Selenium stable isotope ratios in California agricultural drainage water management systems

Selenium stable isotope ratios are known to shift in predictable ways during various microbial, chemical, and biological processes, and can be used to better understand Se cycling in contaminated environments. In this study we used Se stable isotopes to discern the mechanisms controlling the transformation of oxidized, aqueous forms of Se to reduced, insoluble forms in sediments of Se-affected environments. We measured 80Se/76Se in surface waters, shallow ground waters, evaporites, digested plants and sediments, and sequential extracts from several sites where agricultural drainage water is processed in the San Joaquin Valley of California. Selenium isotope analyses of samples obtained from the Tulare Lake Drainage District flow-through wetland reveal small isotopic contrasts (mean difference 0.7%) between surface water and reduced Se species in the underlying sediments. Selenium in aquatic macrophytes was very similar isotopically to the NaOH and Na2SO3 sediment extracts designed to recover soluble organic Se and Se(0), respectively. For the integrated on-farm drainage management sites, evaporite salts were slightly (approximately 0.6%) enriched in the heavier isotope relative to the inferred parent waters, whereas surface soils were slightly (approximately 1.4%) depleted. Bacterial or chemical reduction of Se(VI) or Se(IV) may be occurring at these sites, but the small isotopic contrasts suggest that other, less isotopically fractionating mechanisms are responsible for accumulation of reduced forms in the sediments. These findings provide evidence that Se assimilation by plants and algae followed by deposition and mineralization is the dominant transformation pathway responsible for accumulation of reduced forms of Se in the wetland sediments.     

Strontium isotope study of coal utilization by-products interacting with environmental waters

Sequential leaching experiments on coal utilization by-products (CUB) were coupled with chemical and strontium (Sr) isotopic analyses to better understand the influence of coal type and combustion processes on CUB properties and the release of elements during interaction with environmental waters during disposal. Class C fly ash tended to release the highest quantity of minor and trace elements-including alkaline earth elements, sodium, chromium, copper, manganese, lead, titanium, and zinc-during sequential extraction, with bottom ash yielding the lowest. Strontium isotope ratios ((87)Sr/(86)Sr) in bulk-CUB samples (total dissolution of CUB) are generally higher in class F ash than in class C ash. Bulk-CUB ratios appear to be controlled by the geologic source of the mineral matter in the feed coal, and by Sr added during desulfurization treatments. Leachates of the CUB generally have Sr isotope ratios that are different than the bulk value, demonstrating that Sr was not isotopically homogenized during combustion. Variations in the Sr isotopic composition of CUB leachates were correlated with mobility of several major and trace elements; the data suggest that arsenic and lead are held in phases that contain the more radiogenic (high-(87)Sr/(86)Sr) component. A changing Sr isotope ratio of CUB-interacting waters in a disposal environment could forecast the release of certain strongly bound elements of environmental concern. This study lays the groundwork for the application of Sr isotopes as an environmental tracer for CUB-water interaction.     

Removal of selenate from water by zerovalent iron

Zerovalent iron (ZVI) has been widely used in the removal of environmental contaminants from water. In this study, ZVI was used to remove selenate [Se(VI)] at a level of 1000 microg L(-1) in the presence of varying concentrations of Cl-, SO(2-)4, NO(-)3, HCO(-)3, and PO(3-)4. Results showed that Se(VI) was rapidly removed during the corrosion of ZVI to iron oxyhydroxides (Fe(OH)). During the 16 h of the experiments, 100 and 56% of the added Se(VI) was removed in 10 mM Cl- and SO(2-)4 solutions under a closed contained system, respectively. Under an open condition, 100 and 93% of the added Se(VI) were removed in the Cl- and SO(2-)4 solutions, respectively. Analysis of Se species in ZVI-Fe(OH) revealed that selenite [Se(IV)] and nonextractable Se increased during the first 2 to 4 h of reaction, with a decrease of Se(VI) in the Cl- experiment and no detection of Se(VI) in the SO(2-)4 experiment. Two mechanisms can be attributed to the rapid removal of Se(VI) from the solutions. One is the reduction of Se(VI) to Se(IV), followed by rapid adsorption of Se(IV) to Fe(OH). The other is the adsorption of Se(VI) directly to Fe(OH), followed by its reduction to Se(IV). The results also show that there was little effect on Se(VI) removal in the presence of Cl- (5, 50, and 100 mM), NO(-)3 (1, 5, and 10 mM), SO(2-)4 (5 mM), HCO(-)3 (1 and 5 mM), or PO(3-)4 (1 mM) and only a slight effect in the presence of SO(2-)4 (50 and 100 mM), HCO(-)3 (10 mM), and PO(3-)4 (5 mM) during a 2-d experiment, whereas 10 mM PO(3-)4 significantly inhibited Se(VI) removal. This work suggests that ZVI may be an effective agent to remove Se from Se-contaminated agricultural drainage water.     

A method to quantitatively trap volatilized organoselenides for stable selenium isotope analysis

If volatile organoselenides are to be analyzed for their stable Se isotope composition to elucidate sources and formation processes, organoselenides need to be trapped quantitatively to avoid artificial Se isotope fractionation. We developed an efficient trap of organoselenides to be used in microcosms designed to determine the Se isotope fractionation by microbial transformation of inorganic Se to volatile organoselenides. The recoveries of volatilized dimethyldiselenide (DMDSe) from aqueous standard solutions by activated charcoal and alkaline peroxide solution with subsequent freeze-drying and purification via a cation exchange resin were tested. Microcosm experiments with the Se-methylating fungus in a growth medium were conducted, and tightness of the microcosm was assessed by comparing mass balances of total Se of the fungus, medium, and trapped organoselenides with the supplied Se mass. At the end of the experiment, we calculated δSe values of the whole microcosm and compared them with the δSe value of supplied Se(IV) and Se(VI). Our results demonstrated that activated charcoal cannot be used for quantitative trapping of organoselenides because generally <64% of the outgassed DMDSe were recovered. The mean recovery of Se volatilized from an aqueous DMDSe standard trapped in alkaline peroxide, in contrast, was 96 ± 11% (SD) after 2 h ( = 4). The mass balances of total Se in microcosm experiments with alkaline peroxide traps run for 11 to 15 d were 96 ± 15 and 102 ± 2.4% for Se(IV) and Se(VI) ( = 3), respectively. The mass-weighted mean δSe values for the Se(IV) and Se(VI) batch experiments were -0.31 ± 0.05‰ ( = 3) and -0.76 ± 0.07‰ ( = 3), compared with -0.20 ± 0.10‰ and -0.69 ± 0.10‰ in the supplied Se oxyanions, respectively. We conclude that the alkaline peroxide trap can reliably be used to determine the Se isotope composition of organoselenides.     

Fire effects on stable isotopes in a Sierran forested watershed

This study tested the hypothesis that stable C and N isotope values in surface soil and litter would be increased by fire due to volatilization of lighter isotopes. The hypothesis was tested by: (1) performing experimental laboratory burns of organic and mineral soil materials from a watershed at combinations of temperature ranging 100 to 600 degrees C and duration ranging from 1 to 60 min; (2) testing field samples of upland soils before, shortly after, and 1 yr following a wildfire in the same watershed; and (3) testing field soil samples from a down-gradient ash/sediment depositional area in a riparian zone following a runoff event after the wildfire. Muffle furnace results indicated the most effective temperature range for using stable isotopes for tracing fire impacts is 200 to 400 degrees C because lower burn temperatures may not produce strong isotopic shifts, and at temperatures>or=600 degrees C, N and C content of residual material is too low. Analyses of field soil samples were inconclusive: there was a slightly significant effect of the wildfire on delta15N values in upland watershed analyses 1 yr postburn, while riparian zone analyses results indicated that delta13C values significantly decreased approximately 0.71 per thousand over a 9 mo post-fire period (p=0.015), and ash/sediment layer delta13C values were approximately 0.65 per thousand higher than those in the A horizon. The lack of field confirmation may have been due to overall wildfire burn temperatures being <200 degrees C and/or microbial recovery and vegetative growth in the field. Thus, the muffle furnace experiment supported the hypothesis, but it is as yet unconfirmed by actual wildfire field data.     

STABLE HYDROGEN AND OXYGEN ISOTOPE COMPOSITION OF PRECIPITATION IN NORTHEASTERN COLORADO1

ABSTRACT: Where data are available, hydrologic studies may use precipitation's stable oxygen and hydrogen isotope composition to investigate streamflow, ground water/surface water interaction, and ground water recharge. Paleoclimate studies utilize the δ¹⁸O_{precipitation}‐T_air relationship, in conjunction with lake sediments, fossils, or old ground waters, for example, to estimate pale‐otemperatures. Ecological studies utilize precipitation and soil water isotope composition to track moisture uptake in plants, and to trace species migration patterns. Such studies require that the isotopic composition of precipitation be known. Oxygen‐18 (δ¹⁸O) and deuterium (δ²H) data for precipitation are lacking in the semi‐arid portion of the north‐central U.S. Great Plains, and thus there is a need to establish additional meteoric water lines as isotope input functions across the region, as well as to develop better understanding of the isotopic climate linkages that control oxygen and hydrogen isotope ratios in precipitation. This study determined the δ¹⁸O and δ²H composition of precipitation in the Pawnee Grasslands of northeastern Colorado from 1994 through 1998 using archived National Atmospheric Deposition Program samples. The resulting local water line follows the relationship δ²H = 7.86 δ¹⁸O‐7.66, and the data show a δ¹⁸O_weekly ‐ T_weekly relationship of δ¹⁸O = 0.560‐T (°C)‐18.8.     

Sources and evolution of anthropogenic lead in dated sediments from Lake Clair, Québec, Canada

Two sediments cores were collected from the deepest part of Lake Clair (Québec, Canada) to assess the historical sources of Pb additions to the lake. The cores were collected by divers by carefully inserting a Plexiglas tube into the sediments. To determine the stratigraphic ages of the sediments, (210)Pb and (137)Cs activities were counted by gamma-ray spectroscopy. Lead concentrations and isotopic ratios were performed by inductively coupled plasma-mass spectrometry (ICP-MS), following digestion of the samples with a mixture of HF, HNO(3), and HClO(4) acids and Pb separation by anion-exchange chromatography. Starting at the middle of the 19th century, Pb content of the sediments increased until 1975. The maximum Pb enrichment factor of 35 times (relative to the natural background) was found in sediments deposited in 1975. At this time, excess Pb flux was estimated to be about 0.03 g m(-2) yr(-1). Before 1872, the Pb isotopic ratios were relatively stable (mean (206)Pb/(207)Pb = 1.20 +/- 0.01), reflecting the natural Pb background. Between 1872 and 1894, the source of anthropogenic Pb was highly radiogenic as shown by the Pb isotopic signatures of the sediments (mean (206)Pb/(207)Pb = 1.22 +/- 0.01), possibly reflecting deforestation and agricultural developments in the St.-Lawrence Valley. Between 1894 and 1937, widespread use of industrial and domestic charcoals may explain the isotopic composition of Pb accumulated in the sediments (mean (206)Pb/(207)Pb = 1.19 +/- 0.01). From 1937 to 1975, Pb isotopic compositions became less radiogenic ((206)Pb/(207)Pb from 1.18 to 1.17) even though elemental Pb abundance reached extremely high values (623 mg kg(-1)). This isotopic shift reflects increased use of alkyl-lead in gasoline. For sediments accumulated between 1967 and 1996, the U.S. contribution to anthropogenic Pb accumulated in Lake Clair sediments amounted to between 30 and 63%.     

Characterization of selenate removal from drainage water using rice straw

Removal of selenium (Se) from agricultural drainage water is very important for protecting wildlife in wetland systems. We conducted a series of experiments on selenite [Se(IV)] adsorption and selenate [Se(VI)] reduction to determine Se removal from drainage water amended with 1000 microg/L of Se(VI) or Se(IV) and 5 g of rice (Oryza sativa L.) straw. Under sterile conditions, the added Se(IV) was not adsorbed to the rice straw within 2 d of the experiment and the added Se(VI) was not reduced within 14 d. In contrast, added Se(VI) in a nonsterile rice-straw solution was reduced rapidly, from 930 microg/L at Day 3 to 20 microg/L at Day 5, with an increase in unprecipitated elemental Se [Se(0)] and total Se(0). In the last several days of the experiments, unprecipitated Se(0) was the major Se form in the rice-straw solution, with a small amount of organic Se(-II). This study showed that Se removal from drainage water in the presence of rice straw involves a two-step process. The first is the microbial reduction of Se(VI) to Se(IV) and then to colloidal Se(0). The second is flocculation and precipitation of colloidal Se(0) to the bottom of the experimental flasks and the surface of rice straw.     

Bacterial diversity in selenium reduction of agricultural drainage water amended with rice straw

Bacterial reduction of the Se oxyanions selenate [Se(VI)] and selenite [Se(IV)] to elemental selenium [Se0] is an important biological process in removing Se from drainage water. This study was conducted to characterize the molecular diversity of bacterial populations involved in Se reduction of drainage water amended with rice (Oryza sativa L.) straw and also to monitor the bacterial community shifts during the course of the study. Selenate was removed in the drainage water by the bacteria 5 to 6 d after addition of rice straw. Six Se(VI)- and 32 Se(IV)-reducing bacteria were isolated from rice straw containing sterilized drainage water. Three Se(VI)- and two Se(IV)-reducing bacteria were also isolated from the drainage water. Identification of Se(VI)- and Se(IV)-reducing bacteria by 16S rDNA sequence analysis showed a broad phylogenetic diversity in Se-reducing assemblages. Three major phyla (Proteobacteria, Actinobacteria, and Firmicutes) of bacterial domain with numerous classes, orders, and families constituted the Se-reducing bacterial community. We documented changes in the composition of bacterial assemblages in the drainage water amended with rice straw using polymerase chain reaction (PCR)-denaturing gradient gel electrophoresis (DGGE) of 16S rDNA. The Shannon-Weaver index (H') revealed higher bacterial diversity at Day 6 in the sterilized and Day 4 in the non-sterilized drainage water amended with rice straw. The results of this study suggest that rice straw, a good source of carbon and energy, harbors a wide range of bacteria useful in Se reduction and may be used in removing Se from drainage water.     

Fate of colloidal-particulate elemental selenium in aquatic systems

Bacterial reduction of selenate [Se(VI)] to elemental Se [Se(0)] is considered an effective bioremediation technique to remove selenium (Se) from agricultural drainage water. However, the fate of the newly formed Se(0) in aquatic systems is not known when it flows out of the treatment system. A set of laboratory experiments was conducted to determine the fate of the colloidal-particulate Se(0) in a water column and in a water-sediment system. Results showed that the newly formed colloidal-particulate Se(0) followed two removal pathways in aquatic systems: (i) flocculation-sedimentation to the bottom of the water and (ii) oxidation to selenite [Se(IV)] and Se(VI). During 58 d of the experiments, 51% of the added Se(0) was precipitated to the bottom of the water and 47% was oxidized to Se(IV) in the water column. In the water-sediment system, Se(IV) in the water accounted for 21 to 25% of the added Se(0). Adsorption of Se(IV) to the bottom sediment resulted in a relatively low amount of Se(IV) in the water. This study indicates that the newly formed Se(0) may be an available form of Se for uptake by organisms if it flows to aquatic systems from a treatment site. Therefore, an effective bioremediation system for removing Se from drainage water must reduce Se(VI) to Se(0) and remove Se(0) directly from the drainage water.     

Microbial reduction of hexavalent chromium under vadose zone conditions

Hexavalent chromium [Cr(VI)] is a common contaminant associated with nuclear reactors and fuel processing. Improper disposal at facilities in and and semiarid regions has contaminated underlying vadose zones and aquifers. The objectives of this study were to assess the potential for immobilizing Cr(VI) using a native microbial community to reduce soluble Cr(VI) to insoluble Cr(III) under conditions similar to those in the vadose zone, and to evaluate the potential for enhancing biological Cr(VI) reduction through nutrient addition. Batch microcosm and unsaturated flow column experiments were performed. Native microbial communities in subsurface sediments with no prior Cr(VI) exposure were shown to be capable of Cr(VI) reduction. In both the batch and column experiments, Cr(VI) reduction and loss from the aqueous phase were enhanced by adding high levels of both nitrate (NO3-) and organic C (molasses). Nutrient amendments resulted in up to 87% reduction of the initial 67 mg L(-1) Cr(VI) in an unsaturated batch experiment. Molasses and nitrate additions to 15 cm long unsaturated flow columns receiving 65 mg L(-1) Cr(VI) resulted in microbially mediated reduction and immobilization of 10% of the Cr during a 45-d experiment. All of the immobilized Cr was in the form of Cr(III), as shown by XANES analysis. This suggests that biostimulation of microbial Cr(VI) reduction in vadose zones by nutrient amendment is a promising strategy, and that immobilization of close to 100% of Cr contamination could be achieved in a thick vadose zone with longer flow paths and longer contact times than in this experiment.     

Selenium distribution and fluxes in intertidal wetlands, San Francisco Bay, California

Selenium (Se) concentrations exceeding ecological guidelines for sediments and suspended particulate matter (SPM) have been observed in the northern reach of the San Francisco Bay estuary. Longterm availability of elevated Se in wetland sediments depends in part on the fluxes controlling Se distribution. The relative contribution of sedimentary vs. post-depositional Se fluxes in two San Francisco Bay intertidal wetlands was estimated. Selenium concentrations on surface wetland sediments were compared with levels on SPM, and with previously established background levels in San Francisco Bay sediments. Sediment Se fluxes to the wetlands were measured directly using sediment traps. Although dissolved Se concentrations are higher than particulate Se concentrations in San Francisco Bay water, sediment input into the system provides the major flux of Se. Strong correlation between Se and C on SPM (r2 = 0.81) indicates the importance of organic particulate deposition. Dependence on sediment texture was qualitatively established by measuring Se on particle-size separates. Normalization to Al showed that 65% of Se spatial variability is related to sediment texture. Selenium is further enriched in the marsh via post-depositional inputs, probably due to in situ adsorption from overlying water and chemical reduction. According to sediment flux measurements, enrichment in the marsh is equivalent to 20 to 25% of the particulate Se flux, thereby defining the marsh as a Se sink. These findings highlight the need for more intensive monitoring of SPM as the major source of Se to intertidal wetlands.     

Removal of selenate in simulated agricultural drainage water by a rice straw bioreactor channel system

Removal of selenium (Se) from agricultural drainage water is important in protecting wetland wildlife. Three flow-through bioreactor channel systems (BCSs), each with three channels filled with rice (Oryza sativa L.) straw, were set in the laboratory to determine removal of selenate [Se(VI)] (1020 microg L(-1)) from drainage water with a salinity of 10.4 dS m(-1), a pH of 8.1, and a nitrate (NO3-) range of 0 to 100 mg L(-1). Results showed that the rice straw effectively reduced Se(VI) during 122 to 165 d of the experiments. Calculation of Se mass in the three BCSs showed that 89.5 to 91.9% of the input Se(VI) was reduced to red elemental Se [Se(0)], where 96.6 to 98.2% was trapped in the BCSs. Losses of each gram of rice straw were almost equal to the removal of 1.66 mg of Se from the drainage water as a form of red Se(0), indicating that rice straw is a very effective organic source for removing Se(VI) from drainage water.     

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.     

Effects of plants on the removal of hexavalent chromium in wetland sediments

The effect of two wetland plants, Typha latifolia L. (cattail) and Phragmites australis (Cav.) Trin. ex Steud (common reed), on the fate of Cr(VI) in wetland sediments was investigated using greenhouse bench-scale microcosm experiments. The removal of Cr(VI) was monitored based on the vertical profiles of aqueous Cr(VI) in the sediments. The Cr(VI) removal rates were estimated taking into account plant transpiration, which was found to significantly concentrate dissolved species in the sediments. After correcting for evapotranspiration, the actual Cr(VI) removal rates were significantly higher than would be inferred from uncorrected profiles. On average, the Cr(VI) removal rates were 0.005 to 0.017 mg L(-1) d(-1), 0.0003 to 0.08 mg L(-1) d(-1), and 0.004 to 0.13 mg L(-1) d(-1) for the control, T. latifolia, and P. australis microcosms, respectively. The fate of the removed Cr(VI) was examined by determining the quantity and chemical speciation of the Cr in the sediment and plant materials. Chromium(III) was the dominant form of Cr in both the sediment and plants, and precipitation of Cr(III) in the sediment was the major pathway responsible for the disappearance of aqueous Cr(VI) from the pore water. Incubation results showed that abiotic reduction was the primary mechanism underlying Cr(VI) removal in the microcosm sediments. Organic compounds produced by plants, including root exudates and mineralization products of dead roots, are thought to be the factor that is either directly or indirectly responsible for the gap between Cr(VI) removal efficiencies in the sediments of the vegetated and unvegetated microcosms.     

Selenium removal and mass balance in a constructed flow-through wetland system

A field study on the removal of Se from agricultural subsurface drainage was conducted from May 1997 to February 2001 in the Tulare Lake Drainage District (TLDD) of San Joaquin Valley, California. A flow-through wetland system was constructed consisting of ten 15- x 76-m unlined cells that were continuously flooded and planted with either a monotype or combination of plants, including sturdy bulrush [Schoenoplectus robustus (Pursh) M.T. Strong], baltic rush (Juncus balticus Willd.), smooth cordgrass (Spartina alterniflora Loisel.), rabbitsfoot grass [Polypogon monspeliensis (L.) Desf.], salt-grass lDistichlis spicata (L.) Greene], cattail (Typha latifolia L.), tule [Schoenoplectus acutus (Muhl. ex Bigelow) A. L?ve & D. L?ve], and widgeon grass (Ruppia maritima L.). One cell had no vegetation planted. The objectives of this research were to evaluate Se removal efficiency of each wetland cell and to carry out a mass balance on Se. The inflow drainage water to the cells had average annual Se concentrations of 19 to 22 microg L(-1) dominated by selenate [Se(VI), 95%]. Average weekly water residence time varied from about 3 to 15 d for Cells 1 through 7 (target 7 d), 19 to 33 d for Cells 8 and 9 (target 21 d), and 13 to 18 d for Cell 10 (target 14 d). Average weekly Se concentration ratios of outflow to inflow ranged from 0.45 to 0.79 and mass ratio (concentration x water volume) from 0.24 to 0.52 for year 2000, that is, 21 to 55% reduction in Se concentration and 48 to 76% Se removal in mass by the wetland, respectively. The nonvegetated cell showed the least Se removal both in concentration and in mass. The global mass balance showed that on the average about 59% of the total inflow Se was retained within the cells and Se outputs were outflow (35%), seepage (4%), and volatilization (2%). Independent measurements of the Se retained in the cells totaled 53% of the total Se inflow: 33% in the surface (0-20 cm) sediment, 18% in the organic detrital layer above the sediment, 2% in the fallen litter, < 1% in the standing plants, and < 1% in the surface water. Thus, about 6% of the total Se inflow was unaccounted for in the internal compartments.     

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.     

The reduction of internal phosphorus loading using alum in Spring Lake, Michigan

The release of P from lake sediments, which occurs as a part of internal loading, may contribute a significant portion of the total P load to a lake. Phosphorus release rates from sediments in Spring Lake, Michigan, and the degree to which alum reduces P release from these sediments, were investigated during the summer of 2003. Triplicate sediment cores were sampled from four sites in the lake, and exposed to one of four treatments in the laboratory: (i) aerobic water column/alum, (ii) aerobic water column/no alum, (iii) anaerobic water column/alum, or (iv) anaerobic water column/no alum. Total P (TP) release rates were virtually undetectable in the alum treatments (both aerobic and anaerobic). Low, but detectable, release rates were measured in the aerobic/no alum treatment. The highest release rates were measured in the anaerobic/no alum treatments, and ranged from 1.6 to 29.5 mg P m(-2) d(-1) depending on how the calculations were derived. These fluxes translated to mean internal loads that ranged between 2.7 (low range) and 6.4 (high range) Mg yr(-1) when extrapolated to a whole-lake basis. Internal P loads accounted for between 55 and 65% of the total P load to Spring Lake. Although alum is a potentially effective means of reducing the sediment source of P, there is considerable uncertainty in how long an alum treatment would remain effective in this system given the current rates of external loading and the lack of information on wind-wave action and bioturbation in Spring Lake.     

Bacterial reduction of selenium in coal mine tailings pond sediment

Sediment from a storage facility for coal tailings solids was assessed for its capacity to reduce selenium (Se) by native bacterial community. One Se(6+)-reducing bacterium Enterobacter hormaechei (Tar11) and four Se(4+)-reducing bacteria, Klebsiella pneumoniae (Tar1), Pseudomonas fluorescens (Tar3), Stenotrophomonas maltophilia (Tar6), and Enterobacter amnigenus (Tar8) were isolated from the sediment. Enterobacter hormaechei removed 96% of the added Se(6+) (0.92 mg L(-1)) from the effluents when Se(6+) was determined after 5 d of incubation. Analysis of the red precipitates showed that Se(6+) reduction resulted in the formation of spherical particles (<1.0 microm) of Se(0) as observed under scanning electron microscope (SEM) and confirmed by EDAX. Selenium speciation was performed to examine the fate of the added Se(6+) in the sediment with or without addition of Enterobacter hormaechei cells. More than 99% of the added Se(6+) (approximately 2.5 mg L(-1)) was transformed in the nonsterilized sediment (without Enterobacter hormaechei cells) as well as in the sterilized (heat-killed) sediment (with Enterobacter hormaechei cells). The results of this study suggest that the lagoon sediments at the mine site harbor Se(6+)- and Se(4+)-reducing bacteria and may be important sinks for soluble Se (Se(6+) and Se(4+)). Enterobacter hormaechei isolated from metal-contaminated sediment may have potential application in removing Se from industrial effluents.     

CONTROL OF LAKE PHOSPHORUS WITH ALUMINUM SULFATE: DOSE DETERMINATION AND APPLICATION TECHNIQUES1

ABSTRACT: Nutrient diversion does not always bring about prompt and sufficient reduction in lake phosphorus concentration due to recycling from nutrient rich sediments. Certain lakes and reservoirs may continue to experience nuisance algal blooms and require additional restorative steps. The phosphorus precipitation/inactivation technique is a procedure to remove phosphorus from the water column and to control its release from sediments in order to achieve P-limiting conditions to algal growth. Aluminum salts have been used in advanced waste water treatment to remove phosphorus and this technology was extended to lake rehabilitation. Guidelines for dose calculation and application are generally lacking, and are provided in this report. The dose determination suggested here allows maximum application of aluminum to bottom sediments and thus emphasizes long term control of phosphorus recycling. Dose can be calculated directly from the alkalinity of the water to be treated. Titration of lake water samples of Varying alkalinity allows the establishment of the relationship between residual dissolved aluminum, alkalinity, and dose which can then be employed for lake scale applications of alum to lakes and reservoirs. Application equipment and procedures are described. These depend on site characteristics and treatment objectives and include lakeside stores, a distribution pipe, and an application barge and manifold. Alum may also be used to meet other restoration objectives including the treatment of problem flows and the reduction of particulate concentrations.