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.     

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.     

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.     

Fate of dimethyldiselenide in soil

Volatilization of dimethyldiselenide (DMDSe) is one of the most important processes for removing selenium (Se) from Se-contaminated environments. However, the fate of DMDSe in soil is not known. In this study, we monitored the changes of DMDSe in the head space of soil samples spiked with known amounts of DMDSe gas, and fractionated and speciated the resulting Se forms in soil. Dimethyldiselenide was highly dissolved in water in a closed air-water system and was highly sorbed onto soil in a closed air-soil system. Chemical and biological transformations of DMDSe in soil converted a large amount of DMDSe to nonvolatile Se compounds. Elemental Se [Se(0)] and nonvolatile organic Se were the major forms of Se transformed from spiked DMDSe. Microbial conversion of DMDSe to dimethylselenide (DMSe) in soil increased the production of DMSe. Calculation of the mass recovery showed that about 85 to 93% of the added DMDSe was recovered as Se(0), organic Se, organic material Se (OM-Se), Se(IV), and volatile organic Se in the head space in the non-autoclaved soils and 50 to 70% of the added DMDSe was recovered in the autoclaved soils. These results indicate that DMDSe is not a stable form of Se, and it may be one of the important precursors of DMSe in the soil environment.     

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.     

Selenium stable isotope investigation into selenium biogeochemical cycling in a lacustrine environment: Sweitzer Lake, Colorado

We present a comprehensive set of Se concentration and isotope ratio data collected over a 3-yr period from dissolved, sediment-hosted, and organically bound Se in a Se-contaminated lake and littoral wetland. Median isotope ratios of these various pools of Se spanned a narrow isotopic range (delta80/76Se(SRM-3149)) = 1.14-2.40 per thousand). Selenium (VI) reduction in the sediments is an important process in this system, but its isotopic impact is muted by the lack of direct contact between surface waters and reduction sites within sediments. This indicates that using Se isotope data as an indicator of microbial or abiotic Se oxyanion reduction is not effective in this or other similar systems. Isotopic data suggest that most Se(IV) in the lake originates from oxidation of organically bound Se rather than directly through Se(VI) reduction. Mobilization of Se(VI) from bedrock involves only a slight isotopic shift. Temporally constant isotopic differences observed in Se(VI) from two catchment areas suggest the potential for tracing Se(VI) from different source areas. Phytoplankton isotope ratios are close to those of the water, with a small depletion in heavy isotopes (0.56 per thousand). Fish tissues nearly match the phytoplankton, being only slightly depleted in the heavier isotopes. This suggests the potential for Se isotopes as migration indicators. Volatile, presumably methylated Se was isotopically very close to median values for phytoplankton and macrophytes, indicating a lack of isotopic fractionation during methylation.     

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.     

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.     

Water treatment by aquatic ecosystem: Nutrient removal by reservoirs and flooded fields

Potential use of reservoirs and flooded fields stocked with aquatic plants for reduction of the nutrient levels of organic soil drainage water was evaluated. The treatment systems include 1) a large single reservoir (R1) stocked with waterhyacinth (Eichhornia crassipes), elodea (Egeria densa), and cattails (Typha sp.) in series; 2) three small reservoirs in series with waterhyacinth (R2), elodea (R3), and cattails (R4), grown in independent reservoirs; 3) a control reservoir (R5) with no cultivated plants; 4) a large single flooded field planted to cattails; 5) three small flooded fields in a series planted to cattails; and 6) a flooded field with no cultivated plants. Drainage water was pumped daily (6 hours a day, and 6 days a week) into these systems for a period of 27 months at predetermined constant flow rates. Water samples were collected at the inlet and outlet of each treatment system and analyzed for N and P forms.The series of reservoirs stocked with aquatic plants functioned effectively in the removal of N and P from agricultural drainage water, compared to a single large reservoir. Allowing the water to flow through the reservoir stocked with waterhyacinth plants with a residence time of 3.6 days was adequate to remove about 50% of the incoming inorganic N. Allowing the water to flow through a series of two small reservoirs, R2 and R3, with a residence time of 7.3 days was necessary to remove about 60% of the incoming ortho-P. Flooded fields were effective in the removal of inorganic N, but showed poor efficiency in the removal of ortho-P.Florida Agricultural Experiment Stations Journal Series No. 2320.     

Drinking water treatment residuals: a review of recent uses

Coagulants such as alum [Al2(SO4)3 x 14H2O], FeCl3, or Fe2(SO4)3 are commonly used to remove particulate and dissolved constituents from water supplies in the production of drinking water. The resulting waste product, called water-treatment residuals (WTR), contains precipitated Al and Fe oxyhydroxides, resulting in a strong affinity for anionic species. Recent research has focused on using WTR as cost-effective materials to reduce soluble phosphorus (P) in soils, runoff, and land-applied organic wastes (manures and biosolids). Studies show P adsorption by WTR to be fast and nearly irreversible, suggesting long-term stable immobilization of WTR-bound P. Because excessive WTR application can induce P deficiency in crops, effective application rates and methods remain an area of intense research. Removal of other potential environmental contaminants [ClO4-, Se(+IV and +VI), As(+III and +V), and Hg] by WTR has been documented, suggesting potential use of WTR in environmental remediation. Although the creation of Al plant toxicity and enhanced Al leaching are concerns expressed by researchers, these effects are minimal at circumneutral soil pH conditions. Radioactivity, trace element levels, and enhanced Mn leaching have also been cited as potential problems in WTR usage as a soil supplement. However, these issues can be managed so as not to limit the beneficial use of WTR in controlling off-site P losses to sensitive water bodies or reducing soil-extractable P concentrations.     

TOXIC METALS IN SURFACE WATERS FROM COAL ASH1

ABSTRACT: The concentration of 10 [titanium (Ti), manganese (Mn), copper (Cu), chromium (CR), zinc (Zn), arsenic (As), selenium (Se), cobalt (Co), cadmium (Cd), and mercury (Hg)] toxic elements were measured in the water, benthic sediment, plants, invertebrates, and vertebrates of an ash basin and its drainage system at a coal-fired power plant of the Savannah River Project, Aiken, S.C., over a period of two years. During 12 months of this period the basin was essentially filled and little settling of ash occurred. In the remaining 12 months, dredging had been completed, adequate settling occurred and most of the effluent turbidity was removed. All elements were more concentrated in sediment and biota than in water, and five (Mn, Cu, As, Zn, and Se) were biomagnified by at least one biotic component as compared to concentration in benthic sediment. Plants had high accumulations of Ti, Mn, As, and Hg; invertebrates had high accumulations of Co, Hg, Cu, Cr, Cd, and As; and vertebrates greatly biomagnified Se and Zn. The streamlined biotic community of the system accomplished major removal of Mn, Zn, As, Se, and Cd from the effluent. The magnitude of bioaccumulation of Ti, Mn, Zn, As, Se, Cd, and Hg was increased during the period of adequate settling in the basin.     

Low-temperature chromium(VI) biotransformation in soil with varying electron acceptors

Effective and low-cost strategies for remediating chromium (Cr)-contaminated soil are needed. Chromium(VI) leaching from contaminated soil into ground water and surface water threatens water supplies and the environment. This study tested indigenous Cr(VI) microbial transformation in batch systems at 10 degrees C in the presence of various electron acceptors. The effects of carbon addition, spiked Cr(VI), and mixing highly contaminated soil with less contaminated soil were investigated. The results indicated that Cr(VI) can be biotransformed in the presence of different electron acceptors including oxygen, nitrate, sulfate, and iron. Sugar addition had the greatest effect on enhancing Cr(VI) removal. Less dissolved organic carbon (DOC) was consumed per amount of Cr(VI) transformed under anaerobic conditions [0.8-93 mg DOC/mg Cr(VI)] compared with aerobic conditions [1.4-265 mg DOC/mg Cr(VI)]. Toxicity of high concentrations (< 160 mg/L) of spiked Cr(VI) were not evident. At Cr(VI) concentrations > 40 mg/L, aerobic conditions promoted faster Cr(VI) reduction than anaerobic conditions with nitrate or sulfate present. Biotransformation of Cr(VI) in highly contaminated soil (22,000 mg Cr/kg) was facilitated by mixing with less-contaminated soil. The study results provide a framework for evaluating indigenous Cr(VI) microbial transformation and enhance the ability to develop strategies for soil treatment.     

Miscanthus and switchgrass production in central Illinois: impacts on hydrology and inorganic nitrogen leaching

Biomass crops are being promoted as environmentally favorable alternatives to fossil fuels or ethanol production from maize (Zea mays L.), particularly across the Corn Belt of the United States. However, there are few if any empirical studies on inorganic N leaching losses from perennial grasses that are harvested on an annual basis, nor has there been empirical evaluation of the hydrologic consequences of perennial cropping systems. Here we report on the results of 4 yr of field measurements of soil moisture and inorganic N leaching from a conventional maize-soybean [Glycine max (L.) Merr.] system and two unfertilized perennial grasses harvested in winter for biomass: Miscanthus x giganteus and switchgrass (Panicum virgatum cv. Cave-in-Rock). All crops were grown on fertile Mollisols in east-central Illinois. Inorganic N leaching was measured with ion exchange resin lysimeters placed 50 cm below the soil surface. Maize--soybean nitrate leaching averaged 40.4 kg N ha(-1) yr(-1), whereas switchgrass and Miscanthus had values of 1.4 and 3.0 kg N ha(-1) yr(-1), respectively. Soil moisture monitoring (to a depth of 90 cm) indicated that both perennial grasses dried the soil out earlier in the growing season compared with maize-soybean. Later in the growing season, soil moisture under switchgrass tended to be greater than maize-soybean or Miscanthus, whereas the soil under Miscanthus was consistently drier than under maize--soybean. Water budget calculations indicated that evapotranspiration from Miscanthus was about 104 mm yr(-1) greater than under maize-soybean, which could reduce annual drainage water flows by 32% in central Illinois. Drainage water is a primary source of surface water flows in the region, and the impact ofextensive Miscanthus production on surface water supplies and aquatic ecosystems deserves further investigation.     

Irrigation of broccoli and canola with boron- and selenium-laden effluent

Selenium (Se), boron (B), and salinity contamination of agricultural drainage water is potentially hazardous for water reuse strategies in central California. To demonstrate the feasibility of using plants to extract Se from drainage water, Se accumulation was determined in canola (Brassica napus L.) and broccoli (Brassica oleracea L.) irrigated with drainage effluent in the San Joaquin Valley, California. In the 2-yr field study, both crops were irrigated with a typical drainage water containing Se (150 microg L(-1)), B (5 mg L(-1)), and a sulfate dominated salinity (EC of 7 dS m(-1)). Total dry matter yields were at least 11 Mg ha(-1) for both canola and broccoli, and plant tissue Se concentrations did not exceed 7 mg kg(-1) DM for either crop. Based on the amount of soluble Se applied to crops with drainage water and the estimated amount of soluble Se remaining in soil to a depth of 90 cm at harvest, both canola and broccoli accumulated at least 40% of the estimated soluble Se lost from the soil for both years. Applied Se not accounted for in plant tissue or as soluble Se in the soil was presumably lost by biological volatilization. This study suggests that irrigating two high value crops such as canola and broccoli with Se-laden effluent helps manage Se-laden effluent requiring treatment, and also produces economically viable Se-enriched crops. Future research should focus on managing residual salt and B in the soil for sustaining long time water reuse strategies.     

Modeling Effects of Natural Flow Restoration on Metals Fate and Transport in a Mountain Stream Impacted by Mine Waste1

Abstract: The effects of natural flow restoration on metals fate and transport in the Upper Tenmile Creek Watershed, Montana, were modeled using the Water Quality Analysis Simulation Program developed by the U.S. Environmental Protection Agency (USEPA). This 50‐km² watershed has over 150 historic abandoned mines, including mine waste rock and tailings, as well as adits discharging acid mine drainage, and is the primary drinking water supply for the City of Helena. Water supply diversions almost completely dewater some stream reaches during summer low flows, but the city is considering a new drinking water source and restoration of natural flows in Tenmile Creek as part of acid mine drainage remediation and broader aquatic habitat restoration. One dimensional steady‐state simulation of total recoverable cadmium, copper, lead, and zinc in the mainstem was performed, and the model was calibrated to June 2000 base‐flow data. Representative low‐flows in August and high‐flow snowmelt conditions in June were modeled using mean monthly natural flow estimates from the U.S. Geological Survey and representative USEPA metals concentrations data. The modeling showed that total recoverable metals concentrations, and especially loads, can vary significantly among input locations and over time in the watershed. Some data gaps limit evaluation of variability and increase uncertainty in several locations. Model results indicated, however, that natural low‐ and high‐flow restoration by itself can reduce some metals concentrations in the mainstem compared to June 2000 values, which were influenced by significant water diversion. Some values (such as Zn) may still exceed standards during natural August low flow due to the remaining high concentrations and loads in the primary inputs to the mainstem. Others (such as Cu) can increase during high flow due to remaining mine waste sources and loading of particulate Cu associated with erosion and transport of solids. Greater than 50% reduction in concentrations and loads from some of the main tributaries may be necessary to meet all standards, especially for potential particulate loads with higher flows in June.     

Nitrate loading and isotopic signatures in subsurface agricultural drainage systems

Artificially draining soils using subsurface tiles is a common practice on many agricultural fields. High levels of nitrate-nitrogen (NO-N) are often released from these systems; therefore, knowledge on the sources and processes controlling NO-N in drainage systems is needed. A dual isotope study (δN and δO) was used to investigate three subsurface drainage systems (shallow, conventional, and controlled) in Onslow, Nova Scotia, Canada. The objectives of this study were (i) to identify which drainage system more effectively reduced the NO-N loading, (ii) to examine differences in isotopic signatures under identical nutrient and cropping regimes for a fixed soil type, and (iii) to identify the utility of different drainage systems in controlling nutrient flows. Nitrate concentrations measured ranged from 0.92 to 11.8, from 2.3 to 17.3, and from 2.1 to 19.8 mg L for the shallow, conventional, and controlled drains, respectively. Total NO-N loading from shallow and controlled drains were 20 and 5.6 kg ha, respectively, lower than conventional (39.1 kg ha). The isotopic composition of NO-N for all drainage types appeared to be a mixture of two organic sources (manure and soil organic matter) via the process of nitrification. There was no evidence that denitrification played a significant role in removing NO-N during transport. Overall, shallow drainage reduced NO-N loading but offered no water conservation benefits. Combining the benefits of decreased NO-N loading from shallow systems with water control capability may offer the best solution to reducing nutrient loadings into water systems, achieving optimal crop yield, and decreasing drainage installation costs.     

Evaluation of the macroalga,muskgrass, for the phytoremediation of selenium-contaminated agricultural drainage water by microcosms

Previous field studies suggested that the macroalga, muskgrass (Chara canescens Desv. & Lois), plays an important role in the removal of selenium (Se) from agricultural drainage water. This study evaluated the efficiency of Se removal from drainage water by muskgrass-vegetated wetland microcosms, and determined the extent to which muskgrass removed Se through phytoextraction and biovolatilization. Six flow-through wetland microcosms were continuously supplied with drainage water containing an average Se concentration of 22 microg L(-1) over a 24-d experimental period. The Se mass input and outflow and the rate of Se volatilization were monitored daily for each microcosm. Three microcosms containing muskgrass reduced the daily mass Se input in the inflow drainage water by 72.1%; this compared with a reduction of 50.6% of the mass Se input for three unvegetated control microcosms. Selenium accumulated in muskgrass tissues accounted for 1.9% of the total mass Se input in the microcosm, followed by 0.5% via biological volatilization. The low rates of Se volatilization from selenate-supplied muskgrass, which were 10-fold less than from selenite, were probably due to a major rate limitation in the reduction of selenate to organic forms of Se in muskgrass. This conclusion was derived from X-ray absorption spectroscopy speciation analysis, which showed that muskgrass treated with selenite contained 91% of the total Se in organic forms (selenoethers and diselenides), compared with 47% in muskgrass treated with selenate.     

Light-catalyzed chromium(VI) reduction by organic compounds and soil minerals

Detoxification of Cr(VI) through reduction has been considered an effective method for reclaiming Cr-contaminated soil, sediment, and waste water. Organic matter is widely distributed in soil and aquatic systems; however, low Cr(VI) reduction rates inhibit the adoption of Cr reduction technologies by industry. Scientists have been aware of Cr(VI) reduction catalyzed by soil minerals; however, most of the studies focused on using semiconductors as catalysts with UV irradiation to accelerate the redox reactions. The objective of this study was to evaluate the rates of Cr(VI) reduction by fluorescence light in the presence of organic materials with or without specific soil minerals. Experimental results showed that dissolved organic compounds reduced Cr(VI) slowly under laboratory light; however, Cr(VI) reduction was greatly enhanced when growth chamber light was applied. Low photon flux (i.e., laboratory light) only enhanced Cr(VI) reduction by organics when Fe(III) was also present, because the Fe(II)-Fe(III) redox couple accelerated electron transfer and decreased electrostatic repulsion between reactants. Laboratory light was required to initiate Cr(VI) reduction catalyzed by TiO2; nonetheless, light-catalyzed Cr(VI) reduction by smectite and ferrihydrite could occur only when greater light energy was provided with a growth chamber light. Our results suggest a potential pathway for Cr(VI) reduction using naturally occurring organic compounds and colloids in acidic water systems or in surface soils when light is available.     

Simulating nitrate drainage losses from a Walnut Creek watershed field

This study was designed to evaluate the improved version of the Root Zone Water Quality Model (RZWQM) using 6 yr (1992-1997) of field-measured data from a field within Walnut Creek watershed located in central Iowa. Measured data included subsurface drainage flows, NO3-N concentrations and loads in subsurface drainage water, and corn (Zea mays L.) and soybean [Glycine mar (L.) Merr.] yields. The dominant soil within this field was Webster (fine-loamy, mixed, superactive, mesic Typic Endoaquolls) and cropping system was corn-soybean rotation. The model was calibrated with 1992 data and was validated with 1993 to 1997 data. Simulations of subsurface drainage flow closely matched observed data showing model efficiency of 99% (EF = 0.99), and difference (D) of 1% between measured and predicted data. The model simulated NO3-N losses with subsurface drainage water reasonably well with EF = 0.8 and D = 13%. The simulated corn grain yields were in close agreement with measured data with D < 10%. Nitrogen-scenario simulations demonstrated that corn yield response function reached a plateau when N-application rate exceeded 90 kg ha(-1). Fraction of applied N lost with subsurface drainage water varied from 7 to 16% when N-application rate varied from 30 to 180 kg ha(-1) after accounting for the nitrate loss with no-fertilizer application. These results indicate that the RZWQM has the potential to simulate the impact of N application rates on corn yields and NO3-N losses with subsurface drainage flows for agricultural fields in central Iowa.