Herbicides in ground water beneath Nebraska's Management Systems Evaluation Area

Profiles of ground water pesticide concentrations beneath the Nebraska Management Systems Evaluation Area (MSEA) describe the effect of 20 yr of pesticide usage on ground water in the central Platte Valley of Nebraska. During the 6-yr (1991-1996) study, 14 pesticides and their transformation products were detected in 7848 ground water samples from the unconfined water table aquifer. Triazine and acetamide herbicides applied on the site and their transformation products had the highest frequencies of detection. Atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4,-diamine] concentrations decreased with depth and ground water age determined with 3H/3He dating techniques. Assuming equivalent atrazine input during the past 20 yr, the measured average changes in concentration with depth (age) suggest an estimated half-life of >10 yr. Hydrolysis of atrazine and deethylatrazine (DEA; 2-chloro-4-amino-6-isopropylamino-s-triazine) to hydroxyatrazine [6-hydroxy-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] appeared to be the major degradation route. Aqueous hydroxyatrazine concentrations are governed by sorption on the saturated sediments. Atrazine was detected in the confined Ogallala aquifer in ultra-trace concentrations (0.003 microg L(-1)); however, the possibility of introduction during reverse circulation drilling of these deep wells cannot be eliminated. In fall 1997 sampling, metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] was detected in 57% of the 230 samples. Metolachlor oxanilic acid [(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl) amino]oxo-acetic acid] was detected in most samples. In ground water profiles, concentrations of metolachlor ethane sulfonic acid [2-[(ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxo-ethanesulfonic acid] exceeded those of deethylatrazine. Alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide] was detected in <1% of the samples; however, alachlor ethane sulfonic acid [2-[(2,6-diethylphenyl)(methoxymethyl)amino]-2-oxoethanesulfonic acid] was present in most samples (63%) and was an indicator of past alachlor use.     

Pesticides in rain in four agricultural watersheds in the United States

Rainfall samples were collected during the 2003 and 2004 growing seasons at four agricultural locales across the USA in Maryland, Indiana, Nebraska, and California. The samples were analyzed for 21 insecticides, 18 herbicides, three fungicides, and 40 pesticide degradates. Data from all sites combined show that 7 of the 10 most frequently detected pesticides were herbicides, with atrazine (70%) and metolachlor (83%) detected at every site. Dacthal, acetochlor, simazine, alachlor, and pendimethalin were detected in more than 50% of the samples. Chlorpyrifos, carbaryl, and diazinon were the only insecticides among the 10 most frequently detected compounds. Of the remaining pesticide parent compounds, 18 were detected in fewer than 30% of the samples, and 13 were not detected. The most frequently detected degradates were deethylatrazine; the oxygen analogs (OAs) of the organophosphorus insecticides chlorpyrifos, diazinon, and malathion; and 1-napthol (degradate of carbaryl). Deethylatrazine was detected in nearly 70% of the samples collected in Maryland, Indiana, and Nebraska but was detected only once in California. The OAs of chlorpyrifos and diazinon were detected primarily in California. Degradates of the acetanilide herbicides were rarely detected in rain, indicating that they are not formed in the atmosphere or readily volatilized from soils. Herbicides accounted for 91 to 98% of the total pesticide mass deposited by rain except in California, where insecticides accounted for 61% in 2004. The mass of pesticides deposited by rainfall was estimated to be less than 2% of the total applied in these agricultural areas.     

The acetochlor registration partnership state ground water monitoring program

The Acetochlor Registration Partnership (ARP) conducted a 7-yr ground water monitoring program at a total of 175 sites in seven states: Illinois, Indiana, Iowa, Kansas, Minnesota, Nebraska, and Wisconsin. While acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide] was the primary focus, the analytical methods also quantified alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)-acetamide], atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine], metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide], and two classes of soil degradates for acetochlor, alachlor, and metolachlor. Ground water samples were collected monthly for five years and quarterly for two additional years. All samples were analyzed for the presence of parent herbicides, and degradates were monitored during the last three years. Parent acetochlor was detected above 0.1 microg L(-1) in three or more samples at just seven sites. Alachlor and metolachlor were also rarely detected, but atrazine was detected in 36% of all samples analyzed. Even more widespread were the tertiary amide sulfonic acid (ethanesulfonic acid, ESA) degradates of acetochlor, alachlor, and metolachlor, which were detected at 81, 76, and 106 sites, respectively. The other class of monitored soil degradates (oxanilic acid, OXA) was detected less frequently, at 26, 16, and 63 sites for acetochlor OXA, alachlor OXA, and metolachlor OXA, respectively. The geographic distribution of detections did not follow the pattern originally expected when the study began. Rather than being a function primarily of soil texture, the detection of these herbicides in shallow ground water was related to site-specific factors associated with local topography, the occurrence of surface water drainage features, irrigation practices, and the vertical positioning of the well screen.     

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).     

Differentiating nonpoint sources of deisopropylatrazine in surface water using discrimination diagrams

Pesticide degradates account for a significant portion of the pesticide load in surface water. Because pesticides with similar structures may degrade to the same degradate, it is important to distinguish between different sources of parent compounds that have different regulatory and environmental implications. A discrimination diagram, which is a sample plot of chemical data that differentiates between different parent compounds, was used for the first time to distinguish whether sources other than atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) contributed the chlorinated degradate, deisopropylatrazine (DIA; 6-chloro-N-ethyl-1,3,5-triazine-2,4-diamine) to the Iroquois and Delaware Rivers. The concentration ratio of deisopropylatrazine to deethylatrazine [6-chloro-N-(1-methylethyl)1,3,5-triazine-2,4-diamine], called the D2R, was used to discriminate atrazine as a source of DIA from other parent sources, such as cyanazine (2-[[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino]-2-methylpropionitrile) and simazine (6-chloro-N,N'-diethyl-1,3,5-triazine-2,4diamine). The ratio of atrazine to cyanazine (ACR) used in conjunction with the D2R showed that after atrazine, cyanazine was the main contributor of DIA in surface water. The D2R also showed that cyanazine, and to a much lesser extent simazine, contributed a considerable amount (approximately 40%) of the DIA that was transported during the flood of the Mississippi River in 1993. The D2R may continue to be a useful discriminator in determining changes in the nonpoint sources of DIA in surface water as cyanazine is currently being removed from the market.     

Summer cover crops reduce atrazine leaching to shallow groundwater in southern Florida

At Florida's southeastern tip, sweet corn (Zea Mays) is grown commercially during winter months. Most fields are treated with atrazine (6-chloro-N-ethyl-N'-[1-methylethyl]-1,3,5-triazine-2,4-diamine). Hydrogeologic conditions indicate a potential for shallow groundwater contamination. This was investigated by measuring the parent compound and three degradates--DEA (6-chloro-N-[1-methylethyl]-1,3,5-triazine-2,4-diamine), DIA (6-chloro-N-ethyl)-1,3,5-triazine-2,4-diamine, and HA (6-hydroxy-N-[1-methylethyl]-1,3,5-triazine-2,4-diamine)--in water samples collected beneath sweet corn plots treated annually with the herbicide. During the study, a potential mitigation measure (i.e., the use of a cover crop, Sunn Hemp [Crotalaria juncea L.], during summer fallow periods followed by chopping and turning the crop into soil before planting the next crop) was evaluated. Over 3.5 yr and production of four corn crops, groundwater monitoring indicated leaching of atrazine, DIA, and DEA, with DEA accounting for more than half of all residues in most samples. Predominance of DEA, which increased after the second atrazine application, was interpreted as an indication of rapid and extensive atrazine degradation in soil and indicated that an adapted community of atrazine degrading organisms had developed. A companion laboratory study found a sixfold increase in atrazine degradation rate in soil after three applications. Groundwater data also revealed that atrazine and degradates concentrations were significantly lower in samples collected beneath cover crop plots when compared with concentrations below fallow plots. Together, these findings demonstrated a relatively small although potentially significant risk for leaching of atrazine and its dealkylated degradates to groundwater and that the use of a cover crop like Sunn Hemp during summer months may be an effective mitigation measure.     

Transport and fate of nitrate and pesticides: hydrogeology and riparian zone processes

There is continuing concern over potential impacts of widespread application of nutrients and pesticides on ground- and surface-water quality. Transport and fate of nitrate and pesticides were investigated in a shallow aquifer and adjacent stream, Cow Castle Creek, in Orangeburg County, South Carolina. Pesticide and pesticide degradate concentrations were detected in ground water with greatest frequency and largest concentrations directly beneath and downgradient from the corn (Zea mays L.) field where they were applied. In almost all samples in which they were detected, concentrations of pesticide degradates greatly exceeded those of parent compounds, and were still present in ground waters that were recharged during the previous 18 yr. The absence of both parent and degradate compounds in samples collected from deeper in the aquifer suggests that this persistence is limited or that the ground water had recharged before use of the pesticide. Concentrations of NO(-)(3) in ground water decreased with increasing depth and age, but denitrification was not a dominant controlling factor. Hydrologic and chemical data indicated that ground water discharges to the creek and chemical exchange takes place within the upper 0.7 m of the streambed. Ground water had its greatest influence on surface-water chemistry during low-flow periods, causing a decrease in concentrations of Cl(-), NO(-)(3), pesticides, and pesticide degradates. Conversely, shallow subsurface drainage dominates stream chemistry during high-flow periods, increasing stream concentrations of Cl(-), NO(-)(3), pesticides, and pesticide degradates. These results point out the importance of understanding the hydrogeologic setting when investigating transport and fate of contaminants in ground water and surface water.     

Herbicide loading to shallow ground water beneath Nebraska's Management Systems Evaluation Area

Better management practices can counter deterioration of ground water quality. From 1991 through 1996 the influence of improved irrigation practices on ground water pesticide contamination was assessed at the Nebraska Management Systems Evaluation Area. Three 13.4-ha corn (Zea mays L.) fields were studied: a conventional furrow-irrigated field, a surge-irrigated field and a center pivot-irrigated field, and a center pivot-irrigated alfalfa (Medicago sativa L.) field. The corn fields received one identical banded application of Bicep (atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4,-diamine] + metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamidel) annually; the alfalfa field was untreated. Ground water samples were collected three times annually from 16 depths of 31 multilevel samplers. Six years of sample data indicated that a greater than 50% reduction in irrigation water on the corn management fields lowered average atrazine concentrations in the upper 1.5 m of the aquifer downgradient of the corn fields from approximately 5.5 to <0.5 microg L(-1). Increases in deethylatrazine (DEA; 2-chloro-4-amino-6-isopropylamino-s-triazine) to atrazine molar ratios indicated that reducing water applications enhanced microbial degradation of atrazine in soil zones. The occurrence of peak herbicide loading in ground water was unpredictable but usually was associated with heavy precipitation within days of herbicide application. Focused recharge of storm runoff that ponded in the surge-irrigated field drainage ditch, in the upgradient road ditch, and at the downgradient end of the conventionally irrigated field was a major mechanism for vertical transport. Sprinkler irrigation technology limited areas for focused recharge and promoted significantly more soil microbial degradation of atrazine than furrow irrigation techniques and, thereby, improved ground water quality.     

Simulated fate and transport of metolachlor in the unsaturated zone, Maryland, USA

An unsaturated-zone transport model was used to examine the transport and fate of metolachlor applied to an agricultural site in Maryland, USA. The study site was instrumented to collect data on soil-water content, soil-water potential, ground water levels, major ions, pesticides, and nutrients from the unsaturated zone during 2002-2004. The data set was enhanced with site-specific information describing weather, soils, and agricultural practices. The Root Zone Water Quality Model was used to simulate physical, chemical, and biological processes occurring in the unsaturated zone. Model calibration to bromide tracer concentrations indicated flow occurred through the soil matrix. Simulated recharge rates were within the measured range of values. The pesticide transport model was calibrated to the intensive data collection period (2002-2004), and the calibrated model was then used to simulate the period 1984 through 2004 to examine the impact of sustained agricultural management practices on the concentrations of metolachlor and its degradates at the study site. Simulation results indicated that metolachlor degrades rapidly in the root zone but that the degradates are transported to depth in measurable quantities. Simulations indicated that degradate transport is strongly related to the duration of sustained use of metolachlor and the extent of biodegradation.     

The acetochlor registration partnership surface water monitoring program for four corn herbicides

A surface drinking water monitoring program for four corn (Zea mays L.) herbicides was conducted during 1995-2001. Stratified random sampling was used to select 175 community water systems (CWSs) within a 12-state area, with an emphasis on the most vulnerable sites, based on corn intensity and watershed size. Finished drinking water was monitored at all sites, and raw water was monitored at many sites using activated carbon, which was shown capable of removing herbicides and their degradates from drinking water. Samples were collected biweekly from mid-March through the end of August, and twice during the off-season. The analytical method had a detection limit of 0.05 microg L(-1) for alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)-acetamide] and 0.03 microg L(-1) for acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide], atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine], and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)-acetamide]. Of the 16528 drinking water samples analyzed, acetochlor, alachlor, atrazine, and metolachlor were detected in 19, 7, 87, and 53% of the samples, respectively. During 1999-2001, samples were also analyzed for the presence of six major degradates of the chloroacetanilide herbicides, which were detected more frequently than their parent compounds, despite having higher detection limits of 0.1 to 0.2 microg L(-1). Overall detection frequencies were correlated with product use and environmental fate characteristics. Reservoirs were particularly vulnerable to atrazine, which exceeded its 3 microg L(-1) maximum contaminant level at 25 such sites during 1995-1999. Acetochlor annualized mean concentrations (AMCs) did not exceed its mitigation trigger (2 microg L(-1)) at any site, and comparisons of observed levels with standard measures of human and ecological hazards indicate that it poses no significant risk to human health or the environment.     

Pesticide and Transformation Product Detections and Age‐Dating Relations from Till and Sand Deposits1

Abstract:  Pesticide and transformation product concentrations and frequencies in ground water from areas of similar crop and pesticide applications may vary substantially with differing lithologies. Pesticide analysis data for atrazine, metolachlor, alachlor, acetochlor, and cyanazine and their pesticide transformation products were collected at 69 monitoring wells in Illinois and northern Indiana to document occurrence of pesticides and their transformation products in two agricultural areas of differing lithologies, till, and sand. The till is primarily tile drained and has preferential fractured flow, whereas the sand primarily has surface water drainage and primary porosity flow. Transformation products represent most of the agricultural pesticides in ground water regardless of aquifer material – till or sand. Transformation products were detected more frequently than parent pesticides in both the till and sand, with metolachlor ethane sulfonic acid being most frequently detected. Estimated ground‐water recharge dates for the sand were based on chlorofluorocarbon analyses. These age‐dating data indicate that ground water recharged prior to 1990 is more likely to have a detection of a pesticide or pesticide transformation product. Detections were twice as frequent in ground water recharged prior to 1990 (82%) than in ground water recharged on or after 1990 (33%). The highest concentrations of atrazine, alachlor, metolachlor, and their transformation products, also were detected in samples from ground water recharged prior to 1990. These age/pesticide detection relations are opposite of what would normally be expected, and may be the result of preferential flow and/or ground‐water mixing between aquifers and aquitards as evident by the detection of acetochlor transformation products in samples with estimated ground‐water ages predating initial pesticide application.     

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.     

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.     

Relation Between Flow and Temporal Variations of Nitrate and Pesticides in Two Karst Springs in Northern Alabama1

Abstract: Two karst springs in the Mississippian Carbonate Aquifer of northern Alabama were sampled between March 1999 and March 2001 to characterize the variability in concentration of nitrate, pesticides, selected pesticide degradates, water temperature, and inorganic constituents. Water temperature and inorganic ion data for McGeehee Spring indicate that this spring represents a shallow flow system with a relatively short average ground‐water residence time. Water issuing from the larger of the two springs, Meridianville Spring, maintained a constant temperature, and inorganic ion data indicate that this water represents a deeper flow system having a longer average ground‐water residence time than McGeehee Spring. Although water‐quality data indicate differing short‐term responses to rainfall at the two springs, the seasonal variation of nitrate and pesticide concentrations generally is similar for the two springs. With the exception of pesticides detected at low concentrations, the coefficient of variation for most constituent concentrations was less than that of flow at both springs, with greater variability in concentration at McGeehee Spring. Degradates of the herbicides atrazine and fluometuron were detected at concentrations comparable to or greater than the parent pesticides. Decreases in concentration of the principal degradate of fluometuron from about July to November indicate that the degradation rate may decrease as fluometuron (demethylfluometuron) moves deeper into the soil after application. Data collected during the study show that from about November to March when recharge rates increase, nitrate and residual pesticides in the soil, unsaturated zone, and storage within the aquifer are transported to the spring discharges. Because of the increase in recharge, fluometuron loads discharged from the springs during the winter were comparable to loads discharged at the springs during the growing season.     

ATRAZINE AND METOLACHLOR OCCURRENCE IN SHALLOW GROUND WATER OF THE UNITED STATES, 1993 TO 1995: RELATIONS TO EXPLANATORY FACTORS1

ABSTRACT: Since 1991, the U.S. Geological Survey has been conducting the National Water Quality Assessment (NAWQA) Program to determine the quality of the Nation's water resources. In an effort to obtain a better understanding of why pesticides are found in shallow ground water on a national scale, a set of factors likely to affect the fate and transport of two herbicides in the subsurface were examined. Atrazine and metolachlor were selected for this discussion because they were among the most frequently detected pesticides in ground water during the first phase of the NAWQA Program (1993 to 1995), and each was the most frequently detected compound in its chemical class (triazines and acetanilides, respectively). The factors that most strongly correlated with the frequencies of atrazine detection in shallow ground‐water networks were those that provided either: (1) an indication of the potential susceptibility of ground water to atrazine contamination, or (2) an indication of relative ground‐water age. The factors most closely related to the frequencies of metolachlor detection in ground water, however, were those that estimated or indicated the intensity of the agricultural use of metolachlor. This difference is probably the result of detailed use estimates for these compounds being available only for agricultural settings. While atrazine use is relatively extensive in nonagricultural settings, in addition to its widespread agricultural use, metolachlor is used almost exclusively for agricultural purposes. As a result, estimates of agricultural applications provide a less reliable indication of total chemical use for atrazine than for metolachlor. A multivariate analysis demonstrated that the factors of interest explained about 50 percent of the variance in atrazine and metolachlor detection frequencies among the NAWQA land‐use studies examined. The inclusion of other factors related to pesticide fate and transport in ground water, or improvements in the quality and accuracy of the data employed for the factors examined, may help explain more of the remaining variance in the frequencies of atrazine and metolachlor detection.     

Fate of pesticides in tropical soils of Brazil under field conditions

The potential of pesticides for nonpoint ground water pollution depends on their dissipation and leaching behavior in soils. We investigated the fate of 10 pesticides in two tropical soils of contrasting texture in the Brazilian Cerrado region near Cuiabá during an 80-d period, employing topsoil dissipation studies, soil core analyses, and lysimeter experiments. Dissipation of pesticides was rapid, with field half-lives ranging from 0.8 to 20 d in Ustox and 0.6 to 11.8 d in Psamments soils. Soil core analyses showed progressive leaching of polar pesticides in Psamments, whereas in Ustox pesticides were rapidly transported to 40 cm soil depth regardless of their sorption properties, suggesting that leaching was caused by preferential flow. In lysimeter experiments (35 cm soil depth), cumulative leaching was generally low, with < or = 0.02% and < or = 0.19% of the applied amounts leached in Ustox and Psamments, respectively. In both soils, all pesticides but the pyrethroids were detected in percolate at 35 cm soil depth within the first 6 d after application. Cumulative efflux and mean concentrations of pesticides in percolate were dosely correlated with their Groundwater Ubiquity Score (GUS). The presence of alachlor (2-chloro-2', 6'-diethyl-N-methoxymethylacetanilide), atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine), metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide], simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine], and trifluralin (2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline) throughout the soil profile and in percolate of wick lysimeters at 95 cm soil depth indicated that a nonpoint pollution of ground water resources in tropical Brazil cannot be ruled out for these substances.     

Tillage, intercrop, and controlled drainage-subirrigation influence atrazine, metribuzin, and metolachlor loss

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] have been found with increasing occurrence in rivers and streams. Their continued use will require changes in agricultural practices. We compared water quality from four crop-tillage treatments: (i) conventional moldboard plow (MB), (ii) MB with ryegrass (Lolium multiflorum Lam.) intercrop (IC), (iii) soil saver (SS), and (iv) SS + IC; and two drainage control treatments, drained (D) and controlled drainage-subirrigation (CDS). Atrazine (1.1 kg a.i. ha-1), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one] (0.5 kg a.i. ha-1), and metolachlor (1.68 kg a.i. ha-1) were applied preemergence in a band over seeded corn (Zea mays L.) rows. Herbicide concentration and losses were monitored from 1992 to spring 1995. Annual herbicide losses ranged from < 0.3 to 2.7% of application. Crop-tillage treatment influenced herbicide loss in 1992 but not in 1993 or 1994, whereas CDS affected partitioning of losses in most years. In 1992, SS + IC reduced herbicide loss in tile drains and surface runoff by 46 to 49% compared with MB. The intercrop reduced surface runoff, which reduced herbicide transport. Controlled drainage-subirrigation increased herbicide loss in surface runoff but decreased loss through tile drainage so that total herbicide loss did not differ between drainage treatments. Desethyl atrazine [6-chloro-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine] comprised 7 to 39% of the total triazine loss.     

Runoff and drainage losses of atrazine, metribuzin, and metolachlor in three water management systems

Rainfall can transport herbicides from agricultural land to surface waters, where they become an environmental concern. Tile drainage can benefit crop production by removing excess soil water but tile drainage may also aggravate herbicide and nutrient movement into surface waters. Water management of tile drains after planting may reduce tile drainage and thereby reduce herbicide losses to surface water. To test this hypothesis we calculated the loss of three herbicides from a field with three water management systems: free drainage (D), controlled drainage (CD), and controlled drainage with subsurface irrigation (CDS). The effect of water management systems on the dissipation of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazine-5(4H)-one), and metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] in soil was also monitored. Less herbicide was lost by surface runoff from the D and CD treatments than from CDS. The CDS treatment increased surface runoff, which transported more herbicide than that from D or CD treatments. In one year, the time for metribuzin residue to dissipate to half its initial value was shorter for CDS (33 d) than for D (43 d) and CD (46 d). The half-life of atrazine and metolachlor were not affected by water management. Controlled drainage with subsurface irrigation may increase herbicide loss through increased surface runoff when excessive rain is received soon after herbicide application. However, increasing soil water content in CDS may decrease herbicide persistence, resulting in less residual herbicide available for aqueous transport.     

HERBICIDES AND DEGRADATES IN SHALLOW AQUIFERS OF ILLINOIS: SPATIAL AND TEMPORAL TRENDS1

ABSTRACT: During the fall of 2000, the occurrence was examined of 16 herbicides and 13 herbicide degradates in samples from 55 wells in shallow aquifers underlying grain producing regions of Illinois. Herbicide compounds with concentrations above 0.05 μg/L were detected in 56 percent of the samples. No concentrations exceeded regulatory drinking water standards. The six most frequently detected compounds were degradates. Water age was an important factor in determining vulnerability of ground water to transport of herbicide compounds. Unconsolidated aquifers, which were indicated to generally contain younger ground water than bedrock aquifers, had a higher occurrence of herbicides (73 percent of samples) than bedrock aquifers (22 percent). Temporal analysis to determine if changes in concentrations of selected herbicides and degradates could be observed over a near decadal period indicated a decrease in detection frequency (25 to 18 percent) between samplings in 1991 and 2000. Over this period, significant differences in concentrations were observed for atrazine (decrease) and total acetochlor (increase). The increase in acetochlor compound concentrations corresponds to an increase in acetochlor use during the study period, while the decrease in atrazine concentrations corresponds to relatively consistent use of atrazine. Changes in frequency of herbicide detection and concentration do not appear related to changes in land use near sampled wells.     

Major herbicides in ground water: results from the National Water-Quality Assessment

To improve understanding of the factors affecting pesticide occurrence in ground water, patterns of detection were examined for selected herbicides, based primarily on results from the National Water-Quality Assessment (NAWQA) program. The NAWQA data were derived from 2,227 sites (wells and springs) sampled in 20 major hydrologic basins across the USA from 1993 to 1995. Results are presented for six high-use herbicides--atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), cyanazine (2-[4-chloro-6-ethylamino-1,3,5triazin-2-yl]amino]-2-methylpropionitrile), simazine (2-chloro-4,6-bis-[ethylamino]-s-triazine), alachlor (2-chloro-N-[2,6-diethylphenyl]-N-[methoxymethyl]acetamide), acetochlor (2-chloro-N-[ethoxymethyl]-N-[2-ethyl-6-methylphenyl]acetamide), and metolachlor (2-chloro-N-[2-ethyl-6-methylphenyl]-N-[2-methoxylethyl]acetamide)--as well as for prometon (2,4-bis[isopropylamino]-6-methoxy-s-triazine), a nonagricultural herbicide detected frequently during the study. Concentrations were <1 microg L(-1) at 98% of the sites with detections, but exceeded drinking-water criteria (for atrazine) at two sites. In urban areas, frequencies of detection (at or above 0.01 microg L(-1)) of atrazine, cyanazine, simazine, alachlor, and metolachlor in shallow ground water were positively correlated with their nonagricultural use nationwide (P < 0.05). Among different agricultural areas, frequencies of detection were positively correlated with nearby agricultural use for atrazine, cyanazine, alachlor, and metolachlor, but not simazine. Multivariate analysis demonstrated that for these five herbicides, frequencies of detection beneath agricultural areas were positively correlated with their agricultural use and persistence in aerobic soil. Acetochlor, an agricultural herbicide first registered in 1994 for use in the USA, was detected in shallow ground water by 1995, consistent with previous field-scale studies indicating that some pesticides may be detected in ground water within 1 yr following application. The NAWQA results agreed closely with those from other multistate studies with similar designs.