Pesticide exposure assessment for surface waters in the EU. Part 2: Determination of statistically based run-off and drainage scenarios for Germany.

BACKGROUND: In order to assess surface water exposure to active substances of plant protection products (PPPs) in the European Union (EU), the FOCUS (FOrum for the Co-ordination of pesticide fate models and their USe) surface water workgroup introduced four run-off and six drainage scenarios for Step 3 of the tiered FOCUSsw approach. These scenarios may not necessarily represent realistic worst-case situations for the different Member States of the EU. Hence, the suitability of the scenarios for risk assessment in the national authorisation procedures is not known. RESULTS: Using Germany as an example, the paper illustrates how national soil-climate scenarios can be developed to model entries of active substances into surface waters from run-off and erosion (using the model PRZM) and from drainage (using the model MACRO). In the authorisation procedure for PPPs on Member State level, such soil-climate scenarios can be used to determine exposure endpoints with a defined overall percentile. CONCLUSION: The approach allows the development of national specific soil-climate scenarios and to calculate percentile-based exposure endpoints. The scenarios have been integrated into a software tool analogous to FOCUS-SWASH which can be used in the future to assess surface water exposure in authorisation procedures of PPPs in Germany. © 2017 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

A simple approach for a spatial terrestrial exposure assessment of the insecticide fenoxycarb, based on a high-resolution landscape analysis.

BACKGROUND: The objective was to refine the standard regulatory exposure scenario used in plant protection product authorisations by developing a more realistic landscape-related GIS-based exposure assessment for terrestrial non-target arthropods. We quantified the proportion of adjacent off-target area in agricultural landscapes potentially exposed to insecticide drift from applications of the active substance fenoxycarb. High-resolution imagery, landscape classification and subsequent stepwise analysis of a whole landscape using drift and interception functions were applied to selected areas in representative fruit-producing regions in Germany. RESULTS: Even under worst-case assumptions regarding treated area, use rate and drift, less than 12% of the non-agricultural habitat area would potentially be exposed to fenoxycarb drift above regulatory acceptable concentrations. Additionally, if the filtering effect of tall vegetation were taken into account, this number would decrease to 6.6%. Further refinements to landscape elements and application conditions indicate that less than 5% of the habitat area might be exposed above regulatory acceptable concentrations, meaning that 95% of the non-agricultural habitat area will be unimpacted (i.e. no unacceptable effects) and can serve as refuge for recolonisation. CONCLUSION: Approaches and tools are proposed for standardisable and transparent refinements in regulatory risk assessments on the landscape level. © 2016 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of 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.

Formation of chlorinated disinfection by-products in viticulture.

BACKGROUND, AIM AND SCOPE: The use of sodium hypochlorite (HYP) in viticulture results in effluents which are contaminated with halogenated substances. These disinfection by-products (DBPs) can be quantified as group parameter 'adsorbable organic halogens' (AOX) and have not been determined in effluents of viticulture yet. The substances that are detected as AOX are unknown. The AOX can be composed of harmless substances, but even toxic contaminants. Thus, it is impossible to assess ecological impacts. The aim of this study is to determine the quantification of AOX and DBPs after the use of HYP. This will be helpful to reduce environmental pollution by AOX. MATERIALS AND METHODS: The potential of HYP to generate AOX was determined in laboratory-scale experiments. Different model solutions were treated with HYP according to disinfection processes in viticulture and conditions of AOX formation in effluents were simulated. AOX were quantified using the flask-shaking method and identified DBPs were investigated by gas chromatography-mass spectrometry. RESULTS: Treatment with HYP resulted in the formation of AOX. The percentage conversion of HYP to AOX was up to 11%. Most important identified DBPs in viticulture are chloroform, dichloroacetic acid and trichloroacetaldehyde. In addition, the formation of carbon tetrachloride (CT), 1,1,1-trichloropropanone, 2,4-dichlorobenzoic acid and 2-chloro-/2,4-dichlorophenylacetic acid was investigated. It was demonstrated that reaction temperature, concentration of HYP and type of organic matter have important influence on the formation of chlorinated DBPs. DISCUSSION: The percentage conversion of HYP to AOX was similar to other published studies. Although a correlation of single compounds and AOX is difficult, chloroform was the predominant AOX. Generation of the volatile chloroform should be avoided due to possible adverse effects. The generation of dichloroacetic acid is of minor importance on account of biodegradation. Trichloroacetaldehyde and 1,1,1-trichloropropanone are weak mutagens and their formation should be avoided. CONCLUSIONS: The generation of AOX and chlorinated DBPs can be minimised by reducing the concentrations of the organic materials in the effluents. The removal of organic matter before disinfection results in a decreased formation of AOX. HYP is an effective disinfectant; therefore, it should be used at low temperatures and concentrations to reduce the amount of AOX. If possible, disinfection should be accomplished by the use of no chlorine-containing agents. By this means, negative influences of HYP on the quality of wine can also be avoided. RECOMMENDATIONS AND PERSPECTIVES: Our results indicate that HYP has a high potential to form AOX in effluents of viticulture. The predominant by-products are chloroform, dichloroacetic acid and trichloroacetaldehyde. In further research, wastewaters from a winery and the in- and outflows of two sewage treatment plants were sampled during vintage and analysed. These results will be discussed in a following paper.

Comparison of wind tunnel and field experiments to measure potential deposition of fenpropimorph following volatilisation from treated crops.

The potential for short-range transport via air, i.e. volatilisation from the area of application and subsequent deposition on adjacent non-target areas, was investigated for the fungicide fenpropimorph in a wind tunnel system and under outdoor conditions in a higher-tier field study. Fenpropimorph 750 g L(-1) EC was applied post-emergence to cereal along with a reference standard lindane EC. Stainless steel containers of water were placed at different distances downwind of the application area to trap volatile residues during a study period of 24 h following application. Meteorological conditions in the wind tunnel as well as on the field were constantly monitored during the study period. The wind tunnel system was a partly standardised system on a semi-field scale, i.e. wind direction and wind speed (2 m s(-1)) were constant, but temperature and humidity varied according to the conditions outside. In the field experiment, the average wind speed over the 24 h study period was 3 m s(-1) and no rainfall occurred. Three different measuring lines were installed on the non-target area beside the treated field to cover potential variations in the wind direction. However, no significant differences were observed since the wind direction was generally constant. Fenpropimorph was detected in minor amounts of 0.01-0.05% of the applied material in the wind tunnel experiment. Even at a distance of 1 m beside the treated field, no significant deposition occurred (0.04% of applied material after 24 h). In the field, less than 0.1% of the applied fenpropimorph was detected at 0 m directly beside the treated field. At 5 m distance the deposition values were below 0.04%, and at 20 m distance about 0.01%. In general, the amounts of deposited fenpropimorph detected in the partly standardised wind tunnel system and the higher-tier field study were in good agreement.

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.

Fate of 14C-bisphenol A in soils.

Bisphenol A (BPA; 2,2-(4,4(')-dihydroxydiphenyl)propane) is predominantly used as an intermediate in the production of polycarbonate plastics and epoxy resins. Traces of BPA released into the environment can reach the soil via application of sewage sludge from wastewater treatment systems that receive wastewaters containing BPA, or from leachate from uncontrolled landfills. The biodegradability of BPA has been previously investigated in several studies designed to simulate surface waters and biological wastewater treatment systems. However, there is little information available about the fate of BPA in soil. Therefore, laboratory soil degradation and batch adsorption studies were conducted with 14C-BPA and four soils according to international guidelines. The soils represented a broad range of physico-chemical properties. An important result of the degradation study was that, independent of the soil type, 14C-BPA was rapidly dissipated and not detectable in soil extracts following 3 days of incubation. Based on this result, a dissipation half-life of less than 3 days was estimated. The major route of dissipation of 14C-BPA in soil was the formation of bound residues that could not be recovered by exhaustive Soxhlet extraction. 14C-BPA was also shown to be transiently converted to up to five metabolites, but within 3 days, neither 14C-BPA nor 14C-metabolites were detectable in the soils. After 120 days incubation, significant amounts (up to 20% of the radioactivity applied) of the parent compound were recovered as 14CO(2). Soil adsorption experiments indicated that the distribution coefficients (K(oc)) were between 636 and 931, classifying BPA as having low mobility for all tested soils. From the results of this study, it was concluded that if BPA reaches the soil compartment, it is not expected to be stable, mobile, or bioavailable.

Fate of (14)C-labeled soybean and corn pesticides in tropical soils of Brazil under laboratory conditions.

The dissipation rate of seven currently used soybean and corn pesticides in two tropical soils (Ustox and Psamments) of Brazil was studied in a laboratory incubation experiment. Dissipation half-lives of pesticides ranged between 2 (monocrotofos) and 90 days (endosulfan-beta). The contrasting clay contents of the studied tropical soils (130 versus 470 g of clay kg(-1) of soil) did not influence the dissipation dynamics of pesticides substantially. Mineralization to CO(2) was high [up to 78% of the applied radioactivity (AR)] for the studied organophosphorus compounds and deltamethrin, which also formed considerable amounts of bound residues (>20% of AR) during the 80 days of incubation. The highest portion of nonextractable residues was found for alachlor and simazine (55-60% of AR). In contrast, the nonpolar trifluralin and endosulfan formed only small amounts of bound residues (mostly <20% of AR) but showed the highest dissipation half-lives (>14 days) in the studied soils, also due to a low mineralization rate. When endosulfan-sulfate, as the main metabolite of endosulfan, was considered, the half-life time of endosulfan compounds (sum of -alpha, -beta, and -sulfate) was enhanced to >160 days in both soils. In comparison with the laboratory experiments, dissipation half-life times of chlorpyrifos, endosulfan-alpha, and trifluralin were shortened by a factor of 10-30 in field trials with the same soils, which was related to the volatilization potential of pesticides from soils.