Search

Background: Atrazine (ATZ) has been a key herbicide for annual weed control in corn, with both a soil and post-emergence vegetation application period. Although enhanced ATZ degradation in soil with a history of ATZ use has been reported, the extent and rate of degradation in the US Corn Belt is uncertain. We show that enhanced ATZ degradation exists across much of the country., Results: Soils from 15 of 16 surveyed states had enhanced ATZ degradation. The average ATZ half-life was only 2.3 days in ATZ history soils, compared with an average 14.5 days in soils with no previous ATZ use, meaning that ATZ degrades an average 6 times faster in soils with previous ATZ use., Conclusion: When ATZ is used for several years, enhanced degradation will undoubtedly change the way ATZ is used in agronomic crops and also its ultimate environmental fate. © 2017 Society of Chemical Industry., (© 2017 Society of Chemical Industry.)

Background: There are few reports on the effects of spray adjuvants on pesticide persistence. The role of three adjuvants used with atrazine on the herbicide's degradation in soil was examined. Three mathematical models were used to describe pesticide disappearance from soil: pseudo-first-order kinetics, the non-linear Gustafson-Holden model and the biexponential function., Results: A mixture of atrazine with Atpolan 80 EC significantly inhibited herbicide soil degradation (DT50  = 78 days), while Adpros 85 SL and Break-Thru S 240 (DT50  = 25 and 24 days respectively) had little effect (DT50  = 22 days, atrazine alone). These results suggest that adjuvant can be a factor in field persistence. DT50 values obtained using the Gustafson-Holden and biexponential models were similar. Only the biexponential model requires an iterative method., Conclusion: A significant effect of one adjuvant on atrazine persistence in soil was observed. The biexponential model best described the disappearance of atrazine in the soil, as indicated by the values of R(2) and RMS and the relative concentration of the herbicide in the soil., (© 2013 Society of Chemical Industry.)

Background: The herbicide atrazine was intercalated in the interlayer region of Mg/Al layered double hydroxides in order to produce a nanohybrid that could be used in controlled-release applications., Results: The hydrophobic herbicide was incorporated in artificial membranes formed in the interlayer of the inorganic host by using palmitic acid. The synthetic nanohybrid material was characterised by various techniques, and release studies were carried out. In addition, the photosynthetic alga Chlamydomonas reinhardtii Dang. was treated with the atrazine-containing nanohybrid, which exerted an herbicidal efficacy similar to that of the free herbicide., Conclusion: The herbicide containing nanohybrid could enable a controlled release of the herbicide. In addition, the herbicide would be delivered close to its site of uptake, enhancing efficiency and reducing the required doses., (Copyright © 2011 Society of Chemical Industry.)

Background: A population of waterhemp in a seed maize production field in central Illinois, United States, was not adequately controlled after post-emergence applications of herbicides that inhibit 4-hydroxyphenylpyruvate dioxygenase (HPPD)., Results: Progeny from the field population survived following treatment with mesotrione, tembotrione or topramezone applied to the foliage either alone or in combination with atrazine in greenhouse experiments. Dose-response experiments indicated that the level of resistance to the HPPD inhibitor mesotrione is at least tenfold relative to sensitive biotypes., Conclusion: These studies confirm that waterhemp has evolved resistance to HPPD-inhibiting herbicides., (Copyright © 2011 Society of Chemical Industry.)

Background: Following the discovery of pesticides in wells, the Hawaii Department of Agriculture (HDOA) supported research to evaluate the likelihood of pesticide leaching to the groundwater in Hawaii. The aim of this study was to evaluate the relative leaching pattern of five pesticides at five different sites on three islands and to compare their leaching behavior with bromide and a reference chemical (atrazine) that is known to leach in Hawaiian conditions. Laboratory measurements of sorption and degradation of the pesticides were made., Results: Most of the applied mass of pesticides was still present in the top 80 cm after the 16 week study period. The aggregated oxisol at Kunia showed the most intensive leaching among the five sites. The revised attenuation factor screening approach used by the HDOA indicated that all chemicals, with the exception of trifloxystrobin, had the potential to leach. Similarly, the groundwater ubiquity score ranked trifloxystrobin as a non-leacher. The field leaching data, however, suggested that trifloxystrobin was the most mobile compound among the pesticides tested., Conclusion: Although the results were variable among the sites, the field and laboratory experiments provided useful information for regulating use of these pesticides in Hawaii.

A moderately persistent herbicide, simazine, has been used globally and detected as a contaminant in soil and water. The authors have isolated a simazine-degrading bacterium from a simazine-degrading bacterial consortium that was enriched using charcoal as a microhabitat. The isolate, strain CDB21, was gram-negative, rod-shaped (0.5-0.6 microm x 1.0-1.2 microm) and motile by means of a single polar flagellum. Based on 16S rRNA sequence analysis, strain CDB21 was identified as a novel beta-proteobacterium exhibiting 100% sequence identity with the uncultured bacterium HOClCi25 (GenBank accession number AY328574). PCR using primers that were specific for the genes of the atrazine-degrading enzymes (atzABCDEF) of Pseudomonas sp. strain ADP showed that strain CDB21 also possessed the entire set of genes of these enzymes. Nucleotide sequences of the atzCDEF genes of strain CDB21 were 100% identical to those of Pseudomonas sp. strain ADP. Sequence identity of the atzA genes between these bacteria was 99.7%. The 398-nucleotide upstream fragment of the atzB gene of strain CDB21 was 100% identical to ORF30 of Pseudomonas sp. strain ADP, and the 1526-nucleotide downstream fragment showed 99.8% sequence similarity to the atzB gene of the pseudomonad., (Copyright 2007 Society of Chemical Industry.)

Off-site movement of pesticides from furrow-irrigated agriculture has been a concern in the Ord River Irrigation Area, Western Australia. This paper reports on the effectiveness of incorporation of pesticides by cultivator or power harrows before irrigating, and spraying pesticides only onto beds to minimise off-site transport. Incorporation of pesticides by power harrows prior to irrigation was found to be more effective in decreasing the off-site transport of a more strongly sorbed pesticide, endosulfan. The average load of total endosulfan (alpha + beta + sulfate) decreased by 74% (P < 0.01) from 11.41 g ha(-1) from the conventionally treated bays to 2.96 g ha(-1) from the incorporated irrigation bays. The total average load of atrazine leaving the irrigation bays was decreased by 81% (P < 0.05) from 87.82 g ha(-1) under the conventional practice of spraying the whole field to 16.95 g ha(-1) by spraying the beds only. A reduction of 52% in total average load of metolachlor was observed following incorporation with power harrows, but this was not significant. Incorporation by cultivator or by power harrows decreased the total load of atrazine or metolachlor leaving the irrigation bays over the whole irrigation period, but these treatments were not shown to be statistically significant, which may have been due to the limited number of field replicates. Incorporation of strongly sorbed pesticides (e.g. endosulfan) prior to irrigation significantly decreased the off-site transport of these pesticides in a furrow irrigation system and may be a useful practice to minimise off-site transport of other similar pesticides. Minimising off-site transport of weakly sorbed pesticides (e.g. atrazine and metolachlor) from a furrow irrigation system is more difficult. The nature of furrow irrigation makes it highly conducive to pesticide transport, particularly of weakly sorbed pesticides, and further work is needed to develop strategies to minimise the movement of this group of pesticides to water bodies.

In vegetated filter strips (VFS) the presence of perennial vegetation, rhizodeposition of labile organic substrates and the accumulation of an organic residue thatch layer may enhance microbial numbers and activity, thereby increasing the potential for mineralisation of herbicides and herbicide metabolites retained during run-off events. The objective of this laboratory experiment was to compare the mineralisation of atrazine and metolachlor with that of their respective metabolites in VFS and cultivated soil. With the exception of total bacteria, propagule density of the microbial groups, endogenous soil enzymes and microbial diversity were higher in the VFS soil. This correlated with increased mineralisation of metolachlor and its metabolites in the VFS soil and indicates potential for VFS to curtail the subsequent transport of these compounds. In contrast, the mineralisation of atrazine and the majority of its metabolites was substantially reduced in VFS soil relative to cultivated soil. Consequently, the potential for subsequent transport of atrazine and many of its metabolites may be greater in VFS soil than in cultivated soil if reduced mineralisation is not offset by increased sorption in the VFS., (Copyright (c) 2006 Society of Chemical Industry)

Soil was amended with maize mucilage, a major rhizodeposit, to study its role on the number of culturable soil micro-organisms, the structure of the bacterial community, atrazine mineralization and atzC abundance. The maximal percentage of atrazine mineralization was lower for mucilage-amended than for water-amended soil. Total culturable soil bacteria and 16S rDNA copy number, measured by RT-PCR, presented similar values and were not significantly (P < 0.05) different among treatments. Mucilage applied at a rate of 70 microg C g(-1) dry soil day(-1) over two weeks did not modify the abundance of the total soil microflora. Global structure of soil bacterial communities revealed by RISA analysis was not modified by maize mucilage amendment. Abundance of atzC sequence was only augmented by mucilage addition at the beginning of the experiment. However, this increase was not sustainable in time, as atzC copy number increased in water-amended soil which, in turn, corresponded with the higher percentage of atrazine mineralization observed in this soil. Maize mucilage amendment alone contributed only to minor changes in the atrazine-degrading community in the studied soil., (Copyright 2005 Society of Chemical Industry)

A soil column experiment under outdoor conditions was performed to monitor the fate of 14C-ring-labelled sulcotrione, 2-(2-chloro-4-mesylbenzoyl)cyclohexane-1,3-dione and atrazine, 6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine, in water leachates and in the ploughed horizon of a sandy loam soil. Two months after treatment, the cumulative amounts of herbicide residues leached from the soil were 14.5% and 7% of the applied radioactivity for sulcotrione and atrazine, respectively. Maximum leachate concentrations for each herbicide were observed during the first month following application: 120 and 95 microg litre(-1) for sulcotrione and atrazine respectively. After 2 weeks, 78% of the sulcotrione and atrazine was extractable from the soil, whereas after two months only 10 and 4%, respectively, could be extracted. The maximum sulcotrione content in the first 10 cm of soil was identical with that of atrazine. For both molecules, the content of non-extractable residues was low, being around 15%. Sulcotrione seems to be more mobile than atrazine but the consequences for water contamination are similar since lower doses are used., (Copyright 2005 Society of Chemical Industry)

The spatial variability in mineralization of atrazine, isoproturon and metamitron in soil and subsoil samples taken from a 135-ha catchment in north France was studied. Fifty-one samples from the top layer were taken to represent exhaustively the 31 agricultural fields and 21 soil types of the catchment. Sixteen additional samples were collected between depths of 0.7 and 10 m to represent the major geological materials encountered in the vadose zone of the catchment. All these samples were incubated with 14C-labelled atrazine under laboratory conditions at 28 degrees C. Fourteen selected surface samples which exhibited distinctly different behaviour for atrazine dissipation (including sorption and mineralization) were incubated with 14C-isoproturon and 14C-metamitron. Overall soil microbial activity and specific herbicide degradation activities were monitored during the incubations through measurements of total carbon dioxide and 14C-carbon dioxide respectively. At the end of the incubations, extractable and non-extractable (bound) residues remaining in soils were measured. Variability of herbicide dissipation half-life in soil surface samples was lower for atrazine and metamitron (CV < 12%) than for isoproturon (CV = 46%). The main contributor to the isoproturon dissipation variability was the variability of the extractable residues. For the other herbicides, spatial variability was mainly related to the variability of their mineralization. In all cases, herbicide mineralization half-lives showed higher variability than those of dissipation. Sorption or physicochemical soil properties could not explain atrazine and isoproturon degradation, whose main factors were probably directly related to the dynamics of the specific microbial degradation activity. In contrast, variability of metamitron degradation was significantly correlated to sorption coefficient (K(d)) through correlation with the sorptive soil components, organic matter and clay. Herbicide degradation decreased with depth as did the overall microbial activity. Atrazine mineralization activity was found down to a depth of 2.5 m; beyond that, it was negligible., (Copyright 2005 Society of Chemical Industry)

The degradation, sorption and transport of atrazine, hexazinone and procymidone in saturated coastal sand aquifer media were investigated in batch and column experiments. The pesticides were incubated with sterilised and non-sterilised groundwater or a mixture of groundwater and the aquifer material in the dark at 15 degrees C for 120 days. The estimated half-lives of the pesticides (and their ranges) in the mixture of groundwater and aquifer sand were 36 (31-40), 54 (40-77) and 84 (46-260) days for atrazine, procymidone and hexazinone, respectively. Compared with the relevant results for the groundwater-sand mixture phase, the estimated half-life of pesticides in the groundwater phase alone was shorter for procymidone (21 days) but longer for hexazinone (134 days); atrazine was not degraded in the groundwater phase. Chemical degradation appeared to have played the predominant role in the degradation of hexazinone and procymidone in the aquifer system, while both chemical and biological processes seemed to be important for the degradation of atrazine. Batch isothermal experiments were carried out at pH 4.6-4.7 to obtain sorption coefficients under equilibrium conditions. The isothermal data of the pesticides fitted well with the non-linear Freundlich function with an exponent of sorption coefficient that was greater than one. Contrary to reports in the literature, sorption of atrazine was the greatest, and procymidone was slightly more sorbed than hexazinone. A column experiment was conducted at a typical field-flow velocity of 0.5 m day(-1) over 60 days to study pesticide attenuation and transport in flow dynamic conditions. Retardation factors, R, derived from a two-site sorption/desorption model were 8.22, 1.76 and 1.63 for atrazine, procymidone and hexazinone, respectively. Atrazine displayed the lowest mobility and the mobility of procymidone was only slightly less than that of hexazinone, which is consistent with observations in the batch experiment. A possible explanation for these observations is that ionic atrazine is bound to oppositely charged ionic oxides, and ionic oxides have less effect on the sorption of the non-ionic procymidone. The significant tailing in the pesticide breakthrough curves (BTCs) in comparison with the bromide BTC, together with model-simulated results, suggests that the transport of the pesticides was under chemical non-equilibrium conditions with R values that were less than their equivalent values predicted using the batch equilibrium isothermal data. As a result of non-linear kinetic sorption, retardation factors of the pesticides in groundwater systems would not be constant and will decrease with decreasing pesticide concentrations and increasing flow velocities. Hence, the use of equilibrium isotherm data will probably over-predict the sorption of pesticides in groundwater systems. Rhodamine WT, a commonly used groundwater tracer, was significantly retarded (R = 5.48) and its BTC was much more spread out than the bromide BTC. Therefore, it would not be a good tracer for the indication of groundwater flow velocity and dispersion for the coastal sand aquifer system. In contrast to some aquifer media, the dye tracer was unsuitable as a marker of the appearance of atrazine in a coastal sand aquifer system., (Copyright (c) 2005 Society of Chemical Industry.)

The influence of different moisture and aeration conditions on the degradation of atrazine and isoproturon was investigated in environmental samples aseptically collected from surface and sub-surface zones of agricultural land. The materials were maintained at two moisture contents corresponding to just above field capacity or 90% of field capacity. Another two groups of samples were adjusted with water to above field capacity, and, at zero time, exposed to drying-rewetting cycles. Atrazine was more persistent (t(1/2) = 22-35 days) than isoproturon (t(1/2) = 5-17 days) in samples maintained at constant moisture conditions. The rate of degradation for both herbicides was higher in samples maintained at a moisture content of 90% of field capacity than in samples with higher moisture contents. The reduction in moisture content in samples undergoing desiccation from above field capacity to much lower than field capacity enhanced the degradation of isoproturon (t(1/2) = 9-12 days) but reduced the rate of atrazine degradation (t(1/2) = 23-35 days). This demonstrates the variability between different micro-organisms in their susceptibility to desiccation. Under anaerobic conditions generated in anaerobic jars, atrazine degraded much more rapidly than isoproturon in materials taken from three soil profiles (0-250 cm depth). It is suggested that some specific micro-organisms are able to survive and degrade herbicide under severe conditions of desiccation., (Copyright (c) 2005 Society of Chemical Industry.)

We present a set of adsorption coefficients measured on various Eocene and Quaternary materials sampled from the vadose zone of a catchment in Northern France for three herbicides, atrazine, isoproturon and metamitron. Some vadose zone materials were found to have higher adsorption coefficients than the topsoil. The adsorption coefficients were strongly dependent on the clay content of the material. From 83% to 97% of the variability in the adsorption coefficients could be explained by a linear relationship to the clay content. Adsorption coefficients normalized for clay content, Kclay, ranged between 1.6 and 17.6 litre kg(-1) for atrazine. Neglecting the adsorption properties of the vadose zone and relying exclusively on Koc values to predict mobility may bias regional or local risk assessment of groundwater contamination by pesticides. More information on the adsorption properties of geological materials should be collected to improve our ability to predict pesticide concentrations in groundwaters.

The Root Zone Water Quality Model (RZWQM) is a comprehensive, integrated physical, biological and chemical process model that simulates plant growth and movement of water, nutrients and pesticides in a representative area of an agricultural system. We tested the ability of RZWQM to predict surface runoff losses of atrazine, alachlor, fenamiphos and two fenamiphos oxidative degradates against results from a 2-year mesoplot rainfall simulation experiment. Model inputs included site-specific soil properties and weather, but default values were used for most other parameters, including pesticide properties. No attempts were made to calibrate the model except for soil crust/seal hydraulic conductivity and an adjustment of pesticide persistence in near-surface soil. Approximately 2.5 (+/- 0.9), 3.0 (+/- 0.8) and 0.3 (+/- 0.2)% of the applied alachlor, atrazine and fenamiphos were lost in surface water runoff, respectively. Runoff losses in the 'critical' events--those occurring 24 h after pesticide application--were respectively 91 (+/- 5), 86 (+/- 6) and 96 (+/- 3)% of total runoff losses for these pesticides. RZWQM adequately predicted runoff water volumes, giving a predicted/observed ratio of 1.2 (+/- 0.5) for all events. Predicted pesticide concentrations and loads from the 'critical' events were generally within a factor of 2, but atrazine losses from these events were underestimated, which was probably a formulation effect, and fenamiphos losses were overestimated due to rapid oxidation. The ratios of predicted to measured pesticide concentrations in all runoff events varied between 0.2 and 147, with an average of 7. Large over-predictions of pesticide runoff occurred in runoff events later in the season when both loads and concentrations were small. The normalized root mean square error for pesticide runoff concentration predictions varied between 42 and 122%, with an average of 84%. Pesticide runoff loads were predicted with a similar accuracy. These results indicate that the soil-water mixing model used in RZWQM is a robust predictor of pesticide entrainment and runoff.

Within-event variability in rainfall intensity may affect pesticide leaching rates in soil, but most laboratory studies of pesticide leaching use a rainfall simulator operating at constant rainfall intensity, or cover the soil with ponded water. This is especially true in experiments where macropores are present--macroporous soils present experimental complexities enough without the added complexity of variable rainfall intensity. One way to get around this difficulty is to use a suitable pesticide transport model, calibrate it to describe accurately a fixed-intensity experiment, and then explore the affects of within-event rainfall intensity variation on pesticide leaching through macropores. We used the Root Zone Water Quality Model (RZWQM) to investigate the effect of variable rainfall intensity on alachlor and atrazine transport through macropores. Data were used from an experiment in which atrazine and alachlor were surface-applied to 30 x 30 x 30 cm undisturbed blocks of two macroporous silt loam soils from glacial till regions. One hour later the blocks were subjected to 30-mm simulated rain with constant intensity for 0.5 h. Percolate was collected and analyzed from 64 square cells at the base of the blocks. RZWQM was calibrated to describe accurately the atrazine and alachlor leaching data, and then a median Mid-west variable-intensity storm, in which the initial intensity was high, was simulated. The variable-intensity storm more than quadrupled alachlor losses and almost doubled atrazine losses in one soil over the constant-intensity storm of the same total depth. Also rainfall intensity may affect percolate-producing macroporosity and consequently pesticide transport through macropores. For example, under variable rainfall intensity RZWQM predicted the alachlor concentration to be 2.7 microg ml(-1) with an effective macroporosity of 2.2 E(-4) cm(3) cm(-3) and 1.4 microg ml(-1) with an effective macroporosity of 4.6 E(-4) cm(3) cm(-3). Percolate-producing macroporosity and herbicide leaching under different rainfall intensity patterns, however, are not well understood. Clearly, further investigation of rainfall intensity variation on pesticide leaching through macropores is needed.

The most important results in the field of atrazine and paraquat resistance research by Hungarian researchers are reviewed. Pleiotropic effects accompanying atrazine resistance were investigated in atrazine-resistant (AR) and susceptible (S) biotypes of horseweed (Conyza canadensis (L) Cronq). No significant difference in carbon dioxide assimilation rate was found between the AR and S plants. The rates of the Hill reaction of the AR and S chloroplasts exhibited different temperature dependence. The thylakoid membrane lipids contained a lower amount of polar lipid and the fatty acid content exhibited a higher degree of unsaturation in the AR biotype. Photosynthetic apparatus of the AR biotype had better adaptive ability at low temperature and showed enhanced susceptibility to high-temperature stress. AR horseweed plants had reduced activity of xanthophyll cycle, limited capacity of light-induced non-photochemical and photochemical quenching, higher photosensitivity and susceptibility to photo-inhibition. In the case of paraquat resistance, horseweed found in Hungary exhibited a resistance factor of 450; the resistance is not based on an elevated level and activity of the antioxidant enzyme system. The suggested role of polyamines in the resistance mechanisms can be excluded. The higher putrescine and total polyamine content of paraquat-treated R leaves can be regarded as a general stress response rather than as a symptom of paraquat resistance. A paraquat-inducible, nuclear-coded protein, which presumably functions by carrying paraquat to the vacuole, is supposed to play a role in resistance.

The variation of the sorption isotherm of pesticides has seldom been explored at the catchment scale. Such a study was conducted at the scale of a 187-ha agricultural catchment for three herbicides: atrazine, isoproturon and metamitron. Partition coefficient (Kd) values were measured in batch experiments on 51 topsoil samples, and showed moderate variability at the catchment scale (coefficient of variation CV approximately 30%). Values of Kd ranged from 0.47 to 1.70 litre kg(-1) for atrazine, 0.47 to 1.81 for isoproturon, and 0.55 to 2.21 for metamitron. A clustering method was used to reduce the number of samples on which to measure sorption isotherms to 14. Sorption isotherms agreed with the Freundlich rather than the linear model. Kf parameters had CV values similar to those for Kd, with values ranging from 0.78 to 2.13 mg(1 - Nf) litre(Nf) kg(-1) for atrazine, 0.61 to 1.82 for isoproturon, and 0.69 and 2.58 for metamitron. Nf exponents showed little variation (CV < 5%). Nf values were between 0.86 and 0.98 for atrazine, 0.85 and 0.90 for isoproturon, and 0.82 and 0.87 for metamitron. More than 97% of the Kf catchment-scale variations could be explained by the variations of the soil organic carbon content.

Many chlorine-containing pesticides, for example 2-chloro-s-triazines, are of great concern both environmentally and toxicologically. As a result, ascertaining or predicting the fate and transport of these compounds in soils and water is of current interest. Transformation pathways for 2-chloro-s-triazines in the environment include dealkylation, dechlorination (hydrolysis), and ring cleavage. This study explored the feasibility of using computational chemistry, specifically the hybrid density functional theory method, B3LYP, to predict hydrolysis trends of atrazine (2-chloro-N4-ethyl-N6-isopropyl-1,3,5-triazine-2,4-diamine) and related 2-chloro-s-triazines to the corresponding 2-hydroxy-s-triazines. Gas-phase energetics are described on the basis of calculations performed at the B3LYP/6-311++G(d,p)//B3LYP/6-31G* level of theory. Calculated free energies of hydrolysis (delta h G298) are nearly the same for simazine (2-chloro-N4,N6-diethyl-1,3,5-triazine-2,4-diamine), atrazine, and propazine (2-chloro-N4,N6-di-isopropyl-1,3,5-triazine-2,4-diamine), suggesting that hydrolysis is not significantly affected by the side-chain amine-nitrogen alkyl substituents. High-energy barriers also suggest that the reactions are not likely to be observed in the gas phase. Aqueous solvation effects were examined by means of self-consistent reaction field methods (SCRF). Molecular structures were optimized at the B3LYP/6-31G* level using the Onsager model, and solvation energies were calculated at the B3LYP/6-311++G(d,p) level using the isodensity surface polarizable continuum model (IPCM). Although the extent of solvent stabilization was greater for cationic species than neutral ones, the full extent of solvation is underestimated, especially for the transition state structures. As a consequence, the calculated hydrolysis barrier for protonated atrazine is exaggerated compared with the experimentally determined one. Overall, the hydrolysis reactions follow a concerted nucleophilic aromatic substitution (SNAr) pathway.

In the intensely farmed corn-growing regions of the mid-western USA, surface waters have often been contaminated by herbicides, principally as a result of rainfall runoff occurring shortly after application of these to corn and other crops. In some vulnerable watersheds, water quality criteria for chronic human exposure through drinking water are occasionally exceeded. We selected three settings representative of vulnerable corn-region watersheds, and used the PRZM-EXAMS model with the Index Reservoir scenario to predict corn herbicide concentrations in the reservoirs as a function of herbicide properties and use pattern, site characteristics and weather in the watersheds. We compared herbicide application scenarios, including broadcast surface pre-plant atrazine and alachlor applications with a glyphosate pre-plant application, scenarios in which losses of herbicides were mitigated by incorporation or banding, and scenarios in which only glyphosate or glufosinate post-emergent herbicides were used with corn genetically modified to be resistant to them. In the absence of drift, in almost all years a single runoff event dominates the input into the reservoir. As a result, annual average pesticide concentrations are highly correlated with annual maximum daily values. The modeled concentrations were generally higher than those derived from monitoring data, even for no-drift model scenarios. Because of their lower post-emergent application rates and greater soil sorptivity, glyphosate and glufosinate loads in runoff were generally one-fifth to one-tenth those of atrazine and alachlor. These model results indicate that the replacement of pre-emergent corn herbicides with the post-emergent herbicides allowed by genetic modification of crops would dramatically reduce herbicide concentrations in vulnerable watersheds. Given the significantly lower chronic mammalian toxicity of these compounds, and their vulnerability to breakdown in the drinking water treatment process, risks to human populations through drinking water would also be reduced.

The aim of this study was to investigate the spatial variability in degradation and mineralization of atrazine and isoproturon in subsurface samples taken from sandy loam soils overlying gravel terraces which form part of a groundwater protection zone. Percussion drilling was used to obtain samples from 11 boreholes (maximum depth 3 m). Unlabelled atrazine or isoproturon, and ring-14C-labelled atrazine or isoproturon were added to samples, incubated at 25 degrees C for up to 16 weeks, and analyzed for the residual herbicide or [14C]carbon dioxide. All samples showed the potential to degrade these herbicides, although the percentage degradation decreased by a factor of 2-3 from the surface soil to a depth of 3 m. This was associated with a decrease in organic matter content, but there was no change in the potential to mineralize acetate, indicating that specific changes in the catabolic ability of the microbial population occurred with depth. The capacity of samples to mineralize atrazine and isoproturon to carbon dioxide decreased markedly with depth, with no mineralization potential observed at a depth of 80 cm.

The photolysis of atrazine in the soil surface under UV light and the factors affecting this has been studied. A rate constant of 0.09-0.17 min-1, photolytic depth of 0.1-0.3 mm and half-life of 4-8 min were determined. The results show that soil granularity, pH, humidity, organic content, humic acid and surface-active agents could affect the photolysis of atrazine in soil. GC-MS showed three photolytic products: 1-sec-butyl-4,4-diethyl-1-tetrazene, N2,N4-diethyl-6-methyl-1,3,5-triazine-2,4-diamine and 6-chloro-N2-propyl-1,3,5-triazine-2,4-diamine. The mechanism of the photolytic process is discussed.