDTA complex, liberating Co2+ and FeIIIEDTA. The dissolution rate was an order of magnitude slower at pH 6.5 than at pH 4.5 and was influenced by the re-adsorption of solubilized FeIIIEDTA. Two multireaction kinetic models were developed that each included Langmuir adsorption for Co2+ and metal-EDTA species but differed in their depiction of the dissolution mechanism (i.e., ligand-versus protonpromoted dissolution). Ligand-promoted dissolution was most consistent with the experimental data. It is suggested that CoIIEDTA will undergo similar reactions in subsurface environments causing complex, distance-variant retardation.

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