Sorption of atrazine and dicamba in Delaware coastal plain soils: a comparison of soil thin layer and batch equilibrium results

The mobility and retention of atrazine and dicamba in six Atlantic Coastal Plain soils were estimated by soil thin-layer chromatography (soil-TLC). The soils studied were representative of the major agricultural regions in Delaware and were sampled, by horizon, to the water table. Four horizons from each profile were leached simultaneously with distilled water on one soil-TLC plate. Two values were obtained from each plate: the ratio of the distance traveled by the herbicide center of mass over that traveled by the solvent front (R_m), and a sorption distribution coefficient (K_d). The R_m values ranged from 0·06 to 0·94 for atrazine and from 0·80 to 0·94 for dicamba. Herbicide mobility was found to be greatest in coarse-textured soil horizons that contained low levels of organic matter, clay, and Fe and Al oxides. Correlation analysis indicated that effective cation exchange capacity, exchangeable acidity, exchangeable aluminum, and clay were useful predictive variables or both atrazine mobility and sorption. Organic matter was not useful for predicting soil-TLC derived sorption estimates; however, it was correlated to K_d-batch estimates. Distribution coefficients calculated from soil-TLC data were found to be in general agreement with K_d values obtained for the same soils by batch equilibrium techniques. The average K_d-soil-TLC values for atrazine and dicamba were 2·09(±2·24) and 0·03(±0·02), respectively. The ratio of the batch K_d to the soil-TLC K_d ranged from 0·1 to 19 (x̄=1·6, SD=3·8) for atrazine and from 2·9 to 38 (x̄=12·6, SD=8·7) for dicamba. Thus, although for some horizons agreement between the two methods was good, for other horizons significant discrepancies existed. It is suggested that the soil-TLC gives results under non-equilibrium conditions, whereas the batch procedure is, by definition, at quasi-equilibrium. These fundamental differences may account for the observed differences between the two methods. It is also suggested that, due to this difference, the soil-TLC procedure can provide additional information relevant to herbicide partitioning in the field environment that is not provided by traditional batch equilibrium techniques. © 1998 Society of Chemical Industry     

Sorption of aged dicamba residues in soil

The effect of aging (residence time in soil) on dicamba (3,6-dichloro-2-methoxybenzoic acid) and a major metabolite, 3,6-dichlorosalicylic acid (3,6-DCSA) sorption was determined in an unamended and a carbon-amended sandy loam and in a silt loam soil. During the incubation, sequential solvent extraction with 0.01 M calcium chloride solution and aqueous acetonitrile + hydrochloric acid was used to determine the solution and sorbed concentrations of dicamba and 3,6-DSCA, and sorption coefficients were calculated. Dicamba was weakly sorbed to soil (Kd < 0.7). In contrast to some other classes of pesticides, sorption of dicamba did not significantly increase with aging, at least not until < 15% of the applied dicamba remained. 3,6-DSCA was strongly sorbed to soil (Kd > 8) and the Kd-a value increased by a factor of 2-6 during a 28-day aging period. Addition of a carbon source to the soil had minimal effect on the strength of sorption of aged dicamba. However, it did appear to decrease 3,6-DSCA availability to soil micro-organisms; once formed 3,6-DSCA was not further mineralized. While it appears that sorption can be well characterized for weakly sorbed pesticides using the batch equilibration method with freshly treated soils, this procedure may not be adequate for more strongly sorbed pesticides and their degradates.     

Influence of Soil Moisture on Long-Term Sorption of Diuron and Isoproturon by Soil

Long-term sorption of diuron and isoproturon by a clay loam soil was investigated for nine weeks at two herbicide doses (0·6 or 3 mg kg⁻¹) and two soil moisture contents (35 or 62% w/w, i.e. 3·16 or 1 kPa) by measuring changes in herbicide concentrations in the soil solution sampled by means of glass microfibre filters in presence of sodium azide (200 mg litre⁻¹) which inhibited biodegradation for more than four weeks. After the first day equilibration period, where adsorption mainly occurred (>70% adsorbed), herbicide concentrations in the soil solution decreased (about 50% for diuron; up to 38% for isoproturon) for two weeks but equilibration required about one month. Small amounts of herbicides were sorbed during this process (<10% of the initial (24-h) adsorption). These were similar for both herbicides, although diuron was initially more adsorbed. Values of the partition coefficients of herbicides between soil and soil solution were increased (75–125% for diuron; 29–67% for isoproturon). High soil moisture enhanced sorption speed for both herbicides and increased final sorption only for diuron. Sodium azide inhibited long-term sorption of the more stable diuron and this effect was reversed by low temperature only at the low soil moisture. Sodium azide action might be complex (competition, effect on soil micro-organisms) and was not elucidated.     

Degradation and leaching potential of pesticides in biobed systems

Biobeds provide a potential solution to pesticide contamination of surface waters arising from the farmyard. Previous work has shown that biobeds can effectively treat spills and splashes of pesticide. This study investigated the potential for biobeds to treat much larger volumes and amounts of pesticide waste not only arising from spills but also from washing processes. Two systems were assessed using a range of pesticides at the semi-field scale, ie a lined biobed system and an unlined system. Studies using the lined biobeds demonstrated that water management was crucial, with biobeds needing to be covered to exclude rain-water. Once covered, the top of the biobed became hydrophobic, restricting moisture loss and resulting in saturated conditions at depth. The drying out of the top layer coincided with a measured decrease in microbial biomass in the treated biobeds. Applied pesticides were effectively retained within the 0-5 cm layer. Whilst all pesticides tested degraded, low moisture content and microbial activity meant degradation rates were low. Studies using unlined biobeds showed that only the most mobile pesticides leached, and for these > 99% was removed by the system, with a significant proportion degraded within 9 months. Peak concentrations of the two most mobile pesticides did however exceeded the limits that are likely to be required by regulatory bodies. However, it is thought that these limits could be reached by optimisation of the system.     

Mobility and leaching of glyphosate: a review

There is currently concern that glyphosate, a strongly sorbing non-selective herbicide which is widely used in Europe, may be leached from the root zone into drainage water and groundwater. The purpose of this review is to present and discuss the state of knowledge with respect to the mobility and leaching of glyphosate from agricultural soils. Specific attention is given to the adsorption behaviour of glyphosate and the analysis of available studies on glyphosate transport. In addition, there are a number of experimental and numerical studies indicating that other strongly sorbing substances may be transported rapidly to the sub-surface. The experimental studies analysed in the paper encompass column-, lysimeter- and field-scale experiments on glyphosate transport. The experimental findings, combined with transport studies on other strongly sorbing pesticides in the literature, support the hypothesis that transport of glyphosate may be caused by an interaction of high rainfall events shortly after application on wet soils showing the presence of preferential flow paths. Concentrations of glyphosate in European groundwater have been reported occasionally but monitoring is still limited.     

Adsorption of acetanilide herbicides on soils and its correlation with soil properties

The adsorption of metolachlor, acetochlor, pretilachlor and butachlor, as a group of acetanilide herbicides, on eight soils with various physical and chemical properties was studied. The adsorption isotherms fit the Freundlich equation well. The extent of adsorption increased in the order: metolachlor < acetochlor < pretilachlor < butachlor. The product of the Freundlich adsorption constants, K_f(1/n), showed good correlation with organic matter content (OM) of soils for each of these herbicides, suggesting that the latter is the main factor controlling the adsorption process of these acetanilide herbicides. Multivariant correlation regression between K_f(1/n) and two factors, water solubility (S_w) of herbicides and OM, was also performed. K_f(1/n) correlated well with 1/S_w and OM/S_w, showing that high S_w corresponds to a weak tendency to adsorb on soils. IR spectra and ESR parameters confirmed that multifunctional H bonds and charge-transfer bonds between humic acids (HA) and the herbicides were the main adsorption mechanisms of the latter. The ability of herbicides to form these adsorption bonds with HA increased in the same order as the extent of adsorption. © 1999 Society of Chemical Industry     

双氟磺草胺在不同类型土壤中的吸附与淋溶特性研究

农药在土壤中的吸附和淋溶特性是评价其环境行为的重要指标。采用批量平衡法和土柱淋溶法,研究了双氟磺草胺在小麦种植区3种代表性土壤中的吸附和淋溶特性。结果表明:双氟磺草胺在安徽黏土、山东砂质壤土和河南砂质黏壤土中的吸附规律均可以较好地用Freundlich方程描述,其吸附系数(Kf)在0.39~0.62之间;土壤有机碳归一化吸附系数(Koc)在66.91~81.35之间,表明双氟磺草胺在3种土壤中均属于难吸附型;吸附自由能(ΔG)在-10.90~-10.42kJ/mol之间,均属于物理吸附。双氟磺草胺在3种土壤中的淋出率在71.7%~74.1%之间,说明其在3种土壤中的淋溶性均较强。双氟磺草胺初始添加量和腐殖酸对淋出率具有一定影响。综合试验结果,认为双氟磺草胺在3种土壤中的吸附和淋溶可能受土壤有机质含量、黏粒含量、阳离子交换量和土壤pH值等多个因素的综合影响,其对地下水的污染风险较大,因此应引起高度重视。     

Sorption and dissipation of aged metolachlor residues in eroded and rehabilitated soils

BACKGROUND: Sorption and dissipation of aged metolachlor were characterized in rehabilitated and eroded prairie soils using sequential batch slurry (conventional) and accelerated solvent extraction (ASE). RESULTS: In spite of an almost twofold difference in soil organic carbon (OC) content, S‐metolachlor sorption coefficients (K_d) and dissipation rates (DT₅₀) were the same in soils from different landscape positions within an eroded landform. Soil was moved within the landform to increase productivity. In areas receiving topsoil addition, S‐metolachlor K_d was higher and DT₅₀ was longer than in eroded areas. The efficiency of extraction was higher for ASE than for conventional extractions. No consistent aging effect on K_d was observed. Mineralization in 8 weeks accounted for < 10% of the applied metolachlor. CONCLUSION: The results of this laboratory study support a field dissipation study. Both showed that S‐metolachlor has the same retention and dissipation rate throughout an eroded landform, which was not expected owing to the large variability in soil properties, including OC concentrations. Altering soil properties by adding topsoil increased metolachlor sorption and persistence. The method of extraction (conventional versus ASE) affected calculated sorption coefficients and dissipation rates. In all cases, groundwater ubiquity scores (GUSs) categorized metolachlor as having intermediate mobility. Published 2012 by John Wiley & Sons, Ltd.     

七种农药在3种不同类型土壤中的吸附及淋溶特性

采用振荡平衡法和土柱淋溶法研究了2,4-滴酸、丁噻隆、毒草胺、炔草酸、氟环唑、甲基磺草酮和烯啶虫胺7种农药在江西红壤、太湖水稻土及东北黑土3种不同理化性质土壤中的吸附及淋溶特性,探讨了农药性质及土壤理化性质对供试农药在土壤中吸附、淋溶行为的影响。结果表明:农药的水溶性越大,其在土壤中的吸附性越弱,淋溶性越强;农药在土壤中的吸附性与土壤pH值、有机质含量以及阳离子交换量之间有较好的相关性。土壤pH值、有机质含量以及农药性质是影响农药在土壤中淋溶及迁移的主要因素。     

二氰蒽醌在几种典型土壤中的降解吸附和移动特性

采用室内模拟试验方法,研究了二氰蒽醌在国内3种典型土壤江西红壤、东北黑土和太湖水稻土中的降解、吸附和移动特性。结果表明,25℃下二氰蒽醌在江西红壤、东北黑土与太湖水稻土中的降解半衰期分别为5.614、1.939、4.767d,其在土壤中化学稳定性较弱,易于降解,且pH越高,降解越快。二氰蒽醌在江西红壤的吸附等温线可以Freundlich方程很好地拟合,在东北黑土和太湖水稻土中的则可用线性方程拟合,吸附系数Kd值分别为36.4、114.6和51.9,Koc值分别为3 661.9、6 741.1、4 119.0,二氰蒽醌在土壤中具有中等或较强的吸附性能,在环境中迁移扩散的能力较弱。采用土壤薄层试验得到二氰蒽醌在这三种土壤中的移动分配系数Rf均<0.1,属于难于淋溶的农药,对地下水影响较小。二氰蒽醌在我国的几种典型土壤中均表现出了易降解性,难迁移以及难淋溶的特性,在目前的使用情况下,二氰蒽醌的环境风险较低。     

Fate of the herbicides glyphosate, glufosinate-ammonium, phenmedipham, ethofumesate and metamitron in two Finnish arable soils

The fate of five herbicides (glyphosate, glufosinate-ammonium, phenmedipham, ethofumesate and metamitron) was studied in two Finnish sugar beet fields for 26 months. Soil types were sandy loam and clay. Two different herbicide-tolerant sugar beet cultivars and three different herbicide application schedules were used. Meteorological data were collected throughout the study and soil properties were thoroughly analysed. An extensive data set of herbicide residue concentrations in soil was collected. Five different soil depths were sampled. The study was carried out using common Finnish agricultural practices and represents typical sugar beet cultivation conditions in Finland. The overall observed order of persistence was ethofumesate > glyphosate > phenmedipham > metamitron > glufosinate-ammonium. Only ethofumesate and glyphosate persisted until the subsequent spring. Seasonal variation in herbicide dissipation was very high and dissipation ceased almost completely during winter. During the 2 year experiment no indication of potential groundwater pollution risk was obtained, but herbicides may cause surface water pollution.     

Sorption of isoxaflutole by five different soils varying in physical and chemical properties

Isoxaflutole is a new pre-emergence corn herbicide which controls both grass and broadleaf weeds. Experiments were performed in the laboratory to study the sorption of isoxaflutole in five different soils (Moorhead, MN; East Monroe, CO; Ellendale, MN; South Deerfield, MA; and Chelsea, MI) using the batch equilibration technique. Total initial isoxaflutole solution concentrations for each soil were 0.05, 0.15, 0.3. 0.8, 1.5, 2.0 and 4.0 mg litre⁻¹. Analysis of [ring-¹⁴C] isoxaflutole was performed using liquid scintillation counting, and sorption data were fitted with the Freundlich model. Isotherms of isoxaflutole in all the soils were non-linear as depicted by the exponent (n < 1.0), indicating differential distribution of sorption site energies in various soils. Since the isotherms were non-linear the data fit Freundlich's isotherm well, as was indicated by high values of the regression coefficient (r²). The Freundlich sorption coefficient ranged from 0.555 to 50.0 (litre ⁿmg ^l−nkg⁻¹). Multiple regression of the sorption constant, K_F against selected soil properties indicated that organic matter content was the best single predictor of isoxaflutole sorption (r² = 0.999) followed by soil pH (r² = 0.954). Clay content of the soils did not have a high correlation with K_F values (r² = 0.453), while the sorption of isoxaflutole was not influenced by the Ca²⁺ concentration in the soil solution. Isoxaflutole sorption increased with an increase in organic matter content of soils. Sorption of isoxaflutole decreased as the soil pH increased from 4.5 to 8.5, which was depicted by the reduction of K_F values. Sorption of isoxaflutole to the soils varied with differences in binding energies. At a particular net energy value (E*), the corresponding site energy distribution [F(E*)] values followed the order, Chelsea, MI > Moorhead, MN > East Monroe, CO > South Deerfield, MA > Ellendale, MN. The negative magnitude of Gibbs free energy of sorption (ΔG ^x) indicates the spontaneity of the given sorption process in the soils from Moorhead, MN; East Monroe, CO and Chelsea, MI. © 1999 Society of Chemical Industry     

Modelling the leaching of imazapyr in a railway embankment

The use of herbicides on railway tracks is known to present a risk to groundwater, but little is known of the mechanisms influencing leaching through the coarse material used to construct railway embankments. Therefore, in the present study, four different models based on the convection-dispersion equation (CDE) were compared with previously reported field data on the leaching of imazapyr. In particular, the significance of non-equilibrium processes was investigated by comparing different CDE formulations accounting for preferential finger flow, particle-facilitated transport and kinetic sorption. The traditional CDE assuming 'local equilibrium' based on 24 h batch sorption data gave poor results (model efficiency - 1.1). It strongly underestimated leaching of imazapyr in the first 4 months following application, thus confirming the importance of non-equilibrium transport processes. Accounting for short-term sorption kinetics made little difference, giving similar results to the 'local equilibrium' CDE simulation. A simulation accounting for particle-facilitated transport could accurately match this accelerated transport, and also gave the best overall fit to the data (model efficiency 0.76). However, not even this model could match the long-term retention of imazapyr residues observed close to the soil surface more than 1 year after application, and it also underestimated the time of breakthrough to groundwater. This strongly suggests that a long-term retention/sorption process not included in any of the models tested (i.e. sorption hysteresis or bound residues) acted to retard leaching. The formation of 'protected' residues was also indicated by a much slower degradation of imazapyr more than 1 year after application. Industry.     

Measurement and simulation of herbicide transport in macroporous soils

Lysimeter experiments were carried out to study pesticide transport through macroporous soils. In order to differentiate between the effects of soil structure and chemical behaviour, the leaching experiments were conducted using disturbed and undisturbed soil samples. Two herbicides with different sorption behaviours, and bromide as tracer were applied. The results were used to validate a dynamic simulation model which considers bypass flow in macropores. The simulation results show that the model is able to reproduce the soil suction within the soil as well as the spatial distribution of bromide and the herbicides. The continuity of the macropores is most important for the efficiency of bypass flow. The results indicate that cultivation practices like ploughing significantly influence the temporal and spatial distribution of the macropores. © 1998 SCI.     

新型杀菌剂苯菌酮在3种典型土壤中的淋溶行为

农药在土壤中的淋溶规律已成为研究热点之一,同时也是农药登记的必备数据。建立了土壤中苯菌酮残留量的超高效液相色谱-串联质谱(UPLC-MS/MS)分析方法,并通过土壤薄层层析和土柱淋溶试验,研究了苯菌酮在我国3种典型土壤中的淋溶行为。结果表明:苯菌酮在3种土壤中的平均添加回收率在81%~109%之间,相对标准偏差(RSD)为1.2%~13.4%,检出限(LOD)为0.29~0.30μg/kg。薄层层析试验表明,苯菌酮在河北潮土、湖南红壤和黑龙江黑土中的比移值(Rf)分别为0.17、0.26和0.15。土柱淋溶试验表明,苯菌酮在河北潮土、湖南红壤及黑龙江黑土第1段(0~10 cm)土柱中的含量比例(R1)分别为原始添加量的99%、80%和99%。根据我国化学农药环境安全评价标准,苯菌酮在3种土壤中的迁移特性均为不易移动,因此不易对地下水造成污染。研究结果可为苯菌酮在我国登记以及其安全使用提供基础数据。     

Assessment of leaching potential of aldicarb and its metabolites using laboratory studies

The metabolites of pesticides can contaminate groundwater and pose a risk to human health when this water is used for drinking. This paper reports the results of a laboratory study on aldicarb and its main metabolites, aldicarb sulfone and aldicarb sulfoxide. Aldicarb and its metabolites showed K_oc values (6–31) which were lower than that of atrazine (55), indicating that they are very mobile in soil. They are less persistent than atrazine (DT₅₀ = 25 days), with DT₅₀ values from less than 1 day and up to 12 days. Aldicarb behaved as a non‐leacher, whereas its metabolites clearly showed the characteristics of leachers. Aged residue leaching experiments showed that aldicarb can occur at high concentrations in the leachate, together with its two metabolites. The leachate composition depends on the incubation time of the parent compound. Aldicarb and its metabolites can form various mixtures in groundwater on the basis of the time elapsing between the application of the insecticide and the first significant rainfall. This study confirms the characteristics of contaminants of aldicarb and especially its metabolites, as reported in the literature. © 2001 Society of Chemical Industry     

Mobility of four triazole fungicides in two Indian soils

The sorption and downward mobility of four triazole fungicides, triadimefon, hexaconazole, penconazole and propiconazole, were studied in two Indian soils (New Delhi and Punjab). Punjab soil (organic carbon 0.4%) showed greater sorption capability for triazole fungicides than New Delhi soil (organic carbon 0.5%) and the order of sorption of triazoles in both soils was: penconazole > hexaconazole > propiconazole > triadimefon. Fungicides were more mobile in New Delhi soil columns than Punjab soil columns, and increasing the total water flux from 1 pore volume to 3 pore volumes further increased the transport to lower down in the column. Triadimefon showed maximum mobility while penconazole was the least mobile triazole fungicide. After percolating 3 pore volumes of water, triadimefon leached down to 25-30 cm depth in New Delhi soil and 15-20 cm in Punjab soil columns. Downward mobility of triazole fungicides was in order of their sorption results.     

Herbicide movement in soils: principles, pathways and processes

European legislation concerning ground- and surface-water quality and the protection of non-target organisms in surface-water from pesticide contamination has initiated more stringent data requirements from regulatory authorities concerning the movement of all pesticides in soils. Other interested parties, such as water companies, environment agencies and consumer-driven organizations, have sought to influence the use of herbicides and their impact on the environment. The resulting studies and associated research have led to a better understanding of the fate and behaviour of herbicides in the soil environment. The amount of herbicide that moves away from the area of application will depend on the physico-chemical properties of the chemical and the agroclimatic characteristics of the target site. Under average conditions, the amount of herbicide lost by movement from a soil profile is typically <0.1% to 1% of the applied mass but, under certain localized circumstances, can reach up to 5% or greater. Leaching, drain-flow and surface run-off are the main pathways responsible for herbicide movement within soils. The soil/herbicide processes determining the losses are also variable in both time and space. It is therefore necessary to understand the spatial characteristics of soils, their hydrology and the associated herbicide use patterns.     

吡啶甲酸类除草剂应用研究进展

吡啶甲酸类除草剂属合成激素类, 目前登记使用的有效成分包括氨氯吡啶酸、二氯吡啶酸和氯氨吡啶酸, 分别于1963年、1977年和2005年上市, 主要用于阔叶杂草和灌木的茎叶处理防控, 其中氯氨吡啶酸具有土壤封闭活性。吡啶甲酸类除草剂的作用靶标仍未明确, 有可能来自生长素结合蛋白家族。全世界报道的抗吡啶甲酸类除草剂杂草共涉及7种8个生物型。目前, 我国登记的除草剂品种中共有13个复配剂含氨氯吡啶酸和二氯吡啶酸, 1个含氨氯吡啶酸、氯氨吡啶酸和二氯吡啶酸;国外登记的吡啶甲酸类除草剂复配剂主要为与其他激素型除草剂、ALS(乙酰乳酸合酶)抑制剂、ACCase(乙酰辅酶A羧化酶)抑制剂的组合。该类除草剂仍然具有较好的应用前景, 在主要应用场景下常见杂草对氨氯吡啶酸、二氯吡啶酸、氯氨吡啶酸的敏感性仍需系统研究, 该类除草剂主要靶标杂草种群的抗药性水平也亟须检测。     

Field leaching of pesticides at five test sites in Hawaii: study description and results

BACKGROUND: Following the discovery of pesticides in wells, the Hawaii Department of Agriculture (HDOA) supported research to evaluate the likelihood of pesticide leaching to the groundwater in Hawaii. The aim of this study was to evaluate the relative leaching pattern of five pesticides at five different sites on three islands and to compare their leaching behavior with bromide and a reference chemical (atrazine) that is known to leach in Hawaiian conditions. Laboratory measurements of sorption and degradation of the pesticides were made. RESULTS: Most of the applied mass of pesticides was still present in the top 80 cm after the 16 week study period. The aggregated oxisol at Kunia showed the most intensive leaching among the five sites. The revised attenuation factor screening approach used by the HDOA indicated that all chemicals, with the exception of trifloxystrobin, had the potential to leach. Similarly, the groundwater ubiquity score ranked trifloxystrobin as a non‐leacher. The field leaching data, however, suggested that trifloxystrobin was the most mobile compound among the pesticides tested. CONCLUSION: Although the results were variable among the sites, the field and laboratory experiments provided useful information for regulating use of these pesticides in Hawaii. Copyright © 2010 Society of Chemical Industry