A model for linking the effects of parathion in soil to its degradation and bioavailability kinetics

Parathion is an insecticide of a group of highly toxic organophosphorus compounds. To investigate the dissipation and toxicological impact of parathion [O,O-diethyl O-(4-nitrophenyl) phosphorothioate] and its highly toxic metabolite, paraoxon, soil laboratory experiments were conducted in columns during a 19-d experiment under variably saturated conditions. Water and pesticide transport, sorption, and biodegradation of parathion were measured in three soil pools (soluble phase, weakly and strongly sorbed phases) using C-labeled pesticide. The effects of parathion and its metabolite on the mobility of soil nematodes were observed and then modeled with an effective variable, which combined pesticide concentration and time of application. Results showed that parathion was highly sorbed and slowly degraded to a mixture of metabolites. The parent compound and its metabolites remained located in the top 0.06-m soil layer. A kinetic model describing the sorption, biodegradation, and allocation into different soil pools of parathion and its metabolites was coupled with heat and water transport equations to predict the fate of parathion in soil. Simulated results were in agreement with experimental data, showing that the products remained in the upper soil layers even in the case of long-term (11-mo) simulation. The strongly sorbed fraction may be regarded as a pesticide reservoir that regularly provides pesticide to the weakly sorbed phase, and then, liquid phase, respectively. From both modeling and observations, no major toxicological damage of parathion and paraoxon to soil nematodes was found, although some effects on nematodes were possible, but at the soil surface only (0.01- and 0.02-m depth).     

Effects of commercial diazinon and imidacloprid on microbial urease activity in soil and sod

Diazinon [O,O-diethyl O-2-isopropyl-6-methyl(pyrimidine-4-yl) phosphorothioate] and imidacloprid [1-(1-[6-chloro-3-pyridinyl]methyl)-N-nitro-2-imidazolidinimine] are applied to lawns for insect control simultaneously with nitrogenous fertilizers such as urea, but their potential effect on urease activity and nitrogen availability in turfgrass management has not been evaluated. Urease activity in enzyme assays, washed cell assays, and soil slurries was examined as a function of insecticide concentration. Intact cores from field sites were used to assess the effect of insecticide application on urease activity in creeping bentgrass (Agrostis palustris Huds.) and bluegrass (Poa pratensis L.) sod. Bacterial urease from Bacillus pasteurii and plant urease from jack bean [Canavalia ensiformis (L.) DC.] were unaffected by the insecticides. Both insecticides inhibited the growth of Proteus vulgaris, a urease-producing bacterium, but only diazinon significantly reduced urease activity in washed cells; neither insecticide inhibited urease activity in sonicated cells. Neither diazinon nor imidacloprid inhibited urease activity in Woolper soil (fine, mixed, mesic Typic Argiudoll) slurries, but diazinon slightly inhibited urease activity in Maury soil (fine, mixed, semiactive, mesic Typic Paleudalf) slurries. Imidacloprid had no effect on urease activity in creeping bentgrass or bluegrass sod at up to 10 times the commercial application rate. Diazinon briefly, but significantly, reduced urease activity in bluegrass sod. Co-application of imidacloprid and urea appears to be benign with respect to urease activity in soil and sod. Diazinon, in contrast, appears to have a significant, short-term, inhibitory effect on the microbial urease-producing community, but that effect depends on soil type.     

Effects of dissolved organic matter from animal waste effluent on chlorpyrifos sorption by soils

The increased use of animal waste-derived effluents for irrigation could result in the enhanced movement of pesticides through complexation with dissolved organic materials. Batch equilibrium studies were conducted to measure the interaction among soil, chlorpyrifos [O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate], and dissolved organic matter (DOM) from poultry, swine, and cow waste-derived lagoon effluents. All DOM was found to have a strong affinity for chlorpyrifos, resulting in reduced sorption of chlorpyrifos by soil, thus the potential for DOM-enhanced mobility. Effluent DOM was observed to sorb to soils. Thus, for increasingly higher soil mass to solution volume ratios, the effect of chlorpyrifos association with water-borne DOM on sorption decreases significantly. For high soil mass to solution volume ratios typical of soil profiles in the landscape, the potential for DOM-enhanced transport will be greatly attenuated. Dissolved organic matter concentration and the nonpolar nature of DOM in the lagoon effluent decreased with increasing residence time in the cells of the lagoon system, thus reducing the potential for DOM-enhanced transport.     

Partitioning and persistence of trichlorfon and chlorpyrifos in a creeping bentgrass putting green

Golf course putting greens typically receive high pesticide applications to meet high quality demands. Research on pesticide fate in turf ecosystems is important to better understand the potential impact of pesticide use on the environment and human health. This research was conducted to evaluate the environmental fate of two commonly used insecticides--trichlorfon (dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate) and chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothioate)--in a creeping bentgrass (Agrostis palustris Huds.) putting green under customary field management practices at the University of California-Riverside Turf Research Facility during 1996 and 1997. The two insecticides were chosen because of their difference in water solubility, persistence, adsorption, and vapor pressure. Volatilization, clipping removal, and soil residues of the insecticides were quantified and leaching was monitored using lysimeters installed in putting green plots. Results showed trichlorfon volatilization, clipping removal, and leaching loss was insignificant (in the range of 0.0001-0.06% of applied mass) both in 1996 and 1997. No significant difference in clipping removal of trichlorfon and chlorpyrifos was observed in both years (0.06 and 0.05% of applied mass for trichlorfon and 0.15 and 0.19% of applied mass for chlorpyrifos, respectively, in 1996 and 1997), but significantly lower cumulative leaching and lower soil concentration was observed in 1997 than in 1996. Volatilization loss of chlorpyrifos was not significantly different between 1996 (2.05%) and 1997 (2.71%). Volatilization loss of trichlorfon in 1996 (0.01%) was significantly higher than in 1997 (0.008%). This study demonstrated the fraction of applied insecticides leaving the turf putting greens was minimal.     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.     

Integrating biodegradation and electroosmosis for the enhanced removal of polycyclic aromatic hydrocarbons from creosote-polluted soils

This paper presents a hybrid technology of soil remediation based on the integration of biodegradation and electroosmosis. We employed soils with different texture (clay soil and loamy sand) containing a mixture of polycyclic aromatic hydrocarbons (PAH) present in creosote, and inoculation with a representative soil bacterium able to degrade fluorene, phenanthrene, fluoranthene, pyrene, anthracene, and benzo[a]pyrene. Two different modes of treatment were prospected: (i) inducing in soil the simultaneous occurrence of biodegradation and electroosmosis in the presence of a biodegradable surfactant, and (ii) treating the soils sequentially with electrokinetics and bioremediation. Losses of PAH due to simultaneous biodegradation and electroosmosis (induced by a continuous electric field) were significantly higher than in control cells that contained the surfactant but no biological activity or no current. The method was especially successful with loamy sand. For example, benzo[a]pyrene decreased its concentration by 50% after 7 d, whereas 22 and 17% of the compound had disappeared as a result of electrokinetic flushing and bioremediation alone, respectively. The use of periodical changes in polarity and current pulses increased by 16% in the removal of total PAH and in up to 30% of specific compounds, including benzo[a]pyrene. With the aim of reaching lower residual levels through bioremediation, an electrokinetic pretreatment was also evaluated as a way to mobilize the less bioaccessible fraction of PAH. Residual concentrations of total biodegradable PAH, remaining after bioremediation in soil slurries, were twofold lower in electrokinetically pretreated soils than in untreated soils. The results indicate that biodegradation and electroosmosis can be successfully integrated to promote the removal of PAH from soil.     

Kinetics of monomer biodegradation in soil

In modern intensive agriculture, plastics are used in several applications (i.e. mulch films, drip irrigation tubes, string, clips, pots, etc.). Interest towards applying biodegradable plastics to replace the conventional plastics is promising. Ten monomers, which can be applied in the synthesis of potentially biodegradable polyesters, were tested according to ASTM 5988-96 (standard respirometric test to evaluate aerobic biodegradation in soil by measuring the carbon dioxide evolution): adipic acid, azelaic acid, 1,4-butanediol, 1,2-ethanediol, 1,6-hexanediol, lactic acid, glucose, sebacic acid, succinic acid and terephthalic acid. Eight replicates were carried out for each monomer for 27-45 days. The numerical code AQUASIM was applied to process the CO? experimental data in order to estimate values for the parameters describing the different mechanisms occurring to the monomers in soil: i) the first order solubilization kinetic constant, K(sol) (d?1); ii) the first order biodegradation kinetic constant, K(b) (d?1); iii) the lag time in biodegradation, t(lag) (d); and iv) the carbon fraction biodegraded but not transformed into CO?, Y (-). The following range of values were obtained: [0.006 d?1, 6.9 d?1] for K(sol), [0.1 d?1, 1.2 d?1] for K(b), and [0.32-0.58] for Y; t(lag) was observed for azelaic acid, 1,2-ethanediol, and terephthalic acid, with estimated values between 3.0 e 4.9 d.     

Implementation of sulfate adsorption in the SAFE model

An SO4(2-) adsorption submodel has been implemented in the dynamic soil chemistry model SAFE. The submodel calculates pH-dependent SO4(2-) and H+ adsorption to the soil, as well as the net surface charge development due to uneven adsorption of SO4(2-) and H+, using the empirical equations derived from an electrostatic model (Extended Constant Capacitance Model, ECCM) of SO4(2-) adsorption. The resulting new SAFE model was applied on a roof experiment plot in the Norway spruce [Picea abies (L.) H. Karst.] stand at Solling, Germany, where atmospheric S and N deposition was artificially reduced by the roof construction. The model performance was compared with the previous versions that used a pH-independent Freudlich model of SO4(2-) adsorption or assumed no SO4(2-) adsorption. With the ECCM-based SO4(2-) adsorption submodel, SAFE simulated soil solution SO4(2-) concentration and base saturation better, in comparison with measured data, than with the previous SO4(2-) adsorption formulations. Through the model application, also, need of additional improvement was suggested, such as calibration of mass transfer coefficients.     

Transport and fate modeling of nitrobenzene in groundwater after the Songhua River pollution accident

In 2005 a pollution accident occurred in the Songhua River, which is geographically located next to groundwater supply plants. This caused public concern about the transport and fate of nitrobenzene (NB) in the groundwater. This paper discusses the mechanisms and effects of the transport and fate of NB in groundwater based on pilot scale experiments conducted in the laboratory, including a simulation experiment, bench-scale batch tests and a one-dimensional numerical model. Parallel batch tests showed that the adsorption of NB to the clay and sand followed the Langmuir-type isotherm, and clay had a greater NB adsorption capacity than sand. NB biodegradation in different conditions was well fitted by the Monod equation and the q_max values varied from 0.018 to 0.046 h^?1. Results indicated that NB’s biodegradation was not affected by the initial NB concentration. Numerical modeling results indicated a good match between computed and observed data, and in the prediction model NB entered the groundwater after the pollution accident. However, the highest concentration of NB was much lower than the allowable limit set by the national standard (0.017 mg/L).     

Soil sorption of acidic pesticides: modeling pH effects

A model of acidic pesticide sorption in soils was developed from theoretical modeling and experimental data, which initially considered a combination of a strongly acidic pesticide and a variable-charge soil with high clay content. Contribution of 2,4-D [(2,4-dichlorophenoxy) acetic acid] anionic-form sorption was small when compared with molecular sorption. Dissociation of 2,4-D was not sufficient to explain the variation in Kd as a function of pH. Accessibility of soil organic functional groups able to interact with the pesticide (conformational changes) as a function of organic matter dissociation was proposed to explain the observed differences in sorption. Experimental 2,4-D sorption data and K(oc) values from literature for flumetsulam [N-(2,6-difluorophenyl)-5-methyl [1,2,4] triazolo [1,5-a] pyrimidine-2-sulfonamide] and sulfentrazone [N-[2,4-dichloro-5-[4-(difluromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl] phenyl] methanesulfonamide] in several soils fit the model.     

Free-air CO2 enrichment of sorghum: soil carbon and nitrogen dynamics

The positive impact of elevated atmospheric CO(2) concentration on crop biomass production suggests more carbon inputs to soil. Further study on the effect of elevated CO(2) on soil carbon and nitrogen dynamics is key to understanding the potential for long-term carbon storage in soil. Soil samples (0- to 5-, 5- to 10-, and 10- to 20-cm depths) were collected after 2 yr of grain sorghum [Sorghum bicolor (L.) Moench.] production under two atmospheric CO(2) levels: (370 [ambient] and 550 muL L(-1) [free-air CO(2) enrichment; FACE]) and two water treatments (ample water and limited water) on a Trix clay loam (fine, loamy, mixed [calcareous], hyperthermic Typic Torrifluvents) at Maricopa, AZ. In addition to assessing treatment effects on soil organic C and total N, potential C and N mineralization and C turnover were determined in a 60-d laboratory incubation study. After 2 yr of FACE, soil C and N were significantly increased at all soil depths. Water regime had no effect on these measures. Increased total N in the soil was associated with reduced N mineralization under FACE. Results indicated that potential C turnover was reduced under water deficit conditions at the top soil depth. Carbon turnover was not affected under FACE, implying that the observed increase in soil C with elevated CO(2) may be stable relative to ambient CO(2) conditions. Results suggest that, over the short-term, a small increase in soil C storage could occur under elevated atmospheric CO(2) conditions in sorghum production systems with differing water regimes.     

Adsorption and degradation of the weak acid mesotrione in soil and environmental fate implications

The ability of soils to adsorb and degrade pesticides strongly influences their environmental fate. This paper examines the adsorption and degradation of a weak acid, a new herbicide mesotrione 12-[4-(methylsulfonyl)-2-nitrobenzoyl]-1,3-cyclohexanedione], in 15 different soils from Europe and the USA. Experiments were conducted to understand the influence of soil properties, covering a wide range of soil textures, soil pH values (4.4 to 7.5), and organic carbon contents (0.6 to 3.35%). Mesotrione adsorption (Kd values ranged from 0.13 to 5.0 L/kg) was primarily related to soil pH, and to a lesser extent by percent organic carbon (%OC). As soil pH rose. mesotrione Kd values got smaller as mesotrione dissociated from the molecular to anionic form. Mesotrione degradation (half-lives ranged from 4.5 to 32 d) was also related to soil pH, getting shorter as soil pH rose. Simple regression of mesotrione adsorption against soil pH and %OC and against degradation provided a close fit to the data. The correlation between mesotrione adsorption and degradation means that Kd and half-life values are only relevant for use in environmental fate assessment if these values are "paired" for the same soil pH and %OC. The implications were as illustrated for leaching, raising important issues about combining pesticide adsorption and degradation behavior in environmental fate assessments.     

In vitro pesticide degradation in turfgrass soil incubated under open and sealed conditions

Degradation of selected pesticides was conducted in a turfgrass soil from a golf course under open (i.e., allowing gas exchange with atmosphere) and sealed systems. The time required for 50% of the initial dose of fenitrothion (O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), diazinon (O,O-dimethyl O-2-isopropyl-6-methylpyrimidin4-yl phosphorothioate), iprodione [3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxo-imidazolidine-1-carboxamide], mecoprop [(RS)-2-(4-chloro-otolyloxy)propionic acid], and asulam (4-aminophenylsulfonyl-carbamate) to dissipate (half-life, t 1/2) was less than 2 wk under both conditions. The t 1/2 values of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoro-methylpyridine-3,5-dicarbothioate) were 324 and 185 d under the open and sealed conditions, respectively. The t 1/2 values of isoprothiolane (di-isopropyl 1,3-dithiolan-2-ylidene-malonate), flutolanil (alpha,alpha,alpha-trifluoro-3'-isopropoxy-o-toluanilide), and benefin (N-butyl-N-ethyl-alpha,alpha,alpha-trifluoro-2,6-dinitro-p-toluidine) under the open conditions were 154, 336, and 47 d, respectively. The t 1/2 values of these pesticides increased slightly under the sealed conditions. The t 1/2 values of terbutol (2,6-di-tert-butyl-4-methylphenyl N-methycarbamate) and one of the major degradation products, N-demethyl-terbutol (2,6-di-tert-butyl-4-methylphenyl carbamate), were 182 and 291 d under the open conditions and increased by six- and threefold under the sealed conditions, respectively. The degradation system under the sealed conditions could characterize the persistence of terbutol and N-demethyl-terbutol, which were the most persistent in the field.     

Sorption and biodegradability of sludge bacterial extracellular polymers in soil and their influence on soil copper behavior

Bacterial extracellular polymers (BEP) affect the translocation and fate of organic and inorganic pollutants in terrestrial and aquatic ecosystems. In this study, BEP from activated sludge was compared with sludge dissolved organic matter (DOM) in terms of behavior and effects on the mobilization and bioavailability of Cu in a well-aged Cu-contaminated orchard sandy loam. Addition of sludge BEP (10-200 mg dissolved organic carbon [DOC] L(-1)) to the soil resulted in 1.6- to 12.8-fold-higher soil soluble Cu concentration over the control and 1.3- to 2.2-fold over sludge DOM of the same concentration. Consequently, the Cu uptake by the ryegrass (Lolium perenne L., cv. Target) grown in the soil was increased by 31% due to interval watering of 100 mg DOC L(-1) of sludge BEP solution in a 35-d period. The influence of sludge BEP on mobilizing soil Cu could be maintained as long as 60 d or more, depending on BEP biodegradation status. The findings that sludge BEP promoted Cu mobilization and bioavailability could be attributed to less adsorption of BEP by soil, slow degradation, and higher affinity with Cu. For example, after 3 wk of aerobic incubation, the soluble Cu present in the sludge DOM-treated soil was reduced to about the level of the control, while the concentration of soluble Cu in BEP-treated soil was 6.2 times higher than that in the control. Therefore, sludge BEP could act as a facilitated-transport carrier of Cu. The environmental risk of Cu should receive much attention if BEP is incorporated into soils.     

Sorption and detoxification of toxic compounds by a bifunctional organoclay

Organoclays are excellent sorbents for nonionic contaminants and therefore may have many environmental applications. A major limitation on the use of organoclays is that the contaminant merely changes its location from one environmental compartment to another while still remaining intact. In this study, a new type of organoclay, termed a bifunctional organoclay, has been prepared. It is able not only to sorb organophosphate pesticides, but also to catalyze their hydrolysis, and thereby detoxify them. The bifunctional organoclay prepared in this study is based on sodium montmorillonite, in which the inorganic counter ions are replaced by N-decyl-N,N-dimethyl-N-(2-aminoethyl) ammonium (DDMAEA). The detoxifying capacity of this organoclay for two organophosphate pesticides, methyl parathion [O,O-dimethyl O-(p-nitrophenyl) thionophosphate] and tetrachlorvinphos [2-chloro-1-(2,4,5-trichlorophenyl)ethenyl dimethyl phosphate], was demonstrated. It was shown that although the sorption of these pesticides on the bifunctional organoclay is very similar to that on N-decyl-N,N,N-trimethyl ammonium (DTMA) organoclay (the corresponding nonbifunctional organoclay), the hydrolysis of these pesticides is substantially enhanced only by the bifunctional organoclay. The half-life for the hydrolysis of the investigated pesticides in the presence of the bifunctional organoclay is about 12 times less than for their spontaneous hydrolysis, and the enhancement is even more pronounced relative to the hydrolysis of these pesticides in the presence of the DTMA organoclay (which actually inhibits their hydrolysis). Based on kinetic measurements, the pK(a) of the ethylamino group of the bifunctional organoclay was estimated to be around 9.0. It is postulated that the catalytic effect of the bifunctional organoclay can be attributed to a nucleophilic attack of the unprotonated ethylamino group of the organoclay on the organophosphate ester.     

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.     

Degradation of polycyclic aromatic hydrocarbons by combined chemical pre-oxidation and bioremediation in creosote contaminated soil

The ability of pre-oxidation to overcome polycyclic aromatic hydrocarbons (PAH) recalcitrance to biodegradation was investigated in creosote contaminated soil. Sand and peat artificially spiked with creosote (quality WEI C) were used as model systems. Ozonation and Fenton-like treatment were proved to be feasible technologies for PAH degradation in soil. The efficiency of ozonation was strongly dependent on the water content of treated soil samples. The removal of PAH by Fenton-like treatment depended on the applied H2O2/soil weight ratio and ferrous ions addition. It was determined that the application of chemical oxidation in sand resulted in a higher PAH removal and required lower oxidant (ozone, hydrogen peroxide) doses. The enhancement of PAH biodegradability by different pre-treatment technologies also depended on the soil matrix. It was ascertained that combined chemical and biological treatment was more efficient in PAH elimination in creosote contaminated soil than either one alone. Thus, the combination of Fenton-like and the subsequent biological treatment resulted in the highest removal of PAH in creosote contaminated sand, and biodegradation with pre-ozonation was found to be the most effective technology for PAH elimination in peat.     

Infiltration and adsorption of dissolved atrazine and atrazine metabolites in buffalograss filter strips

Vegetated filter strips (VFS) potentially reduce the off-site movement of herbicides from adjacent agricultural fields by increasing herbicide mass infiltrated (Minf) and mass adsorbed (Mas) compared with bare field soil. However, there are conflicting reports in the literature concerning the contribution of Mas to the VFS herbicide trapping efficiency (TE). Moreover, no study has evaluated TE among atrazine (6-chloro-N-ethyl-N'-isopropyl-[1,3,5]triazine-2,4-diamine) and atrazine metabolites. This study was conducted to compare TE, Minf, and Mas among atrazine, diaminoatrazine (DA, 6-chloro[1,3,5]triazine-2,4-diamine), deisopropylatrazine (DIA, 6-chloro-N-ethyl-[1,3,5]triazine-2,4-diamine), desethylatrazine (DEA, 6-chloro-N-isopropyl-[1,3,5]triazine-2,4-diamine), and hydroxyatrazine (HA, 6-hydroxy-N-ethyl-N'-isopropyl-[1,3,5]triazine-2,4-diamine) in a buffalograss VFS. Runoff was applied as a point source upslope of a 1- x 3-m microwatershed plot at a rate of 750 L h(-1). The point source was fortified at 0.1 microg mL(-1) atrazine, DA, DIA, DEA, and HA. After crossing the length of the plot, water samples were collected at 5-min intervals. Water samples were extracted by solid phase extraction and analyzed by high performance liquid chromatography (HPLC) photodiode array detection. During the 60-min simulation, TE was significantly greater for atrazine (22.2%) compared with atrazine metabolites (19.0%). Approximately 67 and 33% of the TE was attributed to Minf and Mas, respectively. These results demonstrate that herbicide adsorption to the VFS grass, grass thatch, and/or soil surface is an important retention mechanism, especially under saturated conditions. Values for Mas were significantly higher for atrazine compared with atrazine's metabolites. The Mas data indicate that atrazine was preferentially retained by the VFS grass, grass thatch, and/or soil surface compared with atrazine's metabolites.     

Greenhouse gas emissions from two soils receiving nitrogen fertilizer and swine manure slurry

The interactive effects of soil texture and type of N fertility (i.e., manure vs. commercial N fertilizer) on N(2)O and CH(4) emissions have not been well established. This study was conducted to assess the impact of soil type and N fertility on greenhouse gas fluxes (N(2)O, CH(4), and CO(2)) from the soil surface. The soils used were a sandy loam (789 g kg(-1) sand and 138 g kg(-1) clay) and a clay soil (216 g kg(-1) sand, and 415 g kg(-1) clay). Chamber experiments were conducted using plastic buckets as the experimental units. The treatments applied to each soil type were: (i) control (no added N), (ii) urea-ammonium nitrate (UAN), and (iii) liquid swine manure slurry. Greenhouse gas fluxes were measured over 8 weeks. Within the UAN and swine manure treatments both N(2)O and CH(4) emissions were greater in the sandy loam than in the clay soil. In the sandy loam soil N(2)O emissions were significantly different among all N treatments, but in the clay soil only the manure treatment had significantly higher N(2)O emissions. It is thought that the major differences between the two soils controlling both N(2)O and CH(4) emissions were cation exchange capacity (CEC) and percent water-filled pore space (%WFPS). We speculate that the higher CEC in the clay soil reduced N availability through increased adsorption of NH(4)(+) compared to the sandy loam soil. In addition the higher average %WFPS in the sandy loam may have favored higher denitrification and CH(4) production than in the clay soil.     

Retention and runoff losses of atrazine and metribuzin in soil

Minimizing herbicide runoff and mobility in the soil and thus potential contamination of water resources is a national concern. Metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] and atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] dynamics in surface soils and in runoff waters were studied on six 0.2-ha sugarcane (Saccharum spp.) plots of a Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquept) during three growing seasons under different best management practices. Metribuzin was applied in the spring as a postemergence herbicide and atrazine was applied following winter harvest. Both herbicides were applied on top of the sugarcane rows as 0.6- or 0.9-m band width application, or broadcast application, where the entire area was treated. Maximum effluent concentrations were measured from the broadcast treatment and ranged from 600 to 1100 microg L(-1) for atrazine and 250 to 450 microg L(-1) for metribuzin. Atrazine runoff losses were highest for the broadcast treatment (2.8-11% of that applied) and lowest for the 0.6-m band treatment (1.9-7.6%), with a similar trend for metribuzin losses. Measured extractable herbicides from the surface soil exhibited a sharp decrease with time and were well described with a simple first-order decay model. For atrazine, estimates for the decay rate (lambda) were higher than for metribuzin. Results based on laboratory adsorption-desorption (kinetic-batch) measurements were consistent with field observations. The distribution coefficients (Kd) for atrazine exhibited stronger retention over time in comparison with metribuzin on the Commerce soil. Moreover, discrepancies between adsorption isotherm and desorption indicated slower release and that hysteresis was more pronounced for atrazine compared with metribuzin.