28 February 2012 FOCUSsw - Part I 1. Regulatory Affairs Product Safety Consulting Training. Are there any unclear things about yesterday?
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1 INTRODUCTION Kathrin Maaßen Studied environmental science in Landau ( ) Diploma thesis: IMPACT OF PESTICIDES IN SMALL STREAMS IN CENTRAL GERMANY (Project of Renja Bereswill) 2009: start working for DR. KNOELL Consult as a free employee 2010: start working for DR. KNOELL Consult as a Projekt Manager for Environmental Fate/Modelling 28 February 2012 FOCUSsw - Part I 1 RECAPITULATION Are there any unclear things about yesterday? PEC gw or PEC soil modelling? 28 February 2012 FOCUSsw - Part I 2
2 RECAPITULATION What about today? Surface water modelling according to FOCUSsw Introduction Step 1&2 - Theory Step 1&2 - Excercise Step 3 - Theory 28 February 2012 FOCUSsw - Part I 3 RECAPITULATION 09:00Daily Kick-off Recapitulation Presentation timetable Recapitulation, Questions 09:30 Theory PECsw Material and Methods (Stepwise approach, Entry pathways) Surface Water Assessment acc. To FOCUS 10:30 Break 10:45 Theory PECsw Steps 1&2 11:30 Step by Step PECsw Introduction Steps1_2 (Presentation GUI Setup Project) Performing excercised and presentation of results 12:30-14:00 Break 14:00 15:00 Theory PECsw General - Scenarios (10 scenarios, standard water bodies, characteristics); Models + entry pathways, PAT) 15:45 Break 16:00Step by Step PECsw FOCUSsw Modelling 17:00 28 February 2012 FOCUSsw - Part I 4
3 Introduction INTRODUCTION Surface Water Modelling according to FOCUS: FOCUS (2001): "FOCUS Surface Water Scenarios in the EU Evaluation Process under 91/414/EEC". Report of the FOCUS Working Group on Surface Water Scenarios, EC Document Reference SANCO/4802/2001-rev pp. 28 February 2012 FOCUSsw - Part I 6
4 INTRODUCTION FOCUS Forum for the coordination of Pesticide Fate Models and their use Initiative of the European Commission to harmonise the calculation of predicted environ-mental concentrations (PEC) of active substances of plant protection products (PPP) in the frame-work of the EU Directive 91/414/EEC. (now replaced by Regulation 1107/2009) FOCUS is based on co-operation between scientists of regulatory agencies, academia and industry. 28 February 2012 FOCUSsw - Part I 7 INTRODUCTION ENTRY PATHWAYS Pesticide application Volatilisation & Re-deposition Degradation on plants and washoff Plant Uptake Spray drift Runoff Soil Degradation Sorption Leaching Drainage Surface water Groundwater Cranfield 28 February 2012 FOCUSsw - Part I 8
5 INTRODUCTION ENTRY PATHWAYS According to Regulation 1107/2009: The factors to be considered in making PEC SW estimations relate to direct application to water, drift, runoff, discharge via drains and atmospheric deposition Atmospheric deposition is usually of minor importance. Thus the FOCUS surface water scenarios group did not consider this route. Three entry routes which are important: o drift, o runof o drainage 28 February 2012 FOCUSsw - Part I 9 INTRODUCTION ENTRY PATHWAYS Spray Drift Drift of pesticides via air into adjacent water bodies DRIF T 28 February 2012 FOCUSsw - Part I 10
6 INTRODUCTION ENTRY PATHWAYS Spray Drift Spray drift values (percentage of PPP reaching the surface water systems depending on distance and crop): Percentage of PPP reaching the surface water systems for given distances represents a worst case (90 th percentile) o Assumption: prevailing wind direction lineal to the surface water systems o Crop specific (arable, vines, orchards, hops, ornamental, railway tracks) Based on Rautmann et al. (2006); 28 February 2012 FOCUSsw - Part I 11 INTRODUCTION ENTRY PATHWAYS Spray Drift Multiple Application The FOCUSsw group has based its drift deposition on the concept that the cumulative drift deposition for the entire application season represents the 90th percentile drift probabilities, i.e. the drift deposition of a single event is lower in case of multiple applications during the season than in case of one single application in the entire application season. The FOCUSsw group recommended that a 90th percentile cumulative drift probability should be used for all drift applications made during a single cropping season acc. to the BBA drift tables (BBA, 2000). Number of applications Drift percentile of a single Event Cumulative drift Percentile for the Season >8 67 (assumed) February 2012 FOCUSsw - Part I 12
7 INTRODUCTION ENTRY PATHWAYS Single Application, based on 90th percentile Tabelle der Abdrifteckwerte für Einfachanwendungen Bodensedimente in % der Aufwandmenge berechnet auf Basis der 90. Perzentile Auszug aus Bundesanzeiger (Stand: 27. März 2006) Ackerbau Obstbau Weinbau Hopfenbau Flächenkulturen Gemüse, Zierpflanzen, Beerenobst (tragbare Spritz- und Sprühgeräte) Gleisanlagen früh spät > 900 l/ha Höhe < 50 cm Höhe < 50 cm mit Spritzschirm Höhe > 50 cm 2,77 4,44 2,77 0,04 29,20 15,73 8,02 19,33 0,011 (bei 2,5 m) 8,02 0,019 0,57 19,89 8,41 3,62 11,57 0,18 0,57 0,01 3,62 0,014 0,29 11,81 3,60 1,23 5,77 0,05 0,29 1,23 0,010 0,20 5,55 1,81 0,65 3,84 0,02 0,20 0,65 0,008 0,15 2,77 1,09 0,42 1,79 0,012 0,15 0,42 0,007 0,10 1,04 0,54 0,22 0,56 0,005 0,10 0,22 0,006 0,07 0,52 0,32 0,14 0,25 0,003 0,07 0,14 0,06 0,30 0,22 0,10 0,13 0,002 0,06 0,10 0, February 2012 FOCUSsw - Part I 13 INTRODUCTION ENTRY PATHWAYS Double Application, based on 82th percentile (2x82th percentile results in overall 90th percentile Tabelle der Abdrifteckwerte für zweimalige Anwendung Bodensedimente in % der Aufwandmenge berechnet auf Basis der 82. Perzentile (Stand: 27. März 2006) Abstand Ackerbau Obstbau Weinbau Hopfenbau Flächenkulturen [m] Gemüse, Zierpflanzen, Beerenobst (tragbare Spritz- und Sprühgeräte) früh spät > 900 l/ha Höhe < 50 cm Höhe > 50 cm 3,78 2,38 1 2, ,53 12,13 7,23 17,73 7,23 5 0,47 16,87 6,81 3,22 9,60 0,16 0,47 3, ,24 9,61 3,11 1,07 4,18 0,04 0,24 1, ,16 5,61 1,58 0,56 2,57 0,02 0,16 0, ,12 2,59 0,90 0,36 1,21 0,011 0,12 0,36 FOCUS sw: 30 0,08 0,87 0,40 0,19 0,38 0,005 0,08 0, ,06 0,40 0,23 0,12 0,17 0,003 0,06 0,12 Seed & granular application: 0 % 50 0,05 0,22 0,15 0,08 0,09 0,002 0,05 0,08 Aerial drift loadings: 33.2 % 28 February 2012 FOCUSsw - Part I 14
8 INTRODUCTION ENTRY PATHWAYS Drainage Transport of pesticides which are bound to soil particles to drains through soil due to erosion events. The drain water flows into surface water. 28 February 2012 FOCUSsw - Part I 15 INTRODUCTION ENTRY PATHWAYS Runoff & Erosion Transport of pesticides which are bound to soil particles due to erosion events into adjacent water bodies 28 February 2012 FOCUSsw - Part I 16
9 CHEMICAL PROCESSES IN AQUATIC ECOSYSTEMS plants suspended particles Sorption Sorption Volatilisation water phase transport degradation sediment particles degradation Sorption liquid phase 28 February 2012 FOCUSsw - Part I 17 INPUT PARAMETER FOR SW MODELLING Environmental-Fate Parameter for the PECsw calculation: molecular mass saturated vapour pressure water solubility adsorption data (KOC; Freundlich Exponent) DT50 soil DT50 water DT50 sediment DT50 total system (DT50 water/sediment system maximum occurrences observed for the metabolite in sw/sediment/soil 28 February 2012 FOCUSsw - Part I 18
10 INPUT PARAMETER FOR SW MODELLING Molecular mass Molecular mass of the active substance Influence on occurence of metabolites (molar mass correction factor = molar mass metabolite / molar mass parent) 28 February 2012 FOCUSsw - Part I 19 INPUT PARAMETER FOR SW MODELLING Saturated vopour pressure Shows the pressure when the substance changes its state of aggregation Substances which have a vapour pressure < 1E-05 Pa have a tendency to show volatilsation 28 February 2012 FOCUSsw - Part I 20
11 INPUT PARAMETER FOR SW MODELLING Adsorption The K OC describes the partition of a substance between the organic particles and the water phase. Substance with high K OC values have a high sorption to the organic particles in soil/sediment. The Freundlich Exponent describes the linearity of the sorption tendency 28 February 2012 FOCUSsw - Part I 21 INPUT PARAMETER FOR SW MODELLING DT50 soil/ water/sediment Time (days) in which 50% of the substance degrade in compartiment (soil; water/sediment) 28 February 2012 FOCUSsw - Part I 22
12 INPUT PARAMETER FOR SW MODELLING Max. Occurence in soil/water/sediment Maximum occurence observed for each compartment (soil/water/sediment); Results of degradation studies 28 February 2012 FOCUSsw - Part I 23 INPUT PARAMETER FOR SW MODELLING GAP GAP = Good Agricultural Practice Relevant information: application rate (g/ha) crop application timing (BBCH-Stadium) application intervall PHI (=Pre Harvest Interval) 28 February 2012 FOCUSsw - Part I 24
13 RISK ASSESSMENT Ecotox endpoint (TER toxicity/exposureratio) Acut/chronic PEC ini / PEC twa assessment factor Organism which is the most sensistive PEC sw /PEC sed Ecotox-Trigger/assessment factor = RAC (regulatory acceptable concentration) 28 February 2012 FOCUSsw - Part I 25 STEP WISE APPROACH ACCORDING TO FOCUS STEP 1: one application; defined scenarios STEP 2: multiple applications; regional difference in europe STEP 3: modelling with defined scenarios STEP 4: refined modelling for specific regions 28 February 2012 FOCUSsw - Part I 26
14 FOCUS MODELS STEP 1/2: Steps 1-2 (Surface water Tool for Exposure Predictions Step 1-2) Step 1 Single application of overall application rate, no interception Step 2 Single or multiple application, differences in timing of application (Mar-May, Jun-Sep, Oct-Feb), northern or southern europe, interception (depending on crop) STEP 3: SWASH (Surface WAter Scenarios Help) mit drei vers. Unterprogrammen Step 3 10 scenarios with realistic combination of climate, crop, soil and agricultural practice application method (ground spray, air blast, ) applicaton timing based on different crops STEP 4: SWAN (Surface Water Assessment enabler) Step 4 reducing of drift entries (buffer strips, drift reducing nozzles) reducing of runoff entries (vegetated filter strips) 28 February 2012 FOCUSsw - Part I 27 FOCUS Steps 1&2 28 February 2012 FOCUSsw - Part I 28
15 STEP 1&2 Modell: Steps 1-2 in FOCUS (Surface water Tool for Exposure Predictions Steps 1&2) worst-case loading (STEP1) loadings based on sequential appliaction patterns (STEP2) no specific climate, crop, topography, soil type The purpose of formalising Step 1 and Step 2 calculations is to harmonise the methods of calculation and to avoid unnecessarily complex exposure assessments for plant protection products for which large safety margins exist even at the earliest steps of evaluation. 28 February 2012 FOCUSsw - Part I 29 Water body Step 1&2 1 : cm 5 cm; 5% oc BD = 0.8 Standard assumptions for water body and sediment Water depth (cm): 30 Sediment depth (cm): 5 Sediment OC (%): 5 Sed. bulk density (g/ml): 0.8 Ratio of field:water body: 10 Effective sediment depth = 1cm 28 February 2012 FOCUSsw - Part I 30
16 Assumptions at Step 1: Entry routes: Spray drift, runoff, drainage Application: the total dose rate is applied as one single application Substance data: DT50 total system, solubility in water, Koc value Use related assumption: spray drift values for a single application 28 February 2012 FOCUSsw - Part I 31 Spray drift in Step 1: BBA (Rautmann) Drift values for one single application Assumption: the total application rate per year is applied on one single spray occasion example: 6 x 30 g/ha is applied as 1 x 180 g/ha 28 February 2012 FOCUSsw - Part I 32
17 Step 1: Drift values for a singe application based on Rautmann (Ganzelmeier) All runoff, drainage and drift entries are occuring at the same day The distribution between water and sediment due to drift occurs one day after the drift loading into surface water according to the Koc of the substance 28 February 2012 FOCUSsw - Part I 33 Step 1: Drift values for a single application based on Rautmann (Ganzelmeier) All runoff, drainage and drift entries are occuring at the same day 28 February 2012 FOCUSsw - Part I 34
18 Runoff/Drainage The runoff/drainage loading into the water body is 10% of the applied pesticide amount. 28 February 2012 FOCUSsw - Part I 35 Partioning to sediment: The distribution between water and sediment due to drift occurs one day after the drift loading into surface water according to the Koc of the substance 28 February 2012 FOCUSsw - Part I 36
19 Partioning to sediment: Partitioning between water and sediment layer depends on the sorption properties (KOC) of the substance Fraction of runoff in water* = W (W + (Seff.oc.Koc)) where: W = mass of water (30g) Seff = mass of sediment available for partition (0.8g) oc = organic carbon content of sediment (0.05) Koc = pesticide organic carbon partition coefficient (cm 3.g -1 ) 28 February 2012 FOCUSsw - Part I 37 Influence of Koc on % of pesticide entering in water column and sediment 28 February 2012 FOCUSsw - Part I 38
20 Results: PEC-values Days 1, 2, 4, 7, 14, 21, 28, 42, 50, 100 PEC sw, PEC sed actual & TWA (time weighted average) 28 February 2012 FOCUSsw - Part I 39 Assumptions in Step 2: Entry routes: spray drift, runoff, drainage Application rate for multiple applications (g/ha) Specification of the season of application (Oct Feb, Mar May, Jun Sep) Substance properties: DT50 total system, solubility in water, Koc value, DT50 soil, DT50 water, DT50 sediment Use related assumptions: spray drift values for multiple applications, interception values Regional specification: Northern and Southern Europe North South 28 February 2012 FOCUSsw - Part I 40
21 Spray drift in Step 2: BBA Drift values for multiple applications (overall 90th percentile values) 28 February 2012 FOCUSsw - Part I February 2012 FOCUSsw - Part I 42
22 28 February 2012 FOCUSsw - Part I 43 Runoff- and drainage loss in Step 2: A runoff and/or drainage event occurs 4 days after the last application 2 5% of the soil residue is lost via runoff or drainage Runoff and drainage losses are a function of pesticide residue, region and season of application 28 February 2012 FOCUSsw - Part I 44
23 Interception Consideration of crop specific interception values crop no interception minimal crop cover intermediate crop cover full canopy BBCH-code * Cereals, spring and winter Citrus Cotton Field beans Grass / alfalfa Hops Legumes Maize Oil seed rape, spring and winter Olives Pome / stone fruit, early and late Potatoes Soybeans Sugar beet Sunflower Tobacco Vegetables, bulb Vegetables, fruiting Vegetables, leafy Vegetables, root Vines, early and late Application, aerial Application, hand (crop < 50 cm and > 50 cm) No drift (incorporation /seed treatment) February 2012 FOCUSsw - Part I 45 Interception Consideration of crop specific interception values crop no interception minimal crop cover intermediate crop cover full canopy BBCH-code * Cereals, spring and winter Citrus Cotton Field beans Grass / alfalfa Hops Legumes Maize Oil seed rape, spring and winter Olives Pome / stone fruit, early and late Potatoes Soybeans Sugar beet Sunflower Tobacco Vegetables, bulb Vegetables, fruiting Vegetables, leafy Vegetables, root Vines, early and late Application, aerial Application, hand (crop < 50 cm and > 50 cm) No drift (incorporation /seed treatment) February 2012 FOCUSsw - Part I 46
24 Results PEC-values Days: 1, 2, 4, 7, 14, 21, 28, 42, 50, 100 PEC sw, PEC sed actual & TWA (time weighted average) 28 February 2012 FOCUSsw - Part I 47 FOCUS Steps 1&2 Step by Step 28 February 2012 FOCUSsw - Part I 48
25 28 February 2012 FOCUSsw - Part I 49 Define a substance 28 February 2012 FOCUSsw - Part I 50
26 Overview substance and application 28 February 2012 FOCUSsw - Part I 51 Parameterisation of the substance 28 February 2012 FOCUSsw - Part I 52
27 Parameterisation of the substance Definition of the GAP 28 February 2012 FOCUSsw - Part I 53 Active substance/metabolite 28 February 2012 FOCUSsw - Part I 54
28 Active substance/metabolite 28 February 2012 FOCUSsw - Part I February 2012 FOCUSsw - Part I 56
29 Yes: new record No : changes in the existing record 28 February 2012 FOCUSsw - Part I 57 FOCUS Steps 1&2 Model output 28 February 2012 FOCUSsw - Part I 58
30 Results for Step 1 28 February 2012 FOCUSsw - Part I 59 Report file 28 February 2012 FOCUSsw - Part I 60
31 Results for Step 2 28 February 2012 FOCUSsw - Part I 61 E-fate parameters 28 February 2012 FOCUSsw - Part I 62
32 Scenario data 28 February 2012 FOCUSsw - Part I 63 Maximum loading for the entry pathways Results: Overall Maxima PECsw or PECsed occuring on which day 28 February 2012 FOCUSsw - Part I 64
33 Detailed Results with twa 28 February 2012 FOCUSsw - Part I 65 Runoff/Drainage entry Drift entry 28 February 2012 FOCUSsw - Part I 66
34 Draingage/Runoff Peak on day 5 Drift peak 28 February 2012 FOCUSsw - Part I 67 GAP: 3 applications with 0.75 kg/ha in pome and stone fruits South/North Europe Application intervall: 7 days BBCH E-Fate Parameter Water solubility: 2.00 mg/l KOC: 1000 L/kg DT50 soil: 1.50 days DT50 water: 2.0 days DT50 sediment: 8.00 days DT50 water/sediment system: 12 days => Create a pesticide.txt => Insert the application data => Results: PECsw (act, twa), PECsed (act, twa) 28 February 2012 FOCUSsw - Part I 68
35 Results: Step 1: Step 2: 28 February 2012 FOCUSsw - Part I 69 GAP: 5 applications with 0.6 kg/ha; Olives, South Europe Application intervall: 14 Tage BBCH E-Fate Parameter: a.i./metabolit1/metabolit2 KOC: 250/150/900 L/kg DT50 soil: 1.5/55/45 Tage Molecular mass: 720/490/590 g/mol Water solubility: 2.0/13.5/16.0 mg/l DT50 Water: 2/20/45 Tage DT50 Sediment: 8.0/45/35 Tage DT50 Water/Sediment System: 10/60/70 Tage Maximum occurrence in soil: -/60/35 % Maximum occurrence in water/sediment: -/25/45 % 28 February 2012 FOCUSsw - Part I 70
36 Results: Step 1: Step 2: a.i. met1 met2 PECsw(µg/L) PECsed (µg/kg) 2.02E E03 a.i. met1 met2 PECsw(µg/L) PECsed (µg/kg) February 2012 FOCUSsw - Part I 71 Lunch 28 February 2012 FOCUSsw - Part I 72
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