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User Manual ESCAPE Version 2

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1. estimated to occur after 13 years according to the estimation 95 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Metabolidan over 5 cm considering accumulation mg L a tillage depth of 5 cm was considered for calculating the background concentration 242 250 295 27 00387 34 7779 Calculated time dependent pore water concentrations over 5 cm for Metabolidan mg L considering accumulation Time d 100 PECact PECtwa Begin TWAframe d 34 3407 34 7623 65 32 9533 34 6608 65 31 5900 34 3714 112 31 5817 34 2834 112 31 5551 34 1817 200 31 5269 34 1621 219 31 4870 34 1624 200 33 4692 34 1604 200 34 4479 34 1601 200 34 2359 34 0482 195 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION 40 30 20 c mg L ls ss Bas la ss ln Background concentration of Report example 5 Study soil study 2 Made Parent with I metabohte Testicide PEC TWA 28 d Metabolidan PEC TWA 28 d 500 1000 1500 2000 2500 3000 3500 Time after first application d End TWAframe d 66 67 116 119 214 240 228 242 250 295 ESCAPE Estimation of Soil Concentrations After PEsticide Applications
2. Program version Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode developed by Michael Klein 2 0 17 Feb 2009 17 02 2009 16 24 08 Report example 5 Residues from different applications are considered separately over one year Iteration of annual application pattern over 10 years SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Report example 5 Borstel 1 5 5 5 1 5 29 2 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Day Month Rate g ha Interception 01 05 500 0 10 05 750 25 01 06 600 50 01 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Compound Testicide Metabolidan Active compound and a single metabolite Molecular mass g mol 250 200 100 Formation DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics for Testicide Alpha Beta Q10 factor Walker exponent Ref temperature C Kinetics for Metabolidan DT50 d Rate constant 1 d
3. soil study 1 soil study 2 _ als ll ls ls ls ls ll ls hs 0 5 0 50 100 150 200 250 300 350 Time after first application d 105 6 4 Single application parent compound with metabolite several soil studies Table 6 Series of special times used by ESCAPE to calculate PEC and PECtwa Parameter Soil study 1 Soil study 2 Soil study 3 Soil study 4 soil density kg L 1 5 soil depth cm 5 application rate g ha 1000 crop interception parent molecular mass g mol 250 metabolite molecular mass g mol 200 metabolite formation fraction 1 100 parent degradation data SFO FOMC HS DFOP SFO DT50 d alpha 0 2 beta HS DT501 d HS DT50 2 d 70 HS break point d 10 DFOP DT50 1 d 7 d DFOP DT50 2 d 70 parameter g 0 5 metabolite degradation data SFO SFO SFO SFO SFO rate constant 1 d 35 350 140 14 separate consideration of residues within the year of application only related to standard conditions On the following eight pages copies of the ESCAPE report for all four studies are presented summarising the input data and all important results based on Hamburg climatic conditions and considering soil moisture and temperature correction
4. 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 4 Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 Hamburg Single First order SFO DT50 d 14 Rate constant 1 d 0 0495 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 1 Hamburg Calculations over one year Maximum annual total soil concentration for Report example 1 Hamburg over 5 cm mg kg 1 3333 occurring on day 0 Calculated time dependent total soil concentrations over 5 cm for Report example 1 Hamburg after one year mg kg ge Time d PECact 1 1 3160 2 1 3027 4 1 2655 7 1 2194 14 1 1443 21 0 9966 28 0 8623 42 0 6897 50 0 6137 100 0 2127 PECtwa 1 3247 1 3170 1 3016 1 2761 1 2254 1 1767 1 1121 1 0000 0 9433 0 6556 PECact values are related to the time after the first appl
5. parent compound and two metabolites formed in parallel parent compound and two metabolites formed in a sequence Dependent on the calculation mode not all degradation models presented in chapter 3 1 are available 3 3 1 Simulation considering the parent compound only For the parent compound ESCAPE calculates actual and time weighted average concentrations based on all four kinetic models presented in chapter 3 1 SFO single first order FOMC first order multi compartment DFOP double first order in parallel HS hockey stick In this mode ESCAPE considers a single compartment usually Also if multiple applications are simulated only a single compartment is used and internal counter is always set to 0 after a new application has been released However if multiple applications are to be simulated and the user wants to keep residues from previous applications separately important for the FOMC or the HS kinetics only additional compartments are created for each new application as shown in Figure 5 Within each compartment there is only a single concentration defined per time and there is no transport considered between these compartments The soil concentration is calculated as the sum of all pesticide residues at a given time De compartment 1 residues from application 1 degradation internal counter to tapp1 compartment 2 residues from application 2 degradation internal counter to tapp2
6. 0 9 0 8 0 7 0 6 0 5 0 4 0 3 0 2 0 1 o Annual concentration of Report example 1 Study soil study 2 Made Farem onhe presented subsiance Testade fhinetics FOMC TWA 28d _luluuluuluululunluululudunluluuduluuluuluhundunluluuduududun 200 250 300 350 Time after first application d End TWAframe d 67 ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 12 Feb 2009 Date of this simulation 16 02 2009 11 06 49 Calculation problem Report example 1 PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADA
7. Dependent on the application selected u different further input parameters appear on the form Single application means one application per season regular application means a series of application within a year with constant rates constant crop interception and constant intervals between two simulations Finally irregular applications means a series of applications within a year with different rates different crop interception and or different intervals between these applications Application date g ha If single or regular applications have been selected the user has to type the date if the first application The date is important only if degradation rates are corrected using temperature and soil moisture because then time dependent concentrations are dependent whether substances are applied are in spring or autumn Application rate g ha If single or regular applications have been selected the user has to type the respective application rate here Crop interception If single or regular applications have been selected the user has to type the respective crop interception here Number of applications per year If regular or irregular applications have been selected the user has to type the number of simulations per year using the list box If single applications are selected this field dos not appear on the form If the application shall be repeated annually the check box Repeat applications per year
8. OK the main form of ESCAPE is loaded ESCAPE will automatically estimate soil concentrations based on the information found in the file Programcheck txt saved in the subdirectory input In white input fields results of ESCAPE are always directly updated when an input parameter was changed Fields with yellow background colour are updated until the input was finished by pressing ENTER or moving to another field All input data are presented on the main form and can be modified directly Also part of the results is always presented immediately on the screen e g diagram and or tables showing the time dependent concentrations in soil However a full report with all input data listed and with more detailed output is only created after a click at the report button 4 2 Calculation modes considered by ESCAPE ESCAPE can be used in four different calculation modes parent compound only parent compound and a single metabolite parent compound and two metabolites formed in parallel parent compound and two metabolites formed in a sequence The tabs on the main form can be used to switch between the four modes see the red frame in Figure 13 The number of input parameters on the right part of the main form is influenced by the selection of the calculation mode When the calculation mode has been modified ESCAPE tries to perform a new simulation using the current set of input parameters and creates new diagrams aut
9. PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Report example 3 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Day Month Rate g ha Interception 01 05 500 0 10 05 750 25 01 06 600 50 01 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites Pesticide Report example 3 DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Metabolism scheme Parent compound without metabolites Kinetics for Report example 3 Soil study soil study 1 Single First order SFO DT50 d 25 Rate constant 1 d 0 0277 Q10 factor 2 58 Walker exponent 0 7 TReference C 20 Soil study soil study 2 First Order Multi Compartment FOMC alpha i_studie 1 Beta 1 Q10 factor 2 58 1032 Walker exponent 0 7 TReference C 20 RESULTS OF T
10. has to be used 40 Application table The application table only appears on the form if irregular applications have been selected The user has to type the explicit application dates rates and crop interception for each application here All input must be related to the first year In the following years the application pattern may be repeated dependent on the check box Repeat applications per year 4 3 3 Compound specific parameters The compound specific parameters are organised on three green file cards File card Degradation Degradation kinetics related parameters The degradation of the parent compounds or metabolites can be characterised based on eleven different input parameters Soil For up to six soil studies degradation models for parent compounds or metabolites can be defined This field is to characterise a certain study by comment If more soil studies shall be be considered by ESCAPE the add button has to be used If the name of a study should be modified the user has to press the control key and to click at the list box at the same time The colour of the box changes from white to yellow and a new text can be entered as long as the colour remains yellow Compound At the bottom of the file card the substance to which all degradation data is related to can be selected Dependent on the calculation mode compounds may be deactivated Kinetics ESCAPE considers in total 4 different degrada
11. Applikation rate g ha 1000 Calculation problem Programcheck A ta i PROGRAM SETTINGS Crop interception 2 Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year Compound data Copy Programcheck v Del Sot soil study Add study Degradation Name of the scenario Programcheck Name of the soil Borstel Parent Soil density kg L 15 Kinetics SFO z ps0 a 28 Soil depth cm 5 Tillage depth crn 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 SCENARIO DATA USED IN THE CALCULATION Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 12 2 0 7 20 Annual Rainfall mm 701 aut else To Annual pot Evapotranspiration mm 589 na Metab 2 2 9g for calculation of background concentrations Mi Patent C Me Total content Porewater concentration TWA in graph TWA 28 d v Annual 2 Background Save input Report Exit Current Outputfile Programcheck soil study 1 SFO total soil conc C Accum Figure 20 ESCAPE Working with the menu bar File New Pesticide Record This command can be used to load a new set of standard input data into ESCAPE The necessary information on the standard pesticide data is saved in the text file do not delete this file chn The name of the ne
12. Q10 factor Walker exponent Ref temperature C soil study 2 Active compound and a single metabolite First Order Multi Compartment FOMC 4 4 2 58 0 7 20 Single First order SFO 350 0 002 2 58 0 7 20 128 RESULTS OF THE CALCULATION Metabolism scheme Active compound and a single metabolite RESULTS FOR Testicide Calculations over one year Maximum annual pore water concentration for Testicide over 5 cm mg L 0 5748 occurring on day 9 Calculated time dependent pore water concentrations over 5 cm for Testicide after one year mg L Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 4961 0 5354 9 10 2 0 4537 0 5051 9 11 4 0 4089 0 4688 9 13 7 0 3080 0 4268 8 15 14 0 1279 0 3257 8 22 21 0 1046 0 2936 0 21 28 0 1537 0 2512 0 28 42 0 0886 0 2266 0 42 50 0 0626 0 2068 0 50 100 0 0314 0 1344 0 100 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in pore water for Testicide over 5 cm mg L 0 0026 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Testicide over 5 cm considering accumulation mg L 0 5774 a tillage depth of 5 cm was considered for calculating
13. Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Active compound and a single metabolite 110 RESULTS FOR Testicide Calculations over one year Maximum annual total soil concentration for Testicide over 5 cm mg kg on day 0 Calculated time dependent total soil concentrations over 5 cm for Testicide after one year mg kg Time d 100 PECact 1 1268 1 0469 0 9236 0 8409 0 7616 0 6736 0 6227 0 5741 0 5559 0 4687 PECtwa 1 2301 1 1585 1 0725 0 9893 0 8899 0 8329 0 7854 0 7227 0 6972 0 6000 PECact values are related to the time after the first application Calculation of background concentrations after many years Begin TWAframe d 1 51 ani ie gt Final Background concentration in total soil for Testicide over 5 cm mg kg estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Testicide over 5 cm considering accumulation mg kg a tillage depth of 5 cm was considered for calculating the background concentration 1 3333 occurring End TWAframe d 0 5385 1 8718 Calculated time dependent total soil concentrations over 5 cm for Testicide mg kg considering accumulation Time d 100 PECact 1 6653 1 5854 1 4621 1 3794 1 3001 1 21
14. The idea of this approach is that new applications do not change the rate of 26 degradation of residues from previous applications but instead degrade with the same rate as they had done without new applications 22 el Coi aI Me i P C Gi pesticide concentration at time j mg kg J current simulation day i application number napp total number of applications ti day of application i Co initial concentration of application i at time t mg kg Max Maximum function 1 fitting parameter B 2 fitting parameter However as shown in Figure 10 dependent on the rate parameters this equation may lead to a situation where never any final plateau is reached even after many pesticide applications Instead an unrealistic infinite increase of concentration with time is calculated Therefore a third option was implemented Residues from different application are separated within one year but all residues are joined and degraded together with the actual residues after the first application in the new year occurred see the example in Figure 11 Option 3 guarantees a final plateau after many applications but at a higher level than with the first option Shown in Figure 9 Of course there will be no difference between option 1 and option 3 if only a single application per year is simulated or the degradation models SFO or DFOP are used 27 c mg kg Program check Study Sandy loam 1 5 Made Farem anhe presente
15. developed by Michael Klein 130 Program version Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode 2 0 17 Feb 2009 17 02 2009 16 25 17 Report example 5 Residues from different applications are considered separately over one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Report example 5 Borstel 1 5 5 5 1 5 29 2 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Day Month Rate g ha Interception 01 05 500 0 10 05 750 25 01 06 600 50 01 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Compound Testicide Metabolidan Active compound and a single metabolite Molecular mass g mol 250 200 100 Formation DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics for Testicide DT50 1 d DT50 2 d Rate constant 1 1 d Rate constant 2 1 d Parameter Tb Q10 factor Walker
16. 0 0356 estimated to occur within 10 years soil study 4 mg kg lt 0 0001 estimated to occur within 10 years Calculations of concentrations considering accumulation after many years of application Maximum annual concentration in total soil for Report example 1 over 5 cm considering accumulation soil study 1 mg kg 1 3335 occurring on day 0 soil study 2 mg kg 1 3689 occurring on day 0 soil study 3 mg kg 1 3689 occurring on day 0 soil study 4 mg kg 1 3333 occurring on day 0 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Report example 1 mg kg considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 0 1123 1 2651 1 2432 1 2689 2 0000 1 3009 1 1963 1 1294 1 2076 4 0000 1 2691 1 1059 0 9328 1 0938 7 0000 1 2078 1 0225 0 7022 0 9428 14 0000 1 1214 0 9153 0 5117 0 6667 21 0000 0 9430 0 8537 0 4798 0 4714 28 0000 0 7930 0 8113 0 4500 0 3333 42 0000 0 6668 0 7541 0 3964 0 1667 50 0000 0 4716 0 7305 0 3689 0 1122 100 0000 0 3869 0 6429 0 2387 0 0094 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Report example 1 mg kg considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 31
17. 1 3231 1 3134 1 2975 1 2653 1 2355 1 1957 1 1258 1 0890 0 8732 TWA 28 d eee ee ep een Pk ee pen a pe ny Ea 50 100 150 200 250 300 350 Time after first application d TWA in graph TWA 28 d Annual C Background Accum Total content Porewater concentration Current Outputfile Figure 14 ESCAPE Main form Editing input parameters 4 3 1 Scenario parameters Programcheck v Del Borstel Edit FOCUS Hamburg median conditio Application pattern Copy Programcheck v Del single C regular iregular Date of first application zl May zl com Applikation rate g ha Crop interception Compound data Copy Programcheck x bel Seil soil study 1 v Add study Degradation Sorption Metabolism Parent Kinetics SFO otso je 010 BR walker 27 Parent Metab To ab 2 C Me Save input Report Scenario parameter can be divided into soil related and climate related parameters Scenario parameter are not frequently modified Therefore there are not presented on the main form However a special window is loaded when the button Edit in the brown scenario frame on the main form is pressed see Figure 14 and Figure 15 38 w Scenario Programchech orstel FOCUS Hamburg median conditions Figure 15 ESCAPE Editing scenario parameters There are six different soil parameters that ar
18. 106 Program version Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein 2 0 17 Feb 2009 17 02 2009 14 39 50 Report example 4 Residues from different applications are considered separately over one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Programcheck Borstel 1 5 5 5 1 5 29 2 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application date Application rate g ha Crop interception 1 May 1000 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Compound Testicide Metabolidan Active compound and a single metabolite Molecular mass g mol 250 200 100 Formation DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics for Testicide DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature
19. Input parameters are grouped into different blocks according to their meaning namely scenario parameters parameters describing the application pattern of the product parameters describing the degradation kinetics of the parent and metabolites and additional parameters defining the metabolism scheme if metabolites are to be simulated In order to make editing of input data more user friendly necessary input fields are displayed dependent on the selected calculation mode If valid input data have been entered ESCAPE is automatically updating all soil concentrations if the background colour of the field is white Input data from fields with yellow background colours are only updated after the enter key was pressed If the current data is not valid a small message will inform the user about the wrong input JF a ESCAPE Estimation of Soil Concentrations After PEsticide applications File Edit pesticide data View Help Current Simulation Copy Programcheck v Del Description Programcheck Parent only Parent with 1 metabolite Parent and 2 metabolites parallel Parent and 2 metabolites sequence c mg kg Annual concentration of Programcheck Study soil study 1 Made Parent only presented substance Testicide tkinetics SFO Calculated total soil concentrations mg kg Timeld PECactual PECtwa PECmax 1 3333 1 3225 1 3139 1 2913 1 2616 1 2137 1 1258 1 0409 0 9292 0 8706 0 5040
20. of Pages Auf dem Aberg 1 141 D 57392 Schmallenberg Germany 12 No of References 4 13 No of Tables Diagrams 7 Sponsoring Agency Name Address 7 Umweltbundesamt W rlitzer Platz 1 D 06844 Dessau 14 No of Figures 29 15 Supplementary Notes 16 Abstract In this project the computer model ESCAPE Estimation of Soil Concentrations After PEsticide applications originally developed in 2008 to calculate time dependent pesticide concentrations in soil was further developed covering following items Pore water concentrations in addition to the estimation of total contents in soil routines were implemented to calculate time dependent pore water concentrations Temperature dependency of microbial degradation in the present software additional procedures were included which allow to perform the correction of standard biodegradation rates using daily temperatures based on the established methodologies Moisture dependency of microbial degradation A new method was developed which can be used to do soil moisture correction of the biodegradation rate based on the established methodologies and independent on the actual degradation kinetics Implementation of standard scenarios new routines were implemented which allow the defni tion and use collections of weather and soil data as standard scenarios in a user friendly way 17 Keywords ESCAPE soil concentration pesticide metabolite degradation kinetics PECs
21. will remove the table completely from the screen By clicking at the diagram together with the ctrl key pressed will set the table to its original position and it becomes visible again 4 8 4 Manual changing of the time axis A right mouse click at the diagram opens a small form to manually set the minimum and maximum times displayed in the diagram This option only influence the current figure and does not change any setting of additional diagrams prepared in the background 4 8 5 Changing the duration of the TWA frame During the simulation the PEC wa is internally calculated for many time frames as explained earlier in this document in chapter 3 4 3 on page 29 The worst case time frame found is always displayed in the diagram However time weighted average concentrations are available for a list of time durations and dependent on the actual duration different starting and ending days for the time frame are PEC twa are achieved The duration presented in the diagram can be modified using the list box TWA in diagram at the bottom of the form 4 8 6 Selecting the PEC type in the graph ESCAPE is always calculating the soil concentrations over a period of ten years repeating the annual application pattern Depending on the selection of the radio buttons in the right bottom part of the window see Figure 25 three different types of diagram can be displayed either the situation in the first year normal soil depth Annual or the s
22. 0 1 3333 occurring on day 0 1 3333 occurring on day 0 1 3333 occurring on day 0 Calculated PECact in soil over 1 5 cm for Testicide mg kg 120 Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 2989 1 1268 1 2989 1 3144 2 0000 1 2727 1 0469 1 2727 1 2999 4 0000 1 2012 0 9236 1 2012 1 2603 7 0000 1 1152 0 8409 1 1152 1 2125 14 0000 0 9820 0 7616 0 9820 1 1376 21 0000 0 7449 0 6736 0 7449 1 0014 28 0000 0 5577 0 6227 0 5577 0 8899 42 0000 0 3568 0 5741 0 4896 0 7627 50 0000 0 2825 0 5559 0 4783 0 7121 100 0000 0 0339 0 4687 0 3870 0 4788 PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 1 5 cm for Testicide mg kg Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 3161 1 2301 1 3161 1 3239 2 0000 1 3010 1 1585 1 3010 1 3155 4 0000 1 2708 1 0725 1 2708 1 2989 7 0000 1 2222 0 9893 1 2222 1 2719 14 0000 1 1288 0 8899 1 1288 1 2198 21 0000 1 0443 0 8329 1 0443 1 1721 28 0000 0 9417 0 7854 0 9417 1 1130 42 0000 0 7790 0 7227 0 7973 1 0169 50 0000 0 7044 0 6972 0 7470 0 9715 100 0000 0 4076 0 6000 0 5879 0 7693 Calculation of background concentrations after many years Final background concentration in total soil for Testicide over 5 cm soil study 1 mg kg 0 0001 estimated to occur within 10 years soil study 2 mg kg 0 5385 estimated to occur within 10 years soil study 3 mg kg 0 24
23. 0 099 0 0099 5 2 58 0 7 20 soil study 4 Double First Order in Parallel DFOP 7 140 0 099 0 005 0 5 2 58 0 7 20 soil study 1 Single First order SFO 35 0 0099 2 58 0 7 20 soil study 2 Single First order SFO 350 0 005 2 58 0 7 20 soil study 3 Single First order SFO 140 0 001 2 58 0 7 20 soil study 4 Single First order SFO 14 0 0495 2 58 0 7 20 RESULTS OF THE CALCULATION Metabolism scheme Active compound and a single metabolite 138 RESULTS FOR Testicide Calculations over one year Maximum annual pore water concentration for Testicide over 1 5 cm soil study 1 mg L 0 5608 occurring on day 31 soil study 2 mg L 0 5748 occurring on day 9 soil study 3 mg L 0 2759 occurring on day 31 soil study 4 mg L 0 3109 occurring on day 31 Calculated PECact in soil over 1 5 cm for Testicide mg L Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 0 5589 0 4961 0 2723 0 3066 2 0000 0 5567 0 4537 0 2682 0 3017 4 0000 05517 0 4089 0 2595 0 2912 7 0000 0 5456 0 3080 0 2495 0 2794 14 0000 0 5220 0 1279 0 2295 0 2561 21 0000 0 5195 0 1046 0 2275 0 2445 28 0000 0 4807 0 1537 0 2133 0 2187 42 0000 0 5129 0 0886 0 2241 0 2236 50 0000 0 4988 0 0626 0 2180 0 2134 100 0000 0 4029 0 0314 0 1760 0 1734 PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrat
24. 0000 0 6598 0 6290 0 6345 0 2779 2 0000 0 6596 0 6290 0 6337 0 2770 4 0000 0 6581 0 6289 0 6332 0 2753 7 0000 0 6555 0 6287 0 6321 0 2724 14 0000 0 6485 0 6280 0 6299 0 2634 21 0000 0 6399 0 6272 0 6275 0 2523 28 0000 0 6308 0 6266 0 6258 0 2478 42 0000 0 6148 0 6266 0 6255 0 2469 50 0000 0 6069 0 6265 0 6244 0 2480 100 0000 0 5262 0 6258 0 6072 0 1960 Calculation of background concentrations after many years Final background concentration in total soil for Metabolidan over 5 cm soil study 1 mg kg 0 0875 estimated to occur within 10 years soil study 2 mg kg 3 9234 estimated to occur after 13 years soil study 3 mg kg 1 5434 estimated to occur after 11 years soil study 4 mg kg 0 0925 estimated to occur after 10 years Calculations of concentrations considering accumulation after many years of application Maximum annual concentration in total soil for Metabolidan over 5 cm considering accumulation soil study 1 mg kg 0 7479 occurring on day 67 soil study 2 mg kg 4 5524 occurring on day 121 soil study 3 mg kg 2 1789 occurring on day 32 soil study 4 mg kg 0 3707 occurring on day 26 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Metabolidan mg kg considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 0 4289 4 5511 2 1327 0 3484 2 0000 0 6407 4 5515 2 1319 0 3433 ee 4 0000 7 000
25. 0000 0 7561 0 2936 0 3784 0 4985 2 0000 0 9122 0 2450 0 3758 0 4936 4 0000 0 9100 0 1858 0 3720 0 4831 7 0000 0 9049 0 1485 0 3555 0 4713 14 0000 0 8988 0 1050 0 2934 0 4480 21 0000 0 8752 0 0914 0 2955 0 4364 28 0000 0 8727 0 0652 0 3592 0 4106 42 0000 0 8340 0 0638 0 3334 0 4155 50 0000 0 8661 0 0549 0 3205 0 4053 100 0000 0 8521 0 0294 0 2956 0 3653 139 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Testicide mg L considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 0 9131 0 5380 0 3813 0 5006 2 0000 0 9121 0 5078 0 3794 0 4983 4 0000 0 9098 0 4714 0 3765 0 4934 7 0000 0 9063 0 4294 0 3716 0 4862 14 0000 0 8958 0 3283 0 3578 0 4732 21 0000 0 8894 0 2963 0 3509 0 4638 28 0000 0 8807 0 2538 0 3455 0 4545 42 0000 0 8745 0 2292 0 3417 0 4481 50 0000 0 8718 0 2094 0 3396 0 4443 100 0000 0 8414 0 1371 0 3300 0 4239 a tillage depth of 5 cm was considered for calculating the background concentration RESULTS FOR Metabolidan Calculations over one year Maximum annual pore water concentration for Metabolidan over 1 5 cm soil study 1 mg L 1 2833 occurring on day 321 soil study 2 mg L 7 2742 occurring on day 66 soil study 3 mg L 1 6462 occurring on day 321 soil study 4 mg L 0 7
26. 14 5 0555 5 0889 42 56 21 5 0225 5 0723 42 63 28 4 9900 5 0557 42 70 42 4 9262 5 0231 42 84 50 4 8905 5 0048 42 92 100 4 6793 4 8951 41 141 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 2 Study soil study 1 3 a Made Parent onh presented substance Testade thinetics SFO 25 I 2 Bei 15 I 1 J 4 fec TWA 28d 05 4 0 Frrr AAMAARABS aa ANNAE EEEE EMEEN RAGS RAGERS BARS DE 0 50 100 150 200 250 300 350 Time after first application d ESCAPE 85 Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation 17 02 2009 11 46 10 Calculation problem Report example 2 PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Report example 2 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C
27. 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 1st Application date 1 May Application rate g ha 1000 Time between two applications d 14 Crop interception 50 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 2 Metabolism scheme Parent compound without metabolites Kinetics for Report example 2 First Order Multi Compartment FOMC Alpha 0 1 Beta 2 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 2 Calculations over one year 86 Maximum annual total soil concentration for Report example 2 over 5 cm mg kg 2 2061 occurring on day 42 Calculated time dependent total soil concentrations over 5 cm for Report example 2 after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 2 1736 2 1898 42 43 2 2 1497 2 1757 42 44 4 2 1142 2 1534 42 46 T 2 0760 2 1280 42 49 14 2 0155 2 0858 42 56 21 1 9731 2 0550 42 63 28 1 9399 2 0302 42 70 42 1 8890 1 9912 42 84 50 1 8659 1 9731 41 91 100 1 7680 1 8935 41 141 PECact values are related to the time after the maximum concentra
28. 5122 0 4 7 1 3566 1 4636 0 7 14 1 2234 1 3702 0 14 21 0 9863 1 2857 0 21 28 0 7991 1 1831 0 28 42 0 7310 1 0387 0 42 50 0 7197 0 9884 0 50 100 0 6284 0 8293 0 100 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application GRAPHIC REPRESENTATION OF THE CALCULATION 2 3 E s Annual concentration of Report example 1 Hamburg Study soil study 3 Made Parent anf presented substance Testioide kinetics HS 14 13 1 2 11 09 08 0 7 0 6 0 5 0 4 fc Twa oq 0 3 0 2 0 1 o ATT TTT TTT TTT TTT TTT 50 100 150 200 250 300 350 Time after first application d _luuluuleuluuluudulunludunlunlundu uuldulududunbudunduluhundudduduu ESCAPE 80 Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 16 Feb 2009 Date of this simulation 16 02 2009 14 01 20 Calculation problem Report example 1 Hamburg PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content
29. B and the differences in the molar masses according to equation 20 R egA fs M metB 20 RformB SS Meta Ryorms actual formation of metabolite B g ha Raega actual degradation of metabolite A g ha SB formation fraction of metabolite B Mets molecular mass of metabolite A g mol M met molecular mass of metabolite B g mol For the parent compound ESCAPE calculates actual and time weighted average concentrations based on all four kinetic models presented in chapter 3 1 However as the degradation in the degradation models FOMC and HS depends on the time since application but these times cannot be defined for the formation of metabolites the formation takes place over the whole simulation period instantaneously these two models cannot be selected for metabolites The user can decide to keep pesticide residues from different applications separately also in this calculation mode see Figure 5 and the explanation in chapter 3 3 1 25 3 4 Calculation of the total content in soil 3 4 1 Initial concentrations At the beginning of a simulation ESCAPE calculates the initial concentration in soil For the calculation two soil parameters soil depth and soil density and two parameters related to the application pattern application rate and crop interception are used Thus the initial pesticide concentration is calculated based on these four variables according to equation 21 R Ic 21 Co 21
30. Begin TWAframe d End TWAframe d 1 0 3667 0 3704 25 26 2 0 3644 0 3696 25 27 4 0 3602 0 3678 24 28 7 0 3484 0 3650 24 31 14 0 3180 0 3559 22 36 21 0 3269 0 3448 21 42 28 0 3353 0 3403 21 49 42 0 3548 0 3395 23 65 50 0 2848 0 3405 21 71 100 0 1905 0 2885 7 107 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg PEC acumumlation for Report example 3 Study soil study 4 2 Made Faremt with 7 meta amp basie Testicide PEC TWA 28 d TWA 28 d Metabolidan PEC 0 5 0 50 100 150 200 250 300 350 Time after first application d Here the respective report is shown when ESCAPE s summary mode was selected Results of all studies are summarised for the parent compound and the metabolite ESCAPE Estimation of Soil Concentrations After PEsticide Applications 118 Program version Date of this simulation Calculation problem developed by Michael Klein 2 0 17 Feb 2009 17 02 2009 14 48 31 Report example 4 SUMMARY REPORT CONSIDERING ALL SOIL STUDIES PROGRAM SETTINGS Calculation mode Application mode Residues from different applications are considered separately over one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Na
31. Concentrations After PEsticide Applications Program version Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode developed by Michael Klein 2 0 17 Feb 2009 17 02 2009 16 22 52 Report example 5 Residues from different applications are considered separately over one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Report example 5 Borstel 1 5 5 5 1 5 29 2 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Month Rate g ha Interception 05 500 0 05 750 25 06 600 50 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Compound Testicide Metabolidan Active compound and a single metabolite Molecular mass g mol 250 200 100 Formation DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics for Testicide DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C Kinetics f
32. Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 4356 0 6261 9 10 2 0 3056 0 5358 8 10 4 0 1976 0 4286 8 12 T 0 1330 0 3250 8 15 14 0 0778 0 2594 0 14 21 0 0556 0 2128 0 21 28 0 1005 0 1777 0 28 42 0 0493 0 1634 0 42 50 0 0396 0 1468 0 50 100 0 0213 0 0945 0 100 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in total soil for Report example 3 over 5 cm mg kg 0 0006 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 3 over 5 cm considering accumulation mg kg 0 8172 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 3 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 4362 0 6267 9 10 2 0 3061 0 5363 8 10 4 0 1982 0 4291 8 12 7 0 1335 0 3256 8 15 14 0 0783 0 2600 0 14 21 0 0562 0 2133 0 21 28 0 1011 0 1783 0 28 42 0 0499 0 1639 0 42 50 0 0402 0 1473 0 50 100 0 0218 0 0951 0 100 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum conc
33. after many years Final Background concentration in pore water for Metabolidan over 5 cm mg L estimated to occur after 11 years 290 291 326 4 3420 according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Metabolidan over 5 cm considering accumulation mg L 5 9882 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent pore water concentrations over 5 cm for Metabolidan mg L considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 5 9597 5 9853 346 347 2 5 9859 5 9847 345 347 4 5 9200 5 9836 343 347 7 5 8209 5 9615 342 349 14 5 6004 5 9467 274 288 21 5 9694 5 9446 268 289 28 5 8395 5 9411 262 290 42 5 5838 5 9367 248 290 50 5 8824 5 9337 241 291 100 5 5944 5 9150 226 326 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION 6 Made Parent wih 7 meisballte c mg L PEC acumumlation for Report example 5 Study soil study 3 Testicide Metabolidan 0 50 100 150 200 250 Time after first application d 300 350 ESCAPE Estimation of Soil Concentrations After PEsticide Applicati
34. background concentration 1 3333 occurring End TWAframe d 0 0001 1 3334 Calculated time dependent total soil concentrations over 5 cm for Testicide mg kg considering accumulation Time d PECact 1 1 2990 2 1 2727 4 1 2013 7 1 1153 14 0 9820 21 0 7450 28 0 5578 42 0 3568 50 0 2825 100 0 0340 PECtwa 1 3162 1 3010 1 2709 1 2223 1 1288 1 0444 0 9417 0 7790 0 7045 0 4076 Begin TWAframe d Ooo Oo O o o o o o a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application RESULTS FOR Metabolidan Calculations over one year Maximum annual total soil concentration for Metabolidan over 5 cm mg kg on day 67 This is 61 91 of the theoretical maximum concentration of the metabolite End TWAframe d 0 6604 occurring Calculated time dependent total soil concentrations over 5 cm for Metabolidan after one year mg kg Time d PECact 1 0 6591 2 0 6541 4 0 6342 7 0 6035 14 0 5443 21 0 4982 28 0 4375 42 0 3734 PECtwa 0 6598 0 6596 0 6581 0 6555 0 6485 0 6399 0 6308 0 6148 Begin TWAframe d End TWAframe d 108 50 0 3655 0 6069 29 79 100 0 2281 0 5262 18 118 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in total soil for Metabolidan over 5 cm
35. be specified by the user The names will later appear in the report of ESCAPE Molecular mass g mol For the formation of metabolites the user has to enter the molecular masses of all compounds considered for the simulation here Formation rate For the correct calculation of metabolite concentration in soil the user has to enter the formation rates for all metabolites here The formation fraction is not the same as the maximum formation during the study If the formation fraction is not known enter 100 as an worst case estimate 43 4 3 4 Problem characterisation Each combination of input data Scenario application pattern compound data is called a simulation and are saved in a special data base The user may attach a description to this simulation which will later appear in the output documentation The description is localised on top right of the main form see Figure 16 This description has a slight write protection which can be removed if the user presses the control key when he clicks at the form The field background colour will turn into yellow and can be edited now The list box in the top left part of the form is to select pre defined simulations Simulation records can be copied or removed using the respective buttons close to that list box More option for the editing simulation records are available via the menu bar File Load Simulation FJ ESCAPE Estimation of Soil Concentrations After PEstic
36. been selected the first 1 order DT50 has to be selected here HS DT50 _ d 1 d If the HS model has been selected the second 1 order DT50 has to be selected here HS parameter 7b If the HS model has been selected the parameter Tb has to be entered which describes the breakpoint where the degradation switches from the first to the second DT50 42 File card Sorption Sorption related parameters Name of the compounds In these at maximum three fields the names of the parent compound and the metabolite s can be specified by the user The names will later appear in the report of ESCAPE KOC L kg There is currently a single sorption parameter that can be entered here for all compounds simulated the sorption constant related to the organic carbon content The parameter is used to calculate time dependent pore water concentrations in soil File card Metabolism Parameters related to the metabolism scheme If not only the parent compound but also metabolites are considered for a simulation the metabolism scheme can be entered in the third green file card if coloured frames are switched on see preferences As explained earlier in chapter 3 2 ESCAPE is able to consider a maximum two metabolites formed in parallel or in a sequence The metabolism scheme can be characterised by in total eight parameters Name of the compounds In these three fields the names of the parent compound and the metabolite s can
37. cm was considered for calculating the background concentration 0 3109 occurring End TWAframe d O 1919 0 5028 Calculated time dependent pore water concentrations over 5 cm for Testicide mg L considering accumulation Time d PECact PECtwa Begin TWAframe d i 0 4985 0 5006 31 2 0 4936 0 4983 31 4 0 4831 0 4934 St 7 0 4713 0 4862 31 14 0 4480 0 4732 30 21 0 4364 0 4638 30 28 0 4106 0 4545 30 42 0 4155 0 4481 9 50 0 4053 0 4443 9 100 0 3653 0 4239 9 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration RESULTS FOR Metabolidan Calculations over one year Maximum annual pore water concentration for Metabolidan over 5 cm mg L on day 66 This is 86 41 of the theoretical maximum concentration of the metabolite End TWAframe d 0 7749 occurring Calculated time dependent pore water concentrations over 5 cm for Metabolidan after one year mg L Time d PECact PECtwa Begin TWAframe d 1 0 7734 0 7742 66 2 0 7266 0 7706 65 4 0 6310 0 7536 64 7 0 5684 0 7282 62 14 0 4552 0 6944 57 21 0 3794 0 6596 52 28 0 3030 0 6274 49 42 0 2836 0 5803 40 50 0 3199 0 5559 33 End TWAframe d 135 100 0 1612 0 4452 20 120 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in pore w
38. compartment 3 Br degradation residues from application 2 internal counter to tapp3 Figure 5 A series of compartments if residues from different applications are kept separately 3 3 2 Simulation considering the parent compound and a single metabolite In this mode ESCAPE considers two compartments for the parent compound and for the metabolite as shown in Figure 6 compartment 1 degradation pesticide compartment 2 degradation n metabolite Figure 6 Two compartments for parent and metabolite The calculation of the formation of the metabolite is done based on the time dependent degradation of the parent compound the formation fraction of the metabolite and the differences in the molar masses according to equation 17 SOA 17 Raeg BI Moret ay Ryorm er S O Moar Rform actual formation of the metabolite g ha Raeg actual degradation of the parent compound g ha formation fraction of the metabolite Mpar molecular mass of the parent compound g mol Met molecular mass of the metabolite g mol Again for the parent compound ESCAPE calculates actual and time weighted average concentrations based on all four kinetic models presented in chapter 3 1 However as the degradation in the degradation models FOMC and HS depends on the time since application but these times cannot be defined for the formation of metabolites the formation takes place over the whole simulation period instantaneo
39. exponent Ref temperature C Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C soil study 3 Active compound and a single metabolite Hockey Stick HS 7 70 0 099 0 0099 5 2 58 0 7 20 Single First order SFO 140 0 005 2 58 0 7 20 sais RESULTS OF THE CALCULATION Metabolism scheme Active compound and a single metabolite RESULTS FOR Testicide Calculations over one year Maximum annual pore water concentration for Testicide over 5 cm mg L on day 31 Calculated time dependent pore water concentrations over 5 cm for Testicide after one year mg L Time d PECact 1 0 2723 2 0 2682 4 0 2595 7 0 2495 14 0 2295 21 0 2275 28 0 2133 42 0 2241 50 0 2180 100 0 1760 PECtwa 0 2741 0 2722 0 2693 0 2644 0 2506 0 2437 0 2383 0 2345 0 2324 0 2228 Begin TWAframe d 31 31 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in pore water for Testicide over 5 cm mg L estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Testicide over 5 cm considering accumulation mg L a tillage depth of 5 c
40. file At the same time the report is also displayed at the main form see Figure 18 It is possible to do some limited processing scrolling with cursor keys copying into the clipboard with ctrl C After a double click at the report the standard diagram sheet returns on top of the screen Dependent on whether ESCAPES provides information about an individual study or collects summary information the report file looks differentially The menu items View Summary or View Individual studies can be used to switch between these two modes Instead of using the menu bar the user could also use the report button on the right bottom part of the main form Report can be printed using the command File Print in the menu bar Help About Some information about the current model version is faded in after selecting the menu item Help About as shown in Figure 23 53 Pd AppDate EIER ESCAPE Estimation of Soif Concentratians After PEsticide applications Version 2 0 12 Feb 2009 developed by Fraunhofer Institut a larbiologie und dt E mail michael klein ime fraunhofer de fhe development was sponsored by the Umwellbundesamt 06844 Dessau Ro lau Umwelt Bundes Amt F r Mensch und Umwelt Figure 23 ESCAPE Saving input files 4 8 Manipulating the central diagram sheet Dependent on the current input data set much information about soil concentrations might be ava
41. frame assuring that always the worst case PEC wa is found for a given time duration Generally all time weighted average concentrations are calculated by ESCAPE within a two steps procedure In the first step the integral of actual soil concentrations cumulative concentrations for parent compounds and metabolites is calculated according to equation 23 30 n 23 Ceum 1 gt Cj 0 j Ceum j Cumulative soil concentration at time j mg kg Ce actual soil concentration at time 7 mg kg J current simulation day n total number of simulation days Based on the cumulative concentrations a search for the worst case time frame is performed for each TWA in the second step according to the following two equations Cam i dtwa Cam j PECs ee 24 diwa PECrwa Maximum all PECtwa 25 PECrwa Time weighted average concentration mg kg PEC rwaj Time weighted average concentration beginning at time j mg kg Cams Cumulative concentration at time j mg kg Gans Cumulative concentration at time j dew mg kg diwa duration of the time weighted average concentration mg kg 3 4 4 Background concentrations Background concentrations are concentrations after many years with pesticide applications ESCAPE considers the plateau bottom just before a new application is performed as background load In contrast to annual concentrations the tillage depth is used to define the depth of the soil compartment for backgroun
42. i h TWA 28 d Annual g T rable Background Save input Report Current Outputfile an Figure 25 ESCAPE The central diagram selecting the PEC Type in the graph 4 8 7 Scrolling through the list of diagrams prepared in the background If metabolites have been considered for the simulation more than diagram has been prepared in the background By clicking with the left mouse button at the diagram figures in the background become available If ESCAPE is presenting results from individual studies for each compound a diagram has been prepared Examples of these diagrams are presented in the next three figures Figure 26 shows the result for the parent compound which is usually presented in blue colours 57 c mg kg Program check Study Sandy loam 1 1 Made Parent wih I meta amp atie presented suasiance Testne Kinetics FE 0 9 0 8 0 7 0 6 0 5 0 4 0 3 TWA 28 d 0 2 0 1 0 50 100 150 200 250 300 350 Time d Figure 26 ESCAPE Graphical results for the parent compound View Individual study The respective results for the first metabolite is shown in green colours see Figure 27 Results of the second metabolite will always be shown in red colours 58 c mg kg Program check Study Sandy loam 1 Made Parent wit 7 meta amp atie gresemec substance Metaboliden kinetics SEO 0 3 0 2 0 1 PEE TWA 28d 0 0 50 100 150 200 250 300 350 Time d Figure 27 ESCAPE
43. kg soil study 3 mg kg soil study 4 mg kg 2 5635 occurring on day 42 2 2061 occurring on day 42 2 3247 occurring on day 42 2 4106 occurring on day 42 Calculated PECact in soil over 1 5 cm for Report example 2 mg kg Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 2 5587 2 1736 2 3114 2 3987 2 0000 2 5538 2 1497 2 2981 2 3868 4 0000 2 5441 2 1142 2 2720 2 3633 7 0000 2 5297 2 0760 2 2386 2 3284 14 0000 2 4963 2 0155 2 1858 2 2491 21 0000 2 4633 1 9731 2 1407 2 1725 28 0000 2 4308 1 9399 2 1259 2 0985 42 0000 2 3670 1 8890 2 0966 1 9580 50 0000 2 3313 1 8659 2 0801 1 8819 100 0000 2 1202 1 7680 1 9796 1 4693 PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 1 5 cm for Report example 2 mg kg Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 2 5611 2 1898 2 3180 2 4046 2 0000 2 5587 2 1757 2 3114 2 3987 4 0000 2 5538 2 1534 2 2982 2 3868 7 0000 2 5466 2 1280 2 2791 2 3693 14 0000 2 5298 2 0858 2 2455 2 3289 21 0000 2 5131 2 0550 2 2173 2 2895 28 0000 2 4966 2 0302 2 1963 2 2509 42 0000 2 4640 1 9912 2 1680 2 1793 50 0000 2 4456 1 9731 2 1552 2 1393 100 0000 2 3359 1 8935 2 0925 1 9444 93 Calculation of background concentrations after many years Final background concentration in total soil for Report example 2 over 5 cm soil study 1 mg kg 2 5592 estimated to occur after
44. metabolite Parent and 2 metabolites parallel Parent and 2 metabolites sequence Borstel et orstel Edit c mg kg Annual concentration of Programcheck Study soil study 1 Made Parent only presented substance Testicide Kinelics SFO Application pattern Calculated total soil concentrations mg kg Copy Programcheck v Del PECactual PECtwa single C regular iregular 1 3333 1 3225 1 3279 Date of first application 11 Mm zl 1 3139 1 3231 1 2913 1 3134 1 2616 1 2975 Applikation rate g ha 1000 1 2137 1 2653 1 1258 1 2355 Crop interception 0 1 0409 1 1957 0 9292 1 1258 0 8706 1 0890 Compound data 0 5040 0 8732 Copy Programcheck vj Del Sail soil study 1 x Add study Degradaion _ San Metabo Parent TWA 28d __ Kinetics SFO otoa 100 150 200 250 300 350 Time after first application d o Raen C Metab 1 Metab 2 ala ai a TUT TT a g i Bi ha a a LA Uag eas i FALAS E g pE 50 y a 22 waker 07 tofa Total content Porewater concentration TWA in graph TWA 28 d X oe 5 Su i ackgroun ave inpu Current Outputfile Accum Figure 17 ESCAPE Main form Command buttons Save input If the current parameter setting should be saved on the computer the fastest method would be that button It will save all input under the current names 45 4 ESCAPE Estimation of Soil Concentra
45. mg kg 0 0875 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Metabolidan over 5 cm considering accumulation mg kg 0 7479 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Metabolidan mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 7467 0 7473 67 68 2 0 7416 0 7471 66 68 4 0 7217 0 7457 65 69 7 0 6910 0 7430 62 69 14 0 6318 0 7360 58 72 21 0 5857 0 7274 52 73 28 0 5250 0 7184 46 74 42 0 4610 0 7024 35 77 50 0 4530 0 6944 29 79 100 0 3156 0 6137 18 118 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg nnual concentration of Report example 3 Study soil study 1 Made Farem with T metabolite Testicide PEC TWA 28 d Metabolidan PEC TWA 28 d 0 50 100 150 200 250 300 350 Time after first application d ESCAPE Estimation of Soil Concentrations After PEsticide Applications 109 developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation
46. of ESCAPE in addition to traditional total contents also pore water concentrations can be calculated Furthermore degradation rates can be corrected based on actual soil moisture and temperature data Finally realistic worst case scenarios based on specific information on soil cores and climate data sets containing daily weather series can be used for the calculations 2 Background Within the registration of pesticides time dependent concentrations in soil have to be calculated for all active ingredients and their main metabolites Traditionally these estimations are performed considering first order degradation kinetics as described in the FOCUS document Soil persistence models and EU registration finalised in 1997 Calculated actual PECact and time weighted average concentrations PECtwa are used for comparisons with respective results of eco toxicity tests as the base for the risk assessment of these substances in soil As first order degradation means that the half life of a compound is only a function of the rate constant and therefore constant over time and independent on the actual soil concentration this kinetics has many advantages especially when complicated application pattern with different application amounts rates or times have to be considered However in the final report of the FOCUS working group on degradation kinetics which came out recently FOCUS 2006 additional degradation kinetics were described which are often more
47. one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Programcheck Borstel 1 5 5 5 1 5 29 2 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application date Application rate g ha Crop interception 1 May 1000 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Compound Testicide Metabolidan Active compound and a single metabolite Molecular mass g mol 250 200 100 Formation DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics for Testicide DT50 1 d DT50 2 d Rate constant 1 1 d Rate constant 2 1 d Parameter Tb Q10 factor Walker exponent Ref temperature C Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C soil study 3 Active compound and a single metabolite Hockey Stick HS 7 70 0 099 0 0099 10 2 58 0 7 20 Single First order SFO 140 0 005 2 58 0 7 20 RESULTS OF
48. related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 1 5 cm for Report example 3 mg kg Time d soil study 1 soil study 2 1 0000 1 2521 0 6261 2 0000 1 2350 0 5358 4 0000 1 2017 0 4286 7 0000 1 1539 0 3250 14 0000 1 0542 0 2594 21 0000 0 9710 0 2128 28 0000 0 9690 0 1777 42 0000 0 9073 0 1634 50 0000 0 8578 0 1468 100 0000 0 6354 0 0945 Calculation of background concentrations after many years Final background concentration in total soil for Report example 3 over 5 cm soil study 1 mg kg 0 0001 estimated to occur within 10 years soil study 2 mg kg 0 0006 estimated to occur within 10 years Calculations of concentrations considering accumulation after many years of application Maximum annual concentration in total soil for Report example 3 over 5 cm considering accumulation soil study 1 mg kg 1 2695 occurring on day 9 soil study 2 mg kg 0 8172 occurring on day 9 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Report example 3 mg kg considering accumulation Time d soil study 1 soil study 2 1 0000 0 1607 0 4362 101 2 0000 1 2348 0 3061 4 0000 1 2011 0 1982 7 0000 1 1363 0 1335 14 0000 1 0456 0 0783 21 0000 0 8612 0 0562 28 0000 0 7093 0 1011 42 0000 0 9229 0 0499 50 0000 0 6260 0 0402 100 0000 0 5015 0 0218 a tillage depth of 5 cm was consider
49. the background concentration Calculated time dependent pore water concentrations over 5 cm for Testicide mg L considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 4987 0 5380 9 10 2 0 4563 0 5078 9 11 4 0 4116 0 4714 9 13 7 0 3106 0 4294 8 15 14 0 1305 0 3283 8 22 21 0 1073 0 2963 0 21 28 0 1563 0 2538 0 28 42 0 0912 0 2292 0 42 50 0 0652 0 2094 0 50 100 0 0340 0 1371 0 100 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration RESULTS FOR Metabolidan Calculations over one year Maximum annual pore water concentration for Metabolidan over 5 cm mg L 7 2742 occurring on day 66 This is 1363 90 of the theoretical maximum concentration of the metabolite Calculated time dependent pore water concentrations over 5 cm for Metabolidan after one year mg L Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 6 8370 7 2586 65 66 2 5 4496 7 1571 65 67 4 4 0863 6 8677 112 116 7 4 0780 6 7797 112 119 14 4 0514 6 6780 200 214 21 4 0232 6 6584 219 240 28 3 9833 6 6586 200 228 129 42 50 100 5 9655 6 6567 200 6 9442 6 6564 200 6 7322 6 5445 195 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in pore water for Metabolidan over 5 cm mg L
50. 0 14 0000 21 0000 28 0000 42 0000 50 0000 100 0000 0 6434 0 6475 0 6562 0 6606 0 6887 0 7116 0 7467 0 6662 4 5512 4 5505 4 5490 4 5470 4 5437 4 5453 4 5507 4 5388 2 1302 2 1274 2 1194 21102 2 1024 2 0955 2 0998 2 1144 0 3323 0 3206 0 3290 0 3313 0 3459 0 3044 0 2556 0 1801 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Metabolidan mg kg considering accumulation Time d 1 0000 2 0000 4 0000 7 0000 14 0000 21 0000 28 0000 42 0000 50 0000 100 0000 soil study 1 0 7473 0 7471 0 7457 0 7430 0 7360 0 7274 0 7184 0 7024 0 6944 0 6137 soil study 2 4 5524 4 5524 4 5522 4 5520 4 5513 4 5505 4 5500 4 5499 4 5499 4 5491 soil study 3 soil study 4 2 1779 0 3704 2 1771 0 3696 2 1766 0 3678 2 1756 0 3650 2 1733 0 3559 2 1710 0 3448 2 1692 0 3403 2 1689 0 3395 2 1678 0 3405 2 1506 0 2885 a tillage depth of 5 cm was considered for calculating the background concentration GRAPHIC REPRESENTATION OF THE CALCULATION efmalka Moda Parent mith I metatoite prosen Annual concentration of Ri 250 xO 350 Time after first application d c ma ka v Annual concentration of Report example 4 All sail studies Moce Foren mi metatoite gt prese
51. 0 17 Feb 2009 Date of this simulation 17 02 2009 11 44 45 Calculation problem Report example 2 PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Report example 2 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 1st Application date 1 May Application rate g ha 1000 Time between two applications d 14 Crop interception 50 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 1 Metabolism scheme Parent compound without metabolites Kinetics for Report example 2 Single First order SFO DT50 d 365 Rate constant 1 d 0 0019 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report e
52. 00 250 300 350 Time after first application d o a S S 5 a S ESCAPE 87 Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation 17 02 2009 11 47 06 Calculation problem Report example 2 PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Report example 2 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 1st Application date 1 May Application rate g ha 1000 Time between two applications d 14 Crop interception 50 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 3 Metabolism scheme Parent compound without metabolites Kinetics for Report example 2 Hocke
53. 10 1 6970 1 5424 1 7016 4 0000 1 2709 1 6110 1 5122 1 6850 7 0000 1 2223 1 5278 1 4636 1 6581 14 0000 1 1288 1 4284 1 3702 1 6059 2121 21 0000 1 0444 1 3714 1 2857 1 5582 28 0000 0 9417 1 3239 1 1831 1 4991 42 0000 0 7790 1 2612 1 0387 1 4030 50 0000 0 7045 1 2357 0 9884 1 3576 100 0000 0 4076 1 1385 0 8293 1 1554 a tillage depth of 5 cm was considered for calculating the background concentration RESULTS FOR Metabolidan Calculations over one year Maximum annual total soil concentration for Metabolidan over 1 5 cm soil study 1 mg kg 0 6604 occurring on day 67 soil study 2 mg kg 0 6291 occurring on day 121 soil study 3 mg kg 0 6355 occurring on day 32 soil study 4 mg kg 0 2782 occurring on day 26 Calculated PECact in soil over 1 5 cm for Metabolidan mg kg Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 0 6591 0 6289 0 6335 0 2742 2 0000 0 6541 0 6287 0 6313 0 2719 4 0000 0 6342 0 6281 0 6267 0 2677 7 0000 0 6035 0 6271 0 6219 0 2558 14 0000 0 5443 0 6240 0 6215 0 2254 21 0000 0 4982 0 6203 0 6213 0 2343 28 0000 0 4375 0 6171 0 6266 0 2427 42 0000 0 3734 0 6143 0 6232 0 2623 50 0000 0 3655 0 6163 0 6096 0 1923 100 0000 0 2281 0 6224 0 5798 0 0980 PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 1 5 cm for Metabolidan mg kg Time d soil study 1 soil study 2 soil study 3 soil study 4 1
54. 100 PECact 1 2295 1 1607 1 0703 0 9870 0 8797 0 8181 0 7757 0 7185 0 6949 0 6073 PECtwa 1 2814 1 2383 1 1755 1 1118 1 0193 0 9618 0 9203 0 8618 0 8370 0 7411 PECact values are related to the time after the first application Calculation of background concentrations after many years Begin TWAframe d O11 Ore 1S one Final Background concentration in total soil for Report example 1 over 5 cm mg kg estimated to occur after 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 1 over 5 cm considering accumulation mg kg a tillage depth of 5 cm was considered for calculating the background concentration End TWAframe d 0 7261 2 0594 Calculated time dependent total soil concentrations over 5 cm for Report example 1 mg kg considering accumulation Time d 100 PECact 1 9556 1 8868 1 7964 1 7131 1 6058 1 5442 1 5018 1 4446 1 4210 1 3334 PECtwa 2 0075 1 9644 1 9016 1 8374 1 7454 1 6879 1 6464 1 5879 1 5631 1 4672 Begin TWAframe d iS OOO i a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application GRAPHIC REPRESENTATION OF THE CALCULATION mg kg E 14 3 E 13 12 11
55. 11 years soil study 2 mg kg 2 8582 estimated to occur after 11 years soil study 3 mg kg 3 0362 estimated to occur after 11 years soil study 4 mg kg 0 4733 estimated to occur within 10 years Calculations of concentrations considering accumulation after many years of application Maximum annual concentration in total soil for Report example 2 over 5 cm considering accumulation soil study 1 mg kg 5 1227 occurring on day 42 soil study 2 mg kg 5 0643 occurring on day 42 soil study 3 mg kg 5 3609 occurring on day 42 soil study 4 mg kg 2 8839 occurring on day 42 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Report example 2 mg kg considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 4 6793 5 0317 5 3475 2 8720 2 0000 5 1178 5 0078 5 3343 2 8601 4 0000 5 1130 4 9724 5 3082 2 8366 7 0000 5 1033 4 9342 5 2748 2 8018 14 0000 5 0889 4 8737 5 2220 2 7224 21 0000 5 0555 4 8313 5 1768 2 6458 28 0000 5 0225 4 7981 5 1621 2 5718 42 0000 4 9900 4 7472 5 1328 2 4313 50 0000 4 9262 4 7241 5 1163 2 3553 100 0000 4 8905 4 6262 5 0158 1 9426 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Report example 2 mg kg considering
56. 14 estimated to occur within 10 years soil study 4 mg kg 0 3861 estimated to occur after 10 years Calculations of concentrations considering accumulation after many years of application Maximum annual concentration in total soil for Testicide over 5 cm considering accumulation soil study 1 mg kg 1 3334 occurring on day 0 soil study 2 mg kg 1 8718 occurring on day 0 soil study 3 mg kg 1 5747 occurring on day 0 soil study 4 mg kg 1 7195 occurring on day 0 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Testicide mg kg considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 0 0340 1 6653 1 5403 1 7005 2 0000 1 2990 1 5854 1 5141 1 6860 4 0000 1 2727 1 4621 1 4426 1 6465 7 0000 1 2013 1 3794 1 3566 1 5986 14 0000 1 1153 1 3001 1 2234 1 5237 21 0000 0 9820 1 2121 0 9863 1 3876 28 0000 0 7450 1 1612 0 7991 1 2760 42 0000 0 5578 1 1126 0 7310 1 1488 50 0000 0 3568 1 0944 0 7197 1 0982 100 0000 0 2825 1 0072 0 6284 0 8649 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Testicide mg kg considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 3162 1 7686 1 5575 1 7100 2 0000 1 30
57. 17 02 2009 14 42 11 Calculation problem Report example 4 PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Iteration of annual application pattern over 10 years SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application date 1 May Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Active compound and a single metabolite Compound Molecular mass g mol Formation Testicide 250 Metabolidan 200 100 DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 2 Metabolism scheme Active compound and a single metabolite Kinetics for Testicide First Order Multi Compartment FOMC Alpha 0 2 Beta 0 2 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 Kinetics for Metabolidan Single First order SFO DT50 d 350 Rate constant 1 d 0 002 Q10 factor 2 58 Walker exponent 0 7
58. 2 Temperature and soil moisture correction of degradation constants Dependent on the actual soil moisture and temperature conditions ESCAPE corrects the standard degradation rate Temperature correction is done based on the Q10 approach according to following equation T T Ref k k Qo 1 4 k actual rate constant ko rate constant at Trer C Qj Q10 factor T current temperature C The Q o factor the temperature at reference conditions Tre and the rate constant at reference conditions must be given by the user whereas the current temperature is taken from the weather file by ESCAPE Soil moisture equation is done based on the Walker model as shown in following equation S k k oF 5 k actual rate constant ko rate constant at Trey C f moisture exponent current soil moisture m m soil moisture at reference conditions pF 2 field capacity m m 18 The soil moisture exponent field capacity pF 2 must be given by the user whereas the current soil moisture and the rate constant at reference conditions content is calculated by ESCAPE based on the weather conditions and considering worst case assumptions according to following equation MAX MIN O Ra Tle Om 16 soil moisture at the current simulation day m m 2 1 Soil moisture at the previous simulation day m m ETpot potential evapotranspiration at the current simulation day cm R Rainfall a
59. 21 1 1612 1 1126 1 0944 1 0072 PECtwa 1 7686 1 6970 1 6110 1 5278 1 4284 1 3714 1 3239 1 2612 1 2357 1 1385 Begin TWAframe d 9999559599598 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application RESULTS FOR Metabolidan Calculations over one year Maximum annual total soil concentration for Metabolidan over 5 cm mg kg on day 121 This is 58 97 of the theoretical maximum concentration of the metabolite End TWAframe d 0 6291 occurring Calculated time dependent total soil concentrations over 5 cm for Metabolidan after one year mg kg Time d 100 PECact 0 6289 0 6287 0 6281 0 6271 0 6240 0 6203 0 6171 0 6143 0 6163 0 6224 PECtwa 0 6290 0 6290 0 6289 0 6287 0 6280 0 6272 0 6266 0 6266 0 6265 0 6258 Begin TWAframe d 121 120 119 118 116 113 303 289 282 240 PECact values are related to the time after the maximum concentration End TWAframe d 122 122 123 125 130 134 331 331 332 340 eT iis Calculation of background concentrations after many years Final Background concentration in total soil for Metabolidan over 5 cm mg kg 3 9234 estimated to occur after 13 years according to the estimation 95 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of app
60. 5 9836 0 9011 7 0000 2 2473 34 2834 5 9615 0 8757 14 0000 2 2393 34 1817 5 9467 0 8419 21 0000 2 2361 34 1621 5 9446 0 8071 28 0000 2 2172 34 1624 5 9411 0 7749 42 0000 2 2081 34 1604 5 9367 0 7278 50 0000 2 2026 34 1601 5 9337 0 7034 100 0000 2 1859 34 0482 5 9150 0 5927 a tillage depth of 5 cm was considered for calculating the background concentration GRAPHIC REPRESENTATION OF THE CALCULATION e ma t Annual concentration of Report example 5 All soil studies mast Annual concentration of Report example 06 Modo Perant wit 7 mobali presented substance Testcide thinetics SFO J motabasie presented substance Metabo 1 o EEE a aaee 0 0 a 100 150 200 250 0 360 Time alter first application d Time alter hrst application d
61. 7 13 8 11 80 9 30 2 84 9 27 10 67 13 76 15 23 17 81 16 12 9 FN 9354 3 57 9 77 10 57 1352 15 44 17 64 16 65 10 10 74 8 53 3 11 8 49 9 95 13 22 15 41 17 72 16 09 11 10 98 767 3 68 8 91 9 74 13 65 WE 16 73 12 10 72 8 92 3 76 10 38 14 48 14 96 18 06 16 05 13 11 57 8 61 1357 16 05 1851 16 60 14 12 26 4 93 11 04 1499 15 40 18 09 16 46 15 11 9 9 57 5 10 9 30 10 84 14 77 15 61 1885 16 76 16 11 33 8 84 5 04 8 25 10 46 12 94 15 72 18 00 16 28 17 MOA 8 46 2 46 8 31 o2 are 15 78 18 40 17 11 18 10 66 9 03 3 31 8 65 9 86 13 32 15 71 17 91 16 46 19 10 66 8 45 M226 8 79 10 14 14 94 16 03 19 47 16 58 20 12 06 9 80 4 18 9 42 11 06 EB 15 77 18 35 17 16 considered as cold year considered as normal year considered as warm year 34 4 Working with ESCAPE 4 1 Installing ESCAPE Perform following steps for the installation of ESCAPE Call ESCAPE_setup exe Select a directory and start unzipping the files into a temp folder After unzipping close ESCAPE_setup zip call setup exe in the folder where the files were unzipped aS eS SS ESCAPE may be un installed using first the standard MS Windows un install tools provided in the Control Panel under Add Remove Programs After successful installation the program logo appears as shown in the next figure ar ey Estimation of Soil Concentrations After PEsticide applications Eile Edit Yiew Help Figure 12 ESCAPE Intro screen 35 After pressing the button
62. 72 1 3170 1 3061 1 3011 2 0000 1 3011 1 2738 1 2462 1 2697 4 0000 1 2697 1 2111 1 1374 1 2099 7 0000 1 2244 1 1469 0 9982 1 1270 14 0000 1 1270 1 0549 0 7793 0 9620 21 0000 1 0400 0 9973 0 6847 0 8292 28 0000 0 9620 0 9559 0 6297 0 7215 42 0000 0 8292 0 8974 0 5607 0 5612 50 0000 0 7650 0 8725 0 5322 0 4934 100 0000 0 4935 0 7767 0 4153 0 2675 a tillage depth of 5 cm was considered for calculating the background concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 1 All soil studies Made Parent onhe presented substance Testade kinetics SFO wut tun 14 1 3 soil study T soil study 2 soil study 3 soil study 4 12 11 ilpuluulunluulunl 0 9 0 8 07 0 6 05 0 4 03 02 01 o huslushslunlunhbnlunbaslishslnlihulubnbslash 50 100 150 200 250 300 350 Time after first application d 74 On the following four pages copies ofthe ESCAPE report for the same studies are presented summarising the input data and all important results based on Hamburg climatic conditions and considering soil moisture and temperature correction ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 16 Feb 2009 Date of this simulation 16 02 2009 13 49 11 Calculation problem Report example 1 Hamburg PROGRAM SETTINGS Calculation mode Resid
63. 749 occurring on day 66 Calculated PECact in soil over 1 5 cm for Metabolidan mg L Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 2522 6 8370 1 6177 0 7734 2 0000 1 2820 5 4496 1 6438 0 7266 4 0000 1 2101 4 0863 1 5780 0 6310 7 0000 1 1045 4 0780 1 4788 0 5684 14 0000 0 8773 4 0514 1 2584 0 4552 21 0000 1 2210 4 0232 1 6273 0 3794 28 0000 1 0896 3 9833 1 4975 0 3030 42 0000 0 8129 5 9655 1 2418 0 2836 50 0000 1 0895 6 9442 1 5403 0 3199 100 0000 0 6800 6 7322 1 2528 0 1612 PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 1 5 cm for Metabolidan mg L Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 2730 7 2586 1 6433 0 7742 2 0000 1 2730 7 1571 1 6427 0 7706 4 0000 1 2707 6 8677 1 6416 0 7536 7 0000 1 2425 6 7797 1 6195 0 7282 14 0000 1 2345 6 6780 1 6046 0 6944 21 0000 1 2313 6 6584 1 6026 0 6596 28 0000 1 2124 6 6586 1 5991 0 6274 42 0000 1 2033 6 6567 1 5947 0 5803 50 0000 1 1978 6 6564 1 5916 0 5559 100 0000 1 1811 6 5445 1 5729 0 4452 Calculation of background concentrations after many years Final background concentration in pore water for Metabolidan over 5 cm soil study 1 mg L 1 0048 estimated to occur after 10 years soil study 2 mg L 27 5037 estimated to occur after 13 years soil study 3 mg L 4 3420 estimated to occur after 11 years soil study 4 mg L 0 1475 estimated to occ
64. ATION OF THE CALCULATION c mg kg Annual concentration of Report example 2 Study soil study 4 Made Parent ons presented substance Testade thinetics SFO in 0 5 lal l l lilylil lulilililshilihilililihilililil o TTT TTT TTT TTT 250 300 350 Time after first application d o a S S 5 a S w S S 91 Here the respective report is shown when ESCAPE is in its summary mode Results of all four studies are summarised in a single file and the diagram includes results of all studies ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation 17 02 2009 11 51 25 Calculation problem Report example 2 SUMMARY REPORT CONSIDERING ALL SOIL STUDIES PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Iteration of annual application pattern over 10 years SCENARIO DATA USED IN THE CALCULATION Name of the scenario Report example 2 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentra
65. C Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C soil study 1 Active compound and a single metabolite Single First order SFO 7 0 099 2 58 0 7 20 Single First order SFO 35 0 0198 2 58 0 7 20 s107 RESULTS OF THE CALCULATION Metabolism scheme RESULTS FOR Testicide Calculations over one year Active compound and a single metabolite Maximum annual total soil concentration for Testicide over 5 cm mg kg on day 0 Calculated time dependent total soil concentrations over 5 cm for Testicide after one year mg kg Time d PECact 1 1 2989 2 1 2727 4 1 2012 7 1 1152 14 0 9820 21 0 7449 28 0 5577 42 0 3568 50 0 2825 100 0 0339 PECtwa 1 3161 1 3010 1 2708 1 2222 1 1288 1 0443 0 9417 0 7790 0 7044 0 4076 PECact values are related to the time after the first application Calculation of background concentrations after many years Begin TWAframe d sooo eo eo Final Background concentration in total soil for Testicide over 5 cm mg kg estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Testicide over 5 cm considering accumulation mg kg a tillage depth of 5 cm was considered for calculating the
66. CULATION Name of the scenario Report example 2 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 1st Application date 1 May Application rate g ha 1000 Time between two applications d 14 Crop interception 50 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 4 Metabolism scheme Parent compound without metabolites Kinetics for Report example 2 Single First order SFO DT50 d 140 Rate constant 1 d 0 005 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 2 Calculations over one year Maximum annual total soil concentration for Report example 2 over 5 cm mg kg 2 4106 occurring on day 42 90 Calculated time dependent total soil concentrations over 5 cm for Report example 2 after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAfra
67. Calculation of PEC soi including Plateau Concentrations for Pesticides Dependent on FOCUS Degradation Kinetics 360 03 042 User Manual ESCAPE Version 2 Fraunhofer Institut Molekularbiologie und Angewandte kologie 57392 Schmallenberg Institutsleitung Prof Dr R Fischer Projektleitung Dr M Klein Schmallenberg 8 Dezember 2008 2 Berichts Kennblatt Berichtsnummer 1 UBA FB 2 3 Weiterentwicklung des Programms ESCAPE f r Higher Tier Simulationen zur Berechnung von PEC Boden Werten einschlie lich Plateaukonzentrationen f r Pflanzenschutzmittel PSM unter Einbeziehung der FOCUS Abbaukinetiken 5 Autor en Name n Vorname n 8 Abschlussdatum Michael Klein 8 12 2008 9 Ver ffentlichungsdatum 10 UFOPLAN Nr 6 Durchf hrende Institution Name Anschrift 360 03 042 Fraunhofer Institut 11 Seitenzahl Molekularbiologie und Angewandte Okologie 141 Auf dem Aberg 1 12 Literaturangaben 57392 Schmallenberg 4 13 Tabellen und Diagramme 7 F rdernde Institution Name Anschrift 7 Umweltbundesamt W rlitzer Platz 1 06844 Dessau 14 Abbildungen 29 15 Zus tzliche Angaben 16 Kurzfassung In diesem Projekt wurde das im Jahr 2008 erstellte Programm ESCAPE Estimation of Soil Concentrations After PEsticide applications zur Berechnung von zeitabh ngigen Pflanzenschutzmittelkonzentrationen im Boden in folgenden Punkten weiterentwickelt Porenwasse
68. E L Studie 0 2 7 L_Studie u 4 0 0 50 100 150 200 250 300 350 Time d Figure 30 ESCAPE Graphical results for the first metabolite compound View Summary Bi 5 References FOCUS 1996 Soil Persistence Models and EU Registration European Commission Document No 7617 VI 96 URL http europa eu int comm food plant protection evaluation focus_en htm FOCUS 2000 FOCUS groundwater scenarios in the EU review of active substances Report of the FOCUS Groundwater Scenarios Workgroup EC Document Reference Sanco 321 2000 rev 2 202pp FOCUS 2006 Guidance Document on Estimating Persistence and Degradation Kinetics from Environmental Fate Studies on Pesticides in EU Registration Report of the FOCUS Work Group on Degradation Kinetics EC Document Reference Sanco 10058 2005 version 2 0 434 pp Klein M 2008 Calculation of PECsoil including Plateau Concentrations for Pesticides Dependent on FOCUS Degradation Kinetics FKZ 360 03 037 Umweltbundesamt Dessau Ro lau 6 Results of test simulations BD 6 1 Single application parent compound only several soil studies The input parameters for the simulations are summarised in Table 3 TWA times according to EU guidelines were used for the calculations Table 3 Series of special times used by ESCAPE to calculate PEC and PECtwa Parameter Soil study 1 Soil study 2 Soil study 3 Soil study 4 soil density kg L 1 5 soil dep
69. ECtwa 1 5575 1 5424 1 5122 1 4636 1 3702 1 2857 1 1831 1 0387 0 9884 0 8293 Begin TWAframe d SD 9995959 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application RESULTS FOR Metabolidan Calculations over one year Maximum annual total soil concentration for Metabolidan over 5 cm mg kg on day 32 This is 59 58 of the theoretical maximum concentration of the metabolite End TWAframe d 0 6355 occurring Calculated time dependent total soil concentrations over 5 cm for Metabolidan after one year mg kg Time d PECact 0 6335 0 6313 0 6267 0 6219 0 6215 0 6213 0 6266 0 6232 0 6096 0 5798 PECtwa 0 6345 0 6337 0 6332 0 6321 0 6299 0 6275 0 6258 0 6255 0 6244 0 6072 Begin TWAframe d End TWAframe d 114 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in total soil for Metabolidan over 5 cm mg kg 1 5434 estimated to occur after 11 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Metabolidan over 5 cm considering accumulation mg kg 2 1789 a tillage depth of 5 cm was consid
70. Graphical results for the first metabolite View Individual study The final diagram is always a presentation of all compounds involved within one figure as shown in Figure 28 59 c ma kg Program check Study Sandy loam 1 1 Made Farem wih 7 metabole Testicide PEC TWA 28 d 0 8 Metabolidan PEC TWA 28 d 0 50 100 150 200 250 300 350 Time d Figure 28 ESCAPE Graphical results for all compounds View Individual study The diagram presented in the previous figures were all related to the ESCAPE s View Individual study mode However similar diagrams will also be prepared in the View Summary mode of ESCAPE The respective are shown in the following two figures In this mode the blue colour always represent the results of the first and the green colour the results of the second soil study Due to too much complexity there is no diagram available that shows the results of different soil studies and different compounds 60 c ma kg Program check All soil studies Made Farent and 2 melabalies sequence presented suasiance Testode tunes HS L_Studie pae L_Studie 0 6 0 5 0 4 0 3 0 2 0 1 0 50 100 150 200 250 300 350 Time d Figure 29 ESCAPE Graphical results for the parent compound View Summary e mg kg Program check All soil studies Made Faremt wiih 7 meishallte presented suasiance Meiskahdan kineta SO 0 4 4 03 4
71. HE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 3 Calculations over one year Maximum annual total soil concentration for Report example 3 over 1 5 cm soil study 1 mg kg 1 5296 occurring on day 31 soil study 2 mg kg 0 9502 occurring on day 9 Calculated PECact in soil over 1 5 cm for Report example 3 mg kg Time d soil study 1 soil study 2 1 0000 1 5151 0 8008 2 0000 1 4983 0 7167 4 0000 1 4609 0 6309 7 0000 1 4158 0 4751 14 0000 1 3258 0 2167 21 0000 1 2636 0 1614 28 0000 1 1389 0 2370 42 0000 1 0544 0 1421 50 0000 0 9756 0 1061 100 0000 0 5364 0 0526 PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 1 5 cm for Report example 3 mg kg Time d soil study 1 soil study 2 1 0000 1 5224 0 8755 2 0000 1 5146 0 8172 4 0000 1 4973 0 7451 7 0000 1 4712 0 6768 14 0000 1 4232 0 5193 21 0000 1 3849 0 4736 28 0000 1 3432 0 4058 42 0000 1 3241 0 3618 50 0000 1 3058 0 3301 100 0000 1 1340 0 2146 Calculation of background concentrations after many years Final background concentration in total soil for Report example 3 over 5 cm soil study 1 mg kg 0 1096 estimated to occur within 10 years soil study 2 mg kg 0 0043 estimated to occur within 10 years Calculations of concentrations considering accumulation after many years of application Maximum annual concentration in total soil for
72. INGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 4 Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 Single First order SFO DT50 d 14 Rate constant 1 d 0 0495 Q10 factor 1 Walker exponent 0 0 Ref temperature C 0 0 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 1 Calculations over one year Maximum annual total soil concentration for Report example 1 over 5 cm mg kg 1 3333 occurring on day 0 Calculated time dependent total soil concentrations over 5 cm for Repo
73. RAMETERS CONSIDERED FOR THE CALCULATION Metabolism scheme Active compound and a single metabolite Soil study soil study 1 Kinetics for Testicide Single First order SFO DT50 d 70 Rate constant 1 d 0 0099 Q10 factor 2 58 137 Walker exponent Ref temperature C Soil study Kinetics for Testicide alpha i_studie Beta Q10 factor Walker exponent Ref temperature C Soil study Kinetics for Testicide DT50 d DT50 d Rate constant 1 1 d Rate constant 2 1 d Parameter Tb d Q10 factor Walker exponent Ref temperature C Soil study Kinetics for Testicide DT50 d DT50 d Rate constant 1 1 d Rate constant 2 1 d Parameter g Q10 factor Walker exponent Ref temperature C Soil study Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C Soil study Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C Soil study Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C Soil study Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C 0 7 20 soil study 2 First Order Multi Compartment FOMC 4 4 2 58 0 7 20 soil study 3 Hockey Stick HS 7 70
74. Report example 1 Hamburg Calculations over one year 79 Maximum annual total soil concentration for Report example 1 Hamburg over 5 cm mg kg 1 3333 occurring on day 0 Calculated time dependent total soil concentrations over 5 cm for Report example 1 Hamburg after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 2989 1 3161 0 1 2 1 2727 1 3010 0 2 4 1 2012 1 2708 0 4 T 1 1152 1 2222 0 7 14 0 9820 1 1288 0 14 21 0 7449 1 0443 0 21 28 0 5577 0 9417 0 28 42 0 4896 0 7973 0 42 50 0 4783 0 7470 0 50 100 0 3870 0 5879 0 100 PECact values are related to the time after the first application Calculation of background concentrations after many years Final Background concentration in total soil for Report example 1 Hamburg over 5 cm mg kg 0 2414 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 1 Hamburg over 5 cm considering accumulation mg kg 1 5747 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 1 Hamburg mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 5403 1 5575 0 1 2 1 5141 1 5424 0 2 4 1 4426 1
75. Report example 3 over 5 cm considering accumulation soil study 1 mg kg 1 6392 occurring on day 31 soil study 2 mg kg 0 9546 occurring on day 9 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Report example 3 mg kg considering accumulation Time d soil study 1 soil study 2 1 0000 0 8123 0 4532 2 0000 1 4761 0 3782 4 0000 1 4696 0 2869 7 0000 1 4610 0 2293 14 0000 1 4369 0 1687 21 0000 1 3186 0 1436 28 0000 1 2473 0 1104 104 42 0000 1 5370 0 0987 50 0000 1 3813 0 0851 100 0000 1 2485 0 0457 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Report example 3 mg kg considering accumulation Time d soil study 1 soil study 2 1 0000 1 6319 0 8799 2 0000 1 6241 0 8215 4 0000 1 6069 0 7494 7 0000 1 5808 0 6811 14 0000 1 5328 0 5236 21 0000 1 4945 0 4780 28 0000 1 4528 0 4101 42 0000 1 4337 0 3662 50 0000 1 4154 0 3345 100 0000 1 2436 0 2189 a tillage depth of 5 cm was considered for calculating the background concentration GRAPHIC REPRESENTATION OF THE CALCULATION Annual concentration of Report example 3 All soil studies 2 a 3 rr 2 a 2 Made Farent onhe presented substance Testade tRhinetcs FOMC nm
76. THE CALCULATION So RES Metabolism scheme RESULTS FOR Testicide Calculations over one year Active compound and a single metabolite Maximum annual total soil concentration for Testicide over 5 cm mg kg on day 0 Calculated time dependent total soil concentrations over 5 cm for Testicide after one year mg kg Time d 100 PECact 1 2989 1 2727 1 2012 1 1152 0 9820 0 7449 0 5577 0 4896 0 4783 0 3870 PECtwa 1 3161 1 3010 1 2708 1 2222 1 1288 1 0443 0 9417 0 7973 0 7470 0 5879 PECact values are related to the time after the first application Calculation of background concentrations after many years Begin TWAframe d Ore Oi S e O Ore e Final Background concentration in total soil for Testicide over 5 cm mg kg estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Testicide over 5 cm considering accumulation mg kg a tillage depth of 5 cm was considered for calculating the background concentration 1 3333 occurring End TWAframe d 0 2414 1 5747 Calculated time dependent total soil concentrations over 5 cm for Testicide mg kg considering accumulation Time d 100 PECact 1 5403 1 5141 1 4426 1 3566 1 2234 0 9863 0 7991 0 7310 0 7197 0 6284 P
77. TION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 3 Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 Hockey Stick HS 7 DT50 1 d DT50 2 d 70 Rate constant 1 1 d 0 099 Rate constant 2 1 d 0 0099 Parameter Tb 10 Q10 factor 1 Walker exponent 0 0 Ref temperature C 0 0 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 1 Calculations over one year 68 Maximum annual total soil concentration for Report example 1 over 5 cm mg kg 1 3333 occurring on day 0 Calculated time dependent total soil concentrations over 5 cm for Report example 1 after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 2076 1 2705 0 1 2 1 0938 1 2106 0 2 4 0 8973 1 1018 0 4 7 0 6667 0 9626 0 7 14 0 4761 0 7437 0 14 21 0 4442 0 6492 0 21 28 0 4145 0 5942 0 28 42 0 3608 0 5251 0 42 50 0 3333 0 4966 0 50 100 0 2032 0 3798 0 100 PECact values are related to the time after the first application Calculation of background concentrations after many years Final Background concentration in total soil for Report example 1 over 5 cm mg kg 0 0149 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximu
78. a 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 2 Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 Hamburg First Order Multi Compartment FOMC Alpha 0 2 Beta 2 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 1 Hamburg Calculations over one year Maximum annual total soil concentration for Report example 1 Hamburg over 5 cm mg kg 1 3333 occurring on day 0 Calculated time dependent total soil concentrations over 5 cm for Report example 1 Hamburg after one year mg kg 77 Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 3007 1 3170 0 1 2 1 2782 1 3032 0 2 4 1 2251 1 2785 0 4 7 1 1725 1 2438 0 7 14 1 1062 1 1877 0 14 21 1 0136 1 1461 0 21 28 0 9516 1 1036 0 28 42 0 8874 1 0419 0 42 50 0 8624 1 0148 0 50 100 0 7358 0 9004 0 100 PECact values are related to the time after the first application Calculation of background concentrations after many years Final Background concentration in total soil for Report example 1 Hamburg over 5 cm mg kg 1 1094 estimated to occur after 10 years according to the estimation 100 of the final plateau was rea
79. accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 5 1203 5 0480 5 3542 2 8779 2 0000 5 1178 5 0339 5 3476 2 8720 4 0000 5 1130 5 0116 5 3344 2 8602 7 0000 5 1057 4 9862 5 3153 2 8426 14 0000 5 0889 4 9440 5 2817 2 8022 21 0000 5 0723 4 9132 5 2535 2 7628 28 0000 5 0557 4 8884 5 2325 2 7242 42 0000 5 0231 4 8494 5 2041 2 6526 50 0000 5 0048 4 8313 5 1914 2 6126 100 0000 4 8951 4 7517 5 1286 2 4177 a tillage depth of 5 cm was considered for calculating the background concentration GRAPHIC REPRESENTATION OF THE CALCULATION mg kg Background concentration of Report example 2 All soil studies 6 Mode Parentanly presented substance Tosscide neses SFO 0 500 1000 1500 2000 2500 3000 3500 Time after first application d 94 6 3 Irregular applications parent compound only several soil studies The input parameters for the simulations are summarised in Table 5 TWA times according to EU guidelines were used for the calculations Table 5 Series of special times used by ESCAPE to calculate PEC and PECtwa Parameter Soil study 1 Soil study 2 soil density kg L 1 5 soil depth cm 5 application rate g ha 500 750 600 1000 crop interception 0 25 50 90 application dates d 1 May 10 May 1 June 1 July Degradation type SFO FOMC SFO DT50 d 25 alpha 1 beta 1 separate consideration of residues within th
80. adio buttons in the left bottom part of the form can be used to switch between total content in soil and pore water concentrations see the rectangle in Figure 19 The graphs are re constructed instantaneously because calculations are always performed for both endpoints independent on the actual settings A ESCAPE Estimation of Soil Concentrations After PEsticide applications Eile Edit pesticide data View Help Current Simulation Copy Programcheck y Del Description Programcheck _ Programcheck v Del Parent only Parent with 1 metabolite Parent and 2 metabolites parallel Parent and 2 metabolites sequence l Borstel Edit ESCAPE FOCUS Hamburg median conditio Estimation of Soil Concentrations After PEsticide Applications Anolican pplication pattern developed a Michael Klein Copy Programcheck vj Del single C regular irregular Program version 2 0 18 Dec 2008 Date of first application 1 yi May ov Date of this simulation 12 02 2009 11 27 18 Applikation rate g ha 1000 Calculation problem Programcheck r TREN 0 2 PROGRAM SETTINGS Crop interception Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year Compound data Copy Programcheck yj Del Soil soil study 1 v Add study Degradation Sorption Metabolism SCENARIO DATA USED IN THE CALCULATION Name of the scenari
81. ater for Metabolidan over 5 cm mg L 0 1475 estimated to occur after 11 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Metabolidan over 5 cm considering accumulation mg L 0 9224 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent pore water concentrations over 5 cm for Metabolidan mg L considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 9209 0 9217 66 67 2 0 8741 0 9181 65 67 4 0 7785 0 9011 64 68 7 0 7159 0 8757 62 69 14 0 6027 0 8419 57 71 21 0 5269 0 8071 52 18 28 0 4505 0 7749 49 TE 42 0 4311 0 7278 40 82 50 0 4674 0 7034 33 83 100 0 3087 0 5927 20 120 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg L Annual concentration of Report example 5 Study soil study 4 8 Made Farem wih T metabaliie Testicide PEC TWA 28 d TWA 28 d Metabolidan PEC 0 50 100 150 200 250 300 350 Time after first application d 136 Here the respective report is shown when ESCAPE s summary mode was selected Results of all four studies are summar
82. be easily expressed based on the two fitting parameters a and B as shown in the next equations A z DT50 B 2 1 7 DT90 Bl 10 1 8 An example for a time dependent soil concentrations using the FOMC model is presented in Figure 2 13 c mg kg Program check Study Sandy loam 1 Made Farem anhe gresented su stence Testade thinetcs POMC 11 0 9 0 8 u 0 7 0 6 0 5 0 4 PEED4O TWA 28 d 0 3 0 2 0 1 0 50 100 150 200 250 300 350 Time d Figure 2 FOMC model 1 kg ha 0 2 8 2 soil depth 5 cm 3 1 3 DFOP Double First Order in Parallel kinetics DFOP is a bi exponential model that describes degradation by a sum of two normal first order degradation each in different part of the soil compartment It needs in total 3 parameters one more than the FOMC model namely the two different first order rate constants and the fraction of the pesticides being degraded according to the first rate constant The equation of the DFOP model is presented in equation 9 C Cy g exp ki l g exp ko 9 C pesticide concentration at time mg kg Co concentration at time t 0 g fraction of the pesticide applied to the first compartment ky rate constant in the first compartment 1 d kp rate constant in the second compartment 1 d 14 With its two different exponentials terms the model is too complicated to define a differential equation or to calculate DT50 and DT90 values bas
83. central diagram selecting the PEC Type in the graph 56 ESCAPE Graphical results for the parent compound View Individual study 57 ESCAPE Graphical results for the first metabolite View Individual study 58 ESCAPE Graphical results for all compounds View Individual study 59 ESCAPE Graphical results for the parent compound View Summary 60 ESCAPE Graphical results for the first metabolite compound View Summary 60 1 Summary A software called ESCAPE Estimation of Soil Concentration After PEsticide applications was developed that can be used to calculate actual as well as time weighted average concentrations in soil for the parent compound and additional metabolites In addition to SFO kinetics single first order the software is able to consider hockey stick kinetics HS FOMC kinetics first order multi compartment and DFOP kinetics double first order in parallel ESCAPE can handle singular and multiple applications over a simulation period of 10 years The user may also enter irregular application pattern within a year ESCAPE considers different soil depths and performs corrections of actual rates dependent on the current crop interception automatically Visualisation of results is carried out graphically diagram showing the simulated concentrations vs time and tabularly based on time intervals as defined by EU or national regulations In the new version 2 0
84. ched after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 1 Hamburg over 5 cm considering accumulation mg kg 2 4427 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 1 Hamburg mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 2 4101 2 4264 0 1 2 2 3876 2 4126 0 2 4 2 3345 2 3879 0 4 7 2 2819 2 3532 0 7 14 2 2156 2 2971 0 14 21 2 1230 2 2555 0 21 28 2 0610 2 2130 0 28 42 1 9968 2 1513 0 42 50 1 9718 2 1243 0 50 100 1 8452 2 0098 0 100 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application GRAPHIC REPRESENTATION OF THE CALCULATION Annual concentration of Report example 1 Hamburg Study soil study 2 2 3 2 s Made Parent onfe presented substance Testade kinetics FOMC 14 1 3 1 2 11 09 08 0 7 0 6 0 5 0 4 fc mA 0 3 0 2 0 1 gt Emam eer Or ee A uu TTTOTPTOTOOOPTTOTOOOTOOTOOOOOOOTOnnmeon 50 100 150 200 250 300 350 Time after first application d 78 ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Pro
85. concentration TWA in graph TWA 28 d Annual Background Save input Report Exit Current Outputfile Programcheck soil study 1 SFO total soil conc C Accum Figure 18 ESCAPE displaying the report file Parent ce 3 Creating reports A click at this button generates an output file presenting all results of the simulation the current input data setting and the actual diagram shown on the screen The file will be written in RTF format and directly saved in the ESCAPE output folder The name of the file can be customised using the menu bar edit preferences The actual name is echoed at the bottom of the main form current output file When a report is created it is also displayed at the main form see Figure 18 It is possible to do some limited text processing scrolling with cursor keys copying into the clipboard with ctrl C After a double click at the report the standard diagram sheet returns on top of the screen and the report disappears Dependent on whether ESCAPES provides information about an individual study or collects summary information about more than one soil study the report file looks differentially The menu items View Summary or View Individual studies can be used to switch between these two modes Via the menu bar File menu reports can be also printed 46 Exit This button will terminate the program 4 6 Direct endpoint selection The r
86. cted weather year at the FOCUS locations 00 ccccssseeeeceeeeeeseseeeeeeeeeeeeeees 33 Table 3 Series of special times used by ESCAPE to calculate PECa and PECtwa 62 Table 4 Series of special times used by ESCAPE to calculate PECa and PECtwa 82 Table 5 Series of special times used by ESCAPE to calculate PECa and PECtwa 94 Table 6 Series of special times used by ESCAPE to calculate PEC and PECtwa 105 Table 7 Series of special times used by ESCAPE to calculate PECa and PECtwa 123 List of Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 Figure 17 Figure 18 Figure 19 Figure 20 Figure 21 Figure 22 Figure 23 Figure 24 Figure 25 Figure 26 Figure 27 Figure 28 Figure 29 SFO model 1 kg ha ksro 0 05 d soil depth 5 cm 11 FOMC model 1 kg ha a 0 2 B 2 soil depth 5 CM nmeeersemennensnnnnnn 13 DFOP model 1 kg ha k 0 2 d k 0 02 d g 0 8 soil depth 5 cm 14 HS model 1 kg ha k 0 1d k 0 01 d t 10 d soil depth 5 cm 16 A series of compartments if residues from different applications are kept separately wait dutuiebiatan dan tyne E LERERTERRCERERERELETENEBERWELEEEHEEFFEARCHERRERERLEIEHEGERFRERELPRSREHNFBERTERLGERFTEREL ERST 20 Two compartments for parent a
87. d Co initial pesticide concentration mg kg R application rate mg m d soil depth m p soil density kg m Ic crop interception 3 4 2 Time dependent concentrations As analytical solutions are not available for many situations especially when the formation of metabolites is considered ESCAPE generally calculates time dependent concentrations numerically in a stepwise approach assuming a minimum time step of one day Independent on the degradation kinetics the concentrations of the parent compound is calculated based on the initial concentrations at day t 0 and using the integrated mathematical descriptions of the models as explained earlier in chapter 3 1 for all degradation models Dependent on the degradation model it may be important whether or not residues from different application are kept separately Figure 9 shows the time dependent concentration if residues from different applications are not separated Due to the fast degradation shortly after applications for this example of a FOMC kinetics no accumulation in soil is calculated If as a second option residues from different applications are kept separately an initial concentration and an individual starting point will be defined for every application according to equation 27 The actual concentration in soil is then calculated as the sum of all pesticide residues from previous applications This is demonstrated exemplarily for the FOMC kinetics in equation 22
88. d concentrations To estimate the background concentrations calculations are always performed over ten years Dependent on the degradation parameters the final plateau might not be reached within this period Therefore ESCAPE performs an additional estimation about the maximum plateau concentration obtained after infinite years of applications For this estimation the last three maximum annual soil concentrations are considered maximums in the years 8 9 and 10 The derivative of the parabola through these three 31 maximums is calculated and based on this function the final maximum plateau after many years is estimated The final bottom plateau is then calculated by abstracting the maximum concentration in the first year 3 4 5 Annual concentrations considering accumulation ESCAPE uses the background concentration and the time dependent concentrations in the first year for the calculation of annual concentrations including accumulation PEC ccum according to the following equation PE Caden Cbackground P ECyeart 2 6 PECaccum Time dependent concentration including accumulation mg kg PEC ear1 Time dependent concentration in the first year mg kg Chackeronnd background concentration related to tillage depth mg kg 32 3 5 Calculation of pore water concentrations For the calculation of pore water concentrations it is assumed that there is equilibrium between soil water and soil matrix for all compounds Bas
89. d substance Testade thinetos FAC 4 3 2 PEC TWA 28d _ 0 500 1000 1500 2000 2500 3000 3500 Time d Figure 9 FOMC model 10 4 applications 0 2 B 2 separating of residues switched off c mg kg Program check Study Sandy loam 1 20 Made Farem anhe presented su siance Testade thinetcs FOMC 15 10 5 TWA 28 d 0 0 500 1000 1500 2000 2500 3000 3500 Time d Figure 10 FOMC model 10 4 applications a 0 2 B 2 separating of residues switched on 28 c mg kg Program check Study Sandy loam 1 6 Made Farem onhe gresenied suasiance Festode thinetcs FOMC 5 4 3 2 PEC TWA 28 d l 1 0 0 500 1000 1500 2000 2500 3000 3500 Time d Figure 11 FOMC model 10 4 applications a 0 2 B 2 separating of residues within a year Of course the differences between the three options are highly influenced by the fitting parameters used in the calculation As already mentioned if single first order or DFOP kinetics are selected there is no difference between these options The time dependent concentrations for metabolites are calculated similarly as for the parent compound Instead of a series of applications the daily formation is considered as the base for soil concentrations The formation is calculated considering the ratio of the molecular masses and the formation rate according to the equations presented in chapter 3 3 2 to chapter 3 3 4 The degradation of metabolit
90. e used to estimate soil concentrations First the soil density kg L the normal ecologically relevant soil depth cm and the tillage depth cm Whereas the soil density has to be explicitly typed by the user a selection have to be made out of three options for the soil and the tillage depth For the soil depth either radio buttons for 2 5 cm and 5 cm or individual soil depths can be considered For the tillage depth used for background concentrations either radio buttons for 5 cm pasture and 20 cm agriculture field or individual tillage depths can be selected If individual depths are selected a list box will appear to select the favoured value To calculate pore water concentrations the organic carbon content in soil is needed The other two soil parameters field capacity and wilting point are used to estimate dynamic soil moistures dependent on the weather conditions A suitable weather can be attached to the soil profile which itself cannot be modified in the shell However weather files are in ASCII data in the same format as PELMO weather files FOCUS 2000 39 4 3 2 Application related parameters In total seven different parameter define the application pattern summarised in a yellow frame if coloured frames are switched on see preferences Application mode First the user has to decide between three different application models single applications regular application or irregular application
91. e year of application only On the following two pages copies of the ESCAPE report for both soil studies are presented summarising the input data and all important results 95 ESCAPE Estimation of Soil Concentrations After PEsticide Applications Program version Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode developed by Michael Klein 2 0 17 Feb 2009 17 02 2009 13 51 11 Report example 3 Residues from different applications are considered separately over one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Mean temperature C Annual Rainfall mm Report example 3 Borstel 1 5 5 5 1 5 29 2 6 4 Laboratory conditions 19 5 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Month Rate g ha Interception 05 500 0 05 750 25 06 600 50 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics
92. ed for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Report example 3 mg kg considering accumulation Time d soil study 1 soil study 2 1 0000 1 2522 0 6267 2 0000 1 2351 0 5363 4 0000 1 2018 0 4291 7 0000 1 1540 0 3256 14 0000 1 0543 0 2600 21 0000 0 9711 0 2133 28 0000 0 9691 0 1783 42 0000 0 9074 0 1639 50 0000 0 8579 0 1473 100 0000 0 6355 0 0951 a tillage depth of 5 cm was considered for calculating the background concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 3 All soil studies Made Parent onhe presented substance Testade Kihetics FOMC soil study 1 pa soil study 2 0 50 100 150 200 250 300 350 Time after first application d On the following pages copies of the ESCAPE report for the same studies are presented summarising the input data and all important results based on Hamburg climatic conditions and considering soil moisture and temperature correction again summary mode ESCAPE Estimation of Soil Concentrations After PEsticide Applications 102 developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation 17 02 2009 14 16 14 Calculation problem Report example 3 SUMMARY REPORT CONSIDERING ALL SOIL STUDIES
93. ed on the three fitting parameters k k2 and g These parameters have to be found by iterative procedures However an example for the DFOP model that can be used for parent compounds as well as for metabolites is presented in Figure 3 c mg kg Program check Study Sandy loam 1 Made Parent ane mesened su sisnce Testode funetcs OFOF PECs TWA 28 d 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 Time d Figure 3 DFOP model 1 kg ha k 0 2 d k 0 02 d g 0 8 soil depth 5 cm 3 1 4 HS Hockey Stick kinetics In contrast to the DFOP model the hockey stick kinetics consist of two sequential first order declines First the pesticide completely degrades according to the first degradation rate Ata certain time degradation switches completely to a second degradation rate To describe the HS model the same number of parameters three is needed as for the DFOP model A mathematical description of this model is presented in equation 0 15 C Co exp k t Jort t C Co exp k ty exp k gt t ty for t gt t C pesticide concentration at time mg kg Co concentration at time t 0 mg kg ty breakpoint when rate constant changes ky rate constant before t t 1 d ky rate constant after t t 1 d The HS model can be expressed also by its underlying differential equation as presented in equation 77 us k C for tS ty dt 11 dC h2C for t gt tp dt A d
94. ed on this assumption the pore water concentrations are calculated using following equation Cr Loe Ka 27 Crw PELO Cpw pore water concentration mg L Cr total content in soil mg kg Corg organic carbon content in soil Ka sorption constant L kg p soil density kg m actual soil moisture m m mecca 3 6 Consideration of scenario soil profiles and weather files ESCAPE is able to calculate soil concentrations based on pre defined weather and soil scenarios As no special scenarios has been defined in the field of persistence in soil so far the nine FOCUS groundwater standard scenarios have been implemented in this version of ESCAPE All scenarios are based on a combination of the first horizon of the FOCUS soil scenario and a single weather year same location that has been selected based on cold normal warm weather conditions A summary of the annual temperatures at the locations and the respective years selected for ESCAPE is given in Table 2 Table 2 Selected weather year at the FOCUS locations Chateau Krems Oke Year dun Hamburg Jokioinen m nster hampton Piacenza Porto Sevilla Thiva 1 12 41 10 26 5 83 9 89 11 56 13 57 19 35 2 12 52 5 86 8 99 11 64 1426 15 41 18 67 3 11 24 9 80 8 74 10 56 1416 14 94 18 00 15 69 4 11 55 10 29 6 31 9 90 11 62 BEE i488 18 94 16 39 5 10 88 9 17 3 68 9 30 10 78 14 83 15 51 18 46 16 80 6 EE 10 27 493 RGSS 1565 1531 7 11 35 10 20 5 71 9 54 10 83 14 61 1
95. ef temperature C Kinetics for Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C soil study 4 Active compound and a single metabolite Double First Order in Parallel DFOP 7 140 0 099 0 005 0 5 2 58 0 7 20 Single First order SFO 14 0 0495 2 58 0 7 20 RESULTS OF THE CALCULATION siad Metabolism scheme Active compound and a single metabolite RESULTS FOR Testicide Calculations over one year Maximum annual pore water concentration for Testicide over 5 cm mg L on day 31 Calculated time dependent pore water concentrations over 5 cm for Testicide after one year mg L Time d PECact PECtwa Begin TWAframe d 1 0 3066 0 3088 31 2 0 3017 0 3065 31 4 0 2912 0 3015 31 7 0 2794 0 2943 31 14 0 2561 0 2813 30 21 0 2445 0 2719 30 28 0 2187 0 2626 30 42 0 2236 0 2562 9 50 0 2134 0 2524 9 100 0 1734 0 2320 9 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in pore water for Testicide over 5 cm mg L estimated to occur after 11 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Testicide over 5 cm considering accumulation mg L a tillage depth of 5
96. el is so simple and easy to work with because at any time the degradation of pesticide with time is directly proportional to the current concentration in soil as expressed in the following equation a ksro C 1 dt C pesticide concentration mg kg ksro rate constant 1 d As explained earlier after integration of equation 7 an exponential term is obtained for SFO kinetics as shown in the next equation 2 10 C Co exp ksro t 2 C pesticide concentration at time mg kg Co concentration at time t 0 mg kg Independent on the initial concentration the same time is always needed to reduce the concentrations to a fixed extend e g 50 or 90 Therefore simple and easy to interpret DT50 or DT90 values can be obtained when considering SFO kinetics as presented in the next equations Drso PP 3 pr90 ao 4 ksro ksro The SFO model can be used within ESCAPE for calculating the fate of parent compounds as well as for metabolites An example simulations is presented in Figure 1 11 c mg kg Program check Study Sandy loam 1 Made Faremt ONA presented su stance Testode thieves SFO PEC TWA 28 d 0 50 100 150 200 250 300 350 Time d Figure 1 SFO model 1 kg ha ksro 0 05 d soil depth 5 cm 3 1 2 FOMC First Order Multi Compartment kinetics The FOMC model was suggested by Gustafson and Holden 1990 with a mechanistic background As soil is a heterogeneous
97. ent applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 2 Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 First Order Multi Compartment FOMC Alpha 0 2 Beta 2 Q10 factor 1 Walker exponent 0 0 Ref temperature C 0 0 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 1 Calculations over one year Maximum annual total soil concentration for Report example 1 over 5 cm mg kg 1 3333 occurring on day 0 Calculated time dependent total soil concentrations over 5 cm for Report example 1 after one year mg kg 66
98. entration PECact values are related to the time after the first application GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 1 Hamburg Study soil study 1 Made Parent onh presented substance Testade thinetics SFO 14 1 3 1 2 qa 09 08 0 7 0 6 0 5 0 4 pec WA 028d 0 3 0 2 0 1 0 Former r r rr e rrr rrr 0 50 100 150 200 250 300 350 Time after first application d 76 ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 16 Feb 2009 Date of this simulation 16 02 2009 14 00 09 Calculation problem Report example 1 Hamburg PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g h
99. entration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 3 Study soil study 2 093 Made Parent onhe presented substance Testade thinetics FOMC 08 lt 07 4 0 6 0 5 0 4 03 I o2 4 Pec TWA 28d u 3 0 0 50 100 150 200 250 300 350 Time after first application d 99 Here the respective report is shown when ESCAPE is in its summary mode Results of both studies are summarised in a single file and also the diagram includes results of both studies ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation 17 02 2009 14 00 30 Calculation problem Report example 3 SUMMARY REPORT CONSIDERING ALL SOIL STUDIES PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Report example 3 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calculation of background co
100. ered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Metabolidan mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 2 1769 2 1779 32 33 2 2 1747 21771 67 69 4 2 1701 2 1766 66 70 7 2 1654 2 1756 64 71 14 2 1650 2 1733 59 73 21 2 1648 2 1710 54 75 28 2 1700 2 1692 47 75 42 2 1666 2 1689 31 73 50 2 1530 2 1678 30 80 100 2 1283 2 1506 26 126 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 3 Study soil study 3 Made Parent wih 7 meishballte 1 4 1 3 1 2 Testicide TWA 28 d 2 Metabolidan TWA 28 d 1 0 9 0 8 0 7 0 6 u 0 5 0 4 0 3 0 2 0 1 0 0 50 100 150 200 250 300 350 Time after first application d ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation 17 02 2009 14 45 22 115 Calculation problem Report example 4 PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Pro
101. es follows in principle the same equation as explained for parent compounds earlier in this chapter However in contrast to parent compounds there are no counters defined when new pesticide amounts arrive after applications These counters influence the rate of degradation when the kinetics follow the HS or the FOMC model Consequently these two kinetics are generally not available for metabolites 29 For risk assessment purposes some simulation days after the maximum soil concentration are highlighted due to regular comparisons with eco toxicity data ESCAPE considers two different lists of dates as summarised in Table 1 The times listed in this table are also the base for all time weighted average concentrations calculated by ESCAPE see the next chapter It is possible to change the lists by modifying the file ESCAPE ini Table 1 Series of special times used by ESCAPE to calculate PEC and PECtwa EU regulation BBA regulation Germany 1d 30 d 2d 60 d 4d 90 d 7d 120 d 14d 150 d 21d 180 d 28 d 210d 42d 240 d 50d 300 d 100 d 330 d 360 d 3 4 3 Time weighted average TWA concentrations In addition to maximum soil concentrations also time weighted average concentrations PECtwa are important endpoints for comparisons with results of eco toxicity ESCAPE uses two different lists for the duration of time weighted average concentrations see Table 1 These type of concentrations are calculated based on a moving time
102. for Report example 3 DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C soil study 1 Parent compound without metabolites Single First order SFO 25 0 0277 2 58 0 7 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 3 Calculations over one year 96 Maximum annual total soil concentration for Report example 3 over 5 cm mg kg 1 2694 occurring on day 9 Calculated time dependent total soil concentrations over 5 cm for Report example 3 after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 2347 1 2521 9 10 2 1 2010 1 2350 9 11 4 1 1362 1 2017 9 13 T 1 0455 1 1539 9 16 14 0 8611 1 0542 8 22 21 0 7092 0 9710 8 29 28 0 9228 0 9690 9 37 42 0 6259 0 9073 8 50 50 0 5014 0 8578 0 50 100 0 1606 0 6354 0 100 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in total soil for Report example 3 over 5 cm mg kg 0 0001 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 3 over 5 cm considering accumulation mg kg 1 2695 a tillage depth of 5 cm was co
103. gram version 2 0 16 Feb 2009 Date of this simulation 16 02 2009 13 58 47 Calculation problem Report example 1 Hamburg PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 3 Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 Hamburg Hockey Stick HS DT50 1 d 7 DT50 2 d 70 Rate constant 1 1 d 0 099 Rate constant 2 1 d 0 0099 Parameter Tb 10 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR
104. gramcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application date 1 May Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Active compound and a single metabolite Compound Molecular mass g mol Formation Testicide 250 Metabolidan 200 100 DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 4 Metabolism scheme Active compound and a single metabolite Kinetics for Testicide Double First Order in Parallel DFOP DT50 1 d 7 DT50 2 d 70 Rate constant 1 1 d 0 099 Rate constant 2 1 d 0 0099 Parameter g 0 5 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 Kinetics for Metabolidan Single First order SFO DT50 d 14 Rate constant 1 d 0 0495 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Active compound and a single metabolite RESULTS FOR Testicide 116 Calculations over one year Maximum annual total soil conce
105. ground concentration in pore water for Metabolidan over 5 cm mg L 1 0048 estimated to occur after 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Metabolidan over 5 cm considering accumulation mg L 2 2881 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent pore water concentrations over 5 cm for Metabolidan mg L considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 2 2570 2 2779 315 316 2 2 2868 2 2778 315 317 4 2 2149 2 2755 314 318 7 2 1094 2 2473 314 321 14 1 8822 2 2393 313 327 21 2 2258 2 2361 304 325 28 2 0944 2 2172 263 291 42 1 8177 2 2081 250 292 50 2 0943 2 2026 243 293 100 1 6848 2 1859 228 328 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg L Annual concentration of Report example 5 Study soil study 1 Made Farent wih 7 metebolite PEC PEC esticide TWA 28 d etabolidan TWA 28 d o o v ww 0 50 100 150 200 250 300 350 Time after first application d ESCAPE Estimation of Soil Concentrations After PEsticide Applications 127
106. ication Calculation of background concentrations after many years Final Background concentration in total soil for Report example 1 Hamburg over 5 cm mg kg estimated to occur within 10 years Begin TWAframe d sooo according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application End TWAframe d 0 0089 Maximum total soil concentration for Report example 1 Hamburg over 5 cm considering accumulation mg kg 1 3422 atillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 1 Hamburg mg kg considering accumulation Time d PECact 1 1 3249 2 1 3116 4 1 2745 7 1 2283 14 1 1532 21 1 0055 28 0 8712 42 0 6986 50 0 6226 100 0 2216 PECtwa 1 3336 1 3259 1 3105 1 2850 1 2343 1 1857 141211 1 0089 0 9522 0 6645 Begin TWAframe d OO OOS 99998 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 1 Hamburg Study soil study 4 Made Parent anh presented substance Testade kinetics SFO pec TWA 28 d gt a _luuluuluululuduuduulun
107. ide applications Programcheck v Del Borstel Edit c mg kg Annual concentration of Programcheck Study soil study 1 Made Parent only presented substance Testicide Kinelics SFO Parent only Application pattern Copy Programcheck Del PECactual single regular irregular 1 3333 1 3225 3 Date of first application 1 zl May z 1 3139 1 2913 1 2616 Applikation rate g ha 1000 1 2137 2 1 1258 3 Crop interception 0 1 0409 0 9292 0 8706 i Sa 0 5040 Compound data Copy Programcheck v Del Soil soil study 1 v Add study Degradation Metabolism Parent TWA 28d Kinetics SFO z otso f c 250 300 350 Q10 j2 Waker 07 Te Time after first application d den C Me Total content Porewater concentration TWA i h TWA 28 d v Annual z mase Background Save input Report Current Outputfile f Accum Figure 16 ESCAPE Main form Description of the problem 44 4 4 Combining input data for a simulation 4 5 Command buttons There are three buttons on the left bottom part of the main form that can be used for most important commands when working with ESCAPE see Figure 17 PY ESCAPE Estimation of Soil Concentrations After PEsticide applications File Edit pesticide data View Help Current Simulation Copy Programcheck y Del Description Programcheck a Programcheck v Del Parent only ik Parent with 1
108. ilable after an ESCAPE simulation This information cannot be presented in a single figure Therefore the central part of ESCAPE the diagram see Figure 24 can be interactively changed to make available all important aspects of a certain simulation and customise the presentation of results The various user options are presented in the following 54 PY ESCAPE Estimation of Soil Concentrations After PEsticide applications File Edit pesticide data View Help Current Simulation Copy Programcheck x Del Description Programcheck Parent only Parent with 1 metabolite Parent and 2 metabolites parallel Parent and 2 metabolites sequence _ Copy Programcheck v Del c mg kg Annual concentration of Programcheck Study soil study 1 Made Parent only presented substance Testicide Kinelics SFO Calculated total soil concentrations mg kg Time d PECactual PECtwa PECmax 1 3333 1 3225 1 3139 1 2913 1 2616 1 2137 1 1258 1 0409 0 9292 0 8706 0 5040 TWA 28 d AE A na m A A a nn Banane FETT 50 100 150 200 250 300 350 Time after first application d TWA in graph TWAS gt Annual Current Outputfile Accum C Background Borstel Edit ate FOCUS Hamburg median conditio Application pattern Del irregular Copy Programcheck single Date of first application iM 7 zus regular Applikation
109. illage depth of 5 cm was considered for calculating the background concentration Calculated time dependent pore water concentrations over 5 cm for Testicide mg L considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 9122 0 9131 31 32 2 0 9100 0 9121 31 33 4 0 9049 0 9098 31 35 7 0 8988 0 9063 3il 38 14 0 8752 0 8958 31 45 21 0 8727 0 8894 31 52 28 0 8340 0 8807 30 58 42 0 8661 0 8745 31 73 50 0 8521 0 8718 31 81 100 0 7561 0 8414 9 109 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration RESULTS FOR Metabolidan Calculations over one year Maximum annual pore water concentration for Metabolidan over 5 cm mg L 1 2833 occurring on day 321 This is 240 61 of the theoretical maximum concentration of the metabolite Calculated time dependent pore water concentrations over 5 cm for Metabolidan after one year mg L Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 2522 1 2730 315 316 2 1 2820 1 2730 315 317 4 1 2101 1 2707 314 318 7 1 1045 1 2425 314 321 14 0 8773 1 2345 313 327 126 21 1 2210 1 2313 304 325 28 1 0896 1 2124 263 291 42 0 8129 1 2033 250 292 50 1 0895 1 1978 243 293 100 0 6800 1 1811 228 328 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Back
110. ions in soil over 1 5 cm for Testicide mg L Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 0 5599 0 5354 0 2741 0 3088 2 0000 0 5589 0 5051 0 2722 0 3065 4 0000 0 5566 0 4688 0 2693 0 3015 7 0000 0 5531 0 4268 0 2644 0 2943 14 0000 0 5425 0 3257 0 2506 0 2813 21 0000 0 5362 0 2936 0 2437 0 2719 28 0000 0 5274 0 2512 0 2383 0 2626 42 0000 0 5212 0 2266 0 2345 0 2562 50 0000 0 5186 0 2068 0 2324 0 2524 100 0000 0 4882 0 1344 0 2228 0 2320 Calculation of background concentrations after many years Final background concentration in pore water for Testicide over 5 cm soil study 1 mg L 0 3532 estimated to occur after 10 years soil study 2 mg L 0 0026 estimated to occur within 10 years soil study 3 mg L 0 1072 estimated to occur within 10 years soil study 4 mg L 0 1919 estimated to occur after 11 years Calculations of concentrations considering accumulation after many years of application Maximum annual concentration in pore water for Testicide over 5 cm considering accumulation soil study 1 mg L 0 9141 occurring on day 31 soil study 2 mg L 0 5774 occurring on day 9 soil study 3 mg L 0 3831 occurring on day 31 soil study 4 mg L 0 5028 occurring on day 31 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Testicide mg L considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1
111. isadvantage of the HS model is that the degradation depends on time because of the breakpoint t Therefore the model can hardly be used in transport model e g leaching where pesticide movement is simulated However this is not a problem when parent compounds are simulated with ESCAPE and only single applications are considered because the whole pesticide amount is released into a single compartment without further movement For multiple applications it must be defined how residues from previous applications should be handled Due to the permanent formation of metabolites during the simulation no breakpoint can be given for these degradation products and the HS model is therefore also not suitable for these problems However DT50 and DT90 values can be expressed based on the three fitting parameters k k and t as shown in equations 12 and 13 16 In 2 DT50 for DT50 lt ty k 12 DT50 a for DT50 gt ty 2 ptgo PUO for DT50 lt ty ki 13 pros Nee pre k2 An example for a time dependent soil concentrations using the HS model is presented in Figure 4 c mg kg Program check Study Sandy loam 1 Made Parent anie resented su sisnce Testade thinetcs WS 1 4 13 1 2 1 1 0 9 0 8 0 7 0 6 0 4 PECs TWA 28 d 0 3 0 2 0 1 0 10 20 30 40 5 60 70 80 90 100 110 120 130 140 150 Time d Figure 4 HS model 1 kg ha k 0 1 d k 0 01 d t 10 d soil depth 5 cm 17 3
112. ised and the diagram shows the time dependent concentrations based on the DT50 and kinetics found in the different soil studies ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version Date of this simulation Calculation problem 2 0 17 Feb 2009 17 02 2009 16 38 53 Report example 5 SUMMARY REPORT CONSIDERING ALL SOIL STUDIES PROGRAM SETTINGS Calculation mode Application mode Name of the scenario Climatic conditions Residues from different applications are considered separately over one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Report example 5 Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Day Month Rate g ha Interception 01 05 500 0 10 05 750 25 01 06 600 50 01 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Active compound and a single metabolite Compound Molecular mass g mol format_berichtion Testicide 250 Metabolidan 200 100 DEGRADATION KINETICS PA
113. ituation after many years of applications concentrations based on the tillage depth Background or the situation after many years of applications normal soil depth but adding the background concentration Accumulation 56 a ESCAPE Estimation of Soil Concentrations After PEsticide applications File Edit pesticide data View Help Current Simulation Copy Programcheck v Del Description Programcheck Te Programcheck v Del Parent only Parent with 1 metabolite Parent and 2 metabolites parallel Parent and 2 metabolites sequence 1 Borstel et Edit c mg kg Annual concentration of Programcheck Study soil study 1 Made Parent only presented substance Testicide tkinetics SFO Application pattern Calculated total soil concentrations mg kg Copy Programcheck 7j Del Time d PECactual PECtwa single C regular irregular PECmax 1 3333 1 3225 i Date of first application zl May zl 1 3139 1 2913 1 2616 Applikation rate g ha 1000 1 2137 1 1258 Crop interception 0 1 0409 0 9292 0 8706 Compound data 0 5040 Copy Programcheck v Del Soil soil study 1 v Add study Degradation Sorption Metabolism Parent TWA 284 ___ Kinetics SFO oroa 300 350 Time after first application d parent C Metab TTT TTT TTT TTT 50 100 150 200 250 ao 22 waker taf C Me Total content Porewater concentration TWA
114. l concentrations over 5 cm for Report example 1 Hamburg after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 3246 1 3290 0 1 2 1 3179 1 3251 0 2 4 1 2990 1 3173 0 4 T 1 2751 1 3043 0 7 14 1 2352 1 2779 0 14 21 1 1528 1 2517 0 21 28 1 0723 1 2154 0 28 42 0 9590 1 1490 0 42 50 0 9046 1 1136 0 50 100 0 5325 0 9032 0 100 PECact values are related to the time after the first application Calculation of background concentrations after many years Final Background concentration in total soil for Report example 1 Hamburg over 5 cm mg kg 0 1183 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil T Report example 1 Hamburg over 5 cm considering accumulation mg kg a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 1 Hamburg mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 4429 1 4473 0 1 2 1 4362 1 4434 0 2 4 1 4173 1 4356 0 4 7 1 3934 1 4226 0 T 14 1 3534 1 3961 0 14 21 12710 1 3700 0 21 28 1 1905 1 3336 0 28 42 1 0772 1 2673 0 42 50 1 0229 1 2319 0 50 100 0 6508 1 0214 0 100 atillage depth of 5 cm was considered for calculating the background conc
115. lculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Mean temperature C Annual Rainfall mm Report example 3 Borstel 1 5 5 5 1 5 29 2 6 4 Laboratory conditions 19 5 18245 Annual pot Evapotranspiration mm for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Month Rate g ha Interception 05 500 0 05 750 25 06 600 50 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics for Report example 3 Alpha Beta Q10 factor Walker exponent Ref temperature C soil study 2 Parent compound without metabolites First Order Multi Compartment FOMC 4 4 2 58 0 7 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 3 Calculations over one year 98 Maximum annual total soil concentration for Report example 3 over 5 cm mg kg 0 8167 occurring on day 9 Calculated time dependent total soil concentrations over 5 cm for Report example 3 after one year mg kg
116. lication Maximum total soil concentration for Metabolidan over 5 cm considering accumulation mg kg 4 5524 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Metabolidan mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 4 5523 4 5524 121 122 2 4 5520 4 5524 120 122 4 4 5515 4 5522 119 123 a 4 5504 4 5520 118 125 14 4 5474 4 5513 116 130 21 4 5437 4 5505 113 134 28 4 5404 4 5500 303 331 42 4 5377 4 5499 289 Sot 50 4 5397 4 5499 282 332 100 4 5458 4 5491 240 340 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Background concentration of Report example 3 Study soil study 2 5 Made Foran wih 7 meta asie 4 Testicide TWA 28 d J Metabolidan TWA 28 d 4 J g 7 1 0 0 500 1000 1500 2000 2500 3000 3500 Time after first application d ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein 112 Program version Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode 2 0 17 Feb 2009 17 02 2009 14 43 55 Report example 4 Residues from different applications are considered separately over
117. loaded as shown in Fehler Verweisquelle konnte nicht gefunden werden to define the new name File Exit This command will terminate the program A fast alternative would be the button exit at the main form Edit pesticide data Add study Use this command if an additional soil study should be considered for ESCAPE The name of the new soil study can be typed in the yellow field which appears on the right part of the main form frame degradation kinetics parameters Up to six soil studies per data set can be considered for a simulation with ESCAPE Another possibility of adding soil studies is the button add study frame degradation kinetics parameters Edit Delete study Use this button if the soil study selected currently in the degradation kinetics frame on the right part of the main form should be deleted Note that the last soil study in the data set cannot be removed but only modified by the user Edit Preferences Use this command to modify the preferences of ESCAPE The different model switches can be modified in a special form that will appear on the screen see Figure 22 50 FJ Options Language English Appearance C Standard windows forms Coloured forms TWA durations according to EU Requlation C TWA according to JKl Separate consideration of residues from different applications Yes Yes but only withinayear No Concentration expressed in mg C pg Name
118. ludunluulududuuuduundududunludududuudul aa a a a ma Ba Ha a mn BR 250 300 350 Time after first application d End TWAframe d 82 6 2 Regular applications parent compound only several soil studies The input parameters for the simulations are summarised in Table 4 TWA times according to EU guidelines were used for the calculations Table 4 Series of special times used by ESCAPE to calculate PEC and PEC wa Parameter Soil study 1 Soil study 2 Soil study 3 Soil study 4 soil density kg L 1 5 soil depth cm 5 first application date 1 May application rate g ha 4 1000 crop interception 50 application interval d 14d Degradation type SFO FOMC HS SFO SFO DT50 d 365 140 alpha 0 1 beta 2 HS DT50 1 d 70 HS DT50 2 d 700 HS break point d 20 separate consideration of residues within the year of application only related to standard conditions On the following four pages copies of the ESCAPE report for all four studies are presented summarising the input data and all important results under standard laboratory conditions without considering soil moisture and temperature correction 83 ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2
119. ly Note that in the ESCAPE summary mode the check box Soil study will not be taken into consideration Tooltips When working with the model it is possible to fade in a small context sensitive user help These tooltips can be switched off or on here View Individual studies The fate of a pesticides and or its main metabolites can be simulated in up to six soil studies To visualise the results ESCAPE provides output in two different modes In its mode View Individual studies only the results of a one of the soil studies in the input data set the soil study that is selected in the degradation kinetics frame is presented in the output diagrams report file tables View Summary The fate of a pesticides and or its main metabolites can be simulated in up to six soil studies To visualise the results ESCAPE provides output in two different modes In its mode View Summary results of all soil studies in the input data set are presented in summaries diagrams report file tables 52 View Report This menu item generates an output file including all results of the simulation the current input data setting and the actual diagram on the screen The file will be written in RTF format and saved in the ESCAPE output folder The name of the file can be customised using the menu item Edit Preferences The name selected for the data set is echoed at the bottom of the main form current output
120. m total soil concentration for Report example 1 over 5 cm considering accumulation mg kg 1 3482 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 1 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 2225 1 2854 0 1 2 1 1087 1 2255 0 2 4 0 9122 1 1167 0 4 T 0 6816 0 9775 0 T 14 0 4910 0 7586 0 14 21 0 4591 0 6640 0 21 28 0 4294 0 6091 0 28 42 0 3757 0 5400 0 42 50 0 3482 0 5115 0 50 100 0 2181 0 3946 0 100 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application GRAPHIC REPRESENTATION OF THE CALCULATION mg kg Annual concentration of Report example 1 Study soil study 3 Made Parent onhe resented substance Testade kinetics HS Huub 1 4 13 12 11 0 9 0 8 07 0 6 0 5 0 4 TWA 28d 0 3 0 2 0 1 o PE TT TE TT ee 50 100 150 200 250 300 350 Time after first application d _luluul nuluuluuhudunlunhuulunduududunhulunlunhudududududunluduud 69 ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 12 Feb 2009 Date of this simulation 16 02 2009 11 07 50 Calculation problem Report example 1 PROGRAM SETT
121. m was considered for calculating the background concentration 0 2759 occurring End TWAframe d 0 1072 0 3831 Calculated time dependent pore water concentrations over 5 cm for Testicide mg L considering accumulation Time d PECact 1 0 3795 2 0 3754 4 0 3667 7 0 3567 14 0 3367 21 0 3347 28 0 3205 42 0 3313 50 0 3252 100 0 2832 PECtwa 0 3813 0 3794 0 3765 0 3716 0 3578 0 3509 0 3455 0 3417 0 3396 0 3300 Begin TWAframe d 31 31 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration RESULTS FOR Metabolidan Calculations over one year Maximum annual pore water concentration for Metabolidan over 5 cm mg L on day 321 This is 308 66 of the theoretical maximum concentration of the metabolite End TWAframe d 1 6462 occurring Calculated time dependent pore water concentrations over 5 cm for Metabolidan after one year mg L Time d PECact 1 1 6177 2 1 6438 4 1 5780 7 1 4788 14 1 2584 21 1 6273 28 1 4975 PECtwa 1 6433 1 6427 1 6416 1 6195 1 6046 1 6026 1 5991 Begin TWAframe d 346 345 343 342 274 268 262 End TWAframe d 347 347 347 349 288 289 290 sja 42 1 2418 1 5947 248 50 1 5403 1 5916 241 100 1 2523 1 5729 226 PECact values are related to the time after the maximum concentration Calculation of background concentrations
122. me d 1 2 3987 2 4046 42 43 2 2 3868 2 3987 42 44 4 2 3633 2 3868 42 46 7 2 3284 2 3693 42 49 14 2 2491 2 3289 42 56 21 2 1725 2 2895 42 63 28 2 0985 2 2509 42 70 42 1 9580 2 1793 41 83 50 1 8819 2 1393 41 91 100 1 4693 1 9444 28 128 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in total soil for Report example 2 over 5 cm mg kg 0 4733 estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 2 over 5 cm considering accumulation mg kg 2 8839 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 2 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 2 8720 2 8779 42 43 2 2 8601 2 8720 42 44 4 2 8366 2 8602 42 46 7 2 8018 2 8426 42 49 14 2 7224 2 8022 42 56 21 2 6458 2 7628 42 63 28 2 5718 2 7242 42 70 42 2 4313 2 6526 41 83 50 2 3553 2 6126 41 91 100 1 9426 2 4177 28 128 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENT
123. me of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Programcheck Borstel 1 5 5 5 1 5 29 2 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application date Application rate g ha Crop interception 1 May 1000 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Compound Testicide Metabolidan Active compound and a single metabolite Molecular mass g mol 250 200 100 format_berichtion DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Metabolism scheme Soil study Kinetics for Testicide DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C Soil study Kinetics for Testicide alpha i_studie Beta Q10 factor Walker exponent Ref temperature C Active compound and a single metabolite soil study 1 Single First order SFO 7 0 099 2 58 0 7 20 soil study 2 First Order Multi Compartment FOMC 0 2 0 2 2 58 0 7 20 119 Soil study soil study 3 Kinetics for Testicide Hockey Stick HS DT50 d 7 DT50 d 70 Rate constant 1 1 d 0 099 Rate con
124. medium with many regions of different degradation capacity Therefore it is reasonable to divide the soil into a large number of sub compartments each with a different first order degradation rate Assuming the rate constants follow a y distribution an analytical solution can be found to describe this degradation model mathematically as shown in equation 5 a Co 5 C pesticide concentration at time mg kg Co concentration at time t 0 mg kg 1 fitting parameter B 2 fitting parameter The FOMC model is a very simple biphasic degradation approach which needs only two fitting parameter The differential form of this model is shown in equation 6 dC _ S i 6 dt PP B A disadvantage of this approach is that in contrast to the SFO model the degradation depends on time see the difference between equation 1 and 5 Therefore the model cannot be used in transport models e g leaching where pesticide movement is simulated However this is not a problem when parent compounds are simulated with ESCAPE and only single applications are considered because the whole pesticide amount is released into a single compartment without further movement For multiple applications it must be defined how residues from previous applications should be handled Due to the permanent formation of metabolites during the simulation the FOMC model is also not suitable for these degradation products However DT50 and DT90 values can
125. ncentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Day Month Rate g ha Interception 01 05 500 0 10 05 750 25 01 06 600 50 01 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites Pesticide Report example 3 DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Metabolism scheme Parent compound without metabolites Kinetics for Report example 3 Soil study soil study 1 Single First order SFO DT50 d 25 Rate constant 1 d 0 0277 Q10 factor 2 58 Walker exponent 0 7 TReference C 20 100 Soil study soil study 2 First Order Multi Compartment FOMC alpha i_studie 1 Beta 1 Q10 factor 2 58 Walker exponent 0 7 TReference C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 3 Calculations over one year Maximum annual total soil concentration for Report example 3 over 1 5 cm soil study 1 mg kg 1 2694 occurring on day 9 soil study 2 mg kg 0 8167 occurring on day 9 Calculated PECact in soil over 1 5 cm for Report example 3 mg kg Time d soil study 1 soil study 2 1 0000 1 2347 0 4356 2 0000 1 2010 0 3056 4 0000 1 1362 0 1976 7 0000 1 0455 0 1330 14 0000 0 8611 0 0778 21 0000 0 7092 0 0556 28 0000 0 9228 0 1005 42 0000 0 6259 0 0493 50 0000 0 5014 0 0396 100 0000 0 1606 0 0213 PECact values are
126. nd Metabolite ec eee ee eeeeeeeeeeeeeeeeeeeeeeneaaaeees 20 Three compartments for parent and two parallel metabolites gt 21 Three compartments for parent and two metabolites in a sequence 23 FOMC model 10 4 applications a 0 2 B 2 separating of residues switched off27 FOMC model 10 4 applications a 0 2 B 2 separating of residues switched on NEE arate Zin face halen a te tenant Se 27 FOMC model 10 4 applications a 0 2 B 2 separating of residues within a year A ee re 28 MES GAPE INITOSSEIBEN ici Geass este een ea ORo tAr 34 ESCAPE Main form Four different calculation modes 4444 nn 36 ESCAPE Main form Editing input parameters uuunsssssnsnnnsnnnnnnnnnnnnnnnnnnn nn 37 ESCAPE Main form Description of the problem cccceeeeeeeeeeeeeeeeeeeeeeeeeeeees 43 ESCAPE Main form Command buttons 24444ssssennnnennennnnnnnennnnnnennnnnenn 44 ESCAPE Loading input data sets Fehler Textmarke nicht definiert ESCAPE Saving input data setS Fehler Textmarke nicht definiert ESCAPE displaying the report file u44444404n nn nnnnnnnnnnnnnnnnnnennnnnnnnnnn 45 ESCAPE Working with the menu bar 4442u44444444nn nen nnnnnnnnnnnnnnnnnnennannnnnnn 47 ESCAPE Saving Input MSS ea 50 ESCAPE Saving INPRETIES rn ae an 53 ESCAPE The central diagram u na e 54 ESCAPE The
127. nd concentration PECact values are related to the time after the first application RESULTS FOR Metabolidan Calculations over one year Maximum annual total soil concentration for Metabolidan over 5 cm mg kg on day 26 This is 26 08 of the theoretical maximum concentration of the metabolite End TWAframe d 0 2782 occurring Calculated time dependent total soil concentrations over 5 cm for Metabolidan after one year mg kg Time d 100 PECact 0 2742 0 2719 0 2677 0 2558 0 2254 0 2343 0 2427 0 2623 0 1923 0 0980 PECtwa 0 2779 0 2770 0 2753 0 2724 0 2634 0 2523 0 2478 0 2469 0 2480 0 1960 Begin TWAframe d PECact values are related to the time after the maximum concentration End TWAframe d 17 Calculation of background concentrations after many years Final Background concentration in total soil for Metabolidan over 5 cm mg kg 0 0925 estimated to occur after 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Metabolidan over 5 cm considering accumulation mg kg 0 3707 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Metabolidan mg kg considering accumulation Time d PECact PECtwa
128. nsidered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 3 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 2348 1 2522 9 10 2 1 2011 1 2351 9 11 4 1 1363 1 2018 9 13 7 1 0456 1 1540 9 16 14 0 8612 1 0543 8 22 21 0 7093 0 9711 8 29 28 0 9229 0 9691 9 37 42 0 6260 0 9074 8 50 50 0 5015 0 8579 0 50 100 0 1607 0 6355 0 100 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION Annual concentration of Report example 3 Study soil study 1 2 a 3 2 z Made Farent onhe presented substance Testade Kinetics SFO 1 4 1 3 1 2 11 0 9 0 8 0 7 0 6 0 5 0 4 TWA 28 d 0 3 0 2 0 1 flab shba luslunlshulushslul lu 50 100 150 200 250 300 350 Time after first application d 97 ESCAPE Estimation of Soil Concentrations After PEsticide Applications Program version Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode developed by Michael Klein 2 0 17 Feb 2009 17 02 2009 13 52 37 Report example 3 Residues from different applications are considered separately over one year Single annual application pattern ca
129. nted substonce Metatositen meses SFO Time after first application d 123 6 5 Irregular applications parent compound with metabolite several soil studies Table 7 Series of special times used by ESCAPE to calculate PEC and PECtwa Parameter Soil study 1 Soil study 2 Soil study Soil study 4 3 soil density kg L 1 5 soil depth cm 5 application rate g ha 500 750 600 1000 crop interception 0 25 50 90 application dates d 1 May 10 May 1 June 1 July parent molecular mass g mol 250 metabolite molecular mass g mol 200 metabolite formation fraction 1 100 parent KOC L kg 200 100 300 500 parent degradation data SFO FOMC HS DFOP SFO DT50 d 70 alpha 1 beta 1 HS DT501 d 7 HS DT50 2 d 70 HS break point d 5 DFOP DT50 1 d 7 DFOP DT50 2 d 140 parameter g 0 5 metabolite KOC L kg 20 10 30 50 metabolite degradation data SFO SFO SFO SFO SFO rate constant 1 d 35 350 140 14 separate consideration of residues within the year of application only related to standard conditions On the following four pages copies of the ESCAPE report for all four studies are presented summarising the input data and all important results considering pore water concentrations as endpoint 124 ESCAPE Estimation of Soil
130. ntration for Testicide over 5 cm mg kg on day 0 Calculated time dependent total soil concentrations over 5 cm for Testicide after one year mg kg Time d 100 PECact 1 3144 1 2999 1 2603 1 2125 1 1376 1 0014 0 8899 0 7627 0 7121 0 4788 PECtwa 1 3239 1 3155 1 2989 1 2719 1 2198 11721 1 1130 1 0169 0 9715 0 7693 PECact values are related to the time after the first application Calculation of background concentrations after many years Begin TWAframe d OOGOOOCOGGOGGOGOOGOOGO Final Background concentration in total soil for Testicide over 5 cm mg kg estimated to occur after 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Testicide over 5 cm considering accumulation mg kg a tillage depth of 5 cm was considered for calculating the background concentration 1 3333 occurring End TWAframe d 0 3861 1 7188 Calculated time dependent total soil concentrations over 5 cm for Testicide mg kg considering accumulation Time d 100 PECact 1 7005 1 6860 1 6465 1 5986 1 5237 1 3876 1 2760 1 1488 1 0982 0 8649 PECtwa 1 7100 1 7016 1 6850 1 6581 1 6059 1 5582 1 4991 1 4030 1 3576 1 1554 Begin TWAframe d 99959999998 atillage depth of 5 cm was considered for calculating the backgrou
131. o Programcheck Name ofthe soil Borstel Parent Soil density kg L 1 5 Kinetics SFO z prso a 28 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 010 22 Walker Tof20 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 C Metel for calculation of background concentrations Sr 3 Eoaea ARENE ia THAO apt A Baskani Save input Report Exit 2 Z ARTIST 5 sa R PFA CO C Accum Figure 19 ESCAPE Selecting endpoints on the main fram 4 7 The menu bar The menu bar on top of the main form see Figure 20 provides the user with all possible commands when working with ESCAPE 47 Fetimation of Soil Concentrations After PEsticide applications Eile Edit pesticide data View Help Current Simulation Programcheck y Del Description Programcheck Programcheck v Del Parent only Parent with 1 metabolite Parent and 2 metabolites parallel Parent and 2 metabolites sequence Borstel Edit ESCAPE FOCUS Hamburg median conditio Estimation of Soil Concentrations After PEsticide Applications EPET pplication pattern develqued av Michsel Klein Copy Programcheck vj Del single regular iregular Program version 2 0 18 Dec 2008 Date of first application 1 viMy ov Date of this simulation 12 02 2009 11 27 18
132. of output files contains V IV Soil Study MW Kinetics Endpoint Date Time Show tooltips Yes Figure 22 ESCAPE Modifying preferences There are presently seven different options that can be modified by the user Language The user can select the language of the model shell here Note in the current version only English is available Appearance In addition to the windows standard system palette ESCAPE is able to highlight the different forms on the screen using background colours The user can switch on or off this feature here TWA duration scheme The user can decide which list of TWA duration should be considered for the simulation The two lists are shown in Table 1 on page 29 in this document 51 Separate consideration of residues from different applications As explained earlier in chapter 3 4 2 on page 25 ESCAPE has implemented three different procedures of handling residues coming from different applications The desired calculation can be selected here It will be saved also in the input data set and documented in the program report Concentrations expressed in mg kg or ug kg ESCAPE can express the soil concentration either in mg kg or in g kg The user can select the suitable unit for the specific problem here The selection will be saved also in the input data set Naming of output files The user can customise the names of the ESCAPE report files here to make archiving of results more user friend
133. oil TWA computer model mathematical model Plateau concentrations standard scenarios 18 Price 19 20 Content 3 1 3 2 3 3 3 4 3 5 3 6 4 1 4 2 4 3 4 4 4 5 4 6 4 7 4 8 6 1 Summary Background Methodology Degradation models considered by ESCAPE Temperature and soil moisture correction of degradation constant Calculation modes considered by ESCAPE Calculation of total soil concentrations Calculation of pore water concentrations Consideration of scenario soil profiles and weather files Working with ESCAPE Installing ESCAPE Calculation modes considered by ESCAPE Editing input parameters Combining input data for a simulation Command buttons Direct endpoint selection The menu bar Manipulating the central diagram sheet References Results of test simulations Single application parent compound only several soil studies 19 25 32 33 34 34 35 36 44 44 46 46 53 61 62 62 6 2 6 3 6 4 6 5 Regular applications parent compound only several soil studies 82 Irregular applications parent compound only several soil studies 94 Single application parent compound with metabolite several soil studies 105 Irregular applications parent compound with metabolite several soil studies 123 List of Tables Table 1 Series of special times used by ESCAPE to calculate PECa and PECrwa 29 Table 2 Sele
134. omatically if possible 36 BY ESCAPE Estimation of Soil Concentrations After PEsticide applications File Edit pesticide data View Help copy Programcheck v Del Borstel Edit Annual concentration of Programcheck Study soil study 1 i Made Parent only presented substance Testicide tkinetics SFO i Application pattern Parent only Parent with 1 metabolite Parent and 2 metabolites parallel Parent and 2 metabolites sequence Calculated total soil concentrations mg kg Copy Programcheck zl Del Timeld PECactual PECtwa single regular irregular PECmax 1 3333 1 3225 Date of first application 1 x May ov 1 3139 1 2913 k 1 2616 Applikation rate g ha 1000 1 2137 i 1 1258 i Crop interception 0 1 0409 0 9292 aa f Compound data Copy Programcheck v Del Soil soil study 1 v Add study Degradation Metabolism Parent TWA 28 d Kinetics SFO z otso f sllu 250 300 350 Q10 j2 Waker 07 To Time after first application d Parent C Me C amp Total content Porewater concentration TWA i h TWA 28 d v Annual RaR C Background Save input Report Current Outputfile TACI Figure 13 ESCAPE Main form Four different calculation modes 4 3 Editing input parameters Important input parameters can be directly defined or modified at the right hand side of the main form see Figure 14
135. oncentrations considering accumulation after many years of application Maximum total soil concentration for Report example 1 over 5 cm considering accumulation mg kg 1 3335 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 1 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 3009 1 3172 0 1 2 1 2691 1 3011 0 2 4 1 2078 1 2697 0 4 T7 1 1214 1 2244 0 7 14 0 9430 1 1270 0 14 21 0 7930 1 0400 0 21 28 0 6668 0 9620 0 28 42 0 4716 0 8292 0 42 50 0 3869 0 7650 0 50 100 0 1123 0 4935 0 100 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first application GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Testopest Al Study soil study 1 Made Parent onhe presented substance Testade tkinetios SFO TWA 28d ul luulunlu huuluulunbuduulu luhuulnduuhududunlunduun 50 100 150 200 250 300 350 Time after first application d 65 ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 12 Feb 2009 Date of this simulation 16 02 2009 11 04 11 Calculation problem Report example 1 PROGRAM SETTINGS Calculation mode Residues from differ
136. ons developed by Michael Klein Program version 2 0 17 Feb 2009 133 Date of this simulation Calculation problem PROGRAM SETTINGS Calculation mode Application mode 17 02 2009 16 26 34 Report example 5 Residues from different applications are considered separately over one year Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Report example 5 Borstel 1 5 5 5 1 5 29 2 6 4 FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 Month Rate g ha Interception 05 500 0 05 750 25 06 600 50 07 1000 90 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Compound Testicide Metabolidan Active compound and a single metabolite Molecular mass g mol 250 200 100 Formation DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study Metabolism scheme Kinetics for Testicide DT50 1 d DT50 2 d Rate constant 1 1 d Rate constant 2 1 d Parameter g Q10 factor Walker exponent R
137. or Metabolidan DT50 d Rate constant 1 d Q10 factor Walker exponent Ref temperature C soil study 1 Active compound and a single metabolite Single First order SFO 70 0 0099 2 58 0 7 20 Single First order SFO 35 0 0198 2 58 0 7 20 125 RESULTS OF THE CALCULATION Metabolism scheme Active compound and a single metabolite RESULTS FOR Testicide Calculations over one year Maximum annual pore water concentration for Testicide over 5 cm mg L 0 5608 occurring on day 31 Calculated time dependent pore water concentrations over 5 cm for Testicide after one year mg L Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 0 5589 0 5599 31 32 2 0 5567 0 5589 31 33 4 0 5517 0 5566 31 35 ie 0 5456 0 5531 31 38 14 0 5220 0 5425 31 45 21 0 5195 0 5362 31 52 28 0 4807 0 5274 30 58 42 0 5129 0 5212 31 73 50 0 4988 0 5186 31 81 100 0 4029 0 4882 9 109 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in pore water for Testicide over 5 cm mg L 0 3532 estimated to occur after 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum pore water concentration for Testicide over 5 cm considering accumulation mg L 0 9141 a t
138. pplication GRAPHIC REPRESENTATION OF THE CALCULATION Annual concentration of Report example 1 Study soil study 4 Made Farem onhe presented substance Testiode kinetics SFO TWA 28d _uluul nuluuluuhuduulunhuulunuudundunuululuhudududuudundundududud 50 100 150 200 250 300 350 Time after first application d End TWAframe d 71 Here the respective report is shown when ESCAPE is in its summary mode Results of all four studies are summarised in a single file and the diagram includes results of all studies ESCAPE Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein Program version 2 0 12 Feb 2009 Date of this simulation 16 02 2009 11 09 23 Calculation problem Report example 1 SUMMARY REPORT CONSIDERING ALL SOIL STUDIES PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions Laboratory conditions Mean temperature C 19 5 Annual Rainfall mm 18245 Annual pot Evapotranspiration mm for calcula
139. r calculation of background concentrations Programcheck Borstel 1 5 5 5 1 5 29 2 6 4 Laboratory conditions 19 5 18245 APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 1 Metabolism scheme Kinetics for Report example 1 DT50 d 28 Rate constant 1 d 0 0248 Q10 factor 2 2 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme RESULTS FOR Report example 1 Calculations over one year Parent compound without metabolites Single First order SFO Parent compound without metabolites Maximum annual total soil concentration for Report example 1 over 5 cm mg kg on day 0 1 3333 occurring 64 Calculated time dependent total soil concentrations over 5 cm for Report example 1 after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 1 3007 1 3170 0 1 2 1 2689 1 3009 0 2 4 1 2076 1 2695 0 4 7 1 1212 1 2243 0 7 14 0 9428 1 1269 0 14 21 0 7928 1 0398 0 21 28 0 6667 0 9618 0 28 42 0 4714 0 8290 0 42 50 0 3867 0 7648 0 50 100 0 1122 0 4933 0 100 PECact values are related to the time after the first application entrations afte was reached after 10 years Calculations of c
140. rate g ha Crop interception Compound data Copy Programcheck v Del Seit soi study 1 v Add study Degradation Metabolism Parent Kinetics SFO otso Q10 j2 Waker 07 Tof Parent Cc p Save input Report Figure 24 ESCAPE The central diagram selecting pore water or total concentrations 4 8 1 Selecting total content or pore water concentration The radio buttons in the left bottom part of the form can be used to switch between total content in soil and pore water concentrations see the rectangle in Figure 24 The graphs are re constructed instantaneously because calculations are always performed for both endpoints independent on the actual settings 4 8 2 Moving Removing of the legend A left mouse click at the legend turns its background colour to blue and the legend can be moved as long as the left mouse button is pressed A double click or a click at the legend when the ctrl key is pressed will remove it completely from the screen By clicking at the diagram together with the ctrl key pressed will set the legend to its original position and it becomes visible again 4 8 3 Moving Removing of the concentration table A left mouse click at the title of the concentration table turns its background colour to blue and the table can be moved as long as the left mouse button is pressed A double click or a 55 click at the title when the ctrl key is pressed
141. rature and soil moisture This version of ESCAPE is finally able to consider pore water concentrations as e g recommended by EFSA 3 Methodology 3 1 Degradation models considered by ESCAPE ESCAPE considers in total 4 different degradation kinetics SFO Single First Order HS Hockey Stick DFOP Double First Order in Parallel and FOMC First Order Multi Compartment All models are available for parent compounds However the identification of a suitable model for the description of the formation and degradation of metabolites are much more complex As the description of the concentration curve of a single metabolite depends on a correct description of the degradation of the parent substance and of the degradation of the metabolite itself Due to the parallel formation of metabolites only two of the four available models can be used also for metabolites namely the SFO and the DFOP kinetics The other models are not conceptually correct for a metabolite that is gradually formed over a period of time FOCUS 2006 3 1 1 SFO Single first order kinetics SFO is the most simple degradation model using only a single parameter the constant rate constant unit 1 d leads to a simple exponential equation of pesticide concentration with time The main assumption behind that model is that the pesticide concentration is small compared to the number of degrading micro organisms or water molecules if the compound is degraded by hydrolysis The mod
142. rkonzentration Neben Gesamtgehalten im Boden wurde die M glichkeit der Berechnung von Porenwasserkonzentrationen realisiert Temperaturabhangigkeit des Bioabbaus Die bestehende Software wurde so erweitert dass die Ber cksichtigung der Temperaturabh ngigkeit von Abbauraten im Boden mit den etablierten Verfahren ber cksichtigt werden kann Feuchteabhangigkeit des Bioabbaus Es wurde neue eine Methode entwickelt mit der die derzeit etablierten Verfahren zur Ber cksichtigung der Feuchteabh ngigkeit des Bioabbaus unabh ngig von der jeweiligen Abbaukinetik in die Software integriert werden konnte Erstellung von Bodenszenarien Im Rahmen der Erweiterung werden Boden und der Klimaparameter in Bodenszenarien zusammengefasst die der Anwender dann benutzerfreundlich f r eine Simulation ausw hlen kann 17 Schlagw rter ESCAPE Bodenkonzentration Pflanzenschutzmittel Wirkstoff Metabolit PEC Boden TWA Computermodell Abbaukinetik Plateaukonzentration Standardszenario 18 Preis 19 20 Report No 1 UBA FB 2 3 4 Report Title Calculation of PECsoil including Plateau Concentrations for Pesticides Dependent on FOCUS Degradation Kinetics 5 Author s Familiy Name s First Name s 8 Report Date Michael Klein 8 December 2008 9 Publication Date 6 Performing Organisation Name Address 10 UFOPLAN Ref No 360 03 042 Molekularbiologie und Angewandte Okologie 11 No
143. rt example 1 after one year mg kg 70 100 PECact values are related to the time after the first application PECact 1 2689 1 2076 1 0938 0 9428 0 6667 0 4714 0 3333 0 1667 0 1122 0 0094 PECtwa 1 3011 1 2697 1 2099 1 1270 0 9620 0 8292 0 7215 0 5612 0 4934 0 2675 Calculation of background concentrations after many years Begin TWAframe d SS O11 Cree one Final Background concentration in total soil for Report example 1 over 5 cm mg kg estimated to occur within 10 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 1 over 5 cm considering accumulation mg kg a tillage depth of 5 cm was considered for calculating the background concentration End TWAframe d lt 0 0001 1 3333 Calculated time dependent total soil concentrations over 5 cm for Report example 1 mg kg considering accumulation Time d PECact 1 1 2689 2 1 2076 4 1 0938 7 0 9428 14 0 6667 21 0 4714 28 0 3333 42 0 1667 50 0 1122 100 0 0094 PECtwa 1 3011 1 2697 1 2099 1 1270 0 9620 0 8292 0 7215 0 5612 0 4934 0 2675 Begin TWAframe d CHS OOS O S O 10 iS a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the first a
144. se times cannot be defined for the formation of metabolites the formation takes place over the whole simulation period instantaneously these two models cannot be selected for metabolites The user can decide to keep pesticide residues from different applications separately also in this calculation mode see Figure 5 and the explanation in chapter 3 3 1 I 3 3 4 Simulation considering the parent compound and two metabolites in a sequence In this mode ESCAPE considers three compartments for the parent compound and for the two metabolites as shown in Figure 8 compartment 1 dearadation ace pesticide 2 u dearadation metabolite A compartment 3 dearadation metabolite B Figure 8 Three compartments for parent and two metabolites in a sequence The calculation of the formation of metabolite A is done based on the time dependent degradation of the parent compound the formation fraction of metabolite A and the differences in the molar masses according to equation 19 24 19 Rdeg x f Mmet 2 Ryorm er M Moar Rform actual formation of metabolite A g ha Reg actual degradation of the parent compound g ha formation fraction of metabolite A Mpar molecular mass of the parent compound g mol M mer molecular mass of metabolite A g mol The calculation of the formation of metabolite B is done based on the time dependent degradation of metabolite A the formation fraction of metabolite
145. stant 2 1 d 0 0099 Parameter Tb d 10 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 Soil study soil study 4 Kinetics for Testicide Double First Order in Parallel DFOP DT50 d 7 DT50 d 70 Rate constant 1 1 d 0 099 Rate constant 2 1 d 0 0099 Parameter g 0 5 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 Soil study soil study 1 Kinetics for Metabolidan Single First order SFO DT50 d 35 Rate constant 1 d 0 099 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 Soil study soil study 2 Kinetics for Metabolidan Single First order SFO DT50 d 350 Rate constant 1 d 0 005 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 Soil study soil study 3 Kinetics for Metabolidan Single First order SFO DT50 d 140 Rate constant 1 d 0 001 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 Soil study soil study 4 Kinetics for Metabolidan Single First order SFO DT50 d 14 Rate constant 1 d 0 0495 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Active compound and a single metabolite RESULTS FOR Testicide Calculations over one year Maximum annual total soil concentration for Testicide over 1 5 cm soil study 1 mg kg soil study 2 mg kg soil study 3 mg kg soil study 4 mg kg 1 3333 occurring on day
146. suitable to describe the fate of pesticides in soil than the traditional methodology based on single first order degradation FOCUS nomenclature SFO Single First Order Additional recommended kinetics are e g HS hockey stick DFOP double first order in parallel or FOMC first order multi compartment For single applications FOCUS Degradation Kinetics published algorithms allowing the calculation of time dependent concentrations in soil for parent and metabolite compounds Unfortunately for complicated application pattern with irregular application timing and rates currently no bug free and user friendly is available that can be used to calculated actual and average concentrations in soil Additionally tools to estimate plateau concentrations are currently not available The commonly used leaching models PELMO PEARL are also not appropriate as long as they consider first order degradation in soil only The main difficulty is the non existence of simple mathematical solutions for the concentration dependency for more complicated application pattern However consideration of non kinetic sorption modules in these models could be an alternative In contrast to simple first order kinetics the strategy of handling residues from earlier applications has to be defined clearly when using more complicated degradation kinetics To consider also soil concentrations based on different weather conditions the degradation rates can be corrected based on tempe
147. t box and can be modified here Simulation records can be also removed renamed or copied using the respective buttons attached to the list box In addition the description each simulation record contains the names of the scenario application pattern and compound record Also these data can be manipulated in a similar way as simulation records using the respective buttons attached to the list boxes If different input data records have been selected by the user and the simulation organiser is closed Button Done the new collection is automatically saved in the current simulation record Simulation organiser Siders z Copy Rename Delete Pogramcheck SEE Programcheck Copp Rename Delete Edit Application pattern Programcheck Copy Rename Delete Pesticide Programcheck Copy Rename Delete Figure 21 ESCAPE Editing input data sets 49 File Print If a report file was generated this command calls the standard windows printer routines After selecting the desired printer the actual report will be printed If no report was generated so far the option is disabled File Save All input data This command will save all input under the current name given at the bottom of the main form Instead of using the menu bar a fast possibility of saving the current settings would be the use the button save input File Save as This command will save all input under a new name A window is
148. t the current simulation day cm Orc soil moisture at field capacity m m Owe soil moisture at wilting point m m d soil depth cm The functions MAX and MIN in the equation guarantee that only soil moisture contents are calculated between field capacity and wilting point Run off or drainage are not considered as transport processes for soil water The equation is nevertheless conservative because it is assumed that actual evapotranspiration is always as high as the potential evapotranspiration The temperature and soil moisture correction has been originally developed for first order kinetics only For the biphasic kinetics they have to be adapted ESCAPE uses a time step normalisation approach to do the soil moisture and temperature correction independent on the actual degradation kinetics In this method a normalised day length is calculated based on daily variations in soil temperature and moisture content using the equations and assumptions presented above The procedure is described in detail in FOCUS 2006 For example a daily soil temperature of 250C Q10 2 2 and moisture content of 20 vs 25 for pF2 gives a normalised day length of 1 27 days at 20cC and pF2 The daily values are calculated and the cumulative time between sampling points 19 3 3 Calculation modes considered by ESCAPE ESCAPE can be used in four different calculation modes namely parent compound only parent compound and a single metabolite
149. th cm 5 application rate g ha 1000 first application date 1 May crop interception Degradation type SFO FOMC HS SFO SFO DT50 d 28 14 alpha 0 2 beta 0 2 HS DT50 1 1 d 7 HS DT50 2 d 70 HS break point d 10 separate consideration of residues within the year of application only related to standard conditions On the following four pages copies of the ESCAPE report for all four studies are presented summarising the input data and all important results under standard laboratory conditions without considering soil moisture and temperature correction 63 Estimation of Soil Concentrations After PEsticide Applications developed by Michael Klein ESCAPE 12 Feb 2009 Date of this simulation 16 02 2009 10 57 27 Calculation problem PROGRAM SETTINGS Calculation mode one year Application mode Report example 1 Residues from different applications are considered separately over Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Name of the soil Soil density kg L Soil depth cm Tillage depth cm Organic carbon content Field capacity Vol Wilting point Vol Climatic conditions Mean temperature C Annual Rainfall mm Annual pot Evapotranspiration mm fo
150. the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 2 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 5 3475 5 3542 42 43 2 5 3343 5 3476 42 44 4 5 3082 5 3344 42 46 7 5 2748 5 3153 42 49 14 5 2220 5 2817 42 56 21 5 1768 5 2535 42 63 28 5 1621 5 2325 42 70 42 5 1328 5 2041 42 84 50 5 1163 5 1914 42 92 100 5 0158 5 1286 41 141 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 2 Study soil study 3 235 _ Made Parent an presented substance Testicide Kinetics HS rtitititit l l l l l l fc 2 Twa eo gt a o TTT TTT 200 250 300 350 Time after first application d ESCAPE Estimation of Soil Concentrations After PEsticide Applications o a S gt 5 a S 89 developed by Michael Klein Program version 2 0 17 Feb 2009 Date of this simulation 17 02 2009 11 48 31 Calculation problem Report example 2 PROGRAM SETTINGS Calculation mode Residues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CAL
151. tion Calculation of background concentrations after many years Final Background concentration in total soil for Report example 2 over 5 cm mg kg 2 8582 estimated to occur after 11 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 2 over 5 cm considering accumulation mg kg 5 0643 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 2 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 5 0317 5 0480 42 43 2 5 0078 5 0339 42 44 4 4 9724 5 0116 42 46 7 4 9342 4 9862 42 49 14 4 8737 4 9440 42 56 21 4 8313 4 9132 42 63 28 4 7981 4 8884 42 70 42 4 7472 4 8494 42 84 50 4 7241 4 8313 41 91 100 4 6262 4 7517 41 141 atillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration GRAPHIC REPRESENTATION OF THE CALCULATION c mg kg Annual concentration of Report example 2 Study soil study 2 25 _ Made Parent onfe presented substance Testade kinetics FOMC fc ma 0 5 lal l l lilylilil hilihilihilihilililihililitil o TATTOO I I I 2
152. tion kinetics SFO Single First Order HS Hockey Stick DFOP Double First Order in Parallel and FOMC First Order Multi Compartment which are explained in detail in chapter 3 1 For each soil study the suitable degradation model can be selected for the activated compound However only for parent compounds all four models are available For metabolites only the SFO or the DFOP kinetics can be used because the other models are not conceptually correct for a metabolite that is gradually formed over a period of time see chapter 3 1 Dependent on the selection different parameters appear on the form 41 DT50 d If the SFO model has been selected there is only one parameter to characterise the degradation the first order DT50 which has to be entered here DFOP DT50 d If the DFOP model has been selected the first 1 order DT50 has to be selected here DFOP DT50 d If the DFOP model has been selected the second 1 order DT50 has to be selected here DFOP parameter_g If the DFOP model has been selected the parameter g which describes the fraction of the compound that degrades according to the first DT50 has to be entered here Values for g are only accepted in the range of 0 to 1 FOMC parameter a If the FOMC model has been selected the parameter a has to be selected here HS rate constant f If the HS model has been selected the parameter has to be selected here HS DT50 d If the HS model has
153. tion of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites Pesticide Report example 1 DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 Soil study soil study 1 Single First order SFO DT50 d 28 Rate constant 1 d 0 0248 Q10 factor 2 2 Walker exponent 0 7 TReference C 20 Soil study soil study 2 72 First Order Multi Compartment FOMC alpha i_studie 0 2 Beta 2 Q10 factor 1 Walker exponent 0 0 TReference C 0 0 Soil study soil study 3 Hockey Stick HS DT50 d 7 DT50 d 70 Rate constant 1 1 d 0 099 Rate constant 2 1 d 0 0099 Parameter Tb d 10 Q10 factor 1 Walker exponent 0 0 TReference C 0 0 Soil study soil study 4 Single First order SFO DT50 d 14 Rate constant 1 d 0 0495 Q10 factor 1 Walker exponent 0 0 TReference C 0 0 RESULTS OF THE CALCULATION Metabolism scheme RESULTS FOR Report example 1 Calculations over one year Parent compound without metabolites Maximum annual total soil concentration for Report example 1 over 1 5 cm soil study 1 mg kg soil study 2 mg kg soil study 3 mg kg soil study 4 mg kg 1 3333 occurring on day 0 1 3333 occ
154. tions APPLICATION PATTERN USED IN THE CALCULATION Number of Applications 4 1st Application date 1 May Application rate g ha 1000 Time between two applications d 14 Crop interception 50 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites Pesticide Report example 2 DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Metabolism scheme Parent compound without metabolites Kinetics for Report example 2 Soil study soil study 1 Single First order SFO DT50 d 365 Rate constant 1 d 0 0019 Q10 factor 2 58 Walker exponent 0 7 TReference C 20 92 Soil study soil study 2 First Order Multi Compartment FOMC 0 1 alpha i_studie Beta 2 Q10 factor 2 58 Walker exponent 0 7 TReference C 20 Soil study soil study 3 Hockey Stick HS DT50 d 70 DT50 d 700 Rate constant 1 1 d 0 0099 Rate constant 2 1 d 0 001 Parameter Tb d 20 Q10 factor 2 58 Walker exponent 0 7 TReference C 20 Soil study soil study 4 Single First order SFO DT50 d 140 Rate constant 1 d 0 005 Q10 factor 2 58 Walker exponent 0 7 TReference C 20 RESULTS OF THE CALCULATION Metabolism scheme RESULTS FOR Report example 2 Calculations over one year Parent compound without metabolites Maximum annual total soil concentration for Report example 2 over 1 5 cm soil study 1 mg kg soil study 2 mg
155. tions After PEsticide applications File Edit pesticide data View Help Current Simulation Copy Programcheck y Del Description Programcheck a Programcheck v Del l Borstel Edit u ae ns imate FOCUS Harburg medan condo Estimation of Soil Concentrations After PEsticide Applications Application pattern develqued av Michael Kein Copy Programcheck x Del single C regular iregular Program version 2 0 18 Dec 2008 ER yi May v Date ofthis simulation 12 02 2009 11 27 18 Bane Re SEINEN Calculation problem Programcheck Applikation rate g ha 1000 P ees o PROGRAM SETTINGS Crop interception Calculation mode Residues from different applications are considered separately over one year u Application mode Single annual application pattern calculation period 1 year Compound data Copy Programcheck v Del Soil soil stu z Add study Degradation Name ofthe scenario Programcheck Name ofthe soil Borstel Parent Soil density kg L 1 5 inetics SFO v 128 Soil depth cm 5 Kinetics DT50 d je Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 SCENARIO DATA USED IN THE CALCULATION Climatic conditions FOCUS Hamburg median conditians Mean temperature C 8 8 010 22 Walker 07 To20 Annual Rainfall ram 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations Total content Porewater
156. ues from different applications are considered separately over one year Application mode Single annual application pattern calculation period 1 year SCENARIO DATA USED IN THE CALCULATION Name of the scenario Programcheck Name of the soil Borstel Soil density kg L 1 5 Soil depth cm 5 Tillage depth cm 5 Organic carbon content 1 5 Field capacity Vol 29 2 Wilting point Vol 6 4 Climatic conditions FOCUS Hamburg median conditions Mean temperature C 8 8 Annual Rainfall mm 701 Annual pot Evapotranspiration mm 589 for calculation of background concentrations APPLICATION PATTERN USED IN THE CALCULATION Application rate g ha 1000 Crop interception 0 COMPOUNDS CONSIDERED IN THE CALCULATION Metabolism scheme Parent compound without metabolites DEGRADATION KINETICS PARAMETERS CONSIDERED FOR THE CALCULATION Soil study soil study 1 Metabolism scheme Parent compound without metabolites Kinetics for Report example 1 Hamburg Single First order SFO DT50 d 28 Rate constant 1 d 0 0248 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 1 Hamburg Calculations over one year 75 Maximum annual total soil concentration for Report example 1 Hamburg over 5 cm mg kg 1 3333 occurring on day 0 Calculated time dependent total soi
157. ur after 11 years Calculations of concentrations considering accumulation after many years of application 140 Maximum annual concentration in pore water for Metabolidan over 5 cm considering accumulation soil study 1 mg L 2 2881 occurring on day 321 soil study 2 mg L 34 7779 occurring on day 66 soil study 3 mg L 5 9882 occurring on day 321 soil study 4 mg L 0 9224 occurring on day 66 a tillage depth of 5 cm was considered for calculating the background concentration Calculated PECact in soil over 5 cm for Metabolidan mg L considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 8494 33 8106 5 6325 0 3679 2 0000 1 6430 34 0567 5 5207 0 3703 4 0000 1 5706 33 4097 5 3705 0 3646 7 0000 1 4752 32 5791 5 3682 0 3544 14 0000 1 4735 31 1796 5 3644 0 3232 21 0000 1 4724 33 9449 5 3596 0 3401 28 0000 1 4679 32 7289 5 3530 0 3313 42 0000 1 4618 31 1304 5 6076 0 2869 50 0000 1 6786 33 1272 5 7431 0 3088 100 0000 1 8579 31 3590 5 7590 0 2272 a tillage depth of 5 cm was considered for calculating the background concentration PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 5 cm for Metabolidan mg L considering accumulation Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 2 2779 34 7623 5 9853 0 9217 2 0000 2 2778 34 6608 5 9847 0 9181 4 0000 2 2755 34 3714
158. urring on day 0 1 3333 occurring on day 0 1 3333 occurring on day 0 Calculated PECact in soil over 1 5 cm for Report example 1 mg kg Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 3007 1 2295 1 2076 1 2689 2 0000 1 2689 1 1607 1 0938 1 2076 4 0000 1 2076 1 0703 0 8973 1 0938 7 0000 1 1212 0 9870 0 6667 0 9428 14 0000 0 9428 0 8797 0 4761 0 6667 21 0000 0 7928 0 8181 0 4442 0 4714 28 0000 0 6667 0 7757 0 4145 0 3333 42 0000 0 4714 0 7185 0 3608 0 1667 50 0000 0 3867 0 6949 0 3333 0 1122 100 0000 0 1122 0 6073 0 2032 0 0094 PECact values are related to the time after the maximum concentration Calculated time weighted average TWA concentrations in soil over 1 5 cm for Report example 1 mg kg Time d soil study 1 soil study 2 soil study 3 soil study 4 1 0000 1 3170 1 2814 1 2705 1 3011 2 0000 1 3009 1 2383 1 2106 1 2697 4 0000 1 2695 1 1755 1 1018 1 2099 7 0000 1 2243 1 1178 0 9626 1 1270 14 0000 1 1269 1 0193 0 7437 0 9620 21 0000 1 0398 0 9618 0 6492 0 8292 28 0000 0 9618 0 9203 0 5942 0 7215 42 0000 0 8290 0 8618 0 5251 0 5612 50 0000 0 7648 0 8370 0 4966 0 4934 100 0000 0 4933 0 7411 0 3798 0 2675 Calculation of background concentrations after many years 73 Final background concentration in total soil for Report example 1 over 5 cm soil study 1 mg kg 0 0002 estimated to occur within 10 years soil study 2 mg kg 0 0356 estimated to occur after 10 years soil study 3 mg kg
159. usly these two models cannot be selected for metabolites The user can decide to keep pesticide residues from different applications separately also in this calculation mode see Figure 5 and the explanation in chapter 3 3 1 3 3 3 Simulation considering the parent compound and two parallel metabolites In this mode ESCAPE considers three compartments each for the parent compound and for the two metabolites as shown in Figure 7 compartment 1 degradatio pesticide compartment 2 compartment 3 degradatio degradatio metabolite A metabolite B Figure 7 Three compartments for parent and two parallel metabolites Boe The calculation of the formation of the two metabolites is done based on the time dependent degradation of the parent compound the formation fraction of the metabolite and the differences in the molar masses according to equation 8 aus Raeg fa B Mmea B 18 Moar RyormA B actual formation of the metabolite A or B g ha Raeg actual degradation of the parent compound g ha Sa formation fraction of the metabolite A or B Mpar molecular mass of the parent compound g mol M meta B molecular mass of the metabolite A or B g mol For the parent compound ESCAPE calculates actual and time weighted average concentrations based on all four kinetic models presented in chapter 3 1 However as the degradation in the degradation models FOMC and HS depends on the time since application but the
160. w record will be new compound1 If the record is already existing the numbering will be incremented File New Application Record This command can be used to load a new set of standard input data into ESCAPE The necessary information on the standard application data is saved in the text file do not delete this file apn The name of the new record will be new application pattern 1 If the record is already existing the numbering will be incremented File New Scenario This command can be used to load a new set of standard input data into ESCAPE The necessary information on the standard application data is saved in the text file do not delete this file scn The name of the new record will be new scenario If the record is already existing the numbering will be incremented 48 File Load Simulation This command is to load a special form the simulation organiser which allows to edit ESCAPE input data records and simulation collections It is however not absolutely necessary to use this form as the main form has in principle the same functionality as the simulation organiser Each combination of input data scenario application pattern compound data is called a simulation and are saved in a special data base The top list box is to switch between simulations currently saved in the system A simulation description which will appear in the output documentation is shown below that lis
161. xample 2 Calculations over one year 84 Maximum annual total soil concentration for Report example 2 over 5 cm mg kg 2 5635 occurring on day 42 Calculated time dependent total soil concentrations over 5 cm for Report example 2 after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 2 5587 2 5611 42 43 2 2 5538 2 5587 42 44 4 2 5441 2 5538 42 46 T 2 5297 2 5466 42 49 14 2 4963 2 5298 42 56 21 2 4633 2 5131 42 63 28 2 4308 2 4966 42 70 42 2 3670 2 4640 42 84 50 2 3313 2 4456 42 92 100 2 1202 2 3359 41 141 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in total soil for Report example 2 over 5 cm mg kg 2 5592 estimated to occur after 11 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 2 over 5 cm considering accumulation mg kg 5 1227 a tillage depth of 5 cm was considered for calculating the background concentration Calculated time dependent total soil concentrations over 5 cm for Report example 2 mg kg considering accumulation Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 5 1178 5 1203 42 43 2 5 1130 5 1178 42 44 4 5 1033 5 1130 42 46 7 5 0889 5 1057 42 49
162. y Stick HS DT50 1 d 70 DT50 2 d 700 Rate constant 1 1 d 0 0099 Rate constant 2 1 d 0 001 Parameter Tb 20 Q10 factor 2 58 Walker exponent 0 7 Ref temperature C 20 RESULTS OF THE CALCULATION Metabolism scheme Parent compound without metabolites RESULTS FOR Report example 2 88 Calculations over one year Maximum annual total soil concentration for Report example 2 over 5 cm mg kg 2 3247 occurring on day 42 Calculated time dependent total soil concentrations over 5 cm for Report example 2 after one year mg kg Time d PECact PECtwa Begin TWAframe d End TWAframe d 1 2 3114 2 3180 42 43 2 2 2981 2 3114 42 44 4 2 2720 2 2982 42 46 7 2 2386 2 2791 42 49 14 2 1858 2 2455 42 56 21 2 1407 2 2173 42 63 28 2 1259 2 1963 42 70 42 2 0966 2 1680 42 84 50 2 0801 2 1552 42 92 100 1 9796 2 0925 41 141 PECact values are related to the time after the maximum concentration Calculation of background concentrations after many years Final Background concentration in total soil for Report example 2 over 5 cm mg kg 3 0362 estimated to occur after 11 years according to the estimation 100 of the final plateau was reached after 10 years Calculations of concentrations considering accumulation after many years of application Maximum total soil concentration for Report example 2 over 5 cm considering accumulation mg kg 5 3609 a tillage depth of 5 cm was considered for calculating

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