Atrazine, isoproturon, mecoprop, 2,4-D, and bentazone adsorption onto iron oxides

Iron oxides are important components influencing the adsorption of various inorganic and organic compounds in soils and sediments. In this study the adsorption on iron oxides of nonionic and ionic pesticides was determined as a function of solution pH, ionic strength, and pesticide concentration. The investigated iron oxides included two-line ferrihydrite, goethite, and lepidocrocite. Selected pesticides comprised atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine), isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea)], mecoprop [(RS)-2-(4-chloro-2-methylphenoxy)propionic acid], 2,4-D (2,4-dichlorophenoxyacetic acid), and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide]. The adsorption of the nonionic pesticides (atrazine and isoproturon) was insignificant, whereas the adsorption of the acidic pesticides (mecoprop, 2,4-D, and bentazone) was significant on all investigated iron oxides. The adsorption capacity increased with decreasing pH, with maximum adsorption reached close to the pKa values. The addition of CaCl2 in concentrations from 0.0025 to 0.01 M caused the adsorption capacity to diminish. The adsorption of bentazone was significantly lower than the adsorption of mecoprop and 2,4-D, illustrating the importance of a carboxyl group in the pesticide structure. The adsorption capacity on the iron oxides increased in the order: lepidocrocite < goethite < two-line ferrihydrite. The maximum adsorption capacities of meco-prop and 2,4-D on goethite were found to be equivalent to the site density of singly coordinated hydroxyl groups on the faces of the dominant (110) form, suggesting that singly coordinated hydroxyl groups are responsible for adsorption. Differences in adsorption capacities between iron oxides can be explained by differences in the surface site density of singly coordinated hydroxyl groups. The maximum measured adsorption capacity of mecoprop on two-line ferrihydrite was equivalent to 0.2 mol/mol Fe.     

Evaluation of simplifying assumptions on pesticide degradation in soil

There is evidence that degradation of pesticides in simple laboratory systems may differ from that in the field, but it is not clear which of the simplifications inherent in laboratory studies present serious shortcomings. Laboratory experiments evaluated several simplifying assumptions for a clay loam soil and contrasting pesticides. Degradation of cyanazine [2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropiononitrile] and bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 2,2-dioxide] at fluctuating temperature and moisture was predicted reasonably well based on parameters derived from degradation under constant conditions. There was a tendency for slower degradation of cyanazine and bentazone in soil aggregates of 3 to 5 mm in diameter (DT50 at 15 degrees C and 40% maximum water holding capacity of 25.1 and 58.2 d, where DT50 is the time for 50% decline of the initial pesticide concentration) than in soil sieved to <3 mm (DT50 of 19.1 and 37.6 d), but the differences were not significant for most datasets. Degradation of cyanazine, isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea], and chlorotoluron [3-(3-chloro-p-tolyl)-1,1-dimethylurea] was measured in soil amended with different amounts of lignin. The effect of lignin on degradation was small despite considerable differences in sorption. The DT50 values of cyanazine, isoproturon, and chlorotoluron were 16.2, 18.6, and 33.0 d, respectively, in soil without lignin and 19.0, 23.4, and 34.6 d, respectively, in soil amended with 2% lignin. Degradation of bentazone and cyanazine in repacked soil columns was similar under static and flow conditions with 50.1 and 47.2% of applied bentazone and 74.7 and 73.6% of applied cyanazine, respectively, degraded within 20 d of application. Thus, the assumptions underpinning laboratory to field extrapolation tested here were considered to hold for our experimental system. Additional work is required before general conclusions can be drawn.     

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.     

On the interaction mechanisms of atrazine and hydroxyatrazine with humic substances

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) is retained against leaching losses in soils principally by sorption to organic matter, but the mechanism of sorption has been a matter of controversy. Conflicting evidence exists for proton transfer, electron transfer, and hydrophobic interactions between atrazine and soil humus, but no data are conclusive. In this paper we add to the database by investigating the role of (i) hydroxyatrazine (6-hydroxy-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) and (ii) hydrophobicity in the sorption of atrazine by Brazilian soil humic substances. We demonstrate, apparently for the first time, that hydroxyatrazine readily forms electron-transfer complexes with humic substances. These complexes probably are the cause of the well-known strong adsorption by humic acids and they may be the undetected cause of apparent electron-transfer complexes between soil organic matter and atrazine, whose transformation to the hydroxy form is facile. We also present evidence that supports the important contribution of hydrophobic interactions to the pH-dependent sorption of atrazine by humic substances.     

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.     

Potential mineralization of four herbicides in a ground water--fed wetland area

Herbicides may leach from agricultural fields into ground water feeding adjacent wetlands. However, only little is known of the fate of herbicides in wetland areas. The purpose of the study was to examine the potential of a riparian fen to mineralize herbides that could leach from an adjacent catchment area. Slurries were prepared from sediment and ground water collected from different parts of a wetland representing different redox conditions. The slurries were amended with O2, NO3-, SO4(2-), and CO2, or CO2 alone as electron acceptors to simulate the in situ conditions and their ability to mineralize the herbides mecoprop, metsulfuron-methyl, isoproturon and atrazine. In addition, the abundance of bacteria able to utilize O2, NO3-, SO4(2-) + CO2, and CO2 as electron acceptors was investigated along with the O2-reducing and methanogenic potential of the sediment. The recalcitrance to bacterial degradation depended on both the type of herbicide and the redox conditions pertaining. Mecoprop was the most readily degraded herbicide, with 36% of [ring-U-14C]mecoprop being mineralized to 14CO2 under aerobic conditions after 473 d. In comparison, approximately 29% of [phenyl-U-14C]metsulfuron-methyl and 16% of [ring-U-14C]isoproturon mineralized in aerobic slurries during the same period. Surprisingly, 8 to 13% of mecoprop also mineralized under anaerobic conditions. Neither metsulfuron-methyl nor isoproturon were mineralized under anaerobic conditions and atrazine was not mineralized under any of the redox conditions examined. The present study is the first to report mineralization of meco-prop in ground water in a wetland area, and the first to report mineralization of a phenoxyalcanoic acid herbicide under both aerobic and anaerobic conditions.     

Adsorption of 2,4-dichlorophenoxyacetic acid by an Andosol

To identify the important soil components involved in 2,4-dichlorophenoxyacetic acid (2,4-D) adsorption on Andosols, 2,4-D adsorption on a surface horizon of an Andosol was compared with that on hydrogen peroxide (H2O2)-treated (soil organic matter [SOM] was removed), acid-oxalate (OX)-treated (active metal hydroxides and SOM were removed), and dithionite-citrate-bicarbonate (DCB)-treated (free and active metal [hydr]oxides and SOM were removed) soil samples at equilibrium pHs ranging from 4 to 8. Although the untreated soil contained a large amount of organic C (71.9 g kg-1), removal of SOM had little effect on 2,4-D adsorption. Active surface hydroxyls, which were attached to the active and free metal (hydr)oxides and metal SOM complexes, were identified as the most important soil functional group for 2,4-D adsorption. The dominant mechanism of the 2,4-D adsorption was a ligand exchange reaction in which the carboxylic group of 2,4-D displaced the active surface hydroxyl associated with metals and formed a strong coordination bond between the 2,4-D molecule and soil solid phase. The ligand exchange reaction reasonably accounted for the selective adsorption of 2,4-D over Cl-, competitive adsorption of phosphate over 2,4-D, reduction in plant-growth-inhibitory activity of soil-adsorbed 2,4-D, and the high 2,4-D adsorption ability of Andosols. Although a humic acid purified from the soil did not adsorb 2,4-D, the presence of the humic acid increased 2,4-D adsorption on Al and Fe, probably by inhibiting the hydrolysis and polymerization of Al and Fe resulting in the preservation of available adsorption sites on these metals. The adsorption behavior of 2,4-D on soils could be a good index for predicting the adsorption behavior of other organic acids in soils.     

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.     

In vitro pesticide degradation in turfgrass soil incubated under open and sealed conditions

Degradation of selected pesticides was conducted in a turfgrass soil from a golf course under open (i.e., allowing gas exchange with atmosphere) and sealed systems. The time required for 50% of the initial dose of fenitrothion (O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate), diazinon (O,O-dimethyl O-2-isopropyl-6-methylpyrimidin4-yl phosphorothioate), iprodione [3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxo-imidazolidine-1-carboxamide], mecoprop [(RS)-2-(4-chloro-otolyloxy)propionic acid], and asulam (4-aminophenylsulfonyl-carbamate) to dissipate (half-life, t 1/2) was less than 2 wk under both conditions. The t 1/2 values of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoro-methylpyridine-3,5-dicarbothioate) were 324 and 185 d under the open and sealed conditions, respectively. The t 1/2 values of isoprothiolane (di-isopropyl 1,3-dithiolan-2-ylidene-malonate), flutolanil (alpha,alpha,alpha-trifluoro-3'-isopropoxy-o-toluanilide), and benefin (N-butyl-N-ethyl-alpha,alpha,alpha-trifluoro-2,6-dinitro-p-toluidine) under the open conditions were 154, 336, and 47 d, respectively. The t 1/2 values of these pesticides increased slightly under the sealed conditions. The t 1/2 values of terbutol (2,6-di-tert-butyl-4-methylphenyl N-methycarbamate) and one of the major degradation products, N-demethyl-terbutol (2,6-di-tert-butyl-4-methylphenyl carbamate), were 182 and 291 d under the open conditions and increased by six- and threefold under the sealed conditions, respectively. The degradation system under the sealed conditions could characterize the persistence of terbutol and N-demethyl-terbutol, which were the most persistent in the field.     

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.     

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.     

Use of a low-cost biosorbent to remove pesticides from wastewater

A lignocellulosic substrate (LS) obtained from our local agroindustry was used as a low-cost and effective adsorbent for the removal of pesticides from wastewaters. The studied pesticides were terbumeton (N-(1,1-dimethyl)-Nethyl-6-methoxy-1,3,5-triazine-2,4-diamine), desethyl terbumeton (N-(1,1-dimethylethyl)-6-methoxy-1,3,5-triazine-2,4-diamine), dimetomorph (4-[3-(4-chlorophenyl)-3-(3,4-dimethoxyphenyl)acryloyl]morpholine), and isoproturon (3-(4-isopropylphenyl)-1,1-dimethylurea). Batch and column experiments were conducted as a function of pH and pesticide concentration under laboratory and industrial conditions. The concentration range studied for the pesticides varied from 2 x 10(-7) to 3 x 10(-4) mol L(-1). The influence of organic and inorganic pollutants was assessed by studying the retention of pesticide in the presence of copper(II) and a surfactant. These experiments indicated that LS is an efficient adsorbent toward the investigated pesticides and has little influence of the other pollutants. The kinetic adsorptions are fast, and the amounts of adsorbed pesticide varied from 1 to 8 g kg(-1) of LS. These retention capacities show that LS can provide a simple, effective, and cheap method for removing pesticides from contaminated waters. Thus, this biomaterial may be useful for cleaning up polluted waters.     

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.     

Infiltration and adsorption of dissolved atrazine and atrazine metabolites in buffalograss filter strips

Vegetated filter strips (VFS) potentially reduce the off-site movement of herbicides from adjacent agricultural fields by increasing herbicide mass infiltrated (Minf) and mass adsorbed (Mas) compared with bare field soil. However, there are conflicting reports in the literature concerning the contribution of Mas to the VFS herbicide trapping efficiency (TE). Moreover, no study has evaluated TE among atrazine (6-chloro-N-ethyl-N'-isopropyl-[1,3,5]triazine-2,4-diamine) and atrazine metabolites. This study was conducted to compare TE, Minf, and Mas among atrazine, diaminoatrazine (DA, 6-chloro[1,3,5]triazine-2,4-diamine), deisopropylatrazine (DIA, 6-chloro-N-ethyl-[1,3,5]triazine-2,4-diamine), desethylatrazine (DEA, 6-chloro-N-isopropyl-[1,3,5]triazine-2,4-diamine), and hydroxyatrazine (HA, 6-hydroxy-N-ethyl-N'-isopropyl-[1,3,5]triazine-2,4-diamine) in a buffalograss VFS. Runoff was applied as a point source upslope of a 1- x 3-m microwatershed plot at a rate of 750 L h(-1). The point source was fortified at 0.1 microg mL(-1) atrazine, DA, DIA, DEA, and HA. After crossing the length of the plot, water samples were collected at 5-min intervals. Water samples were extracted by solid phase extraction and analyzed by high performance liquid chromatography (HPLC) photodiode array detection. During the 60-min simulation, TE was significantly greater for atrazine (22.2%) compared with atrazine metabolites (19.0%). Approximately 67 and 33% of the TE was attributed to Minf and Mas, respectively. These results demonstrate that herbicide adsorption to the VFS grass, grass thatch, and/or soil surface is an important retention mechanism, especially under saturated conditions. Values for Mas were significantly higher for atrazine compared with atrazine's metabolites. The Mas data indicate that atrazine was preferentially retained by the VFS grass, grass thatch, and/or soil surface compared with atrazine's metabolites.     

Behavior of 14C-atrazine in Argentinean topsoils under different cropping managements

Atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) behavior was studied in four surface soils during incubations in laboratory conditions. Soils were chosen in relation to their cropping management (tillage and no tillage) and crop rotation system (continuous soybean [Glycine mar (L.) Merr.] and maize (Zea mays L.)-soybean rotation). A natural soil under brushwood was sampled as a reference. Atrazine use in field conditions was associated with maize cropping, thus only one soil received atrazine every other year. Atrazine behavior was characterized through the balance of 14C-U-ring atrazine radioactivity among the mineralized fraction, the extractable fraction, and the nonextractable bound residues. Soil organic matter capacity to form bound residues was characterized using soil size fractionation. Accelerated atrazine mineralization was only observed in the soil receiving atrazine in field conditions. Atrazine application every other year was enough to develop a microflora adapted to triazine ring mineralization. Bound residue formation was rapid and increased with soil organic matter content. The coarsest soil size fractions (2000-200 and 200-50 microm) containing the nonhumified organic matter presented the highest capacity to form bound residues. No effect of tillage system was observed, probably because of the uniform sampling depth at 20 cm, hiding the stratification pattern of soil organic matter in non-tilled soils.     

Fate of atrazine in sandy soil cropped with sorghum

A field study was conducted to determine the fate of atrazine (6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine) within the root zone (0 to 90 cm) of a sandy soil cropped with sorghum [Sorghum bicolor (L.) Moench] in Gainesville, Florida. Atrazine was uniformly applied at a rate of 1.12 kg ai. ha(-1) to a sorghum crop under moderate irrigation, optimum irrigation, and no irrigation (rainfed), 2 d after crop emergence. Bromide as a tracer for water movement was applied to the soil as NaBr at a rate of 45 kg Br ha(-1), 3 d before atrazine application. Soil water content, atrazine, and Br concentrations were determined as a function of time using soil samples taken from the root zone. Atrazine sorption coefficients and degradation rates were determined by depth for the entire root zone in the laboratory. Atrazine was strongly adsorbed within the upper 30 cm of soil and most of the atrazine recovered from the soil during the growing season was in that depth. The estimated half-life for atrazine was 32 d in topsoil to 83 d in subsoil. Atrazine concentration within the root zone decreased from 0.44 kg ai. ha(-1) 2 days after application (DAA) to 0.1 kg a.i. ha(-1) 26 DAA. Negligible amounts of atrazine (approximately 5 microg kg(-1)) were detected below the 60-cm soil depth by 64 DAA. Most of the decrease in atrazine concentration in the root zone over time was attributed to degradation. In contrast, all applied bromide had leached past the 60-cm soil depth during the same time interval.     

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.     

Effects of soil variability and weather conditions on pesticide leaching--a farm-level evaluation

In line with European regulations, Dutch law imposes an environmental threshold of 0.1 microg L(-1) on pesticide concentrations in ground water. During registration, the risk of exceeding this threshold is assessed through simulations for one or a few standard scenarios that do not reflect spatial variability under field conditions. The introduction of precision agriculture, where soil variability is actively managed, can increase control over pesticide leaching. This study presents a step-wise evaluation of the effects of soil variability and weather conditions on pesticide leaching. The evaluation was conducted on a 100-ha arable farm and aimed at identifying opportunities for precision management. As a first step, a relative risk assessment identified pesticides presenting a relatively high risk to the environment. Second, the effect of weather conditions was analyzed through 20 years of simulations for three distinct soil profiles. Results were summarized in cumulative probability plots to provide a probabilistic characterization of historical weather data. The year matching 90% probability (1981) served as a reference to simulate pesticide leaching from 612 soil profiles. After interpolation, areas where concentrations exceeded the environmental threshold were identified. Out of a total of 19 pesticides, isoproturon [N-dimethyl-N'-(4-(1-methylethyl)phenyl)urea], metribuzin [4-amino-6-tert-butyl-3-(methylthio)-as-triazin-5(4H)-one], and bentazon [2,1,3-benzothiadiazin-4(3H)-one, 3-isopropyl-, 2,2-dioxide] showed the highest risk for leaching. Leaching was strongly affected by soil variability at the within-field, field, and farm levels. Opportunities for precision management were apparent, but depended on the scale level at which environmental thresholds were implemented. When legislation is formulated in this issue, the presented step-wise evaluation can serve as a basis for identification and precision management of high-risk pesticides.     

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.     

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.