Are honeybees suitable surrogates for use in pesticide risk assessment for non‐Apis bees?

Historically, bee regulatory risk assessment for pesticides has centred on the European honeybee (Apis mellifera), primarily due to its availability and adaptability to laboratory conditions. Recently, there have been efforts to develop a battery of laboratory toxicity tests for a range of non‐Apis bee species to directly assess the risk to them. However, it is not clear whether the substantial investment associated with the development and implementation of such routine screening will actually improve the level of protection of non‐Apis bees. We argue, using published acute toxicity data from a range of bee species and standard regulatory exposure scenarios, that current first‐tier honeybee acute risk assessment schemes utilised by regulatory authorities are protective of other bee species and further tests should be conducted only in cases of concern. We propose similar analysis of alternative exposure scenarios (chronic and developmental) once reliable data for non‐Apis bees are available to expand our approach to these scenarios. In addition, we propose that in silico (simulation) approaches can then be used to address population‐level effects in more field‐realistic scenarios. Such an approach could lead to a protective, but also workable, risk assessment for non‐Apis species while contributing to pollination security in agricultural landscapes around the globe. © 2019 Society of Chemical Industry     

Modelling approaches to compare sorption and degradation of metsulfuron-methyl in laboratory micro-lysimeter and batch experiments

Results of laboratory batch studies often differ from those of outdoor lysimeter or field plot experiments--with respect to degradation as well as sorption. Laboratory micro-lysimeters are a useful device for closing the gap between laboratory and field by both including relevant transport processes in undisturbed soil columns and allowing controlled boundary conditions. In this study, sorption and degradation of the herbicide metsulfuron-methyl in a loamy silt soil were investigated by applying inverse modelling techniques to data sets from different experimental approaches under laboratory conditions at a temperature of 10 degrees C: first, batch-degradation studies and, second, column experiments with undisturbed soil cores (28 cm length x 21 cm diameter). The column experiments included leachate and soil profile analysis at two different run times. A sequential extraction method was applied in both study parts in order to determine different binding states of the test item within the soil. Data were modelled using ModelMaker and Hydrus-1D/2D. Metsulfuron-methyl half-life in the batch-experiments (t1/2 = 66 days) was shown to be about four times higher than in the micro-lysimeter studies (t1/2 about 17 days). Kinetic sorption was found to be a significant process both in batch and column experiments. Applying the one-rate-two-site kinetic sorption model to the sequential extraction data, it was possible to associate the stronger bonded fraction of metsulfuron-methyl with its kinetically sorbed fraction in the model. Although the columns exhibited strong significance of multi-domain flow (soil heterogeneity), the comparison between bromide and metsulfuron-methyl leaching and profile data showed clear evidence for kinetic sorption effects. The use of soil profile data had significant impact on parameter estimates concerning sorption and degradation. The simulated leaching of metsulfuron-methyl as it resulted from parameter estimation was shown to decrease when soil profile data were considered in the parameter estimation procedure. Moreover, it was shown that the significance of kinetic sorption can only be demonstrated by the additional use of soil profile data in parameter estimation. Thus, the exclusive use of efflux data from leaching experiments at any scale can lead to fundamental misunderstandings of the underlying processes.     

Some physicochemical and environmental factors affecting transformation rates and sorption of the herbicide metamitron in soil

In addition to the molecular structure of a pesticide, environmental conditions may influence its persistence through their effect on the growth and activity of pesticide-degrading micro-organisms. As a result, transformation rates may decrease rapidly when a compound is leached into subsoil. Metamitron sorption isotherms were determined and incubation series were set up for a sandy loam soil, simulating single and combination effects that occur during transport of metamitron into subsoils. K_OC values increased with increasing depth from 185 to 700 litre kg⁻¹. A combination of conditions that are unfavourable for microbial activity, such as low temperature (5°C), low concentrations (0·5 mg kg⁻¹) and a large sorbed fraction (K_OC = 700) resulted in half-lives of over one year. Oxygen inhibition decreased the transformation rate of metamitron from 0·058 to 0·019 day⁻¹. In order of significance, the transformation of metamitron appears to be a function of temperature, oxygen availability and sorption to organic carbon. Increasing doses did not change transformation rates significantly, although different transformation pathways were observed.     

几种农药在露地黄瓜上的残留降解动态检测研究

研究了在露地黄瓜栽培中。喷施毒死蜱、甲氰菊酯、氯氰菊酯、吡虫啉、百菌清、甲基硫菌灵和王铜等农药的残留降解动态。结果表明,不同农药在黄瓜果实中的残留量和降解速度有很大差异。在杀虫剂中．甲氰菊酯在喷药后第1d的残留量最大,其后的降解速度较快;毒死蜱残留量位居第二,其降解速度比较稳定;氯氰菊酯在喷药后第1d的残留量超过标准．但第3d以后就检测不到其残留：吡虫啉在施药后第1d的残留量最低,降解速度也比较稳定。在杀菌剂中．甲基硫菌灵的降解速度较快,百菌清和王铜的降解速度较慢。无论是杀虫剂还是杀菌剂,施药后在黄瓜上的残留量随喷药时间的推移而减少。     

Behaviour of sulcotrione and mesotrione in two soils

The behaviour of sulcotrione, a recently introduced triketone herbicide, in various soil types was studied under laboratory conditions. In particular, degradation and sorption processes were examined on Ghent and Perpignan soils. Kinetics showed that the degradation of sulcotrione was influenced by biotic and/or abiotic factors. Half-lives ranged between 45 and 65 days. Among the degradation compounds identified were 1,3-cyclohexanedione (CHD) and 2-chloro-4-mesyl benzoic acid (CMBA), previously described as hydrolysis products, and, under special conditions, a derivative of phenylheptanoic acid (PHD). This new degradation product suggested that sulcotrione could follow two possible pathways in the soil, as in water. During the sorption study, a moderate retention of sulcotrione and CMBA relative to CHD and PHD, which were highly adsorbed whatever the soil type, was reported. Experiments carried out under the same conditions for sulcotrione and mesotrione, another triketone herbicide recommended in maize culture, made it possible to compare the two triketones and to conclude that they exhibited relatively similar behaviour in the soil, i.e. that their leaching potential needs to be properly addressed and risks evaluated. Copyright (c) 2007 Society of Chemical Industry.     

几种高级氧化技术在农药废水处理中的应用研究进展

综述了光催化氧化(photocatalytic oxidation)、臭氧氧化(ozonation,O3)、芬顿试剂氧化(fenton reagent oxidation)等高级氧化技术以及它们的组合技术在农药废水处理中的应用研究进展,比较分析了各种高级氧化技术的特点与处理效果。 就处理效果而言,通常情况下,UV(ultraviolet)/Fenton法＞UV/H2O2/Fe3+＞UV/H2O2＞UV/O3＞Fenton、O3、UV法,其中UV/Fenton法对农药等难降解的有机污染物的降解具有较大的潜力。同时介绍了几种高级氧化技术的经济成本分析方法,分析了目前高级氧化技术应用研究中存在的不足及今后研究中需进一步关注的问题。     

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。     

Sorption–desorption of 'aged' isoxaflutole and diketonitrile degradate in soil

Isoxaflutole is a relatively new herbicide used for weed control in maize. The objective of this research was to increase the understanding of the behaviour and environmental fate of isoxaflutole and its diketonitrile (DKN) degradate in soil, including determination of the strength of sorption to soil and whether sorption is affected by ageing. In sandy loam (SL) and silty clay (SiCl) soils, ¹⁴C‐isoxaflutole was found to dissipate rapidly after application to soil; recovery ranged from ～42% to 68% at week 0, and recovery had decreased to <10% at week 12. Decreases in ¹⁴C isoxaflutole residues over time in SL and SiCl soils are consistent with hydrolysis of isoxaflutole and formation of bound DKN residues in the soil. DKN recovery from freshly treated SiCl and SL soils was 41% to 52%. After a 12‐week incubation in SL soil at pH 7.1 and 8.0, recoveries were similar, ～40%. However, at week 12 in SL soil pH 5.7, DKN recovery decreased to ～28%. DKN recovery in SiCl soil at week 12 was <10%. Increases in sorption of DKN in SL at pH 5.7 and SiCl soil over time indicate that the DKN degradate is tightly bound to the soil and sorption is affected by soil pH and soil type. Sorption of ¹⁴C‐DKN in the SiCl soil more than doubled with ageing compared with the lower K_d sorption coefficient values of the SL soils. In the SiCl soil at time 0, the K_d was 0.6; at 1 week, K_d increased to 2; and at the end of the 12‐week incubation period, K_d was 4.5. This strong binding of DKN to the soil may be due to chelate formation in the interlayer of the clay.