Simultaneous assessment of sources, processes, and factors influencing herbicide losses to surface waters in a small agricultural catchment

To take appropriate measures to minimize agricultural herbicide inputs into surface waters, detailed knowledge is required about all the factors that control the losses of a given compound from point sources (i.e., farmyards) as well as from the diffuse sources (i.e., the fields) within a given catchment. In this and in a companion paper, we present the results of a comprehensive field study, in which the temporal and spatial variability of the losses of three herbicides (atrazine, dimethenamid, and metolachlor) into the surface waters within a small catchment (2.1 km2) were investigated on different scales (i.e., field scale to whole catchment) after a controlled application of the compounds. In this paper, we discuss the loss dynamics of the three herbicides (and some of their metabolites) from the whole catchment over a period of 67 d after application. An identical mixture of the three herbicides was applied on 13 cornfields within 12 h, allowing for a comparison of their losses under identical meteorological conditions. Thanks to a high temporal sampling resolution, it was possible to distinguish between losses from a farmyard and losses from the fields. Farmyard losses contributed less than 20% to the total loads but caused the highest concentrations. The major herbicide losses from the agricultural fields occurred during the first two rain events after application that led to significant surface runoff and preferential flow into tile drains. In the soils of all fields, dimethenamid declined somewhat faster than atrazine and metolachlor, whereas atrazine was mobilized most effectively to runoff water. Relative losses of the three compounds did not vary by more than a factor of 3 (0.82, 0.27, and 0.41% of the mass applied for atrazine, dimethenamid, and metolachlor, respectively). Highest peak concentrations at the outlet of the catchment were found for atrazine (i.e., approximately 8 microg L(-1) for a short period (<2 h) due to point source losses and between 1 and 3.5 microg L(-1) during more than 24 h due to diffuse losses).     

Watershed vulnerability to herbicide transport in northern Missouri and southern Iowa streams

Herbicide contamination of streams has been well documented, but little is currently known about the specific factors affecting watershed vulnerability to herbicide transport. The primary objectives of this study were (1) to document herbicide occurrence and transport from watersheds in the northern Missouri/southern Iowa region; (2) to quantify watershed vulnerability to herbicide transport and relate vulnerability to soil properties; and (3) to compute the contribution of this region to the herbicide load of the Missouri and Mississippi Rivers. Grab samples were collected under baseflow and runoff conditions at 21 hydrologic monitoring stations between April 15 and July 15 from 1996 to 1999. Samples were analyzed for commonly used soil-applied herbicides (atrazine, cyanazine, acetochlor, alachlor, metolachlor, and metribuzin) and four triazine metabolites (deisopropylatrazine, deethylatrazine, hydroxyatrazine, and cyanazine amide). Estimates of herbicide load and relative losses were computed for each watershed. Median parent herbicide losses, as a percentage of applied, ranged from 0.33 to 3.9%; loss rates that were considerably higher than other areas of the United States. Watershed vulnerability to herbicide transport, measured as herbicide load per treated area, showed that the runoff potential of soils was a critical factor affecting herbicide transport. Herbicide transport from these watersheds contributed a disproportionately high amount of the herbicide load to both the Missouri and Mississippi Rivers. Based on these results, this region of the Corn Belt is highly vulnerable to transport of herbicides from fields to streams, and it should be targeted for implementation of management practices designed to reduce herbicide losses in surface runoff.     

Chloroacetanilide herbicide metabolites in Wisconsin groundwater: 2001 survey results

A survey of agricultural chemicals in Wisconsin groundwater was conducted between October 2000 and April 2001 to obtain a current picture of agricultural chemicals in groundwater used for private drinking water. A stratified, random sampling procedure was used to select 336 sampling locations. Water from private drinking water wells randomly selected from within the 336 sampling locations was analyzed for 18 compounds including herbicides, herbicide metabolites, and nitrate. This report focuses on the frequency and concentration of chloroacetanilide herbicides and their metabolites. Analysis of data resulted in an estimated proportion of 38+/-5.0% of wells that contained detectable levels of a herbicide or herbicide metabolite. The most commonly detected compound was alachlor ESA with a proportion estimate of 28+/-4.6%. Other detected compounds in order of prevalence were metolachlor ESA, metolachlor OA, alachlor OA, acetochlor ESA, and parent alachlor. Estimates of the mean concentration for the detects ranged from 0.15+/-0.082 microg/L for acetochlor ESA to 1.8+/-0.60 microg/L for alachlor OA. Water quality standards have not been developed for these chloroacetanilide herbicide metabolites. The results of this survey emphasize the need for toxicological assessments of herbicide metabolite compounds and establishment of water quality standards at the state and federal levels.     

Relative effects of surfactants and humidity on soil/air desorption of chloroacetanilide and dinitroaniline herbicides

Herbicides are typically applied as formulation mixtures in order to ensure uniform application and improve biocide performance, but little is known about the effects of formulated surfactants on herbicide exchange between soil and the atmosphere. Desorption experiments were performed for seven herbicides from the chloroacetanilide and dinitroaniline families with model anionic-nonionic surfactant mixtures under a range of relative humidity (RH) conditions (3-66%) on two soils. Enhanced desorption of herbicides from soil to the gas phase was observed asthe concentration of surfactant mixture or the RH increased. Multiple linear regression models developed to summarize the soil/air desorption behavior of these herbicides revealed that surfactant concentration, relative humidity, and herbicide properties (i.e., K(H), K(OA)) all have significant contributions to herbicide desorption. However, the ANOVA results indicated that surfactant concentration only accounted for 1.4% of the variance in desorption, RH accounted for 40-60%, and herbicide properties, logK(H) or logK(OA), accounted for 20-40%. The study results predict that less than a 20% increase (study range 1.5-21.0%) in surfactant concentration could double the atmospheric losses of herbicide from their soil application sites, and about a 60% increase in ambient RH (3-66%) elevated the losses by 10-40 times.     

除草剂、除草膜防除烟田杂草试验

在云南昭通和曲靖进行了烟田除草试验 ,结果表明 ,相对于普通无色地膜覆盖栽培而言 ,除芽通、敌草胺和金都尔除草膜对烟田杂草的相对防除效果分别为 93.8%、6 1.2 %、4 3.7% ,方差分析证明各处理间差异达极显著水平     

植物源性食品中氨基酸类有机磷除草剂分析方法的研究进展

氨基酸类有机磷除草剂是一类含有膦酸基团且能干扰杂草氨基酸生物合成的除草剂,主要代表品种有草甘膦、草铵膦、双丙氨膦和草硫膦等,因其除草谱广且经济易得,在农业活动中应用广泛,过量与不合理使用除草剂对环境、食品安全造成一定隐患。该类除草剂残留量低,极性较大且缺少生色基团,使得常规分析具有一定挑战性;另外,植物源性食品种类繁多,基质成分复杂,在食品中残留量低,根据样品特点和分析要求选择合适的分析方法对提高检测的准确度和灵敏度至关重要。因此,本文对国内外植物源性食品中氨基酸类有机磷除草剂及其代谢物残留量检测所用的传统和新型样品前处理方法以及检测技术进行综述,总结并展望现有分析方法的优缺点和发展趋势,为开发简单、快速、准确的新技术和新方法提供参考,为食品安全研究提供依据。     

Herbicide runoff along highways. 1. Field observations

Herbicides are widely applied along highways to control roadside vegetation, and surface water is frequently nearby. To determine whether herbicide runoff along highways threatens water quality, a field study was conducted at two sites in northern California for three rainy seasons. The herbicides oryzalin, isoxaben, diuron, glyphosate, and clopyralid were selected for study to include compounds with significant variation in physical/chemical properties. Concentrations of herbicides in runoff were monitored for up to 11 storms following herbicide application, and 24 samples were collected per storm, providing unprecedented temporal detail. Flow-weighted event mean concentrations were calculated for each herbicide in each storm and ranged from below detection limits to 43.13 microg/L for oryzalin. The least soluble compounds, isoxaben and oryzalin, were detected in all storms monitored while the more soluble compounds, diuron and clopyralid, declined to levels below detection limits before monitoring was concluded. Very small amounts of glyphosate were mobilized, but its transformation product aminomethylphosphonic acid was detected at higher concentrations, in more storm events, and at greater depth in the soil profile. A first-order model successfully described the declining herbicide concentrations in spray zone soil and in surface runoff for all sites and herbicides. Fitted first-order coefficients were always higher for runoff than for soil, indicating that the herbicide that persists in the source zone becomes less available for runoff as the time since application increases. The percentage of the applied herbicide that was detected in surface runoff over a season ranged from 0.05% to 43.5%, and the most critical variables in controlling the variation were the solubility of the herbicide and the runoff volume. For a given herbicide and site, the most critical factors in determining seasonal herbicide loss to surface water were the timing and intensity of the first storm following application, affecting total seasonal runoff by up to 2 orders of magnitude. Minimizing runoff of herbicides along highways will thus require careful attention to the intrinsic mobility of the compound and the timing of its application.     

A 75% reduction in herbicide use through integration with sorghum + sunflower extracts for weed management in wheat

BACKGROUND: To reduce herbicide use by 75%, integrated use of sorghum and sunflower extracts each at 18 L ha^?1 combined with 1/4^th (75% less) of label rates of four herbicides (mesosulfuron + idosulfuron, metribuzin, phenoxaprop‐p‐ethyl and isoproturon) were investigated for the management of wild oat and canary grass, the two pernicious weeds in wheat fields worldwide. RESULTS: The results revealed that sorghum + sunflower extracts combined with 1/4^th (75% less) of label rates of herbicides inhibited dry matter production of wild oat by up to 89% and canary grass by up to 92%. The wild oat and canary grass persistence index in sorghum + sunflower extracts combined with 1/4^th (75% less) of label rates of herbicides was either lower or equal to respective label rates of herbicides, except sorghum + sunflower extract + 1/4^th phenoxaprop‐p‐ethyl. Lower herbicide rates + water extracts also produced wheat grain yield statistically equal with label rates of respective herbicides. Two treatments having water extracts + lower herbicides rates were economical and sorghum + sunflower + 1/4^th mesosulfuron + idosulfuron produced the highest (4404%) marginal rate of return. CONCLUSION: Herbicides use can be reduced by 75% through integration with sorghum + sunflower extracts without compromising yield and net benefits for cost‐effective and eco‐friendly management of wild oat and canary grass in wheat. Copyright © 2010 Society of Chemical Industry     

Herbicide sorption to fine particulate matter suspended downwind of agricultural operations: field and laboratory investigations

Tillage-induced erosion of herbicides bound to airborne soil particles has not been quantified as a mechanism for offsite herbicide transport. This study quantifies the release of two preemergent herbicides, metolachlor and pendimethalin, to the atmosphere as gas- and particle-phase species during soil incorporation operations. Fine particulate matter (PM2.5) and gas-phase samples were collected at three sampling heights during herbicide disking into the soil in Davis, CA, in May 2000 and May 2001 using filter/PUF sampling. Quartz fiber filters (QFFs) were used in May 2000, and Teflon membrane filters (TMFs) were used in May 2001. The field data were combined with laboratory filter/PUF partitioning experiments to account for adsorption to the filter surfaces and quantify the mass of PM2.5-bound herbicides in the field samples. Laboratory results indicate a significant adsorption of metolachlor, but not pendimethalin, to the quartz filter surfaces. Metolachlor partitioning to PM2.5 collected on TMF filters resulted in corrected PM2.5 field partition coefficient values, Kp,corr = Cp/Cg, of approximately 10(-3.5) m3/microg, indicating its preference for the gas phase. Pendimethalin exhibited more semivolatile behavior,with Kp,corr values that ranged from 10(-3) to 10(-1) m3/ microg and increased with sampling height and distance downwind of the operation. An increase in pendimethalin enrichment at a height of 5 m suggests winnowing of finer, more sorptive soil components with corresponding higher transport potential. Pendimethalin was enriched in the PM2.5 samples by up to a factor of 250 compared to the field soil, indicating thatfurther research on the processes controlling the generation of PM-bound herbicides during agricultural operations is warranted to enable prediction of off-site mass fluxes by this mechanism.     

硝磺草酮等复配剂对蔗田杂草的防治效果

为了解决蔗田长期使用单一除草剂带来的抗性问题,筛选高效、安全、环保的除草剂新配方,2016年特在广东湛江进行了几种除草剂配方筛选及对照试验。结果表明:硝磺草酮+氯吡+莠灭净三者混配对蔗田杂草的总抑制率达88.51%,防治效果达93.59%。敌草隆+氯吡+莠灭净组合配方和硝磺草酮+氯吡+异丙甲草胺配方对蔗田杂草的总抑制率67.87%和62.13%,总防除效果为78.71和73.89%;与敌二莠、硝磺草酮、莠灭净和莠去津单剂相比,硝磺草酮+氯吡+莠灭净组合配方提高了防效,扩大了杀草谱,适合在蔗田使用。     

Chlorophyll fluorescence imaging of individual algal cells: effects of herbicide on Spirogyra distenta at different growth stages

Serious environmental degradation of aquatic ecosystems has been caused by eutrophication and by pollutants such as herbicides. Therefore, measurement of in situ algal photosynthetic activity is important for environmental monitoring. With ordinary nonimaging fluorometers, algal chlorophyll fluorescence can be measured easily, but heterogeneity within samples cannot be detected. Effects of a herbicide preparation containing 3-(3,4-dichlorophenyl)-1,1 -dimethylurea (DCMU) on photosynthetic activity at different growth stages of Spirogyra distenta were investigated by using a computer-aided microscopic imaging system for chlorophyll afluorescence. Photosystem II photochemical yield (phiPSII) images were used to diagnose photosynthetic activity of spiral filate chloroplasts in algal cells. The herbicide treatment caused a stronger decline in phiPSII values in younger than in mature algae cells. This result indicated that heterogeneity within algal samples should be considered when algae are used for environmental monitoring. Thus, measurement of chlorophyll fluorescence from young and mature chloroplasts with a microscopic imaging system makes it possible to improve the sensitivity for monitoring the environmental degradation of aquatic ecosystems.     

磺酰脲类除草剂毒性及多残留检测技术研究进展

磺酰脲类除草剂是一种高效、广谱、高选择性的除草剂,主要用于防除阔叶杂草和禾本科杂草。磺酰脲类除草剂在现代农业生产中发挥了重要作用,但其农药残留问题也给生态环境和农产品质量安全造成诸多负面影响。本文主要对磺酰脲类除草剂的毒性危害、限量标准、残留检测的前处理以及仪器分析方法进行综述。目前对于磺酰脲类除草剂残留的检测主要涉及到土壤和水,其次还有粮谷、动物源性食品等多种基质,国内对于此类除草剂残留检测常用的前处理方法为固相萃取法,C_(18)为常见填料,在仪器分析方面,液相色谱-质谱联用法以其灵敏度高、能检测痕量水平的残留而成为此类除草剂分析的首选方法。同时,国内外针对此类除草剂的残留检测,已经由过去的单残留检测向多残留检测发展。     

我国主要作物中除草剂登记情况及存在问题

除草剂是全球发展最为迅猛的农药之一,其使用量逐年增加,在农药中的占比不断增加。除草剂的应用对于保障我国粮食、大豆、棉花、油料等农作物安全生产具有重要意义。但随着除草剂的多年连续使用,一些负面问题也不断凸显。本文综述了除草剂不同的分类方式和作用机制。从整体和主要登记作物(稻田、玉米田、大豆田、麦田)2个方面介绍了除草剂在我国的登记情况,包括除草剂的登记数量、有效成分、剂型和生产企业等。对除草剂在登记和使用方面存在的问题进行了分析,如除草剂产品登记混乱、创制新品种能力弱、除草剂药害、杂草抗药性、环境问题等。为除草剂的产业发展、登记管理和标准制定提供依据。     

Identifying sources and mass balance of dioxin pollution in Lake Shinji Basin, Japan

On the basis of congener-specific analysis of dioxins in a dated sediment core, the sources and behavior of dioxins in Lake Shinji Basin, Japan, were estimated. The dioxins in the core showed that their deposition in the lake increased rapidly during the 1960s, peaked in the early 1970s, and then decreased gradually. Principal component analysis of the congener-specific data showed that three major sources existed: pentachlorophenol (PCP), chloronitrophen (CNP), and combustion. PCP and CNP are paddy field herbicides used extensively in the basin. The time trends of source contributions were estimated by multiple regression analysis using the source profiles. The results revealed that dioxin emission from PCP and CNP herbicides was high in the 1960s and the early 1970s, respectively. The contributions from PCP, CNP, and combustion in recent surface sediment were about 68, 16, and 16% in terms of total amount of dioxins. From the decreasing trend of dioxin deposition in the lake after extensive herbicide use, the amount of dioxins that accumulated in the agricultural soil in the basin was estimated to have decreased by about 2%/yr or a half-life of about 35 yr, indicating that dioxin runoff from agricultural fields would continue for a long time.     

Comparison of extraction solvents and conditions for herbicide residues in milled rice with liquid chromatography-diode array detection analysis (LC-DAD)

Different extraction procedures and clean-up methods were compared in order to develop a sample preparation procedure for the multi-residue analysis of six post-emergence herbicides (metsulfuron methyl, bensulfuron methyl, pyrazosulfuron ethyl, bentazone, bispyribac sodium and cyhalofop butyl) in rice grains followed by liquid chromatography-diode array detection (LC-DAD). Optimum results were obtained dispersing milled rice grain in water, followed by the addition of 1% acetic acid in acetonitrile, MgSO₄ and sodium acetate as a modification of the quick, easy, cheap, effective, rugged and safe (QuEChERS) method but no primary and secondary amine (PSA) sorbent was added due to the acidic nature of the herbicides. The method was further expanded to other post-emergence herbicides (quinclorac, clomazone and propanil). Except for quinclorac, which cannot be analysed with this method, the recoveries of the other eight herbicides were in the range 73–111%, with relative standard deviations lower than 12%. Limits of detection (LODs) ranged from 0.03 to 0.08 mg kg^?1. A single analyst can extract twelve samples in 4 h. The method presented here allows the simultaneous residue determination of the most common post-emergence herbicides employed in cultivating rice. It is simple, rapid, sensitive, and can be applied routinely to polished rice grain herbicide residue analysis.     

Detection of herbicide subclasses by an optical multibiosensor based on an array of photosystem II mutants

Massive use of herbicides in agriculture over the last few decades has become a serious environmental problem. The residual concentration of these compounds frequently exceeds the maximum admissible concentration in drinking water for human consumption and is a real environmental risk for the aquatic ecosystem. Herbicides inhibiting photosynthesis via targeting photosystem II function still represent the basic means of weed control. A multibiosensor was constructed for detecting herbicides using as biosensing elements photosynthetic preparations coupled to an optical fluorescence transduction system (Giardi et al. EU patent EP1134585, 01830148.1-2204); this paper is about its application in the detection of herbicide subclasses in river water. Photosynthetic material was immobilized on a silicio septum inside a series of flow cells, close to diodes so as to activate photosystem II (PSII) fluorescence. The principle of the detection was based on the factthat herbicides selectively modify PSII fluorescence activity. The multibiosensor has the original feature of being able to distinguish the subclasses of the photosynthetic herbicides by using specific immobilized biomediators isolated from mutated organisms. This setup resulted in a reusable, portable multibiosensor for the detection of herbicide subclasses with a half-life of 54 h for spinach thylakoids and limit of detection of 3 x 10(-9) M for herbicides present in river water.     

Dioxin concentrations in breast milk of Vietnamese nursing mothers: a survey four decades after the herbicide spraying

In an operation by United States Armed Forces during 1961 to 1971, large quantities of herbicides were sprayed in South Vietnam. These herbicides contained 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-tetraCDD), the most toxic congener of dioxins. Several decades after the herbicide spraying ceased, dioxin concentrations in the environment and human remained elevated in the sprayed areas. Breast milk samples from 520 nursing mothers residing in areas including the hot spots as well as the sprayed and unsprayed areas were collected to quantify the levels of dioxins. The total toxic equivalents of 2,3,7,8-substitued PCDDs/PCDFs in breast milk of mothers living in the hot spots, and the sprayed and unsprayed areas were 14.10 pg/g lipid, 10.89 pg/g lipid, and 4.09 pg/g lipid for primiparae and 11.48 pg/g lipid, 7.56 pg/g lipid, and 2.84 pg/g lipid for multiparae, respectively, with significant differences in the values among the three areas. In the hot spots, dioxin levels were highly correlated with the residency of mothers after adjustment for their age and parity.     

Transformation of herbicide propachlor by an agrochemical thiourea

Propachlor and other chloroacetanilide herbicides are frequently detected contaminants of groundwater and surface water in agricultural regions. The purpose of this work was to develop a new approach to remove propachlor residues from the environment via chemical remediation by the nitrification inhibitor thiourea. The transformation processes of propachlor and thiourea mixed in aqueous solution, sand, and soil were elucidated. Analysis of transformation products and reaction kinetics indicated that an S(N)2 nucleophilic substitution reaction occurred, in which the chlorine of propachlor was replaced by thiourea, detoxifying the herbicide. It appears that propachlor undergoes a catalytic reaction in sand or soil amended with thiourea, which results in a significantly accelerated transformation rate as compared to the reaction in aqueous solution. The second-order reaction process was examined at different temperatures to investigate the role of the activation energy. The enthalpy of activation (deltaH) for the reaction of propachlor with thiourea was demonstrated to be significantly lower in sand than in aqueous solution, which provides evidence that a catalytic transformation mechanism occurs in thiourea-amended sand. The chemical reaction rate increased proportionally to the amount of thiourea added to the sand. Column experiments further suggested that the remediation strategy could be used to remove propachlor residues from sand or soil to reduce leaching and prevent contamination of surface water and groundwater.     

Herbicide runoff along highways. 2. Sorption control

Controversy remains about the importance of nonlinear sorption isotherms, desorption rate limitations, and aging effects, collectively referred to as nonideal sorption processes, in controlling the fate and transport of organic contaminants. Herbicide runoff from highway soils represents a good test case for assessing the relative importance of nonideal sorption because runoff flow rates are often high, soil-water contacttimes are short, and significant time is available for contaminant aging after application. This study examines the sorption and desorption of five herbicides with a wide range of properties (isoxaben, oryzalin, diuron, clopyralid, and glyphosate) on soil samples from two roadsides in northern California and uses the results to examine field runoff data from multiple rainy seasons. Nonideal sorption processes do not appear to be significant in determining herbicide runoff at the field sites because (i) sorption isotherms were linear or slightly nonlinear for all compounds but glyphosate, (ii) field runoff concentration ratios between isoxaben and oryzalin were consistent with linear partitioning predictions, (iii) runoff leaving the site appeared to be in equilibrium with local soil concentrations, and (iv) desorption distribution coefficients for aged herbicides on soil samples collected from the field site did not differ substantially from those obtained in short-term laboratory adsorption experiments. Collectively, these findings indicate that linear equilibrium models are adequate for predicting the concentration of herbicides in runoff in these field settings and that more complicated nonideal models do not need to be invoked. Vegetated slopes effectively reduced the herbicide loads, with average removals of 35-80% occurring as runoff traversed a 3-m segment 1 m from the edge of the spray zone.     

Persistence of herbicides in soil

A survey has been made of some of the physical, chemical and biological interactions that influence the persistence and availability of herbicides applied to the soil. The most important physical interaction between herbicides and soil is considered to be sorption of the pesticide to the soil surface. This influences not only the rate of leaching of the herbicide through the soil and its movement in the vapour phase, but also the rate of chemical and microbial decomposition. An attempt has been made to construct a model for the persistence of some hydrolytically sensitive herbicides to enable their persistence in soils to be deduced from hydrolysis rate-constants and adsorption data. The formulation used and the method of application of the herbicide to the soil can also have an important influence on its persistence.