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Aquifer groundwater quality is largely controlled by sediment composition and physical heterogeneity, which commonly sustains a unique redox gradient pattern. Attenuation of heavy metals within these heterogeneous aquifers is reliant on multiple factors, including redox conditions and redox-active species that can further influence biogeochemical cycling. Here, we simulated an alluvial aquifer system using columns filled with natural coarse-grained sediments and two domains of fine-grained sediment lenses. Our goal was to examine heavy metal (Ni and Zn) attenuation within a complex aquifer network and further explore nitrate-rich groundwater conditions. The fine-grained sediment lenses sustained reducing conditions and served as a sink for Ni sequestration─in the form of Ni-silicates, Ni-organic matter, and a dominant Ni-sulfide phase. The silicate clay and sulfide pools were also important retention mechanisms for Zn; however, Ni was associated more extensively with organic matter compared to Zn, which formed layered double hydroxides. Nitrate-rich conditions promoted denitrification within the lenses that was coupled to the oxidation of Fe(II) and the concomitant precipitation of an Fe(III) phase with higher structural distortion. A decreased metal sulfide pool also resulted, where nitrate-rich conditions generated an average 20% decrease in solid-phase Ni, Zn, and Fe. Ultimately, nitrate plays a significant role in the aquifer's biogeochemical cycling and the capacity to retain heavy metals.

An experimental and modeling study was conducted to investigate pertechnetate (Tc(VII)O4(-)) retardation, reduction, and rate scaling in three sediments from Ringold formation at U.S. Department of Energy's Hanford site, where (99)Tc is a major contaminant in groundwater. Tc(VII) was reduced in all the sediments in both batch reactors and diffusion columns, with a faster rate in a sediment containing a higher concentration of HCl-extractable Fe(II). Tc(VII) migration in the diffusion columns was reductively retarded with retardation degrees correlated with Tc(VII) reduction rates. The reduction rates were faster in the diffusion columns than those in the batch reactors, apparently influenced by the spatial distribution of redox-reactive minerals along transport paths that supplied Tc(VII). X-ray computed tomography and autoradiography were performed to identify the spatial locations of Tc(VII) reduction and transport paths in the sediments, and results generally confirmed the newly found behavior of reaction rate changes from batch to column. The results from this study implied that Tc(VII) migration can be reductively retarded at Hanford site with a retardation degree dependent on reactive Fe(II) content and its distribution in sediments. This study also demonstrated that an effective reaction rate may be faster in transport systems than that in well-mixed reactors.

Biological redox cycling of structural Fe in phyllosilicates is an important but poorly understood process. The objective of this research was to study microbially mediated redox cycles of Fe in nontronite (NAu-2). During the reduction phase, structural Fe(III) in NAu-2 served as electron acceptor, lactate as electron donor, AQDS as electron shuttle, and dissimilatory Fe(III)-reducing bacterium Shewanella putrefaciens CN32 as mediator in bicarbonate- and PIPES-buffered media. During the oxidation phase, biogenic Fe(II) served as electron donor and nitrate as electron acceptor. Nitrate-dependent Fe(II)-oxidizing bacterium Pseudogulbenkiania sp. strain 2002 was added as mediator in the same media. For all three cycles, structural Fe in NAu-2 was able to reversibly undergo three redox cycles without significant dissolution. Fe(II) in bioreduced samples occurred in two distinct environments, at edges and in the interior of the NAu-2 structure. Nitrate reduction to nitrogen gas was coupled with oxidation of edge-Fe(II) and part of interior-Fe(II) under both buffer conditions, and its extent and rate did not change with Fe redox cycles. These results suggest that biological redox cycling of structural Fe in phyllosilicates is a reversible process and has important implications for biogeochemical cycles of carbon, nitrogen, and other nutrients in natural environments.

Chesapeake Bay, the largest and most productive estuary in the U.S., suffers from varying degrees of water quality issues fueled by both point and nonpoint nutrient sources. Restoration of the Bay is complicated by the multitude of nutrient sources, their variable inputs, and complex interaction between imported and regenerated nutrients. These complexities not only restrict formulation of effective restoration plans but also open up debates on accountability issues with nutrient loading. A detailed understanding of sediment phosphorus (P) dynamics provides information useful in identifying the exchange of dissolved constituents across the sediment-water interface as well as helps to better constrain the mechanisms and processes controlling the coupling between sediments and the overlying waters. Here we used phosphate oxygen isotope ratios (δ(18)O(P)) in concert with sediment chemistry, X-ray diffraction, and Mössbauer spectroscopy on sediments retrieved from an organic rich, sulfidic site in the mesohaline portion of the mid-Bay to identify sources and pathway of sedimentary P cycling and to infer potential feedbacks on bottom water hypoxia and surface water eutrophication. Authigenic phosphate isotope data suggest that the regeneration of inorganic P from organic matter degradation (remineralization) is the predominant, if not sole, pathway for authigenic P precipitation in the mid-Bay sediments. This indicates that the excess inorganic P generated by remineralization should have overwhelmed any pore water and/or bottom water because only a fraction of this precipitates as authigenic P. This is the first research that identifies the predominance of remineralization pathway and recycling of P within the Chesapeake Bay. Therefore, these results have significant implications on the current understanding of sediment P cycling and P exchange across the sediment-water interface in the Bay, particularly in terms of the sources and pathways of P that sustain hypoxia and may potentially support phytoplankton growth in the surface water.

Under anoxic conditions, soluble pertechnetate (99TcO4–) can be reduced to less soluble TcO2·nH2O, but the oxide is highly susceptible to reoxidation. Here we investigate an alternative strategy for remediation of Tc-contaminated groundwater whereby sequestration as Tc sulfide is favored by sulfidic conditions stimulated by nano zerovalent iron (nZVI). nZVI was pre-exposed to increasing concentrations of sulfide in simulated Hanford groundwater for 24 h to mimic the onset of aquifer biotic sulfate reduction. Solid-phase characterizations of the sulfidated nZVI confirmed the formation of nanocrystalline FeS phases, but higher S/Fe ratios (>0.112) did not result in the formation of significantly more FeS. The kinetics of Tc sequestration by these materials showed faster Tc removal rates with increasing S/Fe between 0 and 0.056, but decreasing Tc removal rates with S/Fe > 0.224. The more favorable Tc removal kinetics at low S/Fe could be due to a higher affinity of TcO4– for FeS than iron oxides, and electro...

Unconventional natural gas development in Pennsylvania has created a new wastewater stream. In an effort to stop the discharge of Marcellus Shale unconventional natural gas development wastewaters into surface waters, on May 19, 2011 the Pennsylvania Department of Environmental Protection (PADEP) requested drilling companies stop disposing their wastewater through wastewater treatment plants (WWTPs). This research includes a chemical analysis of effluents discharged from three WWTPs before and after the aforementioned request. The WWTPs sampled included two municipal, publicly owned treatment works and a commercially operated industrial wastewater treatment plant. Analyte concentrations were quanitified and then compared to water quality criteria, including U.S. Environmental Protection Agency MCLs and "human health criteria." Certain analytes including barium, strontium, bromides, chlorides, total dissolved solids, and benzene were measured in the effluent at concentrations above criteria. Analyte concentrations measured in effluent samples before and after the PADEP's request were compared for each facility. Analyte concentrations in the effluents decreased in the majority of samples after the PADEP's request (p.05). This research provides preliminary evidence that these and similar WWTPs may not be able to provide sufficient treatment for this wastewater stream, and more thorough monitoring is recommended.

During subsurface bioremediation of uranium-contaminated sites, indigenous metal and sulfate-reducing bacteria may utilize a variety of electron acceptors, including ferric iron and sulfate that could lead to the formation of various biogenic minerals in situ. Sulfides, as well as structural and adsorbed Fe(II) associated with biogenic Fe(II)-sulfide phases, can potentially catalyze abiotic U(VI) reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe 1+x S, x = 0 to 0.11) to reduce U(VI) abiotically was investigated. The biogenic mackinawite produced by Shewanella putrefaciens strain CN32 was characterized by employing a suite of analytical techniques including TEM, SEM, XAS, and Mössbauer analyses. Nanoscale and bulk analyses (microscopic and spectroscopic techniques, respectively) of biogenic mackinawite after exposure to U(VI) indicate the formation of nanoparticulate UO2. This study suggests the relevance of sulfide-bearing biogenic minerals in mediating abiotic U(VI) reduction, an alternative pathway in addition to direct enzymatic U(VI) reduction.

The microbial reduction of Fe(III) and U(VI) was investigated in shallow aquifer sediments collected from subsurface flood deposits near the Hanford Reach of the Columbia River in Washington State. Increases in 0.5 N HCl-extractable Fe(II) were observed in incubated sediments and (57)Fe Mössbauer spectroscopy revealed that Fe(III) associated with phyllosilicates and pyroxene was reduced to Fe(II). Aqueous uranium(VI) concentrations decreased in subsurface sediments incubated in sulfate-containing synthetic groundwater with the rate and extent being greater in sediment amended with organic carbon. X-ray absorption spectroscopy of bioreduced sediments indicated that 67-77% of the U signal was U(VI), probably as an adsorbed species associated with a new or modified reactive mineral phase. Phylotypes within the Deltaproteobacteria were more common in Hanford sediments incubated with U(VI) than without, and in U(VI)-free incubations, members of the Clostridiales were dominant with sulfate-reducing phylotypes more common in the sulfate-amended sediments. These results demonstrate the potential for anaerobic reduction of phyllosilicate Fe(III) and sulfate in Hanford unconfined aquifer sediments and biotransformations involving reduction and adsorption leading to decreased aqueous U concentrations.

A key question to address in the development of oxygen isotope ratios in phosphate (δ(18)O(p)) as a tracer of biogeochemical cycling of phosphorus in ancient and modern environments is the nature of isotopic signatures associated with uptake and cycling of mineral-bound phosphate by microorganisms. Here, we present experimental results aimed at understanding the biotic and abiotic pathways of P cycling during biological uptake of phosphate sorbed to ferrihydrite and the selective uptake of sedimentary phosphate phases by Escherichia coli and Marinobacter aquaeolei. Results indicate that a significant fraction of ferrihydrite-bound phosphate is biologically available. The fraction of phosphate taken up by E. coli attained an equilibrium isotopic composition in a short time (

Mercury (Hg) is a highly toxic element, and its contamination of groundwater presents a significant threat to terrestrial ecosystems. Understanding the geochemical processes that mediate mercury transformations in the subsurface is necessary to predict its fate and transport. In this study, we investigated the redox transformation of mercuric Hg (Hg[II]) in the presence of the Fe(II)/Fe(III) mixed valence iron oxide mineral magnetite. Kinetic and spectroscopic experiments were performed to elucidate reaction rates and mechanisms. The experimental data demonstrated that reaction of Hg(II) with magnetite resulted in the loss of Hg(II) and the formation of volatile elemental Hg (Hg[0]). Kinetic experiments showed that Hg(II) reduction occurred within minutes, with reaction rates increasing with increasing magnetite surface area (0.5 to 2 m2/L) and solution pH (4.8 to 6.7), and decreasing with increasing chloride concentration (10(-6) to 10(-2) mol/L). Mössbauer spectroscopic analysis of reacted magnetite samples revealed a decrease in Fe(II) content, corresponding to the oxidation of Fe(II) to Fe(III) in the magnetite structure. X-ray photoelectron spectroscopy detected the presence of Hg(II) on magnetite surfaces, implying that adsorption is involved in the electron transfer process. These results suggest that Hg(II) reaction with solid-phase Fe(II) is a kinetically favorable pathway for Hg(II) reduction in magnetite-hearing environmental systems.

The extractability of uranium (U) from synthetic uranium-hydrous ferric oxide (HFO) coprecipitates has been shown to decrease as a function of mineral ripening, consistent with the hypothesis that the ripening process will decrease uranium lability. To evaluate this process, three HFO suspensions were coprecipitated with uranyl (UO2(2+)) and maintained at pH 7.0 +/- 0.1. Uranyl was added to the HFO postprecipitation in a fourth suspension. Two suspensions also contained either coprecipitated silicate (Si-U-HFO) or phosphate (P-U-HFO). After precipitation of the HFOs, at time intervals of 1 week, 1 month, 6 months, 1 year, and 2 years, aliquots of each suspension were contacted with five extractant solutions for a range of time. Uranium was preferentially extracted over Fe in varying degrees from all coprecipitates, by all extractants. The preference was dependent on the duration of mineral ripening and adjunct anion. Micro-X-ray diffraction analysis provides evidence for the transformation from amorphous material to phases containing substantial proportions of crystalline goethite and hematite, except the P-U-HFO, which remained primarily amorphous. Analysis of the U-HFO coprecipitate bythe Mössbauertechnique and scanning electron microscopy provides confirmation of an increase in particle size and evidence of mineral ripening to crystalline phases.

Under oxic conditions, Tc exists as the soluble, weakly sorbing pertechnetate [TcO4-] anion. The reduced form of technetium, Tc(IV), is stable in anoxic environments and is sparingly soluble as TcO2 x nH2O(s). Here we investigate the heterogeneous reduction of Tc(VII) by Fe(II) adsorbed on Al (hydr)oxides [diaspore (alpha-AlOOH) and corundum (alpha-Al2O3)]. Experiments were performed to study the kinetics of Tc(VII) reduction, examine changes in Fe surface speciation during Tc(VII) reduction (Mössbauer spectroscopy), and identify the nature of Tc(IV)-containing reaction products (X-ray absorption spectroscopy). We found that Tc(VII) was completely reduced by adsorbed Fe(II) within 11 (diaspore suspension) and 4 days (corundum suspension). Mössbauer measurements revealed thatthe Fe(II) signal became less intense with Tc(VII) reduction and was accompanied by an increase in the intensity of the Fe(III) doublet and magnetically ordered Fe(III) sextet signals. Tc-EXAFS spectroscopy revealed that the final heterogeneous redox product on corundum was similar to Tc(IV) oxyhydroxide, TcO2 x nH2O.

New US EPA regulations place caps on the levels of mercury that can be emitted from coal-burning power plants, with targets to hit in 2010 and 2018. To meet these targets, technologies already available to reduce other pollutants, such as SO{sub 2} and NOx, will probably be modified to reduce mercury as a cobenefit. The authors review the effectiveness of these technologies at holding the line on mercury and explore how they can be improved for deeper emission cuts. 19 refs., 3 figs., 1 tab.

Microbial reduction of Fe(III) in illite was studied to evaluate the possibility of microbial utilization of Fe(III) in sedimentary clays and to determine the effects of bioreduction on clay compos...

The reductive biotransformation of a Ni(2+)-substituted (5 mol %) hydrous ferric oxide (NiHFO) by Shewanella putrefaciens, strain CN32, was investigated under anoxic conditions at circumneutral pH. Our objectives were to define the influence of Ni2+ substitution on the bioreducibility of the HFO and the biomineralization products formed and to identify biogeochemical factors controlling the phase distribution of Ni2+ during bioreduction. Incubations with CN32 and NiHFO were sampled after 14 and 32 d, and both aqueous chemistry and solid phases were characterized. By comparison of these results with a previous study (Fredrickson, J. K.; Zachara, J. M.; Kennedy, D. W.; Dong, H.; Onstott, T. C.; Hinman, N. W.; Li, S. W. Geochim. Cosmochim. Acta 1998, 62, 3239-3257), it was concluded that coprecipitated/sorbed Ni2+ inhibited the bioreduction of HFO through an undefined chemical mechanism. Mössbauer spectroscopy allowed analysis of the residual HFO phase and the identity and approximate mass percent of biogenic mineral phases. The presence of AQDS, a soluble electron shuttle that obviates need for cell--oxide contact, was found to counteract the inhibiting effect of Ni2+. Nickel was generally mobilized during bioreduction in a trend that correlated with final pH, except in cases where PO4(3-) was present and vivianite precipitation occurred. CN32 promoted the formation of Ni(2+)-substituted magnetite (Fe2IIIFe(1-x)IINixIIO4) in media with AQDS but without PO4(3-). The formation of this biogenic coprecipitate, however, had little discernible impact on final aqueous Ni2+ concentrations. These results demonstrate that coprecipitated Ni can inhibit dissimilatory microbial reduction of amorphous iron oxide, but the presence of humic acids may facilitate the immobilization of Ni within the crystal structure of biogenic magnetite.

The article gives results of a characterization of emissions of 76 organic hazardous air pollutants (HAPs) in flue gases from the combustion of pulverized coal in a small-scale down-fired combustor. The combustor was operated under different conditions to simulate baseline, high excess air firing, and nitrogen oxide (NOx) controls by combustion modifications. Samples were extracted near the combustor exit, upstream of any pollution control equipment. Data collected indicate that relatively low levels of organic HAPs are present in the flue gases for any of the combustion conditions; however, several compounds were present that have not been reported in previous studies. To the extent that these small-scale tests accurately simulate full-scale units, estimates based on these experiments indicate that the total HAP emissions from a large utility power plant are not likely to increase significantly due to installation of combustion modification techniques for NOx control.

The dinitroaromatic pesticide dinoseb was incinerated in a 0.6-MW (2000000 Btu/h) precombustion chamber burner/package boiler simulator that employed two combustion-modification technologies for NO x control, staged combustion, and/or reburning. The Salmonella (Ames) mutagenicity assay was used to monitor the effect of these control technologies on the mutagenicity of the particle-bound and semivolatile dichloromethane-extractable organics of the emissions