Model manual (INRA-CREED)

Transcription

1 Model manual (INRA-CREED) Charlotte N. Legind (November 2010), revised by Stefan Trapp, February 2011 Introduction Color code A color code was used to structure the models and to make programming and data entering easier. The colors remain practically the same on earlier Excel versions (ending.xls) and new version (ending.xlsx). The color code is displayed in the screen-shot below: bright yellow pale yellow light blue grey green enter chemical data enter other data results calculations, don't touch! data adapted to new field crops orange recently corrected red false now or in earlier versions rose for copies Figure: Screen-shot of the color code, BUCKETS model for organics 1

2 Design of the Buckets model for Organics (generic simulation) The BUCKETS model for organics, that was used for the generic simulations, received a new design, following suggestions of our users from CREED and INRA :-) It uses less colors, primarily bright yellow for chemical data input; pale yellow for other data input; light blue for results; white for comments from us (names, units etc.); and grey for calculations (do not tough grey cells, please). Updates in the program were, however, also marked in colors, which makes the excel-sheets again more colorful. Green marks cells that where changed to produce the rotating crop scenario. Orange were marked cells where we changed the code (mostly to the new internal unit mg/l for Csoil). Red are cells marked where an error was found (which of course was corrected then). our color code; white for comments bright yellow enter chemical data pale yellow enter other data light blue grey green results calculations, don't touch! data adapted to new field crops orange recently corrected red false now or in earlier versions rose for C air = zero, copy this Figure: The new color code (designed February 2011 by Stefan Trapp). Rose cells for analysis of uptake pathways A special thing in the new buckets model for generic simulation is the cells with the rose color on the first sheet (In & Output). Rose cells are from C55 to F64, and from C67 to F76. To analyse uptake pathways, a simulation run with Cair = 0 has to be done. Follow these steps: 1) Set concentration in air to zero The result of this simulation appears in cells C67 to F76. 2) Copy result from cells C67 to F76 into cells C55 to F64. Use "values and number formatting" as option! so that the numbers in cells C55 to F64 are not updated anymore. 3) Set concentration in air back to original value. 4) The file calculates uptake % from air in cells I42 to M51 5) Save file 2

3 Applicability of the models for organic compounds The models for organic compounds can principally be used for the simulation of neutral organic compounds. Compounds that dissociate at environmental ph can not be simulated. Due to our latest changes (compared to earlier model versions, such as Trapp & Matthies 1995), the model can be used for the following frequent environmental pollutants: - volatile compounds (such as perchloroethene PCE; trichloroethene TCE; benzene, toluene, ethylbenzene, xylene BTEX) - systemic pesticides (except ionizable compounds, such as glyphosate) - persistent organic pollutants POPs, among them PCDD/F (polychlorinated dibenzodioxines and -furanes), PCB (polychlorinated biphenyls), polyaromatic hydrovcarbons (PAH), organochlorine pesticides (DDT, DDE, lindane etc.) - nonionic tensides The model is NOT applicable to - organic acids and bases and other ionizing compounds, among them many pharmaceuticals and daily care products - systemic herbicides (such as glyphosate, 2,4-D, mecoprop) - cyanide compounds (cyan hydrogen, Prussian Blue, ferrocyanide, ferricyanide) - anionic and cationic tensides (except if permanently dissociated and Koc is known, like LAS) - micelle forming compounds (tensides in concentrations above the critical micelle concentrations) - compounds that react if released (e.g., chlorine, hydrogen peroxide) - insoluble, particulate compounds, such as nanomaterials. Simulation of other compounds For the prediction of transport and fate of the neutral organic compounds, a couple of input data have to be adapted. The 10-years-BUCKETS model version for organics has an input sheet (named In- & output). All compoundspecific input data can be entered there and are then automatically updated in all 10 model sheets. - degradation rates cells D2... D6 - Initial concentration in soil: F1 - Chemical properties: F2.. F4 - annual pulse input: B10.. B19 - concentration in air D10.. D19 3

4 It is sufficient to change the data in the sheet named In- & output for the ten years. Then, the data in the ten 1-year-spreadsheets are automatically updated! Principally, the data could also be changed in each sheet for 1 year-calculations, the 1-year-Buckets model for organics. These are (almost - 1 row is less) the same cells that have to be changed in the Cascade (1- year)-model for organic for a change of chemical, namely: - physico-chemical data (cells B3 to B6, yellow) - degradation data (plants: cells B7 to B11, yellow; soils: Buckets model, cells 308 to 374) - concentration in air (F7... AC7) - initial concentrations (F9... F14) - pulse input (cells G21.. AC25) - initial concentrations in soil, bioavailable cells F9..AC9 - initial concentrations in soil, aged cells F10..AC10 This differs in the BUCKETS-modell version, here the initial concentrations in soil are found in the cells B B371. Besides, the cells that have to be changed remain the same (± one row). Applicability of the models for inorganic compounds (heavy metals) The models for metals are more compound-specific. Parameters depending on the metal under consideration are: - the adsorption coefficient between soil and pore water, Kd (sheet In- & output cells E6.. E15; sheet year 1 to 10 cells B125.. B189) - pulse emissions (e.g., with amendments) (sheet In- & output cells B6.. B15; sheet year 1 to 10 cells G13.. AC 14) - initial concentrations in soil (sheet In- & output cells B6.. B15; sheet year 1 to 10 cells G13.. AC 14) - initial concentration in plant (sheet year 1 to 10 cell F9) - concentrations in air (sheet In- & output cells D6.. D15; sheet year 1 to 10 cells F7.. AC 7) Take care: the cells may be slightly different in the various versions of the model (e.g., for Pb). Again, it is sufficient to change the data in the sheet named In- & output (for the ten years). Then, the data in the ten 1-year-spreadsheets are automatically updated! For uptake into plants, two different approaches exist. For non-essential metals (those not required by plants for their growth, examples are Cd and Pb), we assume no enzymatic regulation of uptake, and translocation is with the water. For essential metals (examples are Cu and Zn), better results were obtained 4

5 by using a statistically derived transfer factor. This factor is specific for each (essential) metal, and even for the crop species under consideration. It can be derived from empirical data (e.g., the field measurements), but it cannot be estimated a priori. Buckets model for organic chemicals This section may slightly differ from the current versions, as the model has been changed recently. The buckets model for organic chemicals is the combination of a water balance model in soil and a plant model for metals. It is implemented in the excel sheet Buckets Organic Aug-July.xls. The considered compartments are soil layers 1-5, root, stem, leaf and fruit, where leaf and fruit run in parallel (Figure 11). Given input data refer to an area of 1 m 2. Figure 11. Buckets model for organic chemicals. Soil compartments in grey, plant compartments in white. 5

6 Period independent input for the plant model is on the top left side (box A, Figure 12), whereas period dependent input for both plant and water balance model is on the right side (box B, Figure 12). Figure 12. Period independent (A) and period dependent (B) input. Background total air concentration is entered in cells F7-AC7. Initial concentrations in root, stem, leaf and fruit can be entered in cells F9-F11 and F13. Pulse input, i.e. chemical mass being applied at the first day of a defined period, is specified in rows 21-24, column G-AC. Periods are defined in row 4, column F-AC, by input of end days (day when period ends). The given excel sheet implements 24 periods, that covers one year from August to July. The shown example considers a pulse input of 8.5 x 10-7 mg of chemical in soil at the first day of the 4 th period (September 15). Chemical, root, stem, leaf and fruit input are given in box A. In the yellow fields you can change parameters. Data are constant over all periods by default. Gray fields mean do not change (calculations are performed). Particle deposition and gas exchange: the orange, yellow and grey fields in box C (below box A, Figure 13) are used to calculate input from air to soil and from air to stem, leaves and fruit. 6

7 Figure 13. Particle deposition and gas exchange (box C) Period independent input for the water balance model in soil is far below box A on the left side (box D, Figure 14). 7

8 Figure 14. Period independent input for the water balance model in soil (box D). Initial concentrations in the 5 soil layers can be entered in cells B307, B325, B341, B357 and B373, respectively. Other soil input for the 5 different layers are given in box D. In the yellow fields you can change parameters. Data are constant over all periods by default. Gray fields mean do not change (calculations are performed). Calculations are performed below box B in box E (Figure 15). 8

9 Figure 15. Calculations are performed in box E. Model output for the plant model is to the right of box B in box F, i.e. concentrations vs. time given in columns AH-AK as mg kg fw -1. 9

10 Figure 16. Model output for the plant, concentrations vs. time (box F) Results as the concentration at the end of the last period (24) for soil layers 1-5, root, stem, leaf and fruit are also given in columns C-D, rows 4-28 on the right hand side of box A (Figure 12). Model output for the water balance model in soil can be found in columns F-AC, i.e. leaching of chemical out of first soil layer Rows leaching of chemical into groundwater Rows water content of soil layers 1-5 Rows leaching of water to groundwater Row 387 Calculation of the contribution (%) of air and soil to the final concentration in plant grain must be performed manually (box G, Figure 12). Iterative use The model may be copied several times to extend the model period. Mark the entire spreadsheet by clicking on the topmost left corner (to the left of column A and above row 1), then copy and paste into the next spreadsheet. We might call the first spreadsheet for 1 (year 1) and the second for 2 (year 2) (Figure 6). Periods need to be consistent: if 1 ends July 31, 2 has to begin with August 1. The values that need to be transferred from 1 to 2 are 10

11 the calculated concentrations in soil layers 1-5. So cell B307 of 2 must read = 1!D17, cell B325 must read = 1!D18, cell B341 must read = 1!D19, cell B357 must read = 1!D20 and cell B373 must read = 1!D21. the calculated water content of soil layers 1-5. So cell B303 of 2 must read = 1!AC381, cell B321 must read = 1!AC382, cell B337 must read = 1!AC383, cell B353 must read = 1!AC384 and cell B369 must read = 1!AC385 Input data and results can be typed in and read from the separate sheets or you can add a separate in- and output sheet that links to all sheets. Other scenarios Input of chemical with amendment (mg m -2 ) can be entered in any of the periods in cells G21-AC21. Chemical will be added to the initial concentration of soil in that period. Substance specific data that needs to be entered when changing model substance are: Log K OW (L L -1 ) B4 K AW (L L -1 ) B5 Molar mass (g mol -1 ) B6 Root degradation rate (d -1 ) at 20 C B7 Stem degradation rate (d -1 ) at 20 C B8 Leaf degradation rate (d -1 ) at 20 C B9 Fruit degradation rate (d -1 ) at 20 C B10 Soil degradation rate (d -1 ) at 20 C B310 Crop specific data that needs to be entered when changing crop type are: Transpiration coefficient (L kg fw -1 ) B15 Germination day, this is counted as the number of days after start of period 1 when the plant starts to transpire B16 Water content of root, stem, leaf and fruit (L kg fw -1 ) B18, B26, B35, B45 Lipid content of root, stem, leaf and fruit (kg kg fw -1 ) B19, B27, B36, B46 Specific surface area of root, stem, leaf and fruit exposed to air (m 2 kg fw -1 ) B20, B28, B34, B44 Initial root, stem, leaf and fruit mass (kg fw m -2 ) B22, B30, B40, B47 Final root, stem, leaf and fruit mass (kg fw m -2 ) B23, B31, B41, B48 Overall growth rate of root, stem, leaf and fruit (d -1 ) B24, B32, B42, B49 Default harvest of the plant is at the end of period 24. Scenarios may have changed for the revised report. 11

12 Buckets model for metals The buckets model for metals is the combination of a water balance model in soil and a plant model for metals. It is implemented in the excel sheet Buckets Metal Aug-July.xls. The considered compartments are soil layers 1-5 and plant (Figure 17). Given input data refer to an area of 1 m 2. Figure 17. Buckets model for metals. Soil compartments in grey, plant compartment in white. Period independent input for the plant model is on the top left side (box A, Figure 18), whereas period dependent input for both plant and water balance model is on the right side (box B, Figure 18). 12

13 Figure 18. Period independent (A) and period dependent (B) input. Background air concentration at particles is entered in cells F7-AC7. Initial concentration in plant can be entered in cell F9. Pulse input, i.e. metal mass being applied at the first day of a defined period, is specified in rows 13-14, column G-AC. Periods are defined in row 4, column F-AC, by input of end days (day when period ends). The given excel sheet implements 24 periods, that covers one year from August to July. The shown example considers a pulse input of 4.7 mg of metal in soil at the first day of the 4 th period (September 15). Chemical and plant input is given in box A. In the yellow fields you can change parameters. Data are constant over all periods by default. Gray fields mean do not change (calculations are performed). Particle deposition from air and rain: the orange fields in box A are used to calculate input from air and rain to soil and plant. Period independent input for the water balance model in soil is far below box A on the left side (box C, Figure 19). 13

14 Figure 19. Period independent input for the water balance model in soil (box C). Initial concentrations in the 5 soil layers can be entered in cells B124, B140, B156, B172 and B188, respectively. Other soil input for the 5 different layers are given in box C. In the yellow fields you can change parameters. Data are constant over all periods by default. Gray fields mean do not change (calculations are performed). Calculations are performed below box B in box D (Figure 20). 14

15 Figure 20. Calculations are performed in box D. Model output for the plant model is to the right of box B in box E (Figure 21), i.e. concentrations vs. time given in column AH as mg kg fw -1 and as mg kg dw -1 in column AJ. 15

16 Figure 21. Model output for the plant, concentrations vs. time (box E) Results as the concentration at the end of the last period (24) for soil layers 1-5 and plant are also given in columns C-D, rows 4-20 on the right hand side of box A (Figure 18). Model output for the water balance model in soil can be found in columns F-AC, i.e. leaching of chemical out of first soil layer Rows leaching of chemical into groundwater Rows water content of soil layers 1-5 Rows leaching of water to groundwater Row 203 Calculation of the contribution (%) of air and soil to the final concentration in plant grain must be performed manually (above box C, rows ). Iterative use The model may be copied several times to extend the model period. Mark the entire spreadsheet by clicking on the topmost left corner (to the left of column A and above row 1), then copy and paste into the next spreadsheet. We might call the first spreadsheet for 1 (year 1) and the second for 2 (year 2) (Figure 6). Periods need to be consistent: if 1 ends July 31, 2 has to begin with August 1. The values that need to be transferred from 1 to 2 are the calculated concentrations in soil layers 1-5. So cell B124 of 2 must read = 1!D13, cell B140 must read = 1!D14, cell B156 must read = 1!D15, cell B172 must read = 1!D16 and cell B188 must read = 1!D17. 16

17 the calculated water content of soil layers 1-5. So cell B120 of 2 must read = 1!AC197, cell B136 must read = 1!AC198, cell B152 must read = 1!AC199, cell B168 must read = 1!AC200 and cell B184 must read = 1!AC201 Input data and results can be typed in and read from the separate sheets or you can add a separate in- and output sheet that links to all sheets. Other scenarios Input of metal with amendment (mg m -2 ) can be entered in any of the periods in cells G13-AC13. Metal will be added to the initial concentration of soil in that period. Metal specific data that needs to be entered when changing model substance are: K d (L kg dw -1 ) B126, B142, B158, B174, B190 Wet and dry absorption coefficients, if known (m 2 kg dw -1 ) B14-15 Crop specific data that needs to be entered when changing crop type are: Transpiration coefficient (L kg fw -1 ) B4 Germination day, this is counted as the number of days after start of period 1 when the plant starts to transpire B5 Water content of plant (L kg fw -1 ) B7 Initial plant mass (kg fw m -2 ) B8 Final plant mass (kg fw m -2 ) B9 Overall growth rate of plant (d -1 ) B10 Default harvest of the plant is at the end of period 24. Scenarios may have changed for the revised report. 17