Mapping ground water vulnerability to pesticide leaching with a process-based metamodel of EuroPEARL

To support EU policy, indicators of pesticide leaching at the European level are required. For this reason, a metamodel of the spatially distributed European pesticide leaching model EuroPEARL was developed. EuroPEARL considers transient flow and solute transport and assumes Freundlich adsorption, first-order degradation and passive plant uptake of pesticides. Physical parameters are depth dependent while (bio)-chemical parameters are depth, temperature, and moisture dependent. The metamodel is based on an analytical expression that describes the mass fraction of pesticide leached. The metamodel ignores vertical parameter variations and assumes steady flow. The calibration dataset was generated with EuroPEARL and consisted of approximately 60,000 simulations done for 56 pesticides with different half-lives and partitioning coefficients. The target variable was the 80th percentile of the annual average leaching concentration at 1-m depth from a time series of 20 yr. The metamodel explains over 90% of the variation of the original model with only four independent spatial attributes. These parameters are available in European soil and climate databases, so that the calibrated metamodel could be applied to generate maps of the predicted leaching concentration in the European Union. Maps generated with the metamodel showed a good similarity with the maps obtained with EuroPEARL, which was confirmed by means of quantitative performance indicators.     

Iron and arsenic release from aquifer solids in response to biostimulation

Biostimulation has been used at various contaminated sites to promote the reductive dechlorination of trichloroethylene (TCE), but the addition of carbon and energy donor also stimulates bacteria that use Fe(III) as the terminal electron acceptor (TEA) in potential competition with dechlorination processes. Microcosm studies were conducted to determine the influence of various carbon donors on the extent of reductive dissolution of aquifer solids containing Fe(III) and arsenic. Glucose, a fermentable and respirable carbon donor, led to the production of 1500 mg Fe(II) kg(-1), or 24% of the total Fe in the aquifer sediment being reduced to Fe(II), whereas the same concentration of carbon as acetate resulted in only 300 mg Fe(II) kg(-1) being produced. The biogenic Fe(II) produced with acetate was exclusively associated with the solid phase whereas with fermentable carbon donors as whey and glucose, 22 and 54% of the Fe(II) was in solution. With fermentation, some of the metabolites appear to be electron shuttling chemicals and chelating agents that facilitate the reductive dissolution of even crystalline Fe(III) oxides. Without the presence of electron shuttling chemicals, only surficial Fe in direct contact with the bacteria was bioavailable, as illustrated when acetate was used. Regardless of carbon donor type and concentration, As concentrations in the water exceeded drinking water standards. The As dissolution appears to have been the result of the direct use of As as an electron acceptor by dissimilatory arsenic reducing bacteria. Our findings indicate that selection of the carbon and energy donor for biostimulation for remediation of chlorinated solvent impacted aquifers may greatly influence the extent of the reductive dissolution of iron minerals in direct competition with dechlorination processes. Biostimulation may also result in a significant release of As to the solution phase, contributing to further contamination of the aquifer.     

Bioconversion of selenate in methanogenic anaerobic granular sludge

The capacity of anaerobic granular sludge to remove selenate from contaminated wastewater was investigated. The potential of different types of granular sludge to remove selenate from the liquid phase was compared to that of suspended sludge and contaminated soil and sediment samples. The selenate removal rates ranged from 400 to 1500 microg g VSS(-1) h(-1), depending on the source of biomass, electron donor, and the initial selenate concentration. The granular structure protects the microorganisms when exposed to high selenate concentrations (0.1 to 1 mM). Anaerobic granular sludge "Eerbeek," originating from a UASB reactor treating paper mill wastewater, removed about 90, 50, and 36% of 0.1, 0.5, and 1 mM of Se, respectively, from the liquid phase when incubated with 20 mM lactate at 30 degrees C and pH 7.5. Selenite, elemental Se (Se(o)), and metal selenide precipitates were the conversion products. Enrichments from the anaerobic granular sludge "Eerbeek" were able to convert 90% of the 10-mM selenate to Se(o) at a rate of 1505 microg Se(VI) g cells(-1) h(-1), a specific growth rate of 0.0125 g cells h(-1), and a yield of 0.083 g cells mg Se(-1). Both microbial metabolic processes (e.g dissimilatory reduction) as well as microbially mediated physicochemical mechanisms (adsorption and precipitation) contribute to the removal of selenate from the Se-containing medium.     

Effects of elevated atmospheric carbon dioxide on biomass and carbon accumulation in a model regenerating longleaf pine community

Plant species vary in response to atmospheric CO2 concentration due to differences in physiology, morphology, phenology, and symbiotic relationships. These differences make it very difficult to predict how plant communities will respond to elevated CO2. Such information is critical to furthering our understanding of community and ecosystem responses to global climate change. To determine how a simple plant community might respond to elevated CO2, a model regenerating longleaf pine community composed of five species was exposed to two CO2 regimes (ambient, 365 micromol mol(-1) and elevated, 720 micromol mol(-1)) for 3 yr. Total above- and belowground biomass was 70 and 49% greater, respectively, in CO2-enriched plots. Carbon (C) content followed a response pattern similar to biomass, resulting in a significant increase of 13.8 Mg C ha(-1) under elevated CO2. Responses of individual species, however, varied. Longleaf pine (Pinus palustris Mill.) was primarily responsible for the positive response to CO2 enrichment. Wiregrass (Aristida stricta Michx.), rattlebox (Crotalaria rotundifolia Walt. Ex Gmel.), and butterfly weed (Asclepias tuberosa L.) exhibited negative above- and belowground biomass responses to elevated CO2, while sand post oak (Quercus margaretta Ashe) did not differ significantly between CO2 treatments. As with pine, C content followed patterns similar to biomass. Elevated CO2 resulted in alterations in community structure. Longleaf pine comprised 88% of total biomass in CO2-enriched plots, but only 76% in ambient plots. In contrast, wiregrass, rattlebox, and butterfly weed comprised 19% in ambient CO2 plots, but only 8% under high CO2. Therefore, while longleaf pine may perform well in a high CO2 world, other members of this community may not compete as well, which could alter community function. Effects of elevated CO2 on plant communities are complex, dynamic, and difficult to predict, clearly demonstrating the need for more research in this important area of global change science.     

Behavior of an aerated submerged fixed-film reactor (ASFFR) under simultaneous organic and ammonium loading

The performance of an aerated submerged fixed-film reactor (ASFFR) under simultaneous organic and ammonium loading and its effect on nitrification was studied. Organic loadings varied in the range of 1.93 to 5.29 g chemical oxygen demand (COD) m-2 d-1 and NH4-N loadings were in the range of 116 to 318 mg NH4-N m-2 d-1. Increments of loading rates were obtained both by increasing the flow rate and increasing the influent substrate in individual pilot runs. Results showed that with organic loading rates up to 3.97 g COD m-2 d-1, complete nitrification was achievable. Although high organic loading such as 5.29 g COD m-2 d-1 could cause nitrification to stop, shifting to lower organic loadings made nitrification start and set rapidly to its previous steady-state concentrations. Comparison of results showed that in the ASFFR, nitrification would be severely affected by an organic loading rate of 5.29 g COD m-2 d-1 by increasing either the flow or the influent substrate. It should be noted that the average value of dissolved oxygen was 3.4 mg L-1 with an air supply of 15 L min-1, and there was no indication of oxygen limitation. The results of this study show the flexibility of ASFFRs under changing organic loads. Furthermore, for achieving complete nitrification and optimum application of these reactors for protecting receiving water from the environmental hazards of ammonium, the maximum organic loading that would present complete nitrification should be considered.     

Tillage and field scale controls on greenhouse gas emissions

There is a lack of understanding of how associations among soil properties and management-induced changes control the variability of greenhouse gas (GHG) emissions from soil. We performed a laboratory investigation to quantify relationships between GHG emissions and soil indicators in an irrigated agricultural field under standard tillage (ST) and a field recently converted (2 yr) to no-tillage (NT). Soil cores (15-cm depth) were incubated at 25 degrees C at field moisture content and 75% water holding capacity. Principal component analysis (PCA) identified that most of the variation of the measured soil properties was related to differences in soil C and N and soil water conditions under ST, but soil texture and bulk density under NT. This trend became more apparent after irrigation. However, principal component regression (PCR) suggested that soil physical properties or total C and N were less important in controlling GHG emissions across tillage systems. The CO2 flux was more strongly determined by microbial biomass under ST and inorganic N content under NT than soil physical properties. Similarly, N2O and CH4 fluxes were predominantly controlled by NO3- content and labile C and N availability in both ST and NT soils at field moisture content, and NH4+ content after irrigation. Our study indicates that the field-scale variability of GHG emissions is controlled primarily by biochemical parameters rather than physical parameters. Differences in the availability and type of C and N sources for microbial activity as affected by tillage and irrigation develop different levels and combinations of field-scale controls on GHG emissions.     

Effect of manure application timing, crop, and soil type on nitrate leaching

Timing of manure application affects N leaching. This 3-yr study quantified N losses from liquid manure application on two soils, a Muskellunge clay loam and a Stafford loamy sand, as affected by cropping system and timing of application. Dairy manure was applied at an annual rate of 93 800 L ha(-1) on replicated drained plots under continuous maize (Zea mays L.) in early fall, late fall, early spring, and as a split application in early and late spring. Variable rates of supplemental sidedress N fertilizer were applied as needed. Manure was applied on orchardgrass (Dactylis glomerata L.) in split applications in early fall and late spring, and early and late spring, with supplemental N fertilizer topdressed as NH4NO3 in early spring at 75 kg N ha(-1). Drain water was sampled at least weekly when lines were flowing. Three-year FWM (flow-weighted mean) NO3-N concentrations on loamy sand soil averaged 2.5 times higher (12.7 mg L(-1)) than those on clay loam plots (5.2 mg L(-1)), and those for fall applications on maize-cropped land averaged >10 mg L(-1) on the clay loam and >20 mg L(-1) on the loamy sand. Nitrate-N concentrations among application seasons followed the pattern early fall > late fall > early spring = early + late spring. For grass, average NO3-N concentrations from manure application remained well below 10 mg L(-1). Fall manure applications on maize show high NO3-N leaching risks, especially on sandy soils, and manure applications on grass pose minimal leaching concern.     

Aerating grassland before manure application reduces runoff nutrient loads in a high rainfall environment

The effect of mechanically aerating grassland before liquid manure application in the fall on surface runoff and transport of nutrients and solids was studied in a high rainfall area. The two treatments were control and aeration, the latter receiving one pass with an aerator perpendicular to the slope before fall application of liquid manure (dairy in Years 1-3 and swine in Year 4). Treatments were randomly assigned on 3 to 5% sloping land with a silt loam surface soil (Aquic Dystroxerept) planted in orchardgrass (Dactylis glomerata L.). Runoff from natural rainfall events was sampled for nutrient and solids analysis. Aeration significantly reduced runoff and loads of suspended solids, total Kjeldahl N (TKN), and dissolved reactive P in all years. Annual runoff amounts were reduced by 47 to 81%, suspended and volatile solid loads by 48 to 69% and 42 to 83%, respectively, TKN loads by 56 to 81%, and total P (TP) loads by 25 to 75%. Loads of the soluble nutrient NH4-N, dissolved reactive P, and K were reduced by 41 to 83%. The first three runoff events after manure application accounted for approximately one-third of the annual total runoff and solid and nutrient loads when averaged across treatments, with loads of TKN, K, and NH4-N totaling 4.4, 3.3, and 1.9 kg ha-1, respectively. Aeration slightly increased downward movement of NO3-N, but not other nutrients in the soil. Thus mechanical aeration can be an effective tool for reducing runoff and loads of solids and nutrients after surface application of liquid manure on sloping grassland.     

Management of mine spoil for crop productivity with lignite fly ash and biological amendments

Long-term field trials using lignite fly ash (LFA) were carried out in rice crops during the period 1996-2000 at Mine I, Neyveli Lignite Corporation, Tamil Nadu. LFA, being alkaline and endowed with an excellent pozzolanic nature, silt loam texture, and plant nutrients, has the potential to improve the texture, fertility, and crop productivity of mine spoil. The rice crops were the first, third, fifth, and sixth crops in rotation. The other crops, such as green gram (second) and sun hemp (fourth), were grown as green manure. For experimental trials, LFA was applied at various dosages (0, 5, 10, 20, 50, 100, and 200 t/ha), with and without press mud (10 t/ha), before cultivation of the first crop. Repeat applications of LFA were made at the same dosages in treatments of up to 50 t/ha (with and without press mud) before cultivation of the third and fifth crops. Press mud, a lightweight organic waste product from the sugar industry, was used as an organic amendment and source of plant nutrients. Also, a recommended dosage of chemical fertilizer, along with gypsum, humic acid, and biofertilizer as supplementing agents, was applied in all the treatments, including control. With one-time and repeat applications of LFA, from 5 to 20 t/ha (with and without press mud), the crop yield (grain and straw) increased significantly (p < 0.05), in the range from 3.0 to 42.0% over the corresponding control. The maximum yield was obtained with repeat applications of 20 t/ha of LFA with press mud in the third crop. The press mud enhanced the yield in the range of 1.5-10.2% with various dosages of LFA. The optimum dosage of LFA was 20 t/ha for both one-time and repeat applications. Repeat applications of LFA at lower dosages of up to 20 t/ha were more effective in increasing the yield than the corresponding one-time applications of up to 20 t/ha and repeat applications at 50 t/ha. One-time and repeat applications of LFA of up to 20 t/ha (with and without press mud), apart from increasing the yield, evinced improvement in the texture and fertility of mine spoil and the nutrient content of crop produce. Furthermore, some increase in the content of trace and heavy metals and the level of gamma-emitters in the mine spoil and crop produce was observed, but well within the permissible limits. The residual effect of LFA on succeeding crops was also encouraging in terms of eco-friendliness. Beyond 20 t/ha of LFA, the crop yield decreased significantly (p < 0.05), as a result of the formation of hardpan in the mine spoil and possibly the higher concentration of soluble salts in the LFA. However, the adverse effects of soluble salts were annulled progressively during the cultivation of succeeding crops. A plausible mechanism for the improved fertility of mine spoil and the carryover or uptake of toxic trace and heavy metals and gamma-emitters in mine spoil and crop produce is also discussed.     

Electroosmotic dewatering of dredged sediments: bench-scale investigation

The Indiana Harbor (Indiana, USA) has not been dredged since 1972 due to lack of a suitable disposal site for dredged sediment. As a result of this, over a million cubic yards of highly contaminated sediment has accumulated in the harbor. Recently, the United States Army Corps of Engineers (USACE) has selected a site for the confined disposal facility (CDF) and is in the process of designing it. Although dredging can be accomplished rapidly, the disposal in the CDF has to be done slowly to allow adequate time for consolidation to occur. The sediment possesses very high moisture content and very low hydraulic conductivity, which cause consolidation to occur slowly. Consolidation of the sediment is essential in order to achieve adequate shear strength of sediments and also to provide enough air space to accommodate the large amount of sediment that requires disposal. Currently, it has been estimated that if a one 3-foot (0.9-m) thick layer of sediment was disposed of at the CDF annually, it would take approximately 10 years to dispose of all the sediment that is to be dredged from the Indiana Harbor. This study investigated the feasibility of using an electroosmotic dewatering technology to accelerate dewatering and consolidation of sediment, thereby allowing more rapid disposal of sediment into the CDF. Electroosmotic dewatering essentially involves applying a small electric potential across the sediment layer, thereby inducing rapid flow as a result of physico-chemical and electrochemical processes. A series of bench-scale electrokinetic experiments were conducted on actual dredged sediment samples from the Indiana Harbor to investigate dewatering rates caused by gravity alone, dewatering rates caused by gravity and electric potential, and the effects of the addition of polymer flocculants on dewatering of the sediments. The results showed that electroosmotic dewatering under an applied electric potential of 1.0VDC/cm could increase the rate of dewatering and consolidation by an order of magnitude as compared to gravity drainage alone. Amending the sediment with polymers at low concentrations (0.5-1% by dry weight) will enhance this dewatering process; however, the optimal polymer concentration and the cost-effectiveness of using polymers should be investigated further.