Coupled abiotic-biotic mineralization of 2,4,6-trinitrotoluene (TNT)

Munitions wastes such as TNT are widespread contaminants in soils and ground waters. We investigated a coupled abiotic-biotic treatment scheme for remediation of aqueous solutions of TNT. Mineralization of aqueous TNT (0.22 mM) was initially optimized with minimum reactant use (Fe3+ and H2O2) in light-assisted and dark, modified Fenton reactions at acidic and neutral pH. Complete TNT degradation occurred under all reaction conditions within 24 h. Using the optimum reactant concentrations, coupled abiotic-biotic reactions showed an increase in TNT mineralization, from 47 to 80%, after biomass addition to the acidic, dark Fenton-like reaction. Comparable increases of TNT mineralization were observed under neutral pH with similar reaction conditions. In light-assisted Fenton-like reactions at neutral pH, no increase in cumulative TNT mineralization (66%) was seen in coupled abiotic-biotic reactions. Abiotic photo-Fenton-like reactions alone, at acidic pH, produced complete TNT mineralization and required no biotic assistance. While light-enhanced Fenton reactions alone can provide high levels of TNT mineralization, the dark abiotic-biotic reaction scheme has perhaps a wider use due to a similar extent of TNT mineralization in the absence of light, leading to possible applications in soil slurry and in situ processes in the subsurface.     

Solid-state nitrogen-15 nuclear magnetic resonance analysis of biologically reduced 2,4,6-trinitrotoluene in a soil slurry remediation

Soil contaminated with 2,4,6-trinitrotoluene (TNT) and spiked with [14C]- and [15N3]-TNT was subjected to an anaerobic-aerobic soil slurry treatment and subsequently analyzed by radiocounting and solid-state 15N nuclear magnetic resonance (NMR) spectroscopy. This treatment led to a complete disappearance of extractable radioactivity originating from TNT and almost all of the radioactivity was recovered in the insoluble soil fraction. As revealed by solid-state 15N NMR, a major fraction of partially reduced metabolites of TNT was immobilized into the soil during the early stage of the anaerobic treatment, although some of the compounds (i.e., aminodinitrotoluenes and azoxy compounds) were extractable by methanol. Considerable 15N intensity was assigned to condensation products of TNT metabolites. A smaller signal indicated the formation of azoxy N. This signal and the signal for nitro groups were not observed at the end of the anaerobic phase, revealing further reduction and/or transformation of their corresponding compounds. An increase of the relative proportion of the condensation products occurred with increasing anaerobic incubation. Aerobic incubation resulted in a further decrease of aromatic amines, presumably due to oxidative transformations or their involvement in further condensation reactions. The results of the study demonstrate that the anaerobic-aerobic soil slurry treatment represents an efficient strategy for immobilizing reduced TNT in soils.     

Enzymatic transformation and binding of labeled 2,4,6-trinitrotoluene to humic substances during an anaerobic/aerobic incubation

Organic pollutants are degraded in soil and simultaneously nonextractable residues are formed. However, proof is lacking that this fixation has a detoxifying effect. We investigated the transformation and binding of 2,4,6-trinitrotoluene (TNT) with catechol or soil humic acid as cosubstrates. Carbon-14-labeled TNT and its reaction products were quantified by radiocounting; extractable compounds were identified by high performance liquid chromatography (HPLC). Bound and extractable residues of 15N-labeled TNT and metabolites were studied by 15N nuclear magnetic resonance spectroscopy (15N NMR). Since TNT is not easily transformed under oxidizing conditions an anaerobic/aerobic treatment was used. Anaerobic microorganisms from cow manure were used to reduce TNT during the anaerobic phase and subsequently, a laccase from Trametes villosa was used in the aerobic phase to oxidatively couple the metabolites to humic matter. Seventy-four percent of TNT was immobilized with catechol as cosubstrate, but only 25% with humic acid. With catechol the main extractable component was TNT, while with humic acid it was mostly the metabolite 4-aminodinitrotoluene. For both co-substrates, the spectra of immobilized metabolites obtained by solid-state 15N-cross polarization magic angle spinning (CPMAS) NMR spectroscopy showed signals in the chemical shift region for protonated aromatic amino compounds. However, in the presence of catechol, an additional signal from nonextractable nitro groups was found, which could represent sequestered TNT. The partially reduced metabolites of TNT that formed nonextractable residues in humic acid are not likely to be remobilized easily and are thus regarded as detoxified.     

Redistribution of slurry components as influenced by injection method, soil, and slurry properties

The distribution of moisture, degradable C, and N after direct injection of slurry can affect the turnover and plant availability of slurry N. This study examined effects of injection method, soil conditions, and slurry properties on the infiltration of several slurry components under practical conditions. The water retention capacity of 22 pig and cattle slurries was quantified by dialysis at -0.016, -0.047, and -0.100 MPa. All slurries followed the relationship: relative water loss = 1/(1 + aVS[volatile solids]), indicating that retention of liquids in the slurry injection zone can be predicted from slurry VS and soil water potential. Two-disc injection and harrow tine injection were simulated (no slurry applied) in five trials. Two trials indicated that disc injection resulted in higher permeability compared with harrow tine injection. In a separate experiment, soil moisture and dissolved ions were monitored in and around injection slits amended with pig or cattle slurry. Moisture gradients, which were recorded with small printed-circuit-board (PCB) time-domain-reflectometry (TDR) probes, were temporally stable and reestablished following rainfall. Slit sections with pig and cattle slurry containing 13C-acetate and 15N-ammonium showed a shift in the 13C to 15N ratio of the injection zone within 24 h, which was explained by removal of dissolved C and/or retention of NH4+. Cattle slurry was more concentrated around the injection slit than pig slurry, and greater contact between slurry and soil was obtained with harrow tine injection. The heterogeneity of slurry C and N distribution after direct injection should be accounted for in models describing slurry N turnover.     

Dissolution and transport of TNT, RDX, and composition B in saturated soil columns

Low-order detonations and blow-in-place procedures on military training ranges can result in residual solid explosive formulations to serve as distributed point sources for ground water contamination. This study was conducted to determine if distribution coefficients from batch studies and transport parameters of pure compounds in solution adequately describe explosive transport where compounds are present as solid particles in formulations. Saturated column transport experiments were conducted with 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and the explosive formulation, Composition B (Comp B) (59.5 +/- 2.0% RDX, 39.5 +/- 2.3% TNT, and 1% wax) in solid and dissolved forms. The two soils used were Plymouth loamy sand (mesic, coated Typic Quartzipsamments) from Camp Edwards, MA and Adler silt loam (coarse-silty, mixed, superactive, thermic Fluvaquentic Eutrudepts) from Vicksburg, MS. Interrupted flow experiments were used to determine if explosives were at equilibrium distribution between soil and solution phases. The HYDRUS-1D code was used to determine fate and transport parameters. Results indicated that sorption of high explosives was rate limited. The behavior of dissolved Comp B was similar to the behavior of pure TNT and RDX. Behavior of solid Comp B was controlled by dissolution that depended on physical properties of the Comp B sample. Adsorption coefficients determined by HYDRUS-1D were different from those determined in batch tests for the same soils. Use of parameters specific to formulations will improve fate and transport predictions.     

Impact of methylene chloride on microorganisms and phenanthrene mineralization in soil

This study investigated the effects of the quantity of methylene chloride, used as a carrier solvent for phenanthrene when added to soil, on phenanthrene mineralization kinetics, soil phospholipid fatty add profiles (PLFA), and phenanthrene distribution. Methylene chloride dosages of 25 microL/g soil or more resulted in an enrichment of saturated PLFAs, suggesting soil microorganisms had adjusted their cell membranes in response to the solvent. A greater fraction of phenanthrene mineralized when spiked in 5 microL/g than in 25 microL/g methylene chloride suggesting that the methylene chloride became toxic to phenanthrene-degrading organisms in soil. Phenanthrene was more equally distributed among 0.1 g soil subsamples if spiked in 25 than 5 or 1 microL methylene chloride per gram soil. Thus the amount of methylene chloride used to spike phenanthrene in soil strongly impacted the mineralization kinetics, phenanthrene distribution, and microbial community in soil. Because a variety of spiking methods are used in biodegradation research, scientists should consider the quantity of solvents used when comparing results among different studies.     

Relevance of organic matter fractions as predictors of wastewater sludge mineralization in soil

Seventeen different wastewater sludges were characterized using both chemical and organic matter fractionation methods (water extraction, Van Soest method, and acid hydrolysis) and 6-mo incubation studies to assess their decomposition in soil. Simple correlation and multiple factor analysis (MFA) were then performed to establish relationships between composition and C and N mineralization of sludges. Carbon and N concentrations covered a wide range of values, but organic carbon (C(o)) to organic nitrogen (N(o)) ratios were relatively low (from 5 to 19). Carbon and N were mainly distributed in the most soluble fractions of the Van Soest method and in the water-insoluble fraction at 100 degrees C. Carbon mineralization varied from 180 to 661 g C kg(-1) organic C added during the 168-d incubation. The addition of sludges led to different inorganic N dynamics: from -3.3 to +120.0 g N kg(-1) sludge organic C mineralized after the 168-d incubation. Fractionation studies showed that the most discriminating method was acid hydrolysis. Carbon mineralization was linked with the proportion of sludge N and C present in the lignin-like fraction (r = -0.68 and -0.65, respectively). Significant relationships were established between N mineralization and N(o) to C(o) ratio (0.88 < r < 0.95) and the C(o) to N(o) ratio of sludges, the C to N ratio of the soluble fraction obtained by the Van Soest method, the water-soluble fraction at 100 degrees C, and the C and N present in the acid-hydrolyzable fraction. Finally, multiple factor analysis also enabled establishing a sludge typology using five clusters based on composition and mineralization characteristics.     

Field-scale variation in microbial activity and soil properties in relation to mineralization and sorption of pesticides in a sandy soil

Pesticides applied to agricultural soils are subject to environmental concerns because leaching to groundwater reservoirs and aquatic habitats may occur. Knowledge of field variation of pesticide-related parameters is required to evaluate the vulnerability of pesticide leaching. The mineralization and sorption of the pesticides glyphosate and metribuzin and the pesticide degradation product triazinamin in a field were measured and compared with the field-scale variation of geochemical and microbiological parameters. We focused on the soil parameters clay and organic carbon (C) content and on soil respiratory and enzymatic processes and microbial biomass. These parameters were measured in soil samples taken at two depths (Ap and Bs horizon) in 51 sampling points from a 4-ha agricultural fine sandy soil field. The results indicated that the spatial variation of the soil parameters, and in particular the content of organic C, had a major influence on the variability of the microbial parameters and on sorption and pesticide mineralization in the soil. For glyphosate, with a co-metabolic pathway for degradation, the mineralization was increased in soils with high microbial activity. The spatial variability, expressed as the CV, was about five times higher in the Bs horizon than in the Ap horizon, and the local-scale variation within 100 m(2) areas were two to three times lower than the field-scale variation within the entire field of about 4 ha.     

Pig slurry application and irrigation effects on nitrate leaching in Mediterranean soil lysimeters

Land application of animal manures, such as pig slurry (PS), is a common practice in intensive-farming agriculture. However, this practice has a pitfall consisting of the loss of nutrients, in particular nitrate, toward water courses. The objective of this study was to evaluate nitrate leaching for three application rates of pig slurry (50, 100, and 200 Mg ha(-1)) and a control treatment of mineral fertilizer (275 kg N ha(-1)) applied to corn grown in 10 drainage lysimeters. The effects of two irrigation regimes (low vs. high irrigation efficiency) were also analyzed. In the first two irrigation events, drainage NO(3)-N concentrations as high as 145 and 69 mg L(-1) were measured in the high and moderate PS rate treatments, respectively, in the low irrigation efficiency treatments. This indicates the fast transformation of the PS ammonium into nitrate and the subsequent leaching of the transformed nitrate. Drainage NO(3)-N concentration and load increased linearly by 0.69 mg NO(3)-N L(-1) and 4.6 kg NO(3)-N ha(-1), respectively, for each 10 kg N ha(-1) applied over the minimum of 275 kg N ha(-1). An increase in irrigation efficiency did not induce a significant increase of leachate concentration and the amount of nitrate leached decreased about 65%. Application of low PS doses before sowing complemented with sidedressing N application and a good irrigation management are the key factors to reduce nitrate contamination of water courses.     

Carbon and nitrogen mineralization rates after application of organic amendments to soil

The objective of this study was to quantify C and N mineralization rates from a range of organic amendments that differed in their total C and N contents and C quality, to gain a better understanding of their influence on the soil N cycle. A pelletized poultry manure (PP), two green waste-based composts (GWCa, GWCb), a straw-based compost (SBC), and a vermi-cast (VER) were incubated in a coarse-textured soil at 15 degrees C for 142 d. The C quality of each amendment was determined by chemical analysis and by 13C nuclear magnetic resonance (NMR). Carbon dioxide (CO2-C) evolution was determined using alkali traps. Gross N mineralization rates were calculated by 15N isotopic pool dilution. The CO2-C evolution rates and gross N mineralization rates were generally higher in amended soils than in the control soil. With the exception of GWCb all amendments released inorganic N at concentrations that would be high enough to warrant a reduction in inorganic N fertilizer application rates. The amount of N released from PP was high indicating that application rates should be reduced, or alternative amendments used, to minimize leaching losses in regions where ground water quality is of concern. There was a highly significant relationship between CO2-C evolution and gross N mineralization (R2= 0.95). Some of the chemically determined C quality parameters had significant relationships (p < 0.05) with both the cumulative amounts of C and N evolved. However, we found no significant relationships between 13C NMR spectral groupings, or their ratios, and either the CO2-C evolved or gross N mineralized from the amendments.     

The fate of sulfate in acidified pig slurry during storage and following application to cropped soil

Acidification of slurry with sulfuric acid is a recent agricultural practice that may serve a double purpose: reducing ammonia emission and ensuring crop sulfur sufficiency. We investigated S transformations in untreated and acidified pig slurry stored for up to 11 mo at 2, 10, or 20 degrees C. Furthermore, the fertilizer efficiency of sulfuric acid in acidified slurry was investigated in a pot experiment with spring barley. The sulfate content from acidification with sulfuric acid was relatively stable and even after 11 mo of storage the majority was in the plant-available sulfate form. Microbial sulfate reduction during storage of acidified pig slurry was limited, presumably due to initial pH effects and a limitation in the availability of easily degradable organic matter. Sulfide accumulation was observed during storage but the sulfide levels in acidified slurry did not exceed those of the untreated slurry for several months after addition. The S fertilizer value of the acidified slurry was considerable as a result of the stable sulfate pool during storage. The high content of inorganic S in the acidified slurry may potentially lead to development of odorous volatile sulfur-containing compounds and investigations are needed into the relationship between odor development and the C and S composition of the slurry.     

Biological treatment of 2,4,6-trichlorophenol (TCP) containing wastewater in a hybrid bioreactor system with effluent recycle

Due to the toxic effects of trichlorophenol (TCP) on microorganisms, biological treatment efficiencies of TCP containing wastewaters are usually low. Synthetic wastewater containing 2,4,6-TCP was biologically treated in a hybrid-loop bioreactor system consisting of a packed column biofilm and an aerated tank bioreactor with effluent recycle in order to improve COD and TCP removals. Effects of the feed TCP concentration on COD, TCP and toxicity removal performance of the system were investigated for the feed TCP between 50 and 450 mg L(-1) while the sludge age (solids retention time, SRT) and hydraulic residence time (HRT) were kept constant at 20 d and 25 h, respectively. Biomass concentrations in the packed column and in the aeration tank decreased with increasing feed TCP concentrations due to toxic effects of TCP on the organisms. Low biomass concentrations in the system at high feed TCP contents resulted in low COD, TCP and toxicity removals. Therefore, percent TCP, COD and toxicity removals decreased with increasing feed TCP concentrations especially above 400 mg L(-1). The effluent TCP concentrations were lower than 20 mg L(-1) for the feed TCP concentrations below 390 mg L(-1) resulting in TCP and COD removals above 90%. Specific rates of TCP and COD removals increased with the feed TCP due to low biomass concentrations at high TCP contents. The system should be operated at a feed TCP lower than 400 mg L(-1) in order to obtain more than 90% TCP, COD and toxicity removals under the specified experimental conditions.     

A comparison of in situ methods for measuring net nitrogen mineralization rates of organic soil amendments

In situ incubation methods may help provide site-specific estimates of N mineralization from land-applied wastes. However, there are concerns about the reliability of the data generated by the various methods due to containment artifacts. We amended a sandy soil with either poultry manure, biosolids, or yard-waste compost and incubated the mixtures using four in situ methods (buried bags, covered cylinders, standard resin traps, and "new" soil-resin traps) and a conventional laboratory technique in plastic bags. Each incubation device was destructively sampled at 45-d intervals for 180 d and net N mineralization was determined by measuring the amount of inorganic N that accumulated in the soil or soil plus resin traps. Containment effects were evaluated by comparing water content of the containerized soil to a field-reference soil column. In situ incubation methods provided reasonable estimates of short-term (< 45 d) N mineralization, but long-term (> 45 d) mineralization data were not accurate due to a variety of problems specific to each technique. Buried bags and covered cylinders did not retain mineralized N due to water movement into and out of the containers. Neither resin method captured all of the mineralized N that leached through the soil columns, but the new soil-resin trap method tracked field soil water content better than all other in situ methods evaluated. With further refinement and validation, the new soil-resin trap method may be a useful in situ incubation technique for measuring net N mineralization rates of organic soil amendments.     

Effects of pH and cyclodextrins on pentachlorophenol degradation (mineralization) by white-rot fungi

White-rot fungi (WRF) such as Trametes hirsuta completely degrade (mineralize) pentachlorophenol (PCP) and many other organopollutants. This has led to them being used to decontaminate various substrates (e.g. soil) through biorememediation. However, because PCP is a biocide, it can inhibit fungal growth and thereby its own degradation. It was hypothesized that substrate pH might affect PCP degradation, because when the pH is lower than 4.7 (the pKa for PCP) the phenol predominates, while at higher pH the phenate does. These two PCP species differ markedly in physical and biological properties. The effect of cyclodextrins was also investigated since it is known that the inclusion complexes these form with PCP differ in bioavailability and toxicity from non-complexed PCP. Tests were first made in liquid and agar media (where conditions are relatively easy to control), and then in a sawdust, because it is a common target matrix for WRF bioremediation. Results with the liquid and agar media showed that growth in the presence of inhibitory PCP concentrations decreased as the pH decreased, consistent with the phenol being more toxic. Growth in sawdust was less affected by PCP regardless of the pH, presumably because the PCP sorbed to the wood which decreased its bioavailability. Some cyclodextrins markedly decreased the PCP's toxicity in liquid, agar and sawdust media. Rates of PCP mineralization (measured from production of (14)CO(2) from (14)C PCP) in liquid cultures containing 0.5 mgkg(-1) PCP (a sub-inhibitory concentration) were similar from pH 2.5-7.5, indicating that the phenol and the phenate were equally degradable. Degradation of a growth inhibiting concentration on sawdust (1,000 mgkg(-1)) could be increased slightly by lowering the pH below the pKa, this increasing sorption to the wood. Degradation increased more when the pH was raised well above the pKa, presumably due to the phenate being less toxic and more soluble, making it more available to the degradative system. Although some cyclodextrins decreased growth inhibition, they also interfered with degradation. If this interference could be overcome, cyclodextrins could be used to increase the maximal PCP concentration that could be treated by WRF bioremediation.     

Effects of tree root-derived substrates and inorganic nutrients on pyrene mineralization in rhizosphere and bulk soil

This study investigated the effects of organic and inorganic nutrients on the microbial degradation of the common soil contaminant pyrene. The material used in this investigation was collected from potted trees that had been growing for over a year in a soil artificially contaminated with polycyclic aromatic hydrocarbons. Soil was removed from the nonroot (bulk) and root (rhizosphere) zones of these pots and used in mineralization studies that tracked microbial degradation of 14C-pyrene. The factors influencing degradation in these zones were then tested by amendment with essential inorganic nutrients or with root-derived materials. As expected, pyrene mineralization was greater in soil removed from the rhizosphere than in bulk soil. The rate of mineralization in rhizosphere soil was inhibited by inorganic nutrient amendment, whereas nutrients stimulated mineralization in the bulk soil. Pyrene mineralization in bulk soil was also increased by the addition of root extracts intended to mimic exudation by living roots. However, amendment with excised fine roots that were allowed to decay over time in soil initially inhibited mineralization. With time, the rate of mineralization increased, eventually exceeding that of unamended bulk soil. Combined, the initial inhibition and subsequent stimulation produced a zero net impact of decaying fine roots on bulk soil mineralization. Our results, in conjunction with known temporal patterns of fine root dynamics in natural systems, support the idea that seasonal variations in nutrient and substrate availability may influence the long-term effect of plants on organic degradation in soil, possibly reducing or negating the beneficial effects of vegetation that are often observed in short-term studies.     

Spatial variation in 2-methyl-4-chlorophenoxyacetic acid mineralization and sorption in a sandy soil at field level

The phenoxyacetic acid herbicide MCPA (2-methyl-4-chlorophenoxyacetic acid) is frequently detected in groundwater beneath Danish agricultural fields. We investigated spatial variation in microbial MCPA mineralization potential in a flat agricultural field of fine sandy soil (USDA classification: Humic Dystrudept) located on the Yoldia plains of Northern Jutland, Denmark. Samples for determination of MCPA mineralization and sorption were collected from the Ap and Bs horizons at 51 sampling sites located in a 200 x 220 m grid. Spatial variation in sorption was low in both horizons (distribution coefficient, 0.36-4.16 L kg(-1)). Sorption correlated strongly with soil organic carbon content in both horizons (CV, 93 and 83%, respectively) and negatively with soil pH. [Ring-(14)C]-MCPA mineralized readily in the Ap horizon, with 49 to 62% of the (14)C-MCPA being converted to (14)CO(2) during the 67-d incubation period. With the subsoil, mineralization of (14)C-MCPA varied considerably between samples (0.5-72.8%). At neither depth was there correlation between (14)C-MCPA mineralization and sorption, soil pH, organic carbon content, clay content, number of colony-forming units (CFU), pseudomonad CFU, or any of the four microbial activity parameters measured. The presence of microbial genes encoding for the TfdA enzyme was quantified using real-time polymerase chain reaction. No correlation was found between MCPA mineralization potential and the natural background number of tfdA genes present in the soil samples. The degradation kinetics suggests that the high (14)C-MCPA mineralization rate detected in soil samples was linked to growth of the MCPA-degrading soil microbial community.     

Interactions between soil texture and placement of dairy slurry application: II. Leaching of phosphorus forms

Managing phosphorus (P) losses in soil leachate folllowing land application of manure is key to curbing eutrophication in many regions. We compared P leaching from columns of variably textured, intact soils (20 cm diam., 20 cm high) subjected to surface application or injection of dairy cattle (Bos taurus L.) manure slurry. Surface application of slurry increased P leaching losses relative to baseline losses, but losses declined with increasing active flow volume. After elution of one pore volume, leaching averaged 0.54 kg P ha(-1) from the loam, 0.38 kg P ha(-1) from the sandy loam, and 0.22 kg P ha(-1) from the loamy sand following surface application. Injection decreased leaching of all P forms compared with surface application by an average of 0.26 kg P ha(-1) in loam and 0.23 kg P ha(-1) in sandy loam, but only by 0.03 kg P ha(-1) in loamy sand. Lower leaching losses were attributed to physical retention of particulate P and dissolved organic P, caused by placing slurry away from active flow paths in the fine-textured soil columns, as well as to chemical retention of dissolved inorganic P, caused by better contact between slurry P and soil adsorption sites. Dissolved organic P was less retained in soil after slurry application than other P forms. On these soils with low to intermediate P status, slurry injection lowered P leaching losses from clay-rich soil, but not from the sandy soils, highlighting the importance of soil texture in manageing P losses following slurry application.     

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.     

Regional inventory of soil surface nitrogen balances in Indian agriculture (2000-2001)

Nitrogen regulates several ecological and biogeochemical processes and excess reactive nitrogen in the environment can lead to pollution problems, including the deterioration of air quality, disruption of forest processes, acidification of lakes and streams, and degradation of coastal waters. Much of the excess nitrogen inputs are related to food and energy production. An important step to understanding the sources of nitrogen and ultimately defining solutions to excess nitrogen is to describe the geographic distribution of agricultural nitrogen contributions from different regions. In this study, soil surface nitrogen loads were quantified for different states of India for the period 2000-2001. Nearly 35.4 Tg of nitrogen has been estimated as inputs from different sources, with output nitrogen from harvested crops of about 21.20 Tg. The soil surface nitrogen balance, estimated as inputs minus outputs, is found to be about 14.4 Tg surplus from the agricultural land of India. Livestock manure constituted a major percentage of total inputs (44.06%), followed by inorganic fertilizer (32.48%), atmospheric deposition (11.86%) and nitrogen fixation (11.58%). Nitrogen balance varied from deficit to surplus for different states. The highest nitrogen surplus was found in Uttar Pradesh (2.50 Tg) followed by Madhya Pradesh (1.83 Tg), Andhra Pradesh (1.79 Tg), etc. A negative nitrogen balance was found in Orissa (-0.01 Tg), Andaman Nicobar Islands (-0.32 Tg) and for some of the northeastern states. Major fertilizer consumption states were found to be Tamilnadu (204 kg/ha), Haryana (132 kg/ha), Punjab (148 kg/ha), followed by others. Similarly, nitrogen inputs from total livestock excretions were found to be high for Kerala (616 kg/ha), Jammu and Kashmir (389 kg/ha), Tamil Nadu (338 kg/ha), etc. The average nitrogen surplus of about 54 kg/ha observed for the agricultural land of the entire country of India is comparatively higher than the average surplus of about 31 kg/ha reported for European countries. These results, obtained from nutrient mass balance calculations, will be useful to formulate nutrient management plans relating to fertilizer usage, livestock management and for adopting some best management strategies at a state level in India.     

Coupled effects of treated effluent irrigation and wetting-drying cycles on transport of triazines through unsaturated soil columns

The physical and chemical parameters controlling the movement of atrazine (6-chloro-N2-ethyl-N4-isopropyl-l,3,5-triazine-2,4-diamine; 98.8%) and prometryn [N,N'-bis(1-methylethyl)-6-(methylthio)-l,3,5triazine-2,4-diamine; 99.5%] were investigated in columns infiltrated with treated effluent under unsaturated transient conditions and subjected to drying events at 22 or 60 degrees C followed by rewetting. Three soils varying in soil pH and texture and three solutions were used. The infiltrating solutions consisted of either a CaCl2 matrix (CC), a swine waste-derived lagoon effluent (SW), or a simulated buffer solution (SB) representative of the element composition and pH of the SW but with no dissolved organic matter. Several parameters were monitored including leachate triazine concentrations, pH, dissolved organic carbon (DOC), inorganic carbon, and flow rates. Compared with CC, application of SW and SB increased column leachate pH, enhanced dissolution of organic carbon and particle dispersion, and decreased average flow rates, which allowed for increased desorption time. The coupled effect of these processes enhanced movement of triazines in some cases, with SW generally having the greatest effect. The individual effect of increased pH was more pronounced for prometryn (pKa=4.05) versus atrazine (pKa=1.66), and most dramatic for the soil with the lowest initial pH. High-temperature drying, which simulated intensive evaporation, further enhanced the dissolution of soil organic matter and the reduction in leachate flow rates with SW and SB applications; however, the net effect under the experimental conditions employed varied with soil type. Relative to low-temperature drying, high-temperature drying in the silty clay loam-packed columns reduced pesticide migration.