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.     

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.     

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.     

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.     

Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.     

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.     

Residual and contact herbicide transport through field lysimeters via preferential flow

Usage of glyphosate [N-(phosphonomethyl)-glycine] and glufosinate [2-amino-4-(hydroxy-methylphosphinyl)butanoic acid] may reduce the environmental impact of agriculture because they are more strongly sorbed to soil and may be less toxic than many of the residual herbicides they replace. Preferential flow complicates the picture, because due to this process, even strongly sorbed chemicals can move quickly to ground water. Therefore, four monolith lysimeters (8.1 m(2) by 2.4 m deep) were used to investigate leaching of contact and residual herbicides under a worst-case scenario. Glufosinate, atrazine (6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine), alachlor [2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl) acetamide], and linuron (3-3,4-dichlorophenyl-1-methoxy-1-methylurea) were applied in 1999 before corn (Zea mays L.) planting and glyphosate, alachlor, and metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] were applied in 2000 before soybean [Glycine max (L.) Merr.] planting. A high-intensity rainfall was applied shortly after herbicide application both years. Most alachlor, metribuzin, atrazine, and linuron losses occurred within 1.1 d of rainfall initiation and the peak concentration of the herbicides coincided (within 0.1 d of rainfall initiation in 2000). More of the applied metribuzin leached compared with alachlor during the first 1.1 d after rainfall initiation (2.2% vs. 0.035%, P < 0.05). In 1999, 10 of 24 discrete samples contained atrazine above the maximum contaminant level (atrazine maximum contaminant level [MCL] = 3 mug L(-1)) while only one discrete sample contained glufosinate (19 mug L(-1), estimated MCL = 150 mug L(-1)). The results indicate that because of preferential flow, the breakthrough time of herbicides was independent of their sorptive properties but the transport amount was dependent on the herbicide properties. Even with preferential flow, glyphosate and glufosinate were not transported to 2.4 m at concentrations approaching environmental concern.     

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.     

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.     

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.     

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.     

Adsorption and desorption of metolachlor and metolachlor metabolites in vegetated filter strip and cultivated soil

Previous studies have indicated that dissolved-phase metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(methoxy-1-methylethyl) acetamide] transported in surface runoff is retained by vegetative filter strips to a greater degree than either metolachlor oxanilic acid 12-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl)amino]-2-oxo-acetic acid] (OA) or metolachlor ethanesulfonic acid [2-[(2-ethyl-6-methylphenyl) (2-methoxy-1-methylethyl-1)amino]-2-oxoethanesul-fonic acid] (ESA), two primary metabolites of metolachlor. Adsorption-desorption of ESA and OA in vegetated filter strip soil (VFSS) has not been evaluated, yet these data are required to assess the mobility of these compounds in VFSS. The objective of this experiment was to compare metolachlor, ESA, and OA adsorption and desorption parameters between VFSS and cultivated soil (CS). Adsorption and desorption isotherms were determined using the batch equilibrium procedure. With the exception of a 1.7-fold increase in organic carbon content in the VFSS, the evaluated chemical and physical properties of the soils were similar. Sorption coefficients for metolachlor were 88% higher in VFSS than in CS. In contrast, sorption coefficients for ESA and OA were not different between soils. Relative to metolachlor, sorption coefficients for ESA and OA were at least 79% lower in both soils. Metolachlor desorption coefficients were 59% higher in the VFSS than in the CS. Desorption coefficients for ESA and OA were not different between soils. Relative to metolachlor, desorption coefficients for ESA and OA were at least 66% lower in both soils. These data indicate that the mobility of ESA and OA will be greater than metolachlor in both soils. However, higher organic carbon content in VFSS relative to CS may limit the subsequent transport of metolachlor from the vegetated filter strip.     

Field-scale remediation of a metolachlor-contaminated spill site using zerovalent iron

Pesticide spills are common occurrences at agricultural cooperatives and farmsteads. When inadvertent spills occur, chemicals normally beneficial can become point sources of ground and surface water contamination. We report results from a field trial where approximately 765 m3 of soil from a metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide] spill site was treated with zerovalent iron (Fe0). Preliminary laboratory experiments confirmed metolachlor dechlorination by Fe0 in aqueous solution and that this process could be accelerated by adding appropriate proportions of Al2(SO4)3 or acetic acid (CH3COOH). The field project was initiated by moving the stockpiled, contaminated soil into windrows using common earth-moving equipment. The soil was then mixed with water (0.35-0.40 kg H2O kg(-1)) and various combinations of 5% Fe0 (w/w),2% Al2(SO4)3 (w/w), and 0.5% acetic acid (v/w). Windrows were covered with clear plastic and incubated without additional mixing for 90 d. Approximately every 14 d, the plastic sheeting was removed for soil sampling and the surface of the windrows rewetted. Metolachlor concentrations were significantly reduced and varied among treatments. The addition of Fe0 alone decreased metolachlor concentration from 1789 to 504 mg kg(-1) within 90 d, whereas adding Fe0 with Al2(SO4)3 and CH3COOH decreased the concentration from 1402 to 13 mg kg(-1). These results provide evidence that zerovalent iron can be used for on-site, field-scale treatment of pesticide-contaminated soil.     

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.     

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.     

Kinetic effect of humic acid on alachlor degradation by anodic Fenton treatment

Contamination of water often results from the heavy use of agricultural chemicals, and the disposal of aqueous pesticide waste is a concern. Anodic Fenton treatment (AFT) has been shown to be a successful remediation method for pesticides in solution, but the effect of soil on the degradation kinetics of pesticides using this method has not been determined. The purpose of this study was to study the effect of humic acid, as a soil surrogate, on the degradation kinetics of alachlor [2-chloro-N-(2,6-diethylphenyl-N-(methoxymethyl) acetamide], a heavily used herbicide that has been studied in pure aqueous solution by AFT. The AFT consists of a controlled constant delivery of Fenton reagents, using an electrochemical half-cell to deliver ferrous iron. Alachlor was quickly degraded by AFT, and the kinetics were found to obey the previously developed AFT model well. Degradation of alachlor by AFT in humic acid slurry showed that when the amount of humic acid was increased, alachlor degradation was significantly slowed down and the degradation kinetics were shifted from the AFT model to a first-order model. Further experimentation indicated that humic acid not only competes with alachlor for hydroxyl radicals, reducing the degradation rate of the target compound, but also buffers the slurry at near neutral pH, blocking regeneration of ferrous ion from ferric ion and subsequently shifting the kinetics to first order. Degradation of several other pesticides in humic acid slurry also followed first-order kinetics. These results imply that higher concentrations of Fenton reagents will be required for soil remediation.     

The acetochlor registration partnership: prospective ground water monitoring program

The Acetochlor Registration Partnership conducted a prospective ground water (PGW) monitoring program to investigate acetochlor [2-chloro-N-(ethoxymethyl)-N-(2-ethyl-6-methylphenyl)-acetamide] transport to ground water at eight sites. The distribution of soil textures among these sites was weighted toward coarser soil types, while also including finer-textured soils that dominate most corn (Zea mays L.)-growing areas of the United States. Each site consisted of a 1.2-ha test plot adjacent to a 0.2-ha control plot. Suction lysimeters and monitoring wells were installed at multiple depths within each test and control plot to sample soil-pore water and near-surface ground water. Irrigation was applied to each site during the growing season to ensure water input of 110 to 200% of average historical rainfall. Acetochlor dissipated rapidly from surface soils at all sites with a DT(50) (time for 50% of the initial residues to dissipate) of only 3 to 9 d, but leaching was not an important loss mechanism, with only 0.25% of the 15,312 soil-pore water and ground water samples analyzed containing parent acetochlor at or above 0.05 microg L(-1). However, quantifiable residues of a soil degradation product, acetochlor ethanesulfonic acid, were more common, with approximately 16% of water samples containing concentrations at or above 1.0 microg L(-1). A second soil degradation product, acetochlor oxanilic acid, was present at concentrations at or above 1.0 microg L(-1) in only 0.15% of water samples analyzed. The acetochlor PGW program demonstrated that acetochlor lacks the potential to leach to ground water at detectable concentrations, and when applied in accordance with label restrictions, is unlikely to move to ground water at concentrations hazardous to human health.     

Metolachlor dechlorination by zerovalent iron during unsaturated transport

Permeable zerovalent iron (Fe0) barriers have become an established technology for remediating contaminated ground water. This same technology may be applicable for treating pesticides amenable to dehalogenation as they move downward in the vadose zone. By conducting miscible displacement experiments in the laboratory with metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide; a chloroacetanilide herbicide] under unsaturated flow, we provide proof-of-concept for such an approach. Transport experiments were conducted in repacked, unsaturated soil columns attached to vacuum chambers and run under constant matrix potential (-30 kPa) and Darcy flux (approximately 2 cm d(-1)). Treatments included soil columns equipped with and without a permeable reactive barrier (PRB) consisting of a Fe0-sand (50:50) mixture supplemented with Al2(SO4)3. A continuous pulse of 14C-labeled metolachlor (1.45 mM) and tritiated water (3H2O) was applied to top of the columns for 10 d. Results indicated complete (100%) metolachlor destruction, with the dehalogenated product observed as the primary degradate in the leachate. Similar results were obtained with a 25:75 Fe0-sand barrier but metolachlor destruction was not as efficient when unannealed iron was used or Al2(SO4)3 was omitted from the barrier. A second set of transport experiments used metolachlor-contaminated soil in lieu of a 14C-metolachlor pulse. Under these conditions, the iron barrier decreased metolachlor concentration in the leachate by approximately 50%. These results provide initial evidence that permeable iron barriers can effectively reduce metolachlor leaching under unsaturated flow.     

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.