Modelling pesticide run-off to surface waters. Part I: Model theory and development

A conceptual model is presented to estimate the concentrations of pesticides appearing in surface waters following their application as part of agricultural production. The model has been formulated particularly to deal with soils that are prone to bypass flow and require artificial sub-surface drainage. Pesticide concentrations and loads can be calculated at field drainage outlets or for whole headwater catchments. The data required to run the model are generally readily available from published sources (within the UK) and these data have been detailed. The assumptions made in the model are stated and the limitations with respect to the general applicability of the model are discussed. © 1998 Society of Chemical Industry     

Influence of topsoil tilth and soil moisture status on losses of pesticide to drains from a heavy clay soil

Twelve lysimeters with a surface area of 0.5 m² and a length of 60 cm were taken over mole drains from a Denchworth heavy clay soil and divided into two groups with either a standard agricultural tilth or a finer topsoil tilth. The influence of topsoil tilth on leaching of the herbicide isoproturon and a bromide tracer was evaluated over a winter season. The effect of variations in soil moisture status in the immediate topsoil on leaching of isoproturon, chlorotoluron and linuron was investigated in the following winter season. Here, water inputs were controlled such that lysimeters received 50 mm at a maximum intensity of 2 mm h^?1 over a 4‐week period with herbicides applied on day 15. Three treatments received the water either all prior to application, all after application, or evenly spread over the 4‐week period. Leaching losses of the three herbicides were monitored for a subsequent drainage event. Analysis of covariance showed a significant effect of topsoil tilth and total flow on both the maximum concentrations (P = 0.034) and total losses (P = 0.012) of isoproturon in drainflow. Both concentrations and losses were c 35% smaller from lysimeters with the finer tilth. However, generation of the fine tilth in the field was restricted by a wet autumn and this is not considered a reliable management option for reducing pesticide losses from heavy clay soils. In the second experiment, variation in soil moisture content prior to and after application did not have any significant effect (P < 0.05) upon subsequent losses of the three herbicides to drains. © 2001 Society of Chemical Industry     

Evaluation of uncalibrated preferential flow models against data for isoproturon movement to drains through a heavy clay soil

The uncalibrated predictive ability of four preferential flow models (CRACK‐NP, MACRO/MACRO_DB, PLM, SWAT) has been evaluated against point rates of drainflow and associated concentrations of isoproturon from a highly structured and heterogeneous clay soil in the south of England. Data were available for four plots for a number of storm events in each of three successive growing seasons. The mechanistic models CRACK‐NP and MACRO generally gave reasonable estimates of drainflow over the three seasons, but under‐estimated concentrations of isoproturon over a prolonged period in the first season and over‐estimated them in the two remaining seasons. CRACK‐NP simulated maximum concentrations of isoproturon over the first two events of each of the three seasons of 156, 527 and 24.4 µg litre^?1, respectively, and matched the observed data (465, 65.1 and 0.65 µg litre^?1) slightly better than MACRO (69.1, 566 and 58.5 µg litre^?1). Automatic selection of parameters from soils information within MACRO_DB reduced the emphasis on preferential flow relative to the stand‐alone version of MACRO. This gave a poor simulation of isoproturon breakthrough and simulated maximum concentrations were 0, 50.1 and 35.1 µg litre^?1, respectively. The capacity model PLM gave the best overall simulation of total drainflow for the first two events in each season, but over‐estimated concentrations of isoproturon (967, 808 and 51.3 µg litre^?1). The simple model SWAT represented total drainflow reasonably well and gave the best simulation of maximum isoproturon concentrations (140, 80.2 and 8.2 µg litre^?1). There was no clear advantage here in using the mechanistic models rather than the simpler models. None of the models tested was able to simulate consistently the data set, and uncalibrated modelling cannot be recommended for such artificially drained heavy clay soils. © 2001 Society of Chemical Industry     

Simulation of movement of pesticides towards drains with a preferential flow version of PEARL

BACKGROUND: As part of the Dutch authorisation procedure for pesticides, an assessment of the effects on aquatic organisms in surface waters adjacent to agricultural fields is required. The peak concentration is considered to be the most important exposure endpoint for the ecotoxicological effect assessment. Macropore flow is an important driver for the peak concentration, so the leaching model PEARL was extended with a macropore module. The new model has two macropore domains: a bypass domain and an internal catchment domain. The model was tested against data from a field leaching study on a cracking clay soil in the Netherlands. RESULTS: Most parameters of the model could be obtained from site‐specific measurements, pedotransfer functions and general soil structural knowledge; only three macropore‐flow‐related parameters needed calibration. The flow‐related macropore parameters could not be calibrated without using the concentration in drain water. Sequential calibration strategies, in which firstly the water flow model and then the pesticide fate model are calibrated, may therefore be less suitable for preferential flow models. CONCLUSION: After calibration, PEARL could simulate well the observed rapid movement towards drains of two pesticides with contrasting sorption and degradation rate properties. The calibrated value for the fraction of the internal catchment domain was high (90%). This means that a large fraction of water entering the macropores infiltrates into the soil matrix, thus reducing the fraction of rapid flow. Copyright © 2011 Society of Chemical Industry     

Pesticide exposure assessment for surface waters in the EU. Part 1: Some comments on the current procedure

In 2001, the European Commission introduced a risk assessment project known as FOCUS (FOrum for the Coordination of pesticide fate models and their USe) for the surface water risk assessment of active substances in the European Union. Even for the national authorisation of plant protection products (PPPs), the vast majority of EU member states still refer to the four runoff and six drainage scenarios selected by the FOCUS Surface Water Workgroup. However, our study, as well as the European Food Safety Authority (EFSA), has stated the need for various improvements. Current developments in pesticide exposure assessment mainly relate to two processes. Firstly, predicted environmental concentrations (PECs) of pesticides are calculated by introducing model input variables such as weather conditions, soil properties and substance fate parameters that have a probabilistic nature. Secondly, spatially distributed PECs for soil–climate scenarios are derived on the basis of an analysis of geodata. Such approaches facilitate the calculation of a spatiotemporal cumulative distribution function (CDF) of PECs for a given area of interest and are subsequently used to determine an exposure concentration endpoint as a given percentile of the CDF. For national PPP authorisation, we propose that, in the future, exposure endpoints should be determined from the overall known statistical PEC population for an area of interest, and derived for soil and climate conditions specific to the particular member state. © 2016 Society of Chemical Industry     

Testing MACRO (version 5.1) for pesticide leaching in a Dutch clay soil

Testing of pesticide leaching models against comprehensive field-scale measurements is necessary to increase confidence in their predictive ability when used as regulatory tools. Version 5.1 of the MACRO model was tested against measurements of water flow and the behaviour of bromide, bentazone [3-isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one-2,2-dioxide] and imidacloprid [1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylideneamine] in a cracked clay soil. In keeping with EU (FOCUS) procedures, the model was first calibrated against the measured moisture profiles and bromide concentrations in soil and in drain water. Uncalibrated pesticide simulations based on laboratory measurements of sorption and degradation were then compared with field data on the leaching of bentazone and imidacloprid. Calibrated parameter values indicated that a high degree of physical non-equilibrium (i.e. strong macropore flow) was necessary to describe solute transport in this soil. Comparison of measured and simulated bentazone concentration profiles revealed that the bulk of the bentazone movement in this soil was underestimated by MACRO. Nevertheless, the model simulated the dynamics of the bentazone breakthrough in drain water rather well and, in particular, accurately simulated the timing and the concentration level of the early bentazone breakthrough in drain water. The imidacloprid concentration profiles and its persistence in soil were simulated well. Moreover, the timing of the early imidacloprid breakthrough in the drain water was simulated well, although the simulated concentrations were about 2-3 times larger than measured. Deep groundwater concentrations for all substances were underestimated by MACRO, although it simulated concentrations in the shallow groundwater reasonably well. It is concluded that, in the context of ecotoxicological risk assessments for surface water, MACRO can give reasonably good simulations of pesticide concentrations in water draining from cracking clay soils, but that prior calibration against hydrologic and tracer data is desirable to reduce uncertainty and improve accuracy.     

Leaching of pesticides and a bromide tracer through lysimeters from five contrasting soils

In each of two seasons, undisturbed lysimeters 0.8 m in diameter and 1.05 m in length taken from five soil types were cropped with winter wheat. They received autumn applications of the pesticides isoproturon and linuron as well as a bromide tracer and spring applications of dimethoate and MCPA. Leachate was collected at regular intervals and concentrations of the various solutes determined. Rainfall from December to March was 290 and 191 mm in the first and second seasons, respectively. Both springs were exceptionally dry with less than 50% of the mean April‐to‐June rainfall of 138 mm. Total flow from the lysimeters ranged from 335 to 477 mm (and from 0.78 to 3.95 pore volumes) over the two seasons. Leaching to drainage of bromide highlighted soils where preferential flow was influential with total losses ranging from 24% of applied for a strongly structured, alluvial clay loam to 79% for an unstructured sand. Leaching to drainage of isoproturon (K_oc ≈ 100 ml g⁻¹) was observed from all but a peat soil with losses greater (0.31–1.01% of applied) from the clay loam and a deep medium loam, where patterns of leaching clearly indicated preferential flow mechanisms, than from the sand and a light loam over gravel (0.04–0.18% of applied) where a broad breakthrough curve indicated that matrix flow was more important. Linuron (K_oc ≈ 500 ml g⁻¹) was detected in occasional samples of leachate from the clay loam, the light loam over gravel and the medium loam during the first season only (maximum loss 0.12% of applied). The sandy soil, often considered most vulnerable to leaching, gave the smallest total losses of pesticide of the four mineral soils, whilst significant preferential flow in the deep, medium loam was believed to result from a compacted topsoil. Neither of the spring‐applied pesticides was detected in the leachate, as flow following application was very small and relatively slow. © 2000 Society of Chemical Industry     

Persistence of 2,4,5-T in a heavy clay soil

The persistence of the herbicide 2,4,5-T was studied at different controlled temperatures and moisture levels in Regina heavy clay. Degradation approximated to first-order kinetics and the half-life varied from about 4 days at 35°C and 34% soil moisture to about 60 days at 10°C and 20% soil moisture. The laboratory data were used in conjunction with the appropriate measurements of surface soil temperature and moisture content in the field to simulate the degradation pattern for the herbicide in five separate micro-plot experiments. Satisfactory agreement with the observed patterns of loss was obtained in two of the experiments but in the other three, the model over-estimated rates of loss. It is suggested that the reason for this was the difficulty of obtaining a correct measure of soil moisture content to use in the simulation program.     

Factors controlling degradation of pesticides in soil

Rates of pesticide degradation in soil exhibit a high degree of variability, the sources of which are usually unclear. Combining data from incubations performed using a range of soil properties and environmental conditions has resulted in greater understanding of factors controlling such degradation. The herbicides clomazone, flumetsulam, atrazine, and cloransulam-methyl, as well as the former insecticide naphthalene offer examples of degradation kinetics controlled by coupling competing processes which may in turn be regulated separately by environmental conditions and soil properties. The processes of degradation and volatilization appear to compete for clomazone in solution; sorbed clomazone is degraded only after the solution phase is depleted. Similarly, volatilization of naphthalene is enhanced when degradation has been inhibited by high nutrient levels. Degradation of the herbicide flumetsulam has been shown to be regulated by sorption, even though the compound has a relatively low affinity for the soil. The fate pathway for cloransulam-methyl shifts from mineralization to formation of metabolities, bound residues and physically occluded material as temperature increases. Atrazine degradation in soil may be controlled in part by the presence of inorganic nitrogen, as the herbicide appears to be used as a nitrogen source by micro-organisms. New insight gained from measurement of multiple fate processes is demonstrated by these examples.     

西北春小麦和麦田土壤中15种常用农药残留的检测

为掌握西北春小麦和麦田土壤的农药残留污染状况,在调研和总结分析了西北春小麦的病、虫、草害发生和防治措施基础上,采集了我国西北地区甘肃、青海、宁夏的9个春小麦产区的小麦籽粒和麦田土壤样品。针对春小麦病虫草害防治中常用的农药,使用HPLC-MS/MS和GC-MS方法,测定了吡虫啉、高效氯氰菊酯、辛硫磷、毒死蜱等4种杀虫剂,三唑酮及其代谢物三唑醇、戊唑醇、多菌灵、三环唑、苯醚甲环唑等6种杀菌剂,精噁唑禾草灵、苯磺隆、2,4-滴丁酯、炔草酯及其代谢物炔草酸等5种除草剂,共15种农药及代谢物在小麦籽粒和麦田土壤中的残留量。通过与小麦中农药残留限量相比较,评价了西北春小麦的食品安全。结果显示,仅在采自甘肃金昌的小麦籽粒样品中检出了戊唑醇,且未超过最大残留限量,在其他样品中均未检出15种农药的残留,表明西北春小麦和麦田土壤的农药安全性均较高。本研究为掌握小麦籽粒的农药残留和麦田土壤的农药污染情况提供了研究数据,为进一步指导西北春小麦的绿色无公害病虫害防治提供了参考。     

Fate and transport of glyphosate and aminomethylphosphonic acid in surface waters of agricultural basins

BACKGROUND: Glyphosate [N-(phosphonomethyl)glycine] is a herbicide used widely throughout the world in the production of many crops and is heavily used on soybeans, corn and cotton. Glyphosate is used in almost all agricultural areas of the United States, and the agricultural use of glyphosate has increased from less than 10 000 Mg in 1992 to more than 80 000 Mg in 2007. The greatest intensity of glyphosate use is in the midwestern United States, where applications are predominantly to genetically modified corn and soybeans. In spite of the increase in usage across the United States, the characterization of the transport of glyphosate and its degradate aminomethylphosphonic acid (AMPA) on a watershed scale is lacking. RESULTS: Glyphosate and AMPA were frequently detected in the surface waters of four agricultural basins. The frequency and magnitude of detections varied across basins, and the load, as a percentage of use, ranged from 0.009 to 0.86% and could be related to three general characteristics: source strength, rainfall runoff and flow route. CONCLUSIONS: Glyphosate use in a watershed results in some occurrence in surface water; however, the watersheds most at risk for the offsite transport of glyphosate are those with high application rates, rainfall that results in overland runoff and a flow route that does not include transport through the soil. Copyright © 2011 Society of Chemical Industry     

Movement of pendimethalin,ioxynil and soil particles to field drainage tiles

Knowledge of the movement of herbicides and soil particles to sub-surface tile drainage may help to predict chemical leaching to surface waters and deeper groundwater systems. The movement of pendimethalin (2 years), ioxynil (1 year) and soil particles (3 years) to two tile drains was investigated on a sandy loam soil under natural weather conditions. Herbicide and particle concentrations in the drain water showed a very dynamic pattern. The largest herbicide concentrations were detected during the first tile drain flow events after application. Very little herbicide was lost with drain water later than 2 months after application. The turbidity, reflecting concentrations of soil particles, correlated positively and strongly with the pendimethalin concentration and negatively with the rate of drain water discharge, whereas it was uncorrelated with the ioxynil concentration. Peak turbidity values occurred during or shortly after rainfall events, either in break of frost situations, or on unfrozen soil coinciding with the occurrence of peak moisture contents in the topsoil well (3-7%) above field capacity. On average, 0.0013% of the applied pendimethalin and 0.0015% of the applied ioxynil were lost with drain water. The results suggest that preferential flow promotes the movement of all three substances to the tile drains but indicate somewhat different transport mechanisms for the two herbicides.     

Identification of key climatic factors regulating the transport of pesticides in leaching and to tile drains

BACKGROUND: Key climatic factors influencing the transport of pesticides to drains and to depth were identified. Climatic characteristics such as the timing of rainfall in relation to pesticide application may be more critical than average annual temperature and rainfall. The fate of three pesticides was simulated in nine contrasting soil types for two seasons, five application dates and six synthetic weather data series using the MACRO model, and predicted cumulative pesticide loads were analysed using statistical methods. RESULTS: Classification trees and Pearson correlations indicated that simulated losses in excess of 75th percentile values (0.046 mg m(-2) for leaching, 0.042 mg m(-2) for drainage) generally occurred with large rainfall events following autumn application on clay soils, for both leaching and drainage scenarios. The amount and timing of winter rainfall were important factors, whatever the application period, and these interacted strongly with soil texture and pesticide mobility and persistence. Winter rainfall primarily influenced losses of less mobile and more persistent compounds, while short-term rainfall and temperature controlled leaching of the more mobile pesticides. CONCLUSIONS: Numerous climatic characteristics influenced pesticide loss, including the amount of precipitation as well as the timing of rainfall and extreme events in relation to application date. Information regarding the relative influence of the climatic characteristics evaluated here can support the development of a climatic zonation for European-scale risk assessment for pesticide fate.     

不同粘粒含量土壤水分入渗能力模拟试验研究

为研究土壤粘粒含量对土壤入渗能力的影响,通过向自然土壤中添加沙粒、人工粘土的方法配制不同粘粒含量土壤,用土柱积水入渗模拟了人工配制土壤中粘粒含量对其入渗能力的影响.结果表明:(1) 土壤粘粒含量对土壤入渗能力有较大影响,随粘粒含量增多,入渗能力递减:＜0.001 mm粘粒含量从6%增加至40.4%时,稳定入渗速率从0.0169 cm/min降低至0.0068 cm/min,90 min累积入渗量则从3.66 cm降低至2.02 cm;(2) 稳定入渗速率、90 min累积入渗量与粘粒及物理性粘粒含量分别呈幂函数负相关、指数负相关关系,但与粘粒含量相关性更为显著;(3) 通过对Green-Ampt模型、Philip模型及Kostiakov模型的参数拟合及累积入渗量计算,发现在本试验中Kostiakov模型拟合精度最高,Philip模型次之,Green-Ampt模型较差,说明Kostiakov模型对于均质土体是个比较实用的入渗模型.     

农药污染土壤的植物修复研究

植物可以吸收、转移元素和化合物,可以积累、代谢和稳定污染物,具修复被污染土壤等作用值得关注。本文综述了植物修复被农药污染土壤的机理和研究现状,列举了修复各种有机污染物的典型植物,及对此方法存在的问题和发展前景作了相应的讨论。     

Study of pesticides in waters from a chalk catchment,cambridgeshire

WRc are undertaking a long term study of pesticides in the aquatic environment. A study of the pesticides in the rain, river water and groundwater of the Granta catchment in Cambridgeshire is now in its fourth year. Preliminary results are presented and the concentrations of agricultural pesticides in environmental waters are related to the land-use within the catchment. The Granta study is incomplete but certain anomalies in pesticide occurrence can be identified. In particular, the triazines are much more prevalent in the groundwaters than their agricultural usage would lead one to expect. The limited data base gives problems with modelling the contaminant transport in groundwater. The present situation is reviewed and areas of future work necessary to fulfil the modelling needs identified. These areas of study. The historical land-use and pesticide usage; the groundwater quality data base; the pesticide transport in the unsaturated zone.     

On-farm management practices to minimise off-site movement of pesticides from furrow irrigation

Off-site movement of pesticides from furrow-irrigated agriculture has been a concern in the Ord River Irrigation Area, Western Australia. This paper reports on the effectiveness of incorporation of pesticides by cultivator or power harrows before irrigating, and spraying pesticides only onto beds to minimise off-site transport. Incorporation of pesticides by power harrows prior to irrigation was found to be more effective in decreasing the off-site transport of a more strongly sorbed pesticide, endosulfan. The average load of total endosulfan (alpha + beta + sulfate) decreased by 74% (P < 0.01) from 11.41 g ha(-1) from the conventionally treated bays to 2.96 g ha(-1) from the incorporated irrigation bays. The total average load of atrazine leaving the irrigation bays was decreased by 81% (P < 0.05) from 87.82 g ha(-1) under the conventional practice of spraying the whole field to 16.95 g ha(-1) by spraying the beds only. A reduction of 52% in total average load of metolachlor was observed following incorporation with power harrows, but this was not significant. Incorporation by cultivator or by power harrows decreased the total load of atrazine or metolachlor leaving the irrigation bays over the whole irrigation period, but these treatments were not shown to be statistically significant, which may have been due to the limited number of field replicates. Incorporation of strongly sorbed pesticides (e.g. endosulfan) prior to irrigation significantly decreased the off-site transport of these pesticides in a furrow irrigation system and may be a useful practice to minimise off-site transport of other similar pesticides. Minimising off-site transport of weakly sorbed pesticides (e.g. atrazine and metolachlor) from a furrow irrigation system is more difficult. The nature of furrow irrigation makes it highly conducive to pesticide transport, particularly of weakly sorbed pesticides, and further work is needed to develop strategies to minimise the movement of this group of pesticides to water bodies.     

Risk assessment of dietary exposure to pesticides using a Bayesian method

Risk assessment of pesticides can be a statistically difficult problem because pesticides occur only occasionally, but they may occur on multiple components in the diet. A Bayesian statistical model is presented which incorporates multivariate modelling of food consumption and modelling of pesticide measurements which are for a large part below a measurement threshold. It is shown that Bayesian modelling is feasible for a limited number of food components, and that in a data-rich situation the model compares well with an empirical Monte Carlo modelling.     

农药对害虫天敌的Hormesis效应研究进展

低剂量有毒物质引起的Hormesis效应是毒理学研究的热点问题。近年来,农药对害虫天敌的Hormesis效应引起了研究人员的广泛关注。本文就低剂量农药对天敌发育历期、体重、雌虫生殖率及对天敌控害能力的Hormesis效应及其机制进行了简要总结,并讨论了今后的研究方向。旨在为协调害虫综合防治中生物防治与化学防治的矛盾提供新的思路。