Reductive dechlorination of activated carbon-adsorbed trichloroethylene by zero-valent iron: carbon as electron shuttle

Sequestration of organic contaminants in carbonaceous materials can significantly affect contaminant fate and transport. We investigated the reductive dechlorination of granular-activated carbon (GAC)-adsorbed trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) to understand the effect of sequestration on abiotic reactivity of organic contaminants. Significant reduction of TCE sequestered in GAC micropores was observed, even though direct contact with nZVI was unlikely. Reduction of sequestered TCE by reactive Fe(II) species or molecular hydrogen was ruled out as the reaction mechanisms. We propose that GAC served as the conductor for the transfer of electrons or atomic hydrogen from nZVI to the micropores, wherein adsorbed TCE molecules were reduced. An important implication for environmental remediation is that carbonaceous adsorbents not only function as a superb sink for organic contaminants but also allow them to be slowly degraded while being trapped.     

Anaerobic degradation of vinyl chloride in aquifer microcosms

The anaerobic degradation potential at a chloroethene-contaminated site was investigated by operating two anoxic column aquifer microcosms enriched in iron(III). One column was fed with vinyl chloride (VC) only (column A) and one with VC and acetate (column B). In column A, after about 600 pore volume exchanges (PVEs), VC started to disappear and reached almost zero VC recovery in the effluent after 1000 PVEs. No formation of ethene was observed. In column B, effluent VC was almost always only a fraction of influent VC. Formation of ethene was observed after 800 PVEs and started to become an important degradation product after 1550 PVEs. However, ethene was never observed in stoichiometric amounts compared with disappeared VC. The average stable isotope enrichment factor for VC disappearance in column A was determined to be -4.3‰. In column B, the isotope enrichment factor shifted from -10.7 to -18.5‰ concurrent with an increase in ethene production. Batch microcosms inoculated with column material showed similar isotope enrichment factors as the column microcosms. These results indicated that two degradation processes occurred, one in column A and two in parallel in column B with increasing importance of reductive dechlorination with time. This study suggests that in addition to reductive dechlorination, other degradation processes such as anaerobic oxidation should be taken into account when evaluating natural attenuation of VC and that isotope analysis can help to differentiate between different pathways of VC removal.     

Enhancing metolachlor destruction rates with aluminum and iron salts during zerovalent iron treatment

Pesticide-contaminated soil may require remediation to mitigate ground and surface water contamination. We determined the effectiveness of zerovalent iron (Fe(0)) to dechlorinate metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methyl ethyl) acetamide] in the presence of aluminum and iron salts. By treating aqueous solutions of metolachlor with Fe(0), we found destruction kinetics were greatly enhanced when Al, Fe(II), or Fe(II) salts were added, with the following order of destruction kinetics observed: Al2(SO4)3 > AlCl3 > Fe2(SO4)3 > FeCl3. A common observation was the formation of green rusts, mixed Fe(II)-Fe(III) hydroxides with interlayer anions that impart a greenish-blue color. Central to the mechanism responsible for enhanced metolachlor loss may be the role these salts play in facilitating Fe(II) release. By tracking Al and Fe(II) in a Fe(0) + Al2(SO4)3 treatment of metolachlor, we observed that Al was readily sorbed by the corroding iron with a corresponding release of Fe(II). The manufacturing process used to produce the Fe(0) also profoundly affected destruction rates. Metolachlor destruction rates with salt-amended Fe(0) were greater with annealed iron (indirectly heated under a reducing atmosphere) than unannealed iron. Moreover, the optimum pH for metolachlor dechlorination in water and soil differed between iron sources (pH 3 for unannealed, pH 5 for annealed). Our results indicate that metolachlor destruction by Fe(0) treatment may be enhanced by adding Fe or Al salts and creating pH and redox conditions favoring the formation of green rusts.     

Effect of peroxide on neutralization-potential values of siderite and other carbonate minerals

To assess quantitatively the effect of peroxide addition to standard static tests of the neutralization potential (NP) of mine wastes, 10 specimens of carbonate minerals, including five of siderite (FeCO3) and two of rhodochrosite (MnCO3), were analyzed by electron microprobe. The compositions of the siderite span a range from 60 to 86 mol % Fe. Tests of NP for the siderite diluted with 80% (w/w) kaolinite gave values of 647 to 737 kg CaCO3 equivalent per Mg for determinations by the standard Sobek method. However, if it is assumed that the ferrous carbonate component of the mineral does not contribute to NP in field situations because oxidation of Fe(II) to Fe(III) and the subsequent hydrolysis of Fe(III) leads to the release of an equivalent amount of acid, then the calculated NP for the samples ranges from 110 to 390 kg CaCO3 equivalent per Mg. Two different methods involving the addition of peroxide to the test solutions were successful in bringing the measured NP values closer to the theoretical ones. By contrast, the tests with rhodochrosite indicated the Mn(II) to be stable. For long-term environmental planning, especially for wastes from metalliferous sulfide-poor deposits in which gradual dissolution of silicate and aluminosilicate minerals may be involved in attenuating the acidity, consideration in the overall NP budget needs to be given to the ferrous iron content of those minerals. The presence of Fe2+-bearing minerals, especially carbonates, in tested mine-waste materials may lead to overestimated Sobek NP values, thus increasing the risk of poor-quality drainage and the need for costly remediation.     

Ligand-assisted degradation of carbon tetrachloride by microscale zero-valent iron

Degradation of carbon tetrachloride (CT) by microscale zero-valent iron (ZVI) was investigated in batch systems with or without organic ligands (ethylenediaminetetraacetic acid (EDTA), citric acid, tartaric acid, malic acid and oxalic acid) at pHs from 3.5 to 7.5. The results demonstrated that at 25°C, the dechlorination of CT by microscale ZVI is slow in the absence of organic ligands, with a pseudo-first-order rate constant of 0.0217 h(-1) at pH 3.5 and being further dropped to 0.0052 h(-1) at pH 7.5. However, addition of organic ligands significantly enhanced the rates and the extents of CT removal, as indicated by the rate constant increases of 39, 31, 32, 28 and 18 times in the presence of EDTA, citric acid, tartaric acid, malic acid and oxalic acid, respectively, at pH 3.5 and 25°C. The effect of EDTA was most significant; the dechlorination of CT at an initial concentration of 20 mg l(-1) increased from 16.3% (no ligands) to 89.1% (with EDTA) at the end of 8h reaction. The enhanced CT degradation in the presence of organic ligands was primarily attributed to the elimination of a surface passivation layer of Fe(III) (hydr)oxides on the microscale ZVI through chelating of organic ligands with Fe(III), which maintained the exposure of active sites on ZVI surface to CT.     

Dissipation of pentachlorophenol in the aerobic-anaerobic interfaces established by the rhizosphere of rice ( Oryza sativa L.) root

Phytoremediation is an emerging technology for the detoxification and remediation of organic pollutants such as pentachlorophenol (PCP). To investigate the dissipation behavior of PCP in the aerobic-anaerobic interfaces established by the rhizosphere of rice ( L.) root, a glasshouse experiment was conducted using a specially designed rhizobox. The possible biogeochemical mechanisms were also studied through illustration of the dynamic behavior of important electron acceptors and donors that are potentially involved in the reductive dechlorination and aerobic catabolism processes of PCP. The soil was spiked with 20 ± 0.25 and 45 ± 0.25 mg of PCP kg soil. Soil in the rhizobox was divided into five different compartments at various distances from the root surface. Maximum dissipation of PCP in planted soil was observed at 3-mm distance from the root zone as well as rapid changes in concentrations of sulfate, chloride, nitrate, and ammonium at the same distance from the root. In contrast, in the unplanted soil, no difference was observed in the PCP concentration with increasing distance. After 45 d, a significantly higher concentration of PCP was degraded in planted soil compared with unplanted soil. In the unplanted microcosms, about 45% of the initial PCP was lost at both low and high added rates, respectively. This was, proportionately, a significantly smaller percentage compared with the planted rhizosphere (an average of 66 and 64.5%, respectively). Moreover, the correlations of PCP dissipation with SO, NO, and Fe were significantly negative, while the correlations of PCP dissipation with NH, Fe, and Cl were significantly positive. This suggested the oxidization of soil constituents can inhibit aerobic catabolism of PCP by consuming O, and the reduction of soil constituents can inhibit anaerobic reductive dechlorination of PCP. Therefore, the significance of the rhizosphere in phytoremediation of chlorinated compounds such as PCP differs significantly between wetland and rainfed systems.     

共沉积制备Pd／Cu纳米金属粒子对四氯化碳的脱氯研究

利用电化学共沉积的方法,在玻碳电极表面沉积制备了纳米尺寸的Pd／Cu二相金属粒子。采用循环伏安法研究了四氯化碳在沉积了Pd／Cu纳米粒子的电极表面的电化学还原行为。研究了纳米粒子尺寸、Pd和Cu质量比对四氯化碳还原脱氯效果的影响,并对反应机理进行了探讨。     

Transport and fate of nitrate in a glacial outwash aquifer in relation to ground water age,land use practices,and redox processes

A combination of ground water modeling, chemical and dissolved gas analyses, and chlorofluorocarbon age dating of water was used to determine the relation between changes in agricultural practices, and NO3- concentrations in ground water of a glacial outwash aquifer in west-central Minnesota. The results revealed a redox zonation throughout the saturated zone with oxygen reduction occurring near the water table, NO3- reduction immediately below it, and then a large zone of ferric iron reduction, with a small area of sulfate (SO4(2-)) reduction and methanogenesis (CH4) near the end of the transsect. Analytical and NETPATH modeling results supported the hypothesis that organic carbon served as the electron donor for the redox reactions. Denitrification rates were quite small, 0.005 to 0.047 mmol NO3- yr(-1), and were limited by the small amounts of organic carbon, 0.01 to 1.45%. In spite of the organic carbon limitation, denitrification was virtually complete because residence time is sufficient to allow even slow processes to reach completion. Ground water sample ages showed that maximum residence times were on the order of 50 to 70 yr. Reconstructed NO3- concentrations, estimated from measured NO3- and dissolved N gas showed that NO3- concentrations have been increasing in the aquifer since the 1940s, and have been above the 714 micromol L(-1) maximum contaminant level at most sites since the mid- to late-1960s. This increase in NO3- has been accompanied by a corresponding increase in agricultural use of fertilizer, identified as the major source of NO3- to the aquifer.     

Vivianite precipitation and phosphate sorption following iron reduction in anoxic soils

Phosphorus retention in lowland soils depends on redox conditions. The aim of this study was to evaluate how the Fe(III) reduction degree affects phosphate adsorption and precipitation. Two similarly P-saturated, ferric Fe-rich lowland soils, a sandy and a peat soil, were incubated under anaerobic conditions. M?ssbauer spectroscopy demonstrated that Fe(III) in the sandy soil was present as goethite and phyllosilicates, whereas Fe(III) in the peat soil was mainly present as polynuclear, Fe-humic complexes. Following anoxic incubation, extensive formation of Fe(II) in the solids occurred. After 100 d, the Fe(II) production reached its maximum and 34% of the citrate-bicarbonate-dithionite extractable Fe (Fe(CBD)) was reduced to Fe(II) in the sandy soil. The peat soil showed a much faster reduction of Fe(III) and the maximum reduction of 89% of Fe(CBD) was reached after 200 d. Neoformation of a metavivianite/vivianite phase under anoxic conditions was identified by X-ray diffraction in the peat. The sandy soil exhibited small changes in the point of zero net sorption (EPC?) and P(i) desorption with increasing Fe(III) reduction, whereas in the peat soil P desorption increased from 80 to 3100 μmol kg?1 and EPC? increased from 1.7 to 83 μM, after 322 d of anoxic incubation. The fast Fe(III) reduction made the peat soils particularly vulnerable to changes in redox conditions. However, the precipitation of vivianite/metavivianite minerals may control soluble P(i) concentrations to between 2 and 3 μM in the long term if the soil is not disturbed.     

Anaerobic ammonium oxidation by Nitrosomonas spp. and anammox bacteria in a sequencing batch reactor

A sequencing batch reactor (SBR) was inoculated with mixed nitrifying bacteria from an anoxic tank at the conventional activated sludge wastewater treatment plant in Nongkhaem, Bangkok, Thailand. This enriched nitrifying culture was maintained under anaerobic conditions using ammonium (NH(4)(+)) as an electron donor and nitrite (NO(2)(-)) as an electron acceptor. Autotrophic ammonium oxidizing bacteria survived under these conditions. The enrichment period for anammox culture was over 100 days. Both ammonium and nitrite conversion rates were proportional to the biomass of ammonium oxidizing bacteria; rates were 0.08 g N/gV SS/d and 0.05 g N/g VSS/d for ammonium and nitrite, respectively, in a culture maintained for 3 months at 42 mg N/L ammonium. The nitrogen transformation rate at a ratio of NH(4)(+)-N to NO(2)(-)-N of 1:1.38 was faster, and effluent nitrogen levels were lower, than at ratios of 1:0.671, 1:2.18, and 1:3.05. Fluorescent in situ hybridization (FISH) was used to identify specific autotrophic ammonium oxidizing bacteria (Nitrosomonas spp., Candidatus Brocadia anammoxidans, and Candidatus Kuenenia stuttgartiensis). The ammonium oxidizing culture maintained at 42 mg N/L ammonium was enriched for Nitrosomonas spp. (30%) over Candidati B. anammoxidans and K. stuttgartiensis (2.1%) while the culture maintained at 210 mg N/L ammonium was dominated by Candidati B. anammoxidans and K. stuttgartiensis (85.6%). The specific nitrogen removal rate of anammox bacteria (0.6 g N/g anammox VSS/d) was significantly higher than that of ammonium oxidizing bacteria (0.4 g N/g Nitrosomonas VSS/d). Anammox bacteria removed up to 979 mg N/L/d of total nitrogen (ammonium:nitrite concentrations, 397:582 mg N/L). These results suggest significant promise of this approach for application to wastewater with high nitrogen but low carbon content, such as that found in Bangkok.     

Phytoremediation of polychlorinated biphenyl (PCB)-contaminated sediment: a greenhouse feasibility study

Contaminated sediments dredged from navigable waterways often are placed in confined disposal facilities to prevent further spread of the pollutants. Reducing contaminants to acceptable levels would allow for disposal of the sediments and further dredging activity. A greenhouse study was conducted to evaluate plant treatments and the addition of an organic amendment to decrease the concentration of PCB congeners found in Arochlor 1260. Sediment treated with the amendment and either low transpiring plants or no plants had the greatest removal of the PCB congeners. High-transpiring plants apparently prevented the highly reducing conditions required for reductive dechlorination of highly chlorinated PCBs. Most likely, the amendment provided labile carbon that initiated the reducing conditions needed for dechlorination. The sediment moisture content and moisture-related plant parameters were significant predictors of the PCB loss. Carex aquatalis and Spartina pectinata are predicted to be the most effective plant treatments for phytoremediation of PCBs.     

Perfluorinated phosphine oxide and sulfides as extractants for heavy metals and radionuclides

New highly fluorinated monodentate and bidentate phosphine oxide compounds of the type {CF(3)(CF(2))(n)CH(2)CH(2)}(3)PO (n = 5, 9) and [{CF(3)(CF(2))(5)CH(2)CH(2)}(2)P(O)CH(2)CH(2)P(O){CH(2)CH(2)(CF(2))(5)CF(3)}] have been prepared. Their ability to extract a number of metals and radionuclides from aqueous solutions into perfluorinated solvents has been established and the extractable species investigated. All extractants extract the metals As(V), Cd(II), Co(II), Cr(VI), Hg(II), Pb(II), and Sn(II) with >75% removal. In addition, the radioisotopes (90)Sr(II), (133)Ba(II), and U(VI) have been investigated, whilst (59)Fe(III) has been used to model the extraction of plutonium. (133)Ba(II) shows a high distribution ratio for monodentate phosphine oxides, whilst for UO(2)(2+) and (59)Fe(III) bidentate phosphine oxides are superior.     

Effect of uranium(VI) speciation on simultaneous microbial reduction of uranium(VI) and iron(III)

Uranium is a pollutant of concern to both human and ecosystem health. Uranium's redox state often dictates whether it will reside in the aqueous or solid phase and thus plays an integral role in the mobility of uranium within the environment. In anaerobic environments, the more oxidized and mobile form of uranium (UO2(2+) and associated species) may be reduced, directly or indirectly, by microorganisms to U(IV) with subsequent precipitation of UO. However, various factors within soils and sediments, such as U(VI) speciation and the presence of competitive electron acceptors, may limit biological reduction of U(VI). Here we examine simultaneous dissimilatory reduction of Fe(III) and U(VI) in batch systems containing dissolved uranyl acetate and ferrihydrite-coated sand. Varying amounts of calcium were added to induce changes in aqueous U(VI) speciation. The amount of uranium removed from solution during 100 h of incubation with S. putrefaciens was 77% in absence of Ca or ferrihydrite, but only 24% (with ferrihydrite) and 14% (without ferrihydrite) were removed for systems with 0.8 mM Ca. Dissimilatory reduction of Fe(III) and U(VI) proceed through different enzyme pathways within one type of organism. We quantified the rate coefficients for simultaneous dissimilatory reduction of Fe(III) and U(VI) in systems varying in Ca concecentration (0-0.8 mM). The mathematical construct, implemented with the reactive transport code MIN3P, reveals predominant factors controlling rates and extent of uranium reduction in complex geochemical systems.     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

Comparison of Diuron degradation by direct UV photolysis and advanced oxidation processes

The rates of Diuron elimination by some advanced oxidation processes (AOPs) such as Fe(III)/UV, Ferrioxalate/UV, Fe(III)/H(2)O(2)/UV, Ferrioxalate/UV/H(2)O(2) and Fe(III)/H(2)O(2) have been compared. Experiments have been conducted at pH=2.3+/-0.1 with a batch reactor equipped with a low-pressure mercury lamp emitting mainly at 253.7nm. Data obtained under the following experimental conditions ([H(2)O(2)](0)=10(-3)M, [Diuron](0)=5x10(-5)M and [Fe(III)](0)=10(-3)M) have shown that rates of Diuron oxidation were higher with the systems Fe(III)/H(2)O(2)/UV and Ferrioxalate/UV/H(2)O(2) than with Fe(III)/UV and Fe(III)/H(2)O(2). On the other hand, Fe(III)/UV was found to be very efficient in mineralization of Diuron solution in comparison to direct UV photolysis. The experimental results showed that radical ()OH is the major pathway in the process of Diuron degradation.     

Coal energy conversion with carbon sequestration via combustion in supercritical saline aquifer water

The standard idea for deep saline aquifer sequestration is to separate carbon dioxide from a process stream, compress it, and inject it underground. However, since carbon dioxide is less dense than water, even at the high pressures found in aquifers, it is buoyant and will move towards the surface unless trapped by an impermeable seal. Also, significant energy expenditure is required to separate and compress carbon dioxide, even though neat carbon dioxide is not a desired product. These issues may be addressed by combining the idea of fast dissolution at the surface with supercritical water oxidation (SCWO). By burning coal at high pressure in supercritical water drawn from an aquifer, and then sequestering the entire pre-equilibrated effluent, all carbon from the fuel is captured, as well as all non-mineral coal combustion products including sulfur and metals.A possible block diagram of an SCWO-based electric power plant is proposed, including processes to handle salts from the aquifer brine and minerals from coal. The plant is thermodynamically modeled, using an indirectly fired combined cycle to convert energy from hot combustion products to work. This model estimates the overall thermal efficiency that can be achieved, and reveals unanticipated interactions within the plant that have significant effects on efficiency. The assumptions and results of the model highlight design challenges for an actual system.     

Colloid mobilization and arsenite transport in soil columns: effect of ionic strength

Colloid generation and transport in soils is of significance because of suspected colloid-facilitated transport of contaminants to the groundwater. In this study, colloid mobilization and its effect on the transport of arsenite [As(III)] were investigated in Olivier (fine-silty, mixed, active, thermic Aquic Fraglossudalfs) and Windsor (mixed, mesic typic Udipsamments) soil columns. Input solution of 10 mg L(-1) As(III) in 0.01 M NaCl was applied to water-saturated columns, and followed by leaching with deionized water (DIW). Flow interruptions were performed during the As(III) input and DIW leaching phases. Turbidity, electrical conductivity (EC), and pH of column effluents were monitored with time. Total and dissolved concentrations of As, Fe, and Al were analyzed. Effluent results demonstrated that colloid-facilitated transport contributed little to arsenic movement when the solution ionic strength was maintained constant. Mobilization of colloidal amorphous material and enhanced transport of As(III) were observed as a result of changes in ionic strength of the input solution. The peak of colloid generation coincided with peak concentrations of Fe, suggesting mobilization of Fe oxides and facilitated transport of As(III) adsorbed on oxide surfaces. Colloid mobilization was enhanced due to flow interruption in the Olivier column, which suggests slow dissociation of aggregated colloidal particles. Moreover, effluent results indicate significant effect of organic matter in stabilizing aggregates of colloidal particles.     

Dissolution of phosphate in a phosphorus-enriched ultisol as affected by microbial reduction

Phosphorus dissolution often increases as soils become more reduced, but the mechanisms are not fully understood. The objectives of this research were to determine rates and mechanisms of P dissolution during microbial reduction of a surface soil from the North Carolina Coastal Plain. Duplicate suspensions of silt + clay fractions from a Cape Fear sandy clay loam (fine, mixed, semiactive, thermic Typic Umbraquult) were reduced in a continuously stirred redox reactor for 40 d. We studied the effects of three treatments on P dissolution: (i) 2 g dextrose kg(-1) solids added as a microbial carbon source at time 0 d; (ii) 2 g dextrose kg(-1) solids split into three additions at 0, 12, and 26 d; and (iii) no added dextrose. After 40 d of reduction, concentrations of dissolved reactive phosphorus (DRP) were similar for all treatments and increased up to sevenfold from 1.5 to 10 mg L(-1). The initial rate of reduction and dissolution of DRP was significantly greater for the 0-d treatment. A linear relationship (R(2) = 0.79) was found between DRP and dissolved organic carbon (DOC). Dissolved Fe and Al and pH increased, suggesting the formation of aqueous Fe- and Al-organic matter complexes. Separate batch experiments were performed to study the effects of increasing pH and citrate additions on PO(4) dissolution under aerobic conditions. Increasing additions of citrate increased concentrations of DRP, Fe, and Al, while increasing pH had no effect. Results indicated that increased dissolved organic matter (DOM) during soil reduction contributed to the increase in DRP, perhaps by competitive adsorption or formation of aqueous ternary DOM-Fe-PO(4) or DOM-Al-PO(4) complexes.     

micro-XANES and micro-XRF investigations of metal binding mechanisms in biosolids

Micro-X-ray fluorescence (micro-XRF) microprobe analysis and micro-X-ray absorption near-edge structure (micro-XANES) spectroscopy were employed to identify Fe and Mn phases and their association with selected metals in two biosolids (limed composted [LC] and Nu-Earth) before and after treatment to remove organic carbon (OC). Spatial correlations derived from elemental mapping of XRF images showed strong correlations between Fe and Cd, Cr, Pb, or Zn (r2= 0.65-0.92) before and after removal of most of the OC. The strong correlation between Fe and Cu that was present in intact samples disappeared after OC removal, suggesting that Cu was associated with OC coatings that may have been present on Fe compounds. Except for Fe and Cr, the spatial correlations of metals with Mn were improved after treatment to remove OC, indicating that the treatment may have altered more than the OC in the system. The Fe micro-XANES spectra of the intact biosolids sample showed that every point had varying mixtures of Fe(II and III) species and no two points were identical. The lack of uniformity in Fe species in the biosolids sample illustrates the complexity of the materials and the difficulty of studying biosolids using conventional analytical tools or chemical extraction techniques. Still, these microscopic observations provide independent information supporting the previous laboratory and field hypothesis that Fe compounds play a major role in retention of environmentally important trace elements in biosolids. This could be due to co-precipitation of the metals with Fe, adsorption of metals by Fe compounds, or a combination of both mechanisms.     

Quantifying constraints imposed by calcium and iron on bacterial reduction of uranium(VI)

Uranium is a redox active contaminant of concern to both human health and ecological preservation. In anaerobic soils and sediments, the more mobile, oxidized form of uranium (UO(2)(2+) and associated species) may be reduced by dissimilatory metal-reducing bacteria. Despite rapid reduction in controlled, experimental systems, various factors within soils or sediments may limit biological reduction of U(VI), inclusive of competing electron acceptors and alterations in uranyl speciation. Here we elucidate the impact of U(VI) speciation on the extent and rate of reduction, and we examine the impact of Fe(III) (hydr)oxides (ferrihydrite, goethite, and hematite) varying in free energies of formation. Observed pseudo first-order rate coefficients for U(VI) reduction vary from 12 +/- 0.60 x 10(-3) h(-1) (0 mM Ca in the presence of goethite) to 2.0 +/- 0.10 x 10(-3) h(-1) (0.8 mM Ca in the presence of hematite). Nevertheless, dissolved Ca (at concentrations from 0.2 to 0.8 mM) decreases the extent of U(VI) reduction by approximately 25% after 528 h relative to rates without Ca present. Imparting an important criterion on uranium reduction, goethite and hematite decrease the dissolved concentration of calcium through adsorption and thus tend to diminish the effect of calcium on uranium reduction. Ferrihydrite, in contrast, acts as a competitive electron acceptor and thus, like Ca, decreases uranium reduction. However, while ferrihydrite decreases U(VI) in solutions without Ca, with increasing Ca concentrations U(VI) reduction is enhanced in the presence of ferrihydrite (relative to its absence)-U(VI) reduction, in fact, becomes almost independent of Ca concentration. The quantitative framework described herein helps to predict the fate and transport of uranium within anaerobic environments.