ZOL 814 Chemodynamics

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ZOL 814 Chemodynamics Generic Expected Environmental Concentration Program (GENEEC) Name: Background: The GENEEC model is used to calculate the Expected Environmental Concentration (EEC) for a generic aquatic pond environment adjacent to an agricultural field. The simulation provided an analytical tool to assess the potential for adverse effects of pesticides on adjacent aquatic environments. This is not a predictive tool, but rather used in a conservative Tier I risk assessment. See the users manual for earlier versions (on diskette) for a more detailed description of the model. There is no user manual for the beta version 1.3 (most recent version) that we will be using in class. GENEEC version 1.3 mimics a PRZM/EXAMS simulation of a generic 10-ha row crop field draining into a 1-ha farm pond of depth 1 m. It also incorporates the Tier 1 spray drift model of the U.S. Spray Drift Task Force to provide an estimate of spray drift loading. The model contains numerous conservative assumptions appropriate for a screening level model. One aspect of this generic model that prevents realistic simulation of late-season foliar applications is that it does not take into account foliage factors such as interception of spray, foliar dissipation prior to rainfall, or pesticide wash-off fraction. The predicted generic concentrations should not be interpreted as accurate estimates; instead they are merely screening levels (upper bound estimates). In this exercise we will estimate the environmental concentrations of the organophosphorus insecticide, chlorpyrifos used in cotton under Australia conditions. Application information for this example was provided by Dr. Paul Hughes, Dow AgroSciences, Australia. Chemical properties and environmental fate parameters were 1

taken from the United States Department of Agriculture Agricultural Research Service Pesticide Properties Database. This database has been subjected to peer review by registrants but has not been updated recently. However, it is judged to be a reasonably accurate compilation of data, and representative values provided in the database are based on objective, unbiased selection procedures. Aquatic degradation half-lives for all the processes accounted for in GENEEC (aerobic degradation, hydrolysis, and photolysis) are not uniformly available for all of the compounds in the database. In this example fieldestimated lumped first-order dissipation from the water column was entered arbitrarily as a rate for aerobic degradation. USEPA prefers laboratory values for individual processes. Below you will find the individual screens that will appear when you execute the model. Follow these and input the data into the model. When you have completed the simulation, your instructors will assist you in interpreting the information and discuss how it is used in a Tier I ecological risk assessment. Use GENEEC to simulate the concentration of chlorpyrifos that would be expected to occur in a pond near a cotton field treated with chlorpyrifos. The model can be found at the course website: http://www.msu.edu/course/zol/814. Download the model onto your computer. To run the model, get a dos prompt and type GENEECX at the prompt. Below are the input screens that you will see when making inputs (parameterizing ) into the model. After you run the model, answer the questions. 2

VERSION 1.3 ENVIRONMENTAL FATE AND EFFECTS DIVISION OFFICE OF PESTICIDE PROGRAMS U.S. ENVIRONMENTAL PROTECTION AGENCY TIER ONE SCREENING MODEL FOR AQUATIC PESTICIDE EXPOSURE BETA TEST VERSION PLEASE FAX COMMENTS TO: RON PARKER (703) 305-6309 PLEASE CHOOSE THE LETTER OF THE APPLICATION YOU WISH TO USE: A: ROW CROPS, ORCHARDS, GRASSES AND TURF B: RICE C: CRANBERRIES D: DITCHBANKS AND RIGHTS-OF-WAY ---> A GENEEC FOR ROWCROPS, ORCHARDS AND TURF ENVIRONMENTAL FATE AND EFFECTS DIVISION OFFICE OF PESTICIDE PROGRAMS U.S. ENVIRONMENTAL PROTECTION AGENCY TIER ONE SCREENING MODEL FOR AQUATIC PESTICIDE EXPOSURE THIS IS A PROGRAM TO CALCULATE A SET OF GENERIC ESTIMATED ENVIRONMENTAL CONCENTRATION (GEEC) VALUES RESULTING FROM RUNOFF FROM A TEN HECTARE FIELD INTO A ONE HECTARE BY TWO METER DEEP STATIC WATER BODY ENTER A RUN NUMBER TO CONTINUE ---> 1 3

ENTER AN OUTPUT FILE NAME ---> Cotton1 ENTER CHEMICAL NAME ---> Chlorpyrifos ENTER CROP NAME ---> Cotton THE PROGRAM ASSUMES THAT RUNOFF IS SUFFICIENT TO REMOVE TEN PERCENT OF THE DISSOLVED PESTICIDE FROM THE TEN HECTARE FIELD THE FOLLOWING INFORMATION SHOULD BE TAKEN FROM THE MOST CURRENT, ACCEPTED LABEL FOR THE USE SITE IN QUESTION PLEASE ENTER APPLICATION RATE (IN POUNDS a.i. PER ACRE)---> 1.340 ENTER MAXIMUM NUMBER OF APPLICATIONS PERMITTED PER YEAR---> 2 ENTER INTERVAL BETWEEN APPLICATIONS (DAYS)---> 10 4

THE DISSOLVED PESTICIDE CONCENTRATION IS REDUCED BY ADSORPTION OF THE PESTICIDE TO SOIL OR TO ORGANIC MATTER THE ADSORBED FRACTION IS ESTIMATED BY THE SOIL/WATER EQUILIBRIUM PARTITION COEFFICIENT (Kd) PLEASE ENTER Kd VALUE (WITHOUT COMMAS)---> 115 THE DISSOLVED PESTICIDE CONCENTRATION IS ALSO REDUCED BY DEGREDATION IN THE FIELD PRIOR TO A RAINFALL/RUNOFF EVENT - THE PROGRAM ASSUMES DEGRADATION BY AEROBIC METABOLISM FOR TWO DAYS AFTER THE FINAL APPLICATION (IF STABLE TO AEROBIC METABOLISM OR IF DATA IS UNAVAILABLE, PLEASE ENTER ZERO (0)) ENTER SOIL AEROBIC METABOLIC HALFLIFE (IN DAYS) ---> 30.5 5

SOME PESTICIDE LABELS REQUIRE THAT THE PESTICIDE BE WETTED-IN EITHER THROUGH RAINFALL OR IRRIGATION: IN THIS CASE, RUNOFF TO THE POND IS ASSUMED TO OCCUR IMMEDIATELY RATHER THAN AFTER TWO DAYS IS THIS PESTICIDE TO BE WETTED-IN? (Y or N) ---> N THE DISSOLVED PESTICIDE CONCENTRATION MAY BE INCREASED BY DIRECT DEPOSITION OF SPRAY DRIFT INTO THE POND ENTER A, B or C TO SELECT METHOD OF APPLICATION: A: AERIAL SPRAY B: GROUND SPRAY C: GRANULAR (NON-SPRAY) ---> A 6

SPRAY DRIFT TO THE POND MAY BE REDUCED BY A BUFFER ZONE LOCATED BETWEEN THE TREATED FIELD AND THE WATER BODY PLEASE ENTER THE WIDTH OF THE SPRAY DRIFT BUFFER (FEET) (FOR NO BUFFER, ENTER ZERO (0) ---> 49.2 THE DISSOLVED PESTICIDE CONCENTRATION IN A WATER BODY CANNOT EXCEED THE SOLUBILITY OF THE CHEMICAL ENTER THE SOLUBILITY (IN PPM) ---> 1.2 7

CHRONIC GENERIC EEC VALUES ARE CALCULATED BY SUMMING THE RATES OF THE AQUATIC DEGRADATION PATHWAYS ENTER ANY OR ALL OF THE FOLLOWING WHICH ARE AVAILABLE: (PLEASE ENTER ZERO (0) FOR ANY WHICH ARE STABLE OR FOR WHICH VALUES ARE UNAVAILABLE) AEROBIC AQUATIC METABOLIC HALFLIFE (DAYS) ---> 9 ENTER PHOTOLYSIS HALFLIFE (DAYS) ---> 0 RUN No. 1 FOR Chlorpyrifos ON Cotton * INPUT VALUES * -------------------------------------------------------------------- RATE (#/AC) APPLICATIONS SOIL SOLUBILITY BUFFER(FT) INCORP ONE(MULT) NO.-INTERVAL Kd (PPM ) % DRIFT DEPTH(IN) -------------------------------------------------------------------- 1.340( 2.408) 2 10 115.0 1.2 49.2-11.1 0.0 FIELD AND STANDARD POND HALFLIFE VALUES (DAYS) -------------------------------------------------------------------- METABOLIC DAYS UNTIL HYDROLYSIS PHOTOLYSIS METABOLIC COMBINED (FIELD) RAIN/RUNOFF (POND) (POND-EFF) (POND) (POND) -------------------------------------------------------------------- 30.50 2 N/A 0.00-0.00 9.00 9.00 GENERIC EECs (IN PPB ) -------------------------------------------------------- PEAK AVERAGE 4 AVERAGE 21 AVERAGE 56 GEEC DAY GEEC DAY GEEC DAY GEEC -------------------------------------------------------- 11.01 8.68 2.93 1.17 DO YOU WANT ANOTHER RUN (Y OR N) ---> 8

Questions: 1) What is the estimated What is the estimated environmental concentration (EEC? 2) If the No Observable Effect Concentration (NOEC) for chlorpyrifos is 5 ug/l would adverse effects be expected based on this scenario? 3) Chlorpyriphos is an organo-phosphate insecticide that is acutely toxic by depressing achetylcholinesterase (AchE) activity in the brain. It has a low acute to chronic ration. For these reasons which of the EEC values generated by GENEEC would be the most appropriate to which to compare a threshold for effects concentration? 4) What assumptions are made in this model? 5) How accurate is the model? 9

6) How generalized are the results? 7) What are the most important parameters in the model? 10

8) How could the model predictions be improved? 9) Draw the structure of the model. 10) Perform a sensitivity analysis for the Kd value. To do this, run several simulations with a range of values for Kd. How sensitive is the model to values used for Kd? 11

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