Justificación

sampler data was helpful for verifying model setup of application field connectivity.

MO129

Recalibration and cross-validation of pesticide trapping efficiency equations for vegetative filter strips (VFS) using additional experimental data

S. Reichenberger, DR. KNOELL CONSULT GmbH / Environmental Fate / Modelling / GIS; R. Sur, Bayer AG - Crop Science Division / Environmental Safety; C. Kley, Bayer AG Crop Science Division; S. Sittig, DR. KNOELL CONSULT GmbH / E-Fate Modelling; S. Multsch, DR. KNOELL CONSULT GmbH

Vegetative filter strips (VFS) are widely used for mitigating pesticide inputs into surface waters via surface runoff and erosion. To simulate the effectiveness of VFS in reducing surface runoff volumes, eroded sediment and pesticide loads the model VFSMOD (Muñoz-Carpena and Parsons, 2014) is frequently used. While VFSMOD simulates infiltration and sedimentation mechanistically, the reduction of pesticide load in surface runoff by the VFS (deltaP) is calculated with the empirical multiple regression equation of Sabbagh et al. (2009). This equation uses the following inputs: predicted reduction of total inflow (deltaQ) and eroded sediment load (deltaE), absolute surface runoff volume and eroded sediment load entering the VFS, linear adsorption coefficient Kd of the pesticide, and the clay content of the field soil (as a proxy for the clay content of the eroded sediment). The Sabbagh et al. (2009) equation, the coefficients of which were obtained by calibration against 47 data points, has not been widely accepted by regulatory authorities, on the grounds that its reliability has not been sufficiently established yet. Hence, evaluation against additional experimental data is necessary. Chen et al. (2016) proposed an alternative regression equation with a different structure based on 181 experimental data points. This equation uses fewer independent variables, but has more parameters than the Sabbagh equation. The objective of the present study was to improve the predictive capability of the Sabbagh et al. equation by broadening the underlying experimental data. For this aim, additional experimental VFS datasets were compiled from the available literature and thoroughly checked for their suitability. Moreover, existing errors in the calibration and validation data points of Sabbagh et al. (2009) were corrected. The consolidated experimental dataset (n = 244) was used to recalibrate the Sabbagh and Chen equations. Moreover, a k-fold cross validation analysis was performed to assess the predictive capability of both models. The Sabbagh equation fitted the whole dataset slightly better than the Chen equation (r2 _{= 0.82 vs. r}2 _{= 0.79) and performed consistently} better in the cross-validation exercise (with respect to the prediction performance indicators Q2_{, predictive r}2_{, and RMSEP). Finally, a maximum-likelihood-based} calibration and uncertainty analysis were performed for the Sabbagh equation using the DREAM algorithm.

MO130

VandA - Visualize and Assess: a tool for the pesticide risk mitigation in surface water

F. Galimberti, G. Azimonti, ICPS International Centre for Pesticides and Health Risk Prevention / Public Health; A. Moretto, Università degli Studi di Milano The Directive 2009/128/CE of European Parliament and Council on Sustainable Use of Pesticides introduced a community action framework to protect the Environment of the EU and requested Member States to implement policies and actions in order to reduce the risk of pesticide use. In the Region of Lombardy, in Italy, this Directive was adopted with DGR n. X/3233. The aim of the present work is to develop an innovative, easy to use tool to visualize the pesticide surface water contamination, assess the potential pesticide risk and identify areas where to introduce mitigation measures to reduce the contamination, and consequently to reduce the risk in the surface water compartment. The datasets to start with are the monitored concentrations of pesticides in surface water, produced by the Regional EPA. These values are used in this context as Measured Environmental

Concentration - MEC. . The ratio MEC/PNEC is proposed in this work as a sort of risk assessment, even though the limitation and the complexity of usage of monitored data is well known. In addition, the ratio MEC/EQS - Environmental Qualitative Standard (annual average concentration), is considered, to address the water quality with respect to the regulattory limit for pesticides in surface water (Directive 2000/60/EC). A MS Excel tool has been developed to map the monitored residues of pesticides, assess the potential pesticide risk (MEC/PNEC) and identify “hot spots”, thet is areas where mitigation measures should be included. The tool is thought to be an anyone-can-use one, even with no particular knowledge of GIS or database management. Its peculiarity to be built inside MS Excel gives itself the possibility to share and to ease the dissemination of results. For more advanced mapping, the tool can interact with ESRI ArcGIS. The openness of VandA makes it a tool suitable to work with other environmental compartments or other

environmental thematics.

MO131

Selecting application dates for UK higher tier drainflow modelling:

comparing the FOCUS PAT and CRD PAT rules, and assessing the role of soil trafficability

J. Carnall, G. Hughes, Cambridge Environmental Assessments; J.A. Hingston, J. Evans, Chemicals Regulation Division

Pesticide losses via drainflow are strongly dependent on the soil moisture status at the time of application and the rainfall pattern that follows application. For drainflow simulations, the choice of application date can therefore have a significant influence on predicted environmental concentrations. To standardise the selection of application dates, the FOCUS surface water models include a calculator tool, the Pesticide Application Timer (FOCUS PAT), which selects an application date from a window defined by the user by applying a set of rules to the daily rainfall data used in the simulation. Alternative criteria for selecting application dates for drainflow simulations were proposed by Brown et al. (2004; Pest Manag Sci. 2004 Aug; 60(8); 765-76), and incorporated into a modelling tool developed recently by the HSE’s Chemicals Regulation Division (CRD) for performing UK higher tier drainflow assessments using the MACRO model. Under these rules (referred to herein as CRD PAT) a different set of criteria is applied to the daily rainfall data, with the algorithm selecting the first compliant date on or after a particular target day. Both the FOCUS PAT and CRD PAT algorithms select pesticide application dates based on daily rainfall volumes. In practice, however, application dates can be constrained significantly by the trafficability of the soil. Product GAPs are designed to cover a wide range of application periods to account for seasonal variation, e.g. in dry springs applications might take place in March while in wetter years, when it is more difficult to traffic wet soils, they may take place in April or even early May. When conducting multi-year modelling risk assessments this nuance is often lost from the risk assessment, and applications are forced into months when farmers would not have been able to travel their lands and apply crop protection products. Using a soil moisture deficit based approach to defining soil trafficability, the CRD and FOCUS pesticide application timing algorithms were modified to account for this agronomic restriction. In this poster, the results from the four approaches – namely CRD PAT, FOCUS PAT, CRD Traffic PAT and FOCUS Traffic PAT – are contrasted and compared, with a view to drawing conclusions for the standard and refined UK higher tier drainflow risk assessment process.

MO132

Considering diffuse urban and agricultural sources of pesticides at the landscape and catchment scale

G. Hughes, J. Carnall, Cambridge Environmental Assessments; F. Ericher, CEA For plant protection products (PPPs), there is a strong move towards landscape and catchment scale risk assessments as this allows for integrated risk assessments that consider multiple sources of pollutants, different exposure pathways as well as different receptors within a single framework. This landscape/catchment approach moves away from realistic worst case scenarios, designed to be protective of a wide range of usage situations, to a more realistic representation of usage environments that the risk assessment is trying to protect. Two important diffuse sources of pesticide residues emitted to surface water bodies are from urban and agricultural uses. At present these sources are risk-assessed using very different scenario-based approaches in isolation. Using a multi-disciplinary approach drawing on landscape implementations of the FOCUSsw scenarios to describe possible agricultural sources and an urban emission model to describe possible hard surface usage, this poster considers the likely spatial and temporal coincidence of these different sources of pesticide residues. The need for these two sources to be considered jointly within landscape and catchment scale risk assessments and the possible implications are discussed.

MO133

Calibration of passive samplers for the monitoring of chlordecone in French Caribbean rivers

N. Tapie, Univ. Bordeaux, CNRS, EPOC UMR 5805 / EPOC UMR 5805; T. Risser, Univ. Pau et des Pays Adour, CNRS / IPREM UMR 5254; A. Haouisse, Univ. des Antilles / UMR BOREA UA-CNRS7208-IRD207-MNHN-UPMC-UCN; P. Pardon, UMR CNRS EPOC Universite Bordeaux / EPOC UMR 5805; B. Lauga, Pau et des Pays Adour, CNRS / IPREM UMR 5254; D. Monti, Univ. des Antilles / UMR BOREA UA-CNRS7208-IRD207-MNHN-UPMC-UCN; H. Budzinski, University of Bordeaux

The uncertainty of the tropical weather in the French Caribbean makes spot sampling of chlordecone obsolete and new approaches should be explored to monitor the fate of this molecule in the aquatic system. Here, three types of integrative samplers, differing by their membrane, were calibrated in laboratory and on field for 14 days for the molecule chlordecone: the classical POCIS (Polar Organic Chemical Integrative Sampler) (with Polyethersulfone membranes), the POCISny 30µm (with nylon membranes), and the POCISny 0.1µm. Calculated sampling rates (Rs) were corrected by a PRC ( Performance Reference Compounds) approach. Laboratory calibration was done in triplicates under a continuous flow system, and the field calibration was done in triplicates in river Capesterre (Guadeloupe, French Caribbean). Rs in laboratory calibration were 0.30±0.02 L.day-1 _{for the POCIS, 0.09±0.01 L.day}-1 _{for the POCISny 0.1µm and} 1.54±1.38 L.day-1 _{for the POCISny 30µm. Two distinct Rs have been calculated for} the POCIS and the POCISny 0.1µm: one for the first five days of the experiment (Rs= 0.19±0.01 L.day-1 _{for POCIS; Rs= 0.48±0.50 L.day}-1 _{for NOCIS 0.1µm), and} one for the overall experiment (Rs= 0.19±0.02 L.day-1 _{for POCIS; Rs= 0.43±0.01} L.day-1_{). POCISny 30µm followed the same pattern than in the laboratory} calibration and reached equilibrium after 3 days, with a Rs significantly higher than

in the laboratory calibration (Rs=4.82 ±1.93 L.j-1_{). POCIS and POCISny samplers} can accumulate chlordecone efficiently despite its hydrophobic properties. POCIS 30µm seem to be a useful tool to monitor short flash floods, which happen regularly in this area.

MO134

Temporal patterns of pesticide residues in four major river basins in Korea

C. Kim, K. Son, Y. Ihm, H. Lee, National Institute of Agricultural Sciences / Department of Agro-food Safety & Crop Protection

To evaluate residues of environmental concerned pesticides which mainly include pesticides used for rice cultivation, total ninety four sampling sites were selected through main streams and branch streams of four major river basins. And the water samples at these sites were collected four times per year, April, May-June, July-August, and September-October or November-December in 2012 and 2014. Besides, the water samples at sites of Keum, Mangyung and Dongjin rivers belong to the Keum river basin were regularly collected with a month interval, especially biweekly from May to August in 2013. Of the pesticides monitored, fenoxanil, hexaconazole, isoprothiolane, iprobenfos and thifluzamide as fungicides were mainly detected in rice season. While other fungicides including diniconazole, propiconazole, fenarimol, nuarimol and boscalid, were detected with low frequencies and their average residue levels in positive samples were also fairly low. Of the insecticides monitored, some organophosphoruses, cadusafos, diazinon, fenitrothion, fenthion, phenthoate and prothiofos, two carbamates, carbofuran and fenobucarb, and endosulfan were detected with low frequencies and low residue levels. Of the herbicides monitored, nine pesticides which include alachlor, butachlor, dimethametryn, dithiopyr, ethalfluralin, metolachlr, oxadiazon, simetryn and thiobencarb were detected with frequencies of 1-48% and in their residue level of 0.01-1.9 μg/L. Detection frequencies and residue levels of insecticides and herbicides were the highest in waters sampled in May and June. Almost pesticides detected were for the rice plants and their residue levels were very low to compare with standard values.

MO135

Occurrence of 14 representative pesticides in surface and ground waters of the State of São Paulo, the biggest sugarcane producer in Brazil

R.D. Acayaba, SCHOOL OF TECHNOLOGY UNICAMP; C. Raimundo, UNICAMP / Institute of Chemistry; A. de Albuquerque, G. Umbuzeiro, School of Technology, UNICAMP / LAEG

São Paulo State is the biggest sugarcane producer in Brazil and the second at pesticide consumption. The aim of this project was to develop a method to determine the presence of 14 pesticides representative from sugarcane plantation, 7 herbicides (simazine, atrazine, ametryn, clomazone, diuron, hexazinone and tebuthiuron), 3 fungicides (azoxystrobin, carbendazim and tebuconazole), 3 insecticides (carbofuran, imidacloprid and malathion) and 1 transformation product (atrazine-2-hydroxy) in surface and ground waters using liquid chromatography tandem-mass spectrometry (LC(ESI)MS/MS) and solid phase extraction as sample preparation. Limits of detection (LOD) and quantification (LOQ) were ranged from 0.9 to 22 ng L-1 _{and from 2.8 to 74 ng L}-1_{, respectively, and mean recovery was 66} %, which allowed obtaining a sensitive and accurate method for the determination at trace levels. In total, 196 samples located in the main sugarcane area from São Paulo were analyzed (175 surface waters and 21 groundwaters) between October/2015 to October/2016. The most frequently detected pesticides in surface water were atrazine-2-hydroxy (100%), diuron (94%), carbendazim (93%), tebuthiuron (92%), hexazinone (91%), imidacloprid (96%) and ametryn (81%). The pesticide that presented the highest concentration for this matrix was imidacloprid, reaching 2579 ng L-1_{. The risk to aquatic life were evaluated dividing the maximum} environmental concentration of each pesticide by the lowest water quality criteria found in the literature. The potential risk for aquatic life was observed for imidacloprid, carbendazim, atrazine and malathion. For the groundwaters the most frequently detected pesticides were atrazine-2-hydroxy (24%), imidacloprid (14%), carbendazim (10%), tebuthiuron (10%), atrazine (10%) and diuron (10%). The pesticide that presented the highest concentration for this matrix was tebuthiuron, reaching 107 ng L-1_.

MO136

Exposure scenarios for aquatic risk assessment of pesticides in Brazil

B. Jene, BASF SE / Environmental Fate; R.P. SCORZA JUNIOR, Embrapa / EMBRAPA AGROPECUARIA OESTE; D. Máximo, R. Rebelo, IBAMA / DIQUA / CGASQ; A.V. Waichman, Universidade Federal do Amazonas; N. Peranginangin, Syngenta Crop Protection, LLC / Product Safety; A. Tornisielo, BASF SA / GENCS - E-Fate; L. Murakami, Bayer AG Crop Science Division; O. Perez-Ovilla, Bayer CropScience / Environmental Safety; E. Henry, Bayer / Environmental Safety; T. Haering, BASF SE

A tri-partite technical working group consisting of regulators, academia and industry was formed to develop a framework for aquatic risk assessment of pesticides in Brazil. The framework should include a sophisticated science based approach resulting in a comprehensive guidance. The basis of the exposure assessment is the selection of the 90th _{percentile vulnerability which is seen to} represent a reasonable worst case and is used as basis of the exposure assessment in other parts of the world. Surface water scenarios should be identified in six

pre-defined climatic zones for the seven most important crops soybean, maize, sugar cane, wheat, cotton, citrus and coffee. Runoff and spray drift were found to be the main entrance pathways of pesticides into surface water bodies. Whereas spray drift mainly depends on technology and local climatic conditions during

application, surface runoff is influenced by pedoclimatic conditions that could be assessed in a spatial vulnerability analysis. For this the USDA Runoff Curve Number approach (RCN) which is implemented in PRZM was used. A simple model based on the equations of the RCN approach was developed to calculate daily surface water runoff volumes for the agricultural area of Brazil for 34 climatic years. Calculations were carried out on highest available resolution of soil data resulting in more than 63,000 raster cells. Hydrological soil groups were determined by using a Brazilian specific classification scheme applied to the national soil map. Relative runoff vulnerability for pesticides was estimated with an integrated vulnerability index approach where indices for daily runoff such as average annual number of runoff events and average maximum runoff volume of each year were combined with an index for the expected substance concentration in the runoff water based on organic carbon content of the soil. The 90th _percentile relative vulnerability was determined for the relevant crops for each climatic zone to select the relevant surface water scenarios. For the specific crop area, census data on municipality level were used first, but it was decided to switch to satellite images as far as they become available. After discussions in the technical working group the Brazilian environmental authority IBAMA decided to use the US-EPA PWC model for the surface water exposure assessment. Representative flowing and static water bodies which need to be natural and permanent will be defined for each selected scenario.

MO137

Identification of Herbicide Source Areas and Spatial Variability of

Dominating Transport Processes in a High Agricultural Intensity Catchment

H. Rathjens, M.F. Winchell, Stone Environmental, Inc. / Environmental Systems Modeling; R. Sur, Bayer AG - Crop Science Division / Environmental Safety; D. Baets, Bayer AG Crop Science Division / Sustainable Operations; F. Krebs, DR. KNOELL CONSULT GmbH; D. Lembrich, Bayer AG Crop Science Division The occurrence of herbicides in surface waters of intensively cultivated catchments can originate from a variety of sources. These include transport via runoff and erosion during storm events, subsurface transport through lateral flow and through subsurface tile drainages, and from spray drift during applications. The Soil and Water Assessment Tool (SWAT) is widely used in the United States and the EU for catchment scale hydrologic and water quality modeling of non-point source chemicals in the environment. The SWAT model was applied to a 992 ha agricultural catchment in the Flanders region of Belgium to help in better understanding the sources of the herbicide detections observed in daily sampling over 3.5 years at two locations along the catchment’s primary stream. The SWAT model was calibrated to observed flow and chemical monitoring data, then used to characterize the relative contributions of herbicides via surface processes, subsurface processes, and spray drift. In addition, very vulnerable fields with significant contributions to surface water exposure were identified. A quantitative comparison between monitoring data and simulated exposure profiles was made to single out those high residue concentrations that could not be attributed to any of these traditionally considered exposure pathways, and could ultimately be only explained by point source contributions . The model results demonstrates that SWAT is capable of simulating streamflow in a small agricultural catchment, and is capable of simulating diffuse source pesticide concentrations. This allowed application of an approach that incorporated model uncertainty analysis in distinguishing between diffuse source dominated high concentrations from those most likely affected by point sources. The SWAT model also proved useful in identifying the spatial variability in the dominant transport processes contributing pesticide residues to the stream. While surface runoff of soluble pesticide was the major non-point source contributor on most fields, lateral subsurface flow was found to be important as well, especially in the western portion of the catchment. Spray drift is likely the least significant contributor at the catchment scale. Overall, the analysis of monitoring data and modeling results shows that the potential for reducing herbicide concentrations in the study catchment can be addressed by mitigating both point source contributions from farmyards as well as diffuse sources.

MO138

Pesticides in water and surface sediments from Douro River estuary (Portugal) - assessment of environmentally relevant mixtures using acute toxicity bioassays

M. João Rocha, ICBAS U.Porto, CIIMAR CIMAR LA; C. Cruzeiro, CIIMAR CIMAR LA, Porto, CEF FCTUC U.Coimbra; S. Amaral, ICBAS U.Porto; E. Rocha, ICBAS U.Porto, CIIMAR CIMAR LA

The Douro River is an international water river that passes through extensive agricultural fields, of both Portugal and Spain, before reaching the estuary at Porto and Gaia cities. Therefore, the presence of pesticides is suspected. Accordingly, the