Anaerobic degradation of atrazine and metolachlor and metabolite formation in wetland soil and water microcosms

The half-lives, degradation rates, and metabolite formation patterns of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] were determined in an anaerobic wetland soil incubated at 24 degrees C for 112 d. At 0, 7, 14, 28, 42, 56, and 112 d, the soil and water were analyzed for atrazine and metolachlor, and their major metabolites. The soil oxidation-reduction potential reached -200 mV after 14 d. Degradation reaction rates were first-order for atrazine in anaerobic soil and for metolachlor in the aqueous phase. Zero-order reaction rates were best fit for atrazine in the aqueous phase and metolachlor in anaerobic soil. In anaerobic soil, the half-life was 38 d for atrazine and 62 d for metolachlor. In the aqueous phase above the soil, the half-life was 86 d for atrazine and 40 d for metolachlor. Metabolites detected in the anaerobic soil were hydroxyatrazine and deethylatrazine for atrazine, and relatively small amounts of ethanesulfonic acid and oxanilic acid for metolachlor. Metabolites detected in the aqueous phase above the soil were hydroxyatrazine, deethylatrazine, and deisopropylatrazine for atrazine, and ethanesulfonic acid and oxanilic acid for metolachlor. Concentrations of metabolites in the aqueous phase generally peaked within the first 25 d and then declined. Results indicate that atrazine and metolachlor can degrade under strongly reducing conditions found in wetland soils. Metolachlor metabolites, ethanesulfonic acid, and oxanilic acid are not significantly formed under anaerobic conditions.     

On the interaction mechanisms of atrazine and hydroxyatrazine with humic substances

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) is retained against leaching losses in soils principally by sorption to organic matter, but the mechanism of sorption has been a matter of controversy. Conflicting evidence exists for proton transfer, electron transfer, and hydrophobic interactions between atrazine and soil humus, but no data are conclusive. In this paper we add to the database by investigating the role of (i) hydroxyatrazine (6-hydroxy-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and (ii) hydrophobicity in the sorption of atrazine by Brazilian soil humic substances. We demonstrate, apparently for the first time, that hydroxyatrazine readily forms electron-transfer complexes with humic substances. These complexes probably are the cause of the well-known strong adsorption by humic acids and they may be the undetected cause of apparent electron-transfer complexes between soil organic matter and atrazine, whose transformation to the hydroxy form is facile. We also present evidence that supports the important contribution of hydrophobic interactions to the pH-dependent sorption of atrazine by humic substances.     

Spatial distribution of enhanced atrazine degradation across northeastern Colorado cropping systems

Reports of enhanced atrazine degradation and reduced residual weed control have increased in recent years, sparking interest in identifying factors contributing to enhanced atrazine degradation. The objectives of this study were to (i) assess the spatial distribution of enhanced atrazine degradation in 45 commercial farm fields in northeastern Colorado (Kit Carson, Larimer, Logan, Morgan, Phillips, and Yuma counties) where selected cultural management practices and soil bio-chemo-physical properties were quantified; (ii) utilize Classification and Regression Tree (CART) Analysis to identify cultural management practices and (or) soil bio-chemophysical attributes that are associated with enhanced atrazine degradation; and (iii) translate our CART Analysis into a model that predicts relative atrazine degradation rate (rapid, moderate, or slow) as a function of known management practices and (or) soil properties. Enhanced atrazine degradation was widespread within a 300-km radius across northeastern Colorado, with approximately 44% of the fields demonstrating rapid atrazine degradation activity (laboratory-based dissipation time halflife [DT50] < 3 d). The most rapid degradation rates occurred in fields that received the most frequent atrazine applications. Classification and Regression Tree Analysis resulted in a prediction model that correctly classified soils with rapid atrazine DT50 80% of the time and soils with slow degradation (DT50 > 8 d) 62.5% of the time. Significant factors were recent atrazine use history, soil pH, and organic matter content. The presence/absence of atzC polymerase chain reaction (PCR) product was not a significant predictor variable for atrazine DT50. In conclusion, enhanced atrazine degradation is widespread in northeastern Colorado. If producers know their atrazine use history, soil pH, and OM content, they should be able to identify fields exhibiting enhanced atrazine degradation using our CART Model.     

The effect of five forage species on transport and transformation of atrazine and isoxaflutole (balance) in lysimeter leachate

A field lysimeter study with bare ground and five different ground covers was established to evaluate the effect of forage grasses on the fate and transport of two herbicides in leachate. The herbicides were atrazine (ATR; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and isoxaflutole [IXF; 5-cyclopropyl-4-(2-methylsulfonyl-4-trifluormethyl-benzoyl)isoxazole], which has the commercial name Balance (Aventis Crop Science, Strasbourg, France). The ground covers included orchardgrass (Dactylis glomerata L.), smooth bromegrass (Bromus inermis Leyss.), tall fescue (Festuca arundinacea Schreb.), timothy (Phleum pratense L.), and switchgrass (Panicum virgatum L.). The results suggested that the total IXF (parent + metabolites) showed higher mobility than ATR and its metabolites. Differences in the timing of transport reflected the rapid degradation of IXF to the more soluble, stable, and biologically active diketonitrile (DKN) metabolite in the system. Although grass treatments did not promote the hydrolysis of DKN, they significantly reduced its transport in the leachate through enhanced evapotranspiration. Grass treatments significantly enhanced ATR degradation in the leachates and soils, especially through N dealkylation, but they did not reduce total ATR transported in the leachate. Leachate from the orchardgrass lysimeters contained the highest proportion of ATR metabolites (64.2%). Timothy and smooth bromegrass treatments also displayed a significant increase in ATR metabolites in leachate. Grass-treated lysimeters showed higher microbial biomass carbon than bare ground. For ATR treatments, the proportion of metabolites in the leachate strongly correlated with the elevated soil microbial biomass carbon in forage treatments. In contrast, DKN degradation was poorly correlated with soil microbial biomass carbon, suggesting that DKN degradation is an abiotic process.     

TRANSPORT AND FATE OF ATRAZINE IN MIDWESTERN RIPARIAN BUFFER STRIPS1

ABSTRACT: The fate of pesticides entering the Riparian Buffer Strips (RBS) has not been well documented. This study compared the transport and fate of atrazine in soil of three‐, five‐, and nine‐year‐old switchgrass (Panicum virgatum L.) RBS to that in adjacent soils cropped to a corn‐soybean rotation or a grass‐alfalfa pasture. Undisturbed soil columns were collected from the RBS and cropped areas within the Bear Creek watershed, near Roland, Iowa. Atrazine and bromide breakthrough curves obtained using intact soil columns under saturated conditions were described by a two‐region, mobile‐immobile transport model. Preferential flow of bromide and atrazine was evident in five‐and nine‐year‐old RBS soil, but there was little difference in transport characteristics between these two RBS soils and the adjacent cropped soils. There was a trend towards an increase in dispersion coefficients between the five‐and nine‐year‐old RBS sites, which suggests an increased degree of preferential flow with increasing RBS age. Despite similar texture and organic C contents, atrazine sorption was significantly greater in RBS soil than the adjacent cropped soil. Cropped soil degraded atrazine faster than the RBS soil. The rapid degradation of atrazine in the corn‐soybean soil adjacent to the five‐year‐old RBS (atrazine half‐life of 19 days) appeared to be due to a larger population of atrazine‐degrading microorganisms. Atrazine‐degrading microorganisms in the corn‐soybean soil were 50,940 cells g^‐1 soil compared with 2,970 cells g^‐4 soil in 5‐year‐old RBS soil which resulted in 60 percent mineralization of [¹⁴C‐UL‐atrazine] in the corn‐soybean soil.     

Atrazine degradation and residues distribution in two acid soils from temperate humid zone

Mineralization of atrazine and formation of extractable and non-extractable "bound" residues were followed under laboratory conditions in two contrasting soils (organic C, texture, and atrazine application history) from northern Spain. The soils, a Humic Cambisol (MP) and a Gleyic Cambisol (G) were incubated with labeled atrazine (ring-13C atrazine) at field application dose and measurements were made at different time intervals during 3 mo. Fate and behavior of atrazine along the incubation showed different patterns between the two soils, the time taken for degradation of 50% (DT50) being 9 and 44 d for MP and G soils, respectively. In MP soil, with 40 yr of atrazine application and lower organic C and clay content, more than 89% of U-13C-atrazine added was mineralized after 12 wk, with most mineralization occurring within the first 2 wk. G soil, with 10 yr of atrazine application, exhibited a more progressive U-13C-atrazine mineralization, reaching 54% of initially added atrazine at 12 wk. Hydroxyatrazine and deisopropylatrazine were the metabolites founded in the extractable fraction, demonstrating that both chemical and biological processes are involved in atrazine degradation. Soil G showed during all the incubation times an extractable residues fraction greater than that in MP soil, indicating a high potential risk of soil and water contamination. Rapid microbial degradation through s-triazine ring cleavage was proposed to be the main decomposition pathway of atrazine for the two soils studied. Bound residues pool also differed notably between soils accounting for 9 and 41% of initially added atrazine, the higher values shown by soil with higher organic matter and clay content (G soil).     

Degradation of N,N'-dibutylurea (DBU) in soils treated with only DBU and DBU-fortified benlate fungicides

N,N'-dibutylurea (DBU) is a breakdown product of benomyl [methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate], the active ingredient in Benlate fungicides, and has been proposed to cause crop damage after the use of Benlate 50 DF fungicide (DuPont, Wilmington, DE). Our research focused on DBU persistence after application into soil. We assessed DBU persistence on direct application of DBU (carbonyl-(14)C) at two concentrations (0.08 and 0.8 microg DBU kg(-1)) to seven soils and two potting mixes in soil microcosms incubated at various combinations of soil water potential (-0.03 or -0.1 MPa) and temperature (23, 33, 44 degrees C). For two soils at a subset of treatment variables we assessed DBU persistence in the presence of Benlate DF and SP fungicide formulations. Parent compounds, metabolites, and (14)CO(2) were tracked using chromatographic analysis with radioassay and UV detection, liquid scintillation counting, and post-extraction oxidation of the soil. DBU degradation was primarily microbial and for most soil-treatment combinations, half-lives were less than 2 wk. DBU degradation was retarded at the lower soil water potential and enhanced at 33 degrees C. In the presence of the formulation, DBU degradation was slower for one soil type. The longest half-life observed in any case was less than 7 wk; therefore, long-term persistence of DBU applied to soils through a Benlate application is very unlikely.     

Effect of corn root exudates on the degradation of atrazine and its chlorinated metabolites in soils

DIMBOA (3,4-dihydro-2,4-dihydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), a major benzoxazinone of Poaceae plants, was isolated and purified from corn seedlings. The effect of isolated and purified DIMBOA on the degradation of atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine], and its toxic breakdown products, desethylatrazine [2-chloro-4-amino-6-(isopropylamino)-s-triazine; DEA] and desisopropylatrazine [2-chloro-4-(ethylamino)-6-amino-s-triazine; DIA], was studied in the absence of plants using batch experiments, while the effect of corn root exudates on these compounds was determined in hydroponic experiments. Degradation experiments were performed in the presence and absence of 50 microM, 1 mM, or 5 mM DIMBOA resulting in ratios of DIMBOA to pesticide of 1:1, 20:1, and 100:1. We observed a 100% degradation of atrazine to hydroxyatrazine within 48 h at a ratio of DIMBOA to atrazine of 100:1. DIMBOA had the largest effect on atrazine, while it was about three times less effective on DEA and DIA. Corn (Zea mays L. cv. LG 2185) was exposed to 10 mg L(-1) of either atrazine, DEA, or DIA for 11 d in a growth chamber experiment. Up to 4.3 micromol L(-1) d(-1) of hydroxyatrazine were formed in the nutrient solutions by plants exposed to atrazine, while the formation of hydroxylated metabolites from plants exposed to DEA and DIA was smaller and also delayed. The formation of hydroxylated metabolites increased in the solution with plant age in all atrazine, DEA, and DIA treatments. HMBOA (3,4-dihydro-2-hydroxy-7-methoxy-2H-1,4-benzoxazin-3-one), the lactam precursor of DIMBOA, and a tentatively identified derivative of MBOA (2,3-dihydro-6-methoxy-benzoxazol-2-one) were detected in the corn root exudates. Mass balance calculations revealed that up to 30% of the disappearance of atrazine and DEA, and up to 10% of DIA removal from the solution medium in our study could be explained by the formation of hydroxylated metabolites in the solution itself. Our results show that higher plants such as corn have the potential to promote the hydrolysis of triazine residues in soils by exudation of benzoxazinones.     

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.     

Atrazine and alachlor transport in claypan soils as influenced by differential antecedent soil water content

Increased attention to ground water contamination has encouraged an interest in mechanisms of solute transport through soils. Few studies have investigated the effect of the initial soil water content on the transport and degradation of herbicides for claypan soils. We investigated the effect of claypan soils at initial field capacity vs. permanent wilting level on atrazine and alachlor transport. The soil studied was Mexico silt loam (fine, smectitic, mesic Aeric Vertic Epiaqualf) with a subsoil clay content, primarily montmorillonite, of >40%. Strontium bromide, atrazine, and alachlor were applied to plots; half were at field capacity (Wet treatment), and half were near the permanent wilting point (Dry treatment). Soil cores were removed at selected depths and times, and cores were analyzed for bromide and herbicide concentrations. Bromide, atrazine, and alachlor were detected at the 0.90-m depth in dry plots within 15 d after experiment initiation. Bromide was detected 0.15 m deeper (P < 0.05) in the Dry compared with the Wet treatment at 1, 7, and 60 d after application and >0.30 m deeper (P < 0.01) in the Dry treatment at 15 and 30 d after application; similar treatment results were found for atrazine and alachlor, although on fewer dates with significant differences. The mobility order of the applied chemicals was bromide > atrazine > alachlor. The atrazine apparent half-life was significantly longer in the Dry plots compared with the Wet plots. The retardation factor determined from the relative velocity of each herbicide to that of bromide was higher for alachlor than for atrazine. This study identifies the impact that shrinkage cracks have for different moisture conditions on preferential transport of herbicides in claypan soils.     

Impact of climatic and soil conditions on environmental fate of atrazine used under plantation forestry in Australia

We studied the leaching and dissipation of atrazine (2-chloro-4-ethylamino-6-isopropylamino-1, 3, 5-s-triazine) and its two principal metabolites (desethylatrazine and desisopropylatrazine) for more than two years through soil profiles at five forestry sites across Australia (representing subtropical, temperate and Mediterranean climatic conditions with rainfall ranging from 780 to 1536 mm yr^?1). Following atrazine applications at local label rates, soil cores were collected at regular intervals (up to depths of 90–150 cm), and the residues of the three compounds in soil were analysed in composite samples using liquid chromatography. Bromide was applied simultaneously with atrazine to follow the movement of the soil water. While bromide ion rapidly leached through the entire profile, in most cases the bulk of atrazine, desethylatrazine and desisopropylatrazine remained in the top 45 cm of the soil profile. However, a small fraction of residue moved deeper into the soil profile and at a subtropical site (Toolara) trace levels (ng L^?1) of atrazine and one of its metabolites (DEA) were detected in perched groundwater located at a depth of 1.8 m. Data on the total residues of atrazine in soil profiles from all sites except the Tasmanian site fitted a first-order decay model. The half-life of atrazine in surface soils at the subtropical sites (Toolara and Imbil) ranged from 11 to 21 days. Four separate applications of atrazine at Toolara resulted in a narrow range of half-lives (16 ± 3.6 days), confirming relatively rapid dissipation of atrazine under subtropical conditions (Queensland). In contrast, a prominent biphasic pattern of initial rapid loss followed by very slow phase of degradation of atrazine was observed under the colder temperate climate of Highclere (Tasmania). The data showed that while its 50% (DT₅₀) loss occurred relatively rapidly (36 days), more than 10% of herbicide residue was still detectable in the profile even a year after application (DT₉₀ = 375 days). The rate of dissipation of atrazine at warm subtropical Queensland sites (Imbil and Toolara) was 2–3 times faster than sites located in colder climate of Tasmania. The marked contrast in DT₅₀ values between subtropical and temperate sites suggest that climatic conditions (soil temperature) is one of the key factors affecting atrazine dissipation. At the Tasmanian site, the combination of leaching of the herbicide in subsoil and slower microbial activity at cooler temperatures would have caused a longer persistence of atrazine.     

Measured concentrations of herbicides and model predictions of atrazine fate in the Patuxent River estuary

The environmental fate of herbicides in estuaries is poorly understood. Estuarine physical transport processes and the episodic nature of herbicide release into surface waters complicate interpretation of water concentration measurements and allocation of sources. Water concentrations of herbicides and two triazine degradation products (CIAT [6-amino-2-chloro-4-isopropylamino-s-triazine] and CEAT [6-amino-2-chloro-4-ethylamino-s-triazine]) were measured in surface water from four sites on 40 d from 4 Apr. through 29 July 19% in the Patuxent River estuary, part of the Chesapeake Bay system. Atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) was most persistent and present in the highest concentrations (maximum = 1.29 microg/L). Metolachlor [2-chloro-6'-ethyl-N-(2-methoxy-1-methylethyl)-o-acetoluidide], CIAT, CEAT, and simazine (1-chloro-3,5-bisethylamino-2,4,6-triazine) were frequently detected with maximum concentration values of 0.61, 1.1, 0.76, and 0.49 microg/L, respectively. A physical transport model was used to interpret atrazine concentrations in the context of estuarine water transport, giving estimates of in situ degradation rates and total transport. The estimated half-life of atrazine in the turbid, shallow upper estuary was t(1/2) = 20 d, but was much longer (t(1/2) = 100 d) in the deeper lower estuary. Although most (93%) atrazine entered the estuary upstream via the river, simulations suggested additional inputs directly to the lower estuary. The total atrazine load to the estuary from 5 April to 15 July was 71 kg with 48% loss by degradation and 31% exported to the Chesapeake Bay. Atrazine persistence in the estuary is directly related to river flows into the estuary. Low flows will increase atrazine residence time in the upper estuary and increase degradation losses.     

Pesticide fate and transport throughout unsaturated zones in five agricultural settings, USA

Pesticide transport through the unsaturated zone is a function of chemical and soil characteristics, application, and water recharge rate. The fate and transport of 82 pesticides and degradates were investigated at five different agricultural sites. Atrazine and metolachlor, as well as several of the degradates of atrazine, metolachlor, acetochlor, and alachlor, were frequently detected in soil water during the 2004 growing season, and degradates were generally more abundant than parent compounds. Metolachlor and atrazine were applied at a Nebraska site the same year as sampling, and focused recharge coupled with the short time since application resulted in their movement in the unsaturated zone 9 m below the surface. At other sites where the herbicides were applied 1 to 2 yr before sampling, only degradates were found in soil water. Transformations of herbicides were evident with depth and during the 4-mo sampling time and reflected the faster degradation of metolachlor oxanilic acid and persistence of metolachor ethanesulfonic acid. The fraction of metolachlor ethanesulfonic acid relative to metolachlor and metolachlor oxanilic acid increased from 0.3 to >0.9 at a site in Maryland where the unsaturated zone was 5 m deep and from 0.3 to 0.5 at the shallowest depth. The flux of pesticide degradates from the deepest sites to the shallow ground water was greatest (3.0-4.9 micromol m(-2) yr(-1)) where upland recharge or focused flow moved the most water through the unsaturated zone. Flux estimates based on estimated recharge rates and measured concentrations were in agreement with fluxes estimated using an unsaturated-zone computer model (LEACHM).     

Bioremediation of atrazine-contaminated soil by forage grasses: transformation, uptake, and detoxification

A sound multi-species vegetation buffer design should incorporate the species that facilitate rapid degradation and sequestration of deposited herbicides in the buffer. A field lysimeter study with six different ground covers (bare ground, orchardgrass, tall fescue, timothy, smooth bromegrass, and switchgrass) was established to assess the bioremediation capacity of five forage species to enhance atrazine (ATR) dissipation in the environment via plant uptake and degradation and detoxification in the rhizosphere. Results suggested that the majority of the applied ATR remained in the soil and only a relatively small fraction of herbicide leached to leachates (<15%) or was taken up by plants (<4%). Biological degradation or chemical hydroxylation of soil ATR was enhanced by 20 to 45% in forage treatment compared with the control. Of the ATR residues remaining in soil, switchgrass degraded more than 80% to less toxic metabolites, with 47% of these residues converted to the less mobile hydroxylated metabolites 25 d after application. The strong correlation between the degradation of N-dealkylated ATR metabolites and the increased microbial biomass carbon in forage treatments suggested that enhanced biological degradation in the rhizosphere was facilitated by the forages. Hydroxylated ATR degradation products were the predominant ATR metabolites in the tissues of switchgrass and tall fescue. In contrast, the N-dealkylated metabolites were the major degradation products found in the other cool-season species. The difference in metabolite patterns between the warm- and cool-season species demonstrated their contrasting detoxification mechanisms, which also related to their tolerance to ATR exposure. Based on this study, switchgrass is recommended for use in riparian buffers designed to reduce ATR toxicity and mobility due to its high tolerance and strong degradation capacity.     

Competitive degradation between the fumigants chloropicrin and 1,3-dichloropropene in unamended and amended soils

The mixture of 1,3-dichloropropene (1,3-D) and chloropicrin (CP) is used as a preplant soil fumigant. In comparison with individual fumigants, application of a mixture may affect the environmental dissipation and fate of each chemical, such as emission and degradation. We investigated the degradation of CP, 1,3-D, and their mixture in fresh soils and sterile soils, and evaluated the competitive characteristic of fumigants in the mixture. The degradation of low concentrations of CP in fresh soil was accelerated at early times in the presence of 1,3-D, whereas the addition of CP reduced the degradation rate of trans-1,3-D, possibly by inhibiting the activity of trans-1,3-D degrading microorganisms. The potential of applying amendments to the soil to increase the rate of CP and 1,3-D degradation was also illustrated. The degradation of both fumigants was significantly enhanced in soils amended with ammonium thiosulfate (ATS) and sodium diethyldithiocarbamate (Na-DEDTC) compared with unamended soil. Competitive degradation was observed for CP in amended soils in the presence of 1,3-D. The degradation of cis-1,3-D in amended soils spiked as a mixture of 1,3-D and CP was repressed compared with the rate of degradation in samples spiked with 1,3-D only. This implied that in abiotic degradation, CP and cis-1,3-D competed for a limited number of reaction sites in amended soil, resulting in decreased degradation rates. No significant influence of fumigant mixtures was observed for trans-1,3-D in amended soil.     

Regression models for estimating concentrations of atrazine plus deethylatrazine in shallow groundwater in agricultural areas of the United States

Tobit regression models were developed to predict the summed concentration of atrazine [6-chloro--ethyl--(1-methylethyl)-1,3,5-triazine-2,4-diamine] and its degradate deethylatrazine [6-chloro--(1-methylethyl)-1,3,5,-triazine-2,4-diamine] (DEA) in shallow groundwater underlying agricultural settings across the conterminous United States. The models were developed from atrazine and DEA concentrations in samples from 1298 wells and explanatory variables that represent the source of atrazine and various aspects of the transport and fate of atrazine and DEA in the subsurface. One advantage of these newly developed models over previous national regression models is that they predict concentrations (rather than detection frequency), which can be compared with water quality benchmarks. Model results indicate that variability in the concentration of atrazine residues (atrazine plus DEA) in groundwater underlying agricultural areas is more strongly controlled by the history of atrazine use in relation to the timing of recharge (groundwater age) than by processes that control the dispersion, adsorption, or degradation of these compounds in the saturated zone. Current (1990s) atrazine use was found to be a weak explanatory variable, perhaps because it does not represent the use of atrazine at the time of recharge of the sampled groundwater and because the likelihood that these compounds will reach the water table is affected by other factors operating within the unsaturated zone, such as soil characteristics, artificial drainage, and water movement. Results show that only about 5% of agricultural areas have greater than a 10% probability of exceeding the USEPA maximum contaminant level of 3.0 μg L. These models are not developed for regulatory purposes but rather can be used to (i) identify areas of potential concern, (ii) provide conservative estimates of the concentrations of atrazine residues in deeper potential drinking water supplies, and (iii) set priorities among areas for future groundwater monitoring.     

Environmental fate of triasulfuron in soils amended with municipal waste compost

The amendment of soil with compost may significantly influence the mobility and persistence of pesticides and thus affect their environmental fate. Factors like adsorption, kinetics, and rate of degradation of pesticides could be altered in amended soils. The aim of this study was to determine the effects of the addition of compost made from source-separated municipal waste and green waste, on the fate of triasulfuron [(2-(2-chloroethoxy)-N-[[4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]benzenesulfonamide], a sulfonylurea herbicide used in postemergence treatment of cereals. Two native soils with low organic matter content were used. A series of analyses was performed to evaluate the adsorption and degradation of the herbicide in soil and in solution after the addition of compost and compost-extracted organic fractions, namely humic acids (HA), fulvic acids (FA), and hydrophobic dissolved organic matter (HoDOM). Results have shown that the adsorption of triasulfuron to soil increases in the presence of compost, and that the HA and HoDOM fractions are mainly responsible for this increase. Hydrophobic dissolved organic matter applied to the soils underwent sorption reactions with the soils, and in the sorbed state, served to increase the adsorption capacity of the soil for triasulfuron. The rate of hydrolysis of triasulfuron in solution was significantly higher at acidic pH and the presence of organic matter fractions extracted from compost also slightly increased the rate of hydrolysis. The rate of degradation in amended and nonamended soils is explained by a two-stage degradation kinetics. During the initial phase, although triasulfuron degradation was rapid with a half-life of approximately 30 d, the presence of compost and HoDOM was found to slightly reduce the rate of degradation with respect to that in nonamended soil.     

Prediction of the Fate and Transport Processes of Atrazine in a Reservoir

The fate and transport processes of a toxic chemical such as atrazine, an herbicide, in a reservoir are significantly influenced by hydrodynamic regimes of the reservoir. The two-dimensional (2D) laterally-integrated hydrodynamics and mass transport model, CE-QUAL-W2, was enhanced by incorporating a submodel for toxic contaminants and applied to Saylorville Reservoir, Iowa. The submodel describes the physical, chemical, and biological processes and predicts unsteady vertical and longitudinal distributions of a toxic chemical. The simulation results from the enhanced 2D reservoir model were validated by measured temperatures and atrazine concentrations in the reservoir. Although a strong thermal stratification was not identified from both observed and predicted water temperatures, the spatial variation of atrazine concentrations was largely affected by seasonal flow circulation patterns in the reservoir. In particular, the results showed the effect of flow circulation on spatial distribution of atrazine during summer months as the river flow formed an underflow within the reservoir and resulted in greater concentrations near the surface of the reservoir. Atrazine concentrations in the reservoir peaked around the end of May and early June. A good agreement between predicted and observed times and magnitudes of peak concentrations was obtained. The use of time-variable decay rates of atrazine led to more accurate prediction of atrazine concentrations, while the use of a constant half-life (60 days) over the entire period resulted in a 40% overestimation of peak concentrations. The results provide a better understanding of the fate and transport of atrazine in the reservoir and information useful in the development of reservoir operation strategies with respect to timing, amount, and depth of withdrawal.     

Biotic and abiotic degradation of CL-20 and RDX in soils

The caged cyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a new explosive that has the potential to replace existing military explosives, but little is known about its environmental toxicity, transport, and fate. We quantified and compared the aerobic environmental fate of CL-20 to the widely used cyclic nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in surface and subsurface soil microcosms. Soil-free controls and biologically attenuated soil controls were used to separate abiotic processes from biologically mediated processes. Both abiotic and biological processes significantly degraded CL-20 in all soils examined. Apparent abiotic, first-order degradation rates (k) for CL-20 were not significantly different between soil-free controls (0.018 < k < 0.030 d(-1)) and biologically attenuated soil controls (0.003 < k < 0.277 d(-1)). The addition of glucose to biologically active soil microcosms significantly increased CL-20 degradation rates (0.068 < k < 1.22 d(-1)). Extents of mineralization of (14)C-CL-20 to (14)CO(2) in biologically active soil microcosms were 41.1 to 55.7%, indicating that the CL-20 cage was broken, since all carbons are part of the heterocyclic cage. Under aerobic conditions, abiotic degradation rates of RDX were generally slower (0 < k < 0.032 d(-1)) than abiotic CL-20 degradation rates. In biologically active soil microcosms amended with glucose aerobic RDX degradation rates varied between 0.010 and 0.474 d(-1). Biodegradation was a key factor in determining the environmental fate of RDX, while a combination of biotic and abiotic processes was important with CL-20. Our data suggest that CL-20 should be less recalcitrant than RDX in aerobic soils.     

Sorption kinetics and equilibria of organic pesticides in carbonatic soils from South Florida

A batch reactor was used to determine sorption kinetic parameters (k2, F, and K*) and the equilibrium sorption coefficient (K). The two-site nonequilibrium (TSNE) batch sorption kinetics model was used to calculate the kinetic parameters. Two probe organic pesticides, atrazine [2-chloro-4-ethylamino-6-isopropylamino-s-triazine] and diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] were studied using three carbonatic soils from South Florida (Chekika, Perrine, and Krome), one noncarbonatic soil from Iowa (Webster), and one organic soil (Lauderhill) from South Florida. Carbonatic soils contained more than 600 g kg(-1) CaCO3. Sorption is initially very fast up to 3 h and then slowly reaches equilibrium. All soil-chemical combinations reached sorption equilibrium after about 24 h and all sorption isotherms were linear. The sorption kinetics data were well described by the TSNE model for all soil-chemical combinations except for the marl soil data (Perrine-Atrazine), which were better described by the one-site nonequilibrium (OSNE) model. Diuron, with higher K, undergoes slower sorption kinetics than atrazine. The Lauderhill soil containing organic carbon (OC) of 450 g kg(-1) exhibited slowest sorption kinetics for both pesticides. An inverse relationship between k3 and K was observed for atrazine and diuron separately in Chekika, Webster, and Lauderhill soils but not in Perrine and Krome soils. The sorption kinetic parameters were used to distinguish the sorption behavior between atrazine and diuron and to identify differences between soils. Normalizing the sorption coefficient (K) to OC showed that atrazine and diuron had K oc values in carbonatic soils that were a third of reported literature values for noncarbonatic soils. Using existing literature K oc values in solute transport models will most likely underestimate the mobility of atrazine, diuron, and other neutral organic chemicals in carbonatic soils.