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.     

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.     

Tillage and nutrient source effects on surface and subsurface water quality at corn planting

This study quantified the effects of tillage (moldboard plowing [MP], ridge tillage [RT]) and nutrient source (manure and commercial fertilizer [urea and triple superphosphate]) on sediment, NH4+ -N, NO3- -N, total P, particulate P, and soluble P losses in surface runoff and subsurface tile drainage from a clay loam soil. Treatment effects were evaluated using simulated rainfall immediately after corn (Zea mays L.) planting, the most vulnerable period for soil erosion and water quality degradation. Sediment, total P, soluble P, and NH4+ -N losses mainly occurred in surface runoff. The NO3- -N losses primarily occurred in subsurface tile drainage. In combined (surface and subsurface) flow, the MP treatment resulted in nearly two times greater sediment loss than RT (P < 0.01). Ridge tillage with urea lost at least 11 times more NH4+ -N than any other treatment (P < 0.01). Ridge tillage with manure also had the most total and soluble P losses of all treatments (P < 0.01). If all water quality parameters were equally important, then moldboard plow with manure would result in least water quality degradation of the combined flow followed by moldboard plow with urea or ridge tillage with urea (equivalent losses) and ridge tillage with manure. Tillage systems that do not incorporate surface residue and amendments appear to be more vulnerable to soluble nutrient losses mainly in surface runoff but also in subsurface drainage (due to macropore flow). Tillage systems that thoroughly mix residue and amendments in surface soil appear to be more prone to sediment and sediment-associated nutrient (particulate P) losses via surface runoff.     

Stream transport of herbicides and metabolites in a tile-drained, agricultural watershed

The occurrence of metabolites of many commonly used herbicides in streams has not been studied extensively in tile-drained watersheds. We collected water samples throughout the Upper Embarras River watershed [92% corn, Zea mays L., and soybean, Glycine max (L.) Merr.] in east-central Illinois from March 1999 through September 2000 to study the occurrence of atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), metolachlor 12-chloro-N-(2-ethyl-6-methylphenyl)-N-(methoxy-1-methylethyl) acetamide], alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide], acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl) acetamide], and their metabolites. River water samples were collected from three subwatersheds of varying tile density (2.8-5.3 km tile km(-2)) and from the outlet (United States Geological Survey [USGS] gage site). Near-record-low totals for stream flow occurred during the study, and nearly all flow was from tiles. Concentrations of atrazine at the USGS gage site peaked at 15 and 17 microg L(-1) in 1999 and 2000, respectively, and metolachlor at 2.7 and 3.2 microg L(-1); this was during the first significant flow event following herbicide applications. Metabolites of the chloroacetanilide herbicides were detected more often than the parent compounds (evaluated during May to July each year, when tiles were flowing), with metolachlor ethanesulfonic acid [2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoethanesulfonic acid] detected most often (> 90% from all sites), and metolachlor oxanilic acid [2-[(2-ethyl-6-methylphenyl)(2-methoxy-1-methylethyl)amino]-2-oxoacetic acid] second (40-100% of samples at the four sites). When summed, the median concentration of the three chloroacetanilide parent compounds (acetochlor, alachlor, and metolachlor) at the USGS gage site was 3.4 microg L(-1), whereas it was 4.3 microg L(-1) for the six metabolites. These data confirm the importance of studying chloroacetanilide metabolites, along with parent compounds, in tile-drained watersheds.     

Comparison of field-scale herbicide runoff and volatilization losses: an eight-year field investigation

An 8-yr study was conducted to better understand factors influencing year-to-year variability in field-scale herbicide volatilization and surface runoff losses. The 21-ha research site is located at the USDA-ARS Beltsville Agricultural Research Center in Beltsville, MD. Site location, herbicide formulations, and agricultural management practices remained unchanged throughout the duration of the study. Metolachlor [2-chloro--(2-ethyl-6-methylphenyl)--(2-methoxy-1-methylethyl) acetamide] and atrazine [6-chloro--ethyl--(1-methylethyl)-1,3,5-triazine-2,4-diamine] were coapplied as a surface broadcast spray. Herbicide runoff was monitored from a month before application through harvest. A flux gradient technique was used to compute volatilization fluxes for the first 5 d after application using herbicide concentration profiles and turbulent fluxes of heat and water vapor as determined from eddy covariance measurements. Results demonstrated that volatilization losses for these two herbicides were significantly greater than runoff losses ( < 0.007), even though both have relatively low vapor pressures. The largest annual runoff loss for metolachlor never exceeded 2.5%, whereas atrazine runoff never exceeded 3% of that applied. On the other hand, herbicide cumulative volatilization losses after 5 d ranged from about 5 to 63% of that applied for metolachlor and about 2 to 12% of that applied for atrazine. Additionally, daytime herbicide volatilization losses were significantly greater than nighttime vapor losses ( < 0.05). This research confirmed that vapor losses for some commonly used herbicides frequently exceeds runoff losses and herbicide vapor losses on the same site and with the same management practices can vary significantly year to year depending on local environmental conditions.     

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.     

Herbicide incorporation by irrigation and tillage impact on runoff loss

Runoff from farm fields is a common source of herbicide residues in surface waters. Incorporation by irrigation has the potential to reduce herbicide runoff risks. To assess impacts, rainfall was simulated on plots located in a peanut (Arachis hypogaea L.) field in Georgia's Atlantic Coastal Plain region after pre-emergence application of metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-[(1S)-2-methoxy-1-methylethyl]-acetamide) and pendimethalin (N-(1-ethylpropyl)-3,4-dimethyl-2,6-dinitro-benzenamine). Runoff, sediment, and herbicide loss as function of strip tillage (ST) versus conventional tillage (CT) were compared with and without irrigation (12.5 mm) after application of an herbicide tank mixture. For the CT system, metolachlor runoff was reduced 2x and pendimethalin 1.2x when compared with the non-irrigated treatment. The difference in irrigated and non-irrigated metolachlor means was significant (P = 0.05). Irrigation reduced metolachlor runoff by 1.3x in the ST system, but there was a 1.4x increase for pendimethalin. Overall results indicated that irrigation incorporation reduces herbicide runoff with the greatest impact when CT is practiced and products like metolachlor, which have relatively low K(oc) and high water solubility, are used. The lower ST system response was likely due to a combination of spray interception and retention by the ST system cover crop mulch and higher ST soil organic carbon content and less total runoff. During the study, the measured K(oc) of both herbicides on runoff sediment was found to vary with tillage and irrigation after herbicide application. Generally, K(oc) was higher for ST sediment and when irrigation incorporation was used with the CT system. These results have significant implications for simulation model parametization.     

Alachlor and bentazone losses from subsurface drainage of two soils

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) is frequently detected at high concentrations in ground water. Bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] plus alachlor (2-chloro-2',6'-diethyl-N-methoxymethylacetanilide) is a potential herbicide combination used as a substitute for atrazine. Thus, the objective of this study was to assess the environmental risk of this blend. Drainage water contamination by bentazone and alachlor was assessed in silty clay (Vertic Eutrochrept) and silt loam (Aquic Hapludalf) soils under the same management and climatic conditions. Drainage volumes and concentrations of alachlor and bentazone were monitored after application. Herbicides first arrived at the drains after less than 1 cm of net drainage. This is consistent with preferential flow and suggests that about 3% of the pore volume was active in rapid transport. During the monitoring periods, bentazone losses were higher (0.11-2.40% of the applied amount) than alachlor losses (0.00-0.28%) in the drains of the silty clay and silt loam. The rank order of herbicide mass losses corresponded with the rank order of herbicide adsorption coefficients. More herbicide residues were detected in drainage from the silty clay, probably due to preferential flow and more intensive drainage in this soil than the silt loam. Surprisingly, herbicide losses were higher in the drains of both soils in the drier of the two study years. This could be explained by the time intervals between the treatments and first drainage events, which were longer in the wetter year. Results suggest that the drainage phases occurred by preferential flow in the spring-summer period, with correspondingly fast leaching of herbicides, and by matrix flow during the fall-winter period, with slower herbicide migration.     

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.     

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.     

Diuron in surface runoff and tile drainage from two grass-seed fields

The typical method of cool-season grass-seed production in Mediterranean climates briefly exposes surface waters to potentially high concentrations of the herbicide diuron [3-(3,4-dichlorophenyl)-1,1-dimethyl urea] during the initial season of growth. To better understand the process, and the degree, of diuron transport from agricultural fields, two grass-seed fields in the Willamette Valley of Oregon were monitored for diuron loss in surface runoff and tile drainage during the first wet season after planting. Initial diuron concentrations in surface runoff were high (>1000 microg L(-1) in one field and >100 microg L(-1) in the other), though they decreased by two orders of magnitude by the end of the season. Concentrations in the tile drains were as much as 1000 times lower than in the surface runoff during the first few weeks of runoff events, and they remained lower than surface water concentrations throughout the season. Total losses in surface runoff were between 1.3 and 3% of the amount applied-much higher than losses via the tile drains. It is also shown by means of a simple first-order decay model that, when little information is available, it may be best to describe diuron depletion in runoff water as a function of cumulative rainfall during the wet season.     

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).     

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.     

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.     

Spatial variability of atrazine and metolachlor dissipation on dryland no-tillage crop fields in Colorado

An area of interest in precision farming is variable-rate application of herbicides to optimize herbicide use efficiency and minimize negative off-site and non-target effects. Site-specific weed management based on field scale management zones derived from soil characteristics known to affect soil-applied herbicide efficacy could alleviate challenges posed by post-emergence precision weed management. Two commonly used soil-applied herbicides in dryland corn (Zea mays L.) production are atrazine and metolachlor. Accelerated dissipation of atrazine has been discovered recently in irrigated corn fields in eastern Colorado. The objectives of this study were (i) to compare the rates of dissipation of atrazine and metolachlor across different soil zones from three dryland no-tillage fields under laboratory incubation conditions and (ii) to determine if rapid dissipation of atrazine and/or metolachlor occurred in dryland soils. Herbicide dissipation was evaluated at time points between 0 and 35 d after soil treatment using a toluene extraction procedure with GC/MS analysis. Differential rates of atrazine and metolachlor dissipation occurred between two soil zones on two of three fields evaluated. Accelerated atrazine dissipation occurred in soil from all fields of this study, with half-lives ranging from 1.8 to 3.2 d in the laboratory. The rapid atrazine dissipation rates were likely attributed to the history of atrazine use on all fields investigated in this study. Metolachlor dissipation was not considered accelerated and exhibited half-lives ranging from 9.0 to 10.7 d in the laboratory.     

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.     

Comparative losses of glyphosate and selected residual herbicides in surface runoff from conservation-tilled watersheds planted with corn or soybean

Residual herbicides regularly used in conjunction with conservation tillage to produce corn ( L.) and soybean [ (L.) Merr] are often detected in surface water at concentrations that exceed their U.S. maximum contaminant levels (MCL) and ecological standards. These risks might be reduced by planting glyphosate-tolerant varieties of these crops and totally or partially replacing the residual herbicides alachlor, atrazine, linuron, and metribuzin with glyphosate, a contact herbicide that has a short half-life and is strongly sorbed to soil. Therefore, we applied both herbicide types at typical rates and times to two chisel-plowed and two no-till watersheds in a 2-yr corn/soybean rotation and at half rates to three disked watersheds in a 3-yr corn/soybean/wheat-red clover ( L.- L.) rotation and monitored herbicide losses in surface runoff for three crop years. Average dissolved glyphosate loss for all tillage practices, as a percentage of the amount applied, was significantly less ( ≤ 0.05) than the losses of atrazine (21.4x), alachlor (3.5x), and linuron (8.7x) in corn-crop years. Annual, flow-weighted, concentration of atrazine was as high as 41.3 μg L, much greater than its 3 μg L MCL. Likewise, annual, flow-weighted alachlor concentration (MCL = 2 μg L) was as high as 11.2 and 4.9 μg L in corn- and soybean-crop years, respectively. In only one runoff event during the 18 watershed-years it was applied did glyphosate concentration exceed its 700 μg L MCL and the highest, annual, flow-weighted concentration was 3.9 μg L. Planting glyphosate-tolerant corn and soybean and using glyphosate in lieu of some residual herbicides should reduce the impact of the production of these crops on surface water quality.     

Multiyear nutrient removal performance of three constructed wetlands intercepting tile drain flows from grazed pastures

Subsurface tile drain flows can be a major s ource of nurient loss from agricultural landscapes. This study quantifies flows and nitrogen and phosphorus yields from tile drains at three intensively grazed dairy pasture sites over 3- to 5-yr periods and evaluates the capacity of constructed wetlands occupying 0.66 to 1.6% of the drained catchments too reduce nutrient loads. Continuous flow records are combined with automated flow-proportional sampling of nutrient concentrations to calculate tile drain nutrient yields and wetland mass removal rates. Annual drainage water yields rangedfrom 193 to 564 mm (16-51% of rainfall) at two rain-fed sites and from 827 to 853 mm (43-51% of rainfall + irrigation) at an irrigated site. Annually, the tile drains exported 14 to 109 kg ha(-1) of total N (TN), of which 58 to 90% was nitrate-N. Constructed wetlands intercepting these flows removed 30 to 369 gTN m(-2) (7-63%) of influent loadings annually. Seasonal percentage nitrate-N and TN removal were negatively associated with wetland N mass loadings. Wetland P removal was poor in all wetlands, with 12 to 115% more total P exported annually overall than received. Annually, the tile drains exported 0.12 to 1.38 kg ha of total P, of which 15 to 93% was dissolved reactive P. Additional measures are required to reduce these losses or provide supplementary P removal. Wetland N removal performance could be improved by modifying drainage systems to release flows more gradually and improving irrigation practices to reduce drainage losses.     

Anionic polyacrylamide effects on soil sorption and desorption of metolachlor,atrazine, 2,4-D,and picloram

Polyacrylamide (PAM) treatment of irrigation water is a growing conservation technology in irrigated agriculture in recent years. There is a concern regarding the environmental impact of PAM after its application. The effects of anionic PAM on the sorption characteristics of four widely used herbicides (metolachlor, atrazine, 2,4-D, and picloram) on two natural soils were assessed in batch equilibrium experiments. Results showed that PAM treatment kinetically reduced the sorption rate of all herbicides, possibly due to the slower diffusion of herbicide molecules into interior sorption sites of soil particles that were covered and/or cemented together by PAM. The equilibrium sorption and desorption amounts of nonionic herbicides (metolachlor and atrazine) were essentially unaffected by anionic PAM, even under a high PAM application rate, while the sorption amounts of anionic herbicides (2,4-D and picloram) were slightly decreased and their desorption amounts increased little. The impact mechanisms of PAM were related to the molecular characteristics of PAM and herbicides. The negative effects of PAM on the sorption of anionic herbicides are possibly caused by the enhancement of electrostatic repulsion by presorbed anionic PAM and competition for sorption sites. However, steric hindrance of the large PAM molecule weakens its influence on herbicide sorption on interior sorption sites of soil particles, which probably leads to the small interference on herbicide sorption, even under high application rates.