Picloram and napropamide sorption as affected by polymer addition and salt concentration

Polymer application to soil is a growing practice to improve soil physical properties and reduce soil erosion. Polymer addition can potentially influence herbicide and pesticide sorption in soil. The one-point distribution coefficient Kd values of two herbicides in the absence and presence of each of 10 polymers (7 polyacrylamides and 3 polysaccharides) were determined by the batch equilibrium method. The results showed that nonionic napropamide [2-(alpha-naphthoxy)-N,N-diethyl propionamide] sorption was essentially unaffected by the presence of any of the polymers. The influence of polymers on anionic picloram (4-amino-3,5,6-trichloropicolinic acid) sorption depends on the charge characteristics of polymers and salt concentrations in the solution. Electrostatic interaction and competition for sorption sites are two primary underlying mechanisms for the polymer influence. At low salt concentration, the increased picloram sorption in the presence of both cationic and anionic polymers was attributed to different electrostatic interactions and polymer partitioning between soil and solution phases. At high salt levels, the presence of polymers had either no influence or a slightly negative influence on the picloram sorption, which was attributed to competition for sorption sites. In field conditions, it is more likely that polymers have no or a slightly negative influence on herbicide sorption due to the presence of salts.     

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.     

Aging effects on the sorption-desorption characteristics of anthropogenic organic compounds in soil

Field studies have demonstrated that prolonged pesticide-soil contact times (aging) may lead to unexpected persistence of these compounds in the environment. Although this phenomenon is well documented in the field, there have been very few controlled laboratory studies that have tested the effects of long-term aging and the role of differing sorbates on contaminant sorption-desorption behavior and fate in soils. This study examines the sorption-desorption behavior of chlorobenzene, ethylene dibromide (1,2-dibromomethane), atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), and 2, 4-D (2,4-dichlorophenoxyacetic acid) on one soil type after 1 d, 30 d, and 14 mo of aging. Sorption isotherms were evaluated after each aging period to observe changes in the uptake of each compound by soil. Desorption kinetic data were generated after each aging period to observe changes in release from soil, and desorption parameters were evaluated using a three-site desorption model that includes equilibrium, nonequilibrium, and nondesorption sites. The data indicate no statistically significant increase in sorption for ethylene dibromide or chlorobenzene from 1 to 30 d, although sorption of 2,4-D increased slightly, and sorption of atrazine decreased slightly. Statistically significant increases in linear sorption coefficients (Kd), from 1 d to 14 mo of aging, were apparent for ethylene dibromide and 2,4-D. The Kd values for chlorobenzene, measured after 1 d, 30 d, and 14 mo of aging, were statistically indistinguishable. Aging affected the distribution of chemicals within sorption sites. With aging, the desorbable fraction decreased and the nondesorbable fraction, which was apparent after only 1 d of pesticide-soil contact, increased for all chemicals studied.     

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.     

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.     

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.     

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).     

Herbicide sorption coefficients in relation to soil properties and terrain attributes on a cultivated prairie

The sorption of 2,4-D and glyphosate herbicides in soil was quantified for 287 surface soils (0-15 cm) collected in a 10 x 10 m grid across a heavily eroded, undulating, calcareous prairie landscape. Other variables that were determined included soil carbonate content, soil pH, soil organic carbon content (SOC), soil texture, soil loss or gain by tillage and water erosion, and selected terrain attributes and landform segments. The 2,4-D sorption coefficient (Kd) was significantly associated with soil carbonate content (-0.66; P < 0.001), soil pH (-0.63; P < 0.001), and SOC (0.47; P < 0.001). Upper slopes were strongly eroded and thus had a significantly greater soil carbonate content and less SOC compared with lower slopes that were in soil accumulation zones. The 2,4-D Kd was almost twice as small in upper slopes than in lower slopes. The 2,4-D Kd was also significantly associated with nine terrain attributes, particularly with compounded topographic index (0.59; P < 0.001), gradient (-0.48; P < 0.001), mean curvature (-0.43; P < 0.001), and plan curvature (-0.42 P < 0.001). Regression equations were generated to estimate herbicide sorption in soils. The predicted power of these equations increased for 2,4-D when selected terrain attributes were combined with soil properties. In contrast, the variation of glyphosate sorption across the field was much less dependent on our measured soil properties and calculated terrain attributes. We conclude that the integration of terrain attributes or landform segments in pesticide fate modeling is more advantageous for herbicides such as 2,4-D, whose sorption to soil is weak and influenced by subtle changes in soil properties, than for herbicides such as glyphosate that are strongly bound to soil regardless of soil properties.     

Vegetative Buffer Strips for Reducing Herbicide Transport in Runoff: Effects of Buffer Width,Vegetation, and Season

The effectiveness of vegetative buffer strips (VBS) for reducing herbicide transport has not been well documented for runoff prone soils. A multi‐year plot‐scale study was conducted on an eroded claypan soil with the following objectives: (1) assess the effects of buffer width, vegetation, and season on runoff transport of atrazine (ATR), metolachlor (MET), and glyphosate; (2) develop VBS design criteria for herbicides; and (3) compare differences in soil quality among vegetation treatments. Rainfall simulation was used to create uniform antecedent soil water content and to generate runoff. Vegetation treatment and buffer width impacted herbicide loads much more than season. Grass treatments reduced herbicide loads by 19‐28% and sediment loads by 67% compared to the control. Grass treatments increased retention of dissolved‐phase herbicides by both infiltration and adsorption, but adsorption accounted for the greatest proportion of retained herbicide load. This latter finding indicated VBS can be effective on poorly drained soils or when the source to buffer area ratio is high. Grass treatments modestly improved surface soil quality 8‐13 years after establishment, with significant increases in organic C, total N, and ATR and MET sorption compared to continuously tilled control. Herbicide loads as a function of buffer width were well described by first‐order decay models which indicated VBS can provide significant load reductions under anticipated field conditions.     

Regional assessment of herbicide sorption and degradation in two sampling years

Sorption and degradation of the herbicide 2,4-D [2,4-dichlorophenoxyacetic acid] were determined for 123 surface soils (0 to 15 cm) collected in 2002 and in 2004 between 49 degrees to 60 degrees north longitude and 110 degrees to 120 degrees west latitude in Alberta, Canada. The soils were characterized by soil organic carbon content (SOC), pH, electrical conductivity, soil texture, cation exchange capacity, carbonate content, and total soil microbial activity. The 2,4-D sorption coefficients, Kd and Koc, were highly variable with coefficients of variation of 89 and 59%, respectively, at the provincial scale. Both Kd and Koc were well described by regression models with SOC and soil pH as variables, regardless of scale. Surprisingly, variations in 2,4-D mineralization were much smaller than variations in sorption. Variability in total 2,4-D mineralization was particularly low, with a coefficient of variation of only 7% at the provincial scale. Average 2,4-D half-lives in ecoregions ranged from 1.7 to 3.5 d, much lower than the field dissipation half-life of 10 d reported for 2,4-D in general pesticide property databases. Regression models describing degradation parameters were generally poor or not significant because 2,4-D mineralization was only weakly associated with measured 2,4-D sorption parameters and soil properties. As such, regional variations in herbicide sorption coefficients should be measured or calculated based on soil properties, to assign distinct pesticide fate model input parameters when estimating 2,4-D off-site transport at the provincial scale. Spatial variations in herbicide degradation appear less important for Alberta as 2,4-D half-lives were similar in soils across the province. The rapid mineralization of 2,4-D is noteworthy because 2,4-D is widely used in Alberta and perhaps adaptation of soil microbial communities allowed for accelerated degradation regardless of soil properties or the extent of 2,4-D sorption by soil.     

Assessment of herbicide leaching risk in two tropical soils of Reunion Island (France)

Application of organic chemicals to a newly irrigated sugarcane (Saccharum officinarum L.) area located in the semiarid western part of Reunion Island has prompted local regulatory agencies to determine their potential to contaminate ground water resources. For that purpose, simple indices known as the ground water ubiquity score (Gustafson index, GUS), the retardation factor (RF), the attenuation factor (AF), and the log-transformed attenuation factor (AFT) were employed to assess the potential leaching of five herbicides in two soil types. The herbicides were alachlor [2-chloro-2',6'-diethyl-N-(methoxy-methy) acetanilide], atrazine [2-chloro-4-(ethylamino)-6-(isopropylamino)-1,3,5-triazine], diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea], 2,4-D [(2,4-dichlorophenoxy) acetic-acid], and triclopyr [((3,5,6-trichloro-2-pyridyl)oxy) acetic-acid]. The soil types were Vertic (BV) and Andepts (BA) Inceptisols, which are present throughout the Saint-Gilles study area on Reunion Island. To calculate the indices, herbicide sorption (K(oc)) and dissipation (half-life, DT50) properties were determined from controlled batch experiments. Water fluxes below the root zone were estimated by a capacity-based model driven by a rainfall frequency analysis performed on a 13-yr data series. The results show a lower risk of herbicide leaching than in temperate regions due to the tropical conditions of the study area. Higher temperatures and the presence of highly adsorbent soils may explain smaller DT50 and higher K(oc) values than those reported in literature concerning temperate environments. Based on the RF values, only 2,4-D and triclopyr appear mobile in the BV soil, with all the other herbicides being classified from moderately to very immobile in both soils. The AFT values indicate that the potential leaching of the five herbicides can be considered as unlikely, except during the cyclonic period (about 40 d/yr) when there is a 2.5% probability of recharge rates equal to or higher than 50 mm/d. In that case, atrazine in both soils, 2,4-D and triclopyr in the BV soil, and diuron and alachlor in the BA soil present a high risk of potential contamination of ground water resources.     

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.     

Using nonequilibrium thin-disc and batch equilibrium techniques to evaluate herbicide sorption

Nonequilibrium disc-flow techniques may better reproduce dynamic soil-pesticide interactions than traditional batch sorption studies. Batch kinetic and equilibrium experiments and dual-label thin-disc flow experiments were conducted with atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazine-2,4-diamine) and imazaquin [2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-3-quinolinecarboxylic acid] using a Demopolis silt loam (loamy-skeletal, carbonatic, thermic, shallow Typic Udorthent; 8% clay, 62 g kg(-1) organic matter, 7.6 pH). Batch kinetic studies with both herbicides revealed an almost instantaneous rapid phase and a much slower gradual phase. The rapid phase was complete after 5 min and equilibrium was reached at 24 h. The rapid phase accounted for 74% and 12 to 30% of the total amounts adsorbed for atrazine and imazaquin, respectively. The sorption of both the rapid and 24-h isotherms for each herbicide best fit the Freundlich equation. The rapid and 24-h K(f) values of atrazine were 1.38 and 2.41, respectively, and the N value of both phases was approximately 0.93. For imazaquin, the rapid and 24-h K(f) values were 0.056 and 035, respectively, and the N value for the rapid phase of imazaquin was 0.71, compared with 0.86 for the 24-h isotherm. In the dual-label thin-disc flow experiments, the average partition coefficient for atrazine at the peak soil concentration point was 1.54. This value closely agreed with the observed rapid-phase K(f) value of 1.38. In contrast, the thin-disc flow experiments failed to detect any imazaquin retention. The thin-disc flow method can allow for a greater resolution of rapid sorption kinetics, which is impractical with batch studies. Along with dynamic partitioning data, the thin-disc flow method may provide kinetics data that may better complement environmental models than coefficients generated with batch techniques.     

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.     

Small-scale spatial variability of atrazine and dinoseb adsorption parameters in an alluvial soil

Soil sorption processes largely control the environmental fate of herbicides. Therefore, accuracy of sorption parameters is crucial for accurate prediction of herbicide mobility in agricultural soils. A combined experimental and statistical study was performed to investigate the small-scale spatial variability of sorption parameters for atrazine and dinoseb in soils and to establish the number of samples needed to provide a value of the distribution coefficient (K(d)) next to the mean, with a given precision. The study explored sorption properties of the two herbicides in subsurface samples collected from four pits distributed along a transect of an alluvial soil; two to four samples were taken at about 30 cm apart at each sampling location. When considering all the data, the distribution coefficients were found to be normally and log-normally distributed for atrazine and dinoseb, respectively; the CVs were relatively high (close to 50% for dinoseb and 40% for atrazine). When analyzed horizon by horizon, the data revealed distribution coefficients normally distributed for both herbicides, whatever the soil layer, with lower CVs. The K(d) values were shown to vary considerably between samples collected at very short distance (a few centimeters), suggesting that taking a single soil sample to determine sorption properties through batch experiments can lead to highly unrepresentative results and to poor sorption/mobility predictions.     

Field history and dissipation of atrazine and metolachlor in Colorado

Farmers in eastern Colorado have commented that atrazine does not provide the length of weed control that they expected in fields that have received multiple applications of the herbicide. Multiple laboratory studies suggest that atrazine dissipates more rapidly in soils with a history of atrazine use compared with soils that had not been treated with the herbicide and this could be related to the above observation. Field and laboratory studies were conducted to determine the rate of dissipation of atrazine and metolachlor in fields in Colorado. The published half-lives of atrazine and metolachlor are 60 and 56 d, respectively. In the field studies, the half-lives of atrazine and metolachlor in the top 15 cm of the soil ranged between 3.5 and 7.2 d and 17.9 and 18.8 d, respectively. In laboratory studies, the half-life of atrazine varied from 1.4 to 19.8 d with the shortest half-life occurring in soils which had been treated with atrazine for at least 5 yr. The longest half-life was in a soil that had never received atrazine. The half-life of metolachlor in these same soils varied from 10.6 to 28.2 d. There was no apparent relationship between the half-life of metolachlor and the half-life of atrazine in the laboratory studies. These results confirm farmers' observation of the shorter residual activity of atrazine in Colorado fields receiving atrazine over multiple years.     

Enhanced desorption of herbicides sorbed on soils by addition of Triton X-100

A study of the desorption of atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine) and linuron [1-methoxy-1-methyl-3-(3,4-dichlorophenyl)urea] adsorbed on soils with different organic matter (OM) and clay contents was conducted in water and in the presence of the non-ionic surfactant Triton X-100 at different concentrations. The aim was to gain insight into soil characteristics in surfactant-enhanced desorption of herbicides from soils. Adsorption and desorption isotherms in water, in all Triton X-100 solutions for atrazine, and in solutions of 0.75 times the critical micelle concentration (cmc) and 1.50cmc for linuron fit the Freundlich equation. All desorption isotherms showed hysteresis. Hysteresis coefficients decreased for linuron and increased or decreased for atrazine in Triton X-100 solutions. These variations were dependent on surfactant concentration and soil OM and clay contents. In the soil-water-surfactant system desorption of linuron from all soils was always greater than in the soil-water system but for atrazine this only occurred at concentrations higher than 50cmc. For the highest Triton X-100 concentration (100cmc), the desorption of the most hydrophobic herbicide (linuron) was increased more than 18-fold with respect to water in soil with an OM content of 10.3% while the atrazine desorption was increased 3-fold. The effect of Triton X-100 on the desorption of both herbicides was very low in soil with a high clay content. The results indicate the potential use of Triton X-100 to facilitate the desorption of these herbicides from soil to the water-surfactant system. They also contribute to better understanding of the interactions of different molecules and surfaces in the complex soil-herbicide-water surfactant system.     

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.     

Retention and runoff losses of atrazine and metribuzin in soil

Minimizing herbicide runoff and mobility in the soil and thus potential contamination of water resources is a national concern. Metribuzin [4-amino-6-(1,1-dimethylethyl)-3-(methylthio)-1,2,4-triazin-5(4H)-one] and atrazine [2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine] dynamics in surface soils and in runoff waters were studied on six 0.2-ha sugarcane (Saccharum spp.) plots of a Commerce silt loam (fine-silty, mixed, superactive, nonacid, thermic Fluvaquentic Endoaquept) during three growing seasons under different best management practices. Metribuzin was applied in the spring as a postemergence herbicide and atrazine was applied following winter harvest. Both herbicides were applied on top of the sugarcane rows as 0.6- or 0.9-m band width application, or broadcast application, where the entire area was treated. Maximum effluent concentrations were measured from the broadcast treatment and ranged from 600 to 1100 microg L(-1) for atrazine and 250 to 450 microg L(-1) for metribuzin. Atrazine runoff losses were highest for the broadcast treatment (2.8-11% of that applied) and lowest for the 0.6-m band treatment (1.9-7.6%), with a similar trend for metribuzin losses. Measured extractable herbicides from the surface soil exhibited a sharp decrease with time and were well described with a simple first-order decay model. For atrazine, estimates for the decay rate (lambda) were higher than for metribuzin. Results based on laboratory adsorption-desorption (kinetic-batch) measurements were consistent with field observations. The distribution coefficients (Kd) for atrazine exhibited stronger retention over time in comparison with metribuzin on the Commerce soil. Moreover, discrepancies between adsorption isotherm and desorption indicated slower release and that hysteresis was more pronounced for atrazine compared with metribuzin.     

REGIONAL PATTERNS OF PESTICIDE CONCENTRATIONS IN SURFACE WATERS OF NEW YORK IN 19971

ABSTRACT: The predominant mixtures of pesticides found in New York surface waters consist of five principal components. First, herbicides commonly used on corn (atrazine, metolachlor, alachlor, cyanazine) and a herbicide degradate (deethylatrazine) were positively correlated to a corn‐herbicide component, and watersheds with the highest corn‐herbicide component scores were those in which large amounts of row crops are grown. Second, two insecticides (diazinon and carbaryl) and one herbicide (prometon) widely used in urban and residential settings were positively correlated to an urban/residential component. Watersheds with the highest urban/residential component scores were those with large amounts of urban and residential land use. A third component was related to two herbicides (EPTC and cyanazine) used on dry beans and corn, the fourth to an herbicide (simazine) and an insecticide (carbaryl) commonly used in orchards and vineyards, and the fifth to an herbicide (DCPA). Results of this study indicate that this approach can be used to: (1) identify common mixtures of pesticides in surface waters, (2) relate these mixtures to land use and pesticide applications, and (3) indicate regions where these mixtures of pesticides are commonly found.