Mecoprop, dichlorprop and metolachlor concentrations and enantiomer signatures were determined in Ontario streams in 2006-2007 and compared to results from 2003 to 2004. Median concentrations of dichlorprop and metolachlor were not significantly different between the two campaigns, but mecoprop was higher in 2006-2007. Concentrations of mecoprop and dichlorprop in Lake Ontario surface water were 1-2 orders of magnitude lower than stream averages. Enantiomer fractions (EFs) > 0.5 of mecoprop in high-concentration stream water samples during 2006-2007 were related to replacement of racemic mecoprop by single (+) enantiomer mecoprop-P after 2004. EFs <0.5 in low-concentration samples suggested enantioselective degradation and/or interconversion. Metolachlor profiles were expressed as SF, the fraction of herbicidally active/(active + inactive) stereoisomers. Samples with higher concentrations of metolachlor had SFs similar to S-metolachlor which is enriched in the active stereoisomers. Low concentrations were associated with lower and more variable SFs, suggesting mixed input of racemic and S-metolachlor or stereoselective degradation.

Dichlorprop (2-(2,4-dichlorophenoxy) propionic acid, DCPP), a commonly used herbicide for weed control, can be residually detected in soil. It is still unclear whether chiral DCPP exerts an enantioselective adverse effect on plant metabolism and the microbial community of the phyllosphere. In this study, we selected Arabidopsis thaliana as a model plant to explore the effects of R- and S-DCPP enantiomers on plant physiological activities, metabolism, and associated changes in the phyllosphere microbial community. Results indicated that the fresh weight of plants decreased by 37.6% after R-DCPP treatment, whereas it increased by 7.6% after S-DCPP treatment. The R-DCPP enantiomer also caused stronger disturbance to leaf morphology, mesophyll cell structure, and leaf metabolites compared with S-DCPP. GC–MS analysis of DCPP-treated Arabidopsis leaves pointed out a differential profile mostly in carbohydrates, organic acids, and fatty acids, between S-DCPP and R-DCPP treatments. The diversity of phyllospheric microorganisms decreased and the stability of microbial community in the phyllosphere increased after R-DCPP treatment, whereas the opposite result was detected after S-DCPP exposure. The correlation analysis revealed that chiral herbicides may affect microbial communities in the phyllosphere by influencing leaf metabolism, while sugars and terpenoids were considered the main factors in reshaping the microbial community structure in the phyllosphere. Our study provides a new perspective for evaluating the effect of residual DCPP enantiomers on plant physiology and corresponding phyllosphere microorganism changes via the regulation of leaf metabolism, and clarifies the ecological risk of DCPP enantiomer application in agriculture.

Biofilters have been shown to be efficient for removing pollutants from different water effluents, but little information is available about their capacity to remove highly polar pesticides from agricultural run-off waters. In this study, we assess the capacity of three different biofilter-supporting materials (sand, peat soil, and pine bark) to remove five phenoxyacid herbicides (mecoprop, dicamba, MCPA, dichlorprop and 2,4-D) and five non-ionic pesticides (atrazine, simazine, fenitrotion, diazinon, and alachlor) from real agricultural run-off waters. The experimental design included three columns 120 cm in length and 15 cm in diameter, each filled with 100 cm of one of the selected supporting materials. After 30 days of acclimation, the columns were fed with agricultural run-off water spiked at 10 μg L⁻¹ with each of the studied pesticides for 20 days at a hydraulic loading rate (HLR) of 0.32 m day⁻¹. The results show that the sand filter was the best supporting material for removing phenoxyacid herbicides (77% on average), whereas peat soil and pine bark were best for removing non-ionic pesticides (72% on average). The attenuation of mecoprop and dichlorprop correlated negatively with the enantiomeric fraction. Therefore, this study shows that the use of waste-to-product materials in biofilter systems is a good solution for removing pollutants from agricultural run-off waters.

Vegetated filter strips (VFSs) are planted at the edge of agricultural fields to reduce pesticide run-off and its consequent potential toxicological effects on ecosystem biota; however, little attention has been paid to date to the attenuation of highly polar and ionisable pesticides such as phenoxyacid herbicides. This study assesses the effect of soil moisture, run-off flow and vegetation on the attenuation of MCPA, mecoprop, dicamba, dichlorprop, fenitrothion, atrazine and simazine by VFSs. Reactors measuring 5 m long by 0.1 m wide were each filled with 60 kg of soil from a real field VFS. VFSs planted with Phragmites australis and unvegetated control reactors were assessed. After a simulated rainfall event of 50 mm, two hydraulic loading rates (HLRs) were assessed (1 and 2 cm h⁻¹). These results were compared to those from the same systems under water-saturated conditions. The results show that VFSs reduced the peak inlet concentration and pesticide mass by more than 90 % and that the presence of vegetation increased that attenuation (82–90 % without vegetation and 90–93 % with vegetation, on average). The laboratory-scale study showed that such attenuation was due to sorption into the soil. The toxicity units of pesticides fell by more than 90 % in all cases, except under the water-saturated conditions, in which the decrease was lower (16 vs 54 %, for unvegetated and vegetated reactors). Therefore, the presence of vegetation was shown to be effective for reducing mass discharge of ionisable and highly polar pesticides into surface-water bodies.

Acidic herbicides are used to control broad-leaved weeds. They are stable, water-soluble, and with low binding to soil are found frequently in surface waters, often at concentrations above the EU Drinking Water Directive limit of 0.10 μg L⁻¹. This presents a problem when such waters are abstracted for potable supplies. Understanding their sources, transport and fate in river catchments is important. We developed a new Chemcatcher® passive sampler, comprising a 3M Empore™ anion-exchange disk overlaid with a polyethersulphone membrane, for monitoring acidic herbicides (2,4-D, dicamba, dichlorprop, fluroxypyr, MCPA, MCPB, mecoprop, tricolpyr). Sampler uptake rates (Rₛ = 0.044–0.113 L day⁻¹) were measured in the laboratory. Two field trials using the Chemcatcher® were undertaken in the River Exe catchment, UK. Time-weighted average (TWA) concentrations of the herbicides obtained using the Chemcatcher® were compared with concentrations measured in spot samples of water. The two techniques gave complimentary monitoring data, with the samplers being able to measure stochastic inputs of MCPA and mecoprop occurring in field trial 1. Chemcatcher® detected a large input of MCPA not found by spot sampling during field trial 2. Devices also detected other pesticides and pharmaceuticals with acidic properties. Information obtained using the Chemcatcher® can be used to develop improved risk assessments and catchment management plans and to assess the effectiveness of any mitigation and remediation strategies.

An analytical methodology using automatic thermal desorption (ATD) and GC/MS was developed for the determination of 28 pesticides of different chemical classes (dichlobenil, carbofuran, trifluralin, clopyralid, carbaryl, flazasulfuron, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, cyprodinil, bromoxynil, fluroxypyr, oxadiazon, myclobutanil, buprofezin, picloram, trinexapac-p-ethyl, ioxynil, diflufenican, tebuconazole, bifenthrin, isoxaben, alphacypermethrin, fenoxaprop and tau-fluvalinate) commonly used in nonagricultural areas in atmospheric samples. This methodology was developed to evaluate the indoor and outdoor atmospheric contamination by nonagricultural pesticides. Pesticides were sampled passive sampling tubes containing Tenax® adsorbent. Since most of these pesticides are polar (clopyralid, mecoprop-P, dicamba, 2,4-MCPA, dichlorprop, 2,4-D, triclopyr, bromoxynil, fluroxypyr, picloram, trinexapac-p-ethyl and ioxynil), a derivatisation step is required. For this purpose, a silylation step using N-(t-butyldimethylsilyl)-N-methyltrifluoroacetamide (MtBSTFA) was added before thermal desorption. This agent was chosen since it delivers very specific ions on electronic impact (m/z = M-57). This method was established with special consideration for optimal thermal desorption conditions (desorption temperature, desorb flow and duration; trap heating duration and flow; outlet split), linear ranges, limits of quantification and detection which varied from 0.005 to 10 ng and from 0.001 to 2.5 ng, respectively, for an uncertainty varied from 8 to 30 %. The method was applied in situ to the analysis of passive tubes exposed during herbicide application to an industrial site in east of France.