VI. Aquatic Exposure and Risk Assessment a. Hazard Summary Acutely, mancozeb is highly toxic to cold water ( freshwater) fish ( LC 50 = 460  640 ppb) and moderately toxic to warm water ( freshwater) fish and estuarine/ marine fish ( LC 50 = 1,350  4,200 ppb). The acute toxicity classification of estuarine/ marine fish is based on supplemental studies. 31 EFED needs a core study ( guideline 72 3a) to fulfill this requirement ( see Appendix III). Chronic freshwater NOAEC and LOAEC values were determined to be 2.19 and 4.56 ppb, respectively, with survival and lack of growth being the endpoints affected. No acceptable data has been filed to assess the chronic effects of mancozeb to estuarine/ marine fish. EFED needs an estuarine/ marine fish early life stage toxicity test ( guideline 72 4a) to fulfill this requirement ( see Appendix III). Acute toxicity values for aquatic invertebrates suggest that mancozeb is highly toxic to freshwater invertebrates ( Daphnia EC 50 = 580  1,000 ppb) and moderately to very highly toxic to estuarine/ marine invertebrates ( oyster EC 50 = 1,600 ppb and mysid shrimp EC 50 = 10.5 ppb). The toxicity classification of shrimp is based on supplemental studies and EFED needs a core study to fulfill this guideline ( 72 3c) ( see Appendix III). A chronic freshwater invertebrate life cycle study on Daphnia magna showed the NOAEC was 7.3 ppb and the LOAEC was 12 ppb. The endpoints affected in this study were immobility of the test species and length and time until first brood. No acceptable data has been filed to assess the chronic effects of mancozeb to estuarine/ marine invertebrates. EFED needs an estuarine/ marine invertebrate life cycle toxicity test ( guideline 72 4b) to fulfill this requirement ( see Appendix III). A Tier II aquatic plant growth study reviewed on mancozeb showed the EC 50 was 47 ppb and the NOAEC was 22 ppb. The endpoint affected was growth inhibition. The test species in the study was green algae ( Selenastrum capricornutum), a freshwater nonvascular plant. There was no data submitted to evaluate the affects mancozeb has on the additional aquatic test species: duckweed ( Lemna gibba), marine diatom ( Skeletonema costatum), blue green algae ( Anabaena flosaquae and a freshwater diatom. Aquatic plant growth studies at the Tier I or Tier II level ( guidelines 123 1 or 123 2, respectively) needs to be submitted for these additional species ( see Appendix III).

The EDBCs ( metiram, mancozeb, and maneb), unlike most pesticide active ingredients are not welldefined monomeric substances. The EBDCs are polymeric complexes and are nearly insoluble in water with a high affinity to adsorption by soil or sediment particles. The EBDC portion that dissolves in water and breaks up into a suite of transient species and degradates, is the EBDC complex. This complex is not the parent material by itself.

Studies provided estimates of the EBDC parent material in test concentrations used for evaluating the toxicity to aquatic organisms. These studies showed low recoveries of the test substance. For example, measuring carbon disulfide ( CS 2 ) containing residues, using gas chromatography, one study found roughly a 40% ± 10% average of nominal levels of the " parent complexes". Through filtering and measuring the treatment water, the recovery of " parent complexes" was around 15% ± 10% average of nominal levels ( MRID No. 43525001, Monk, 1994). Filtering of the test solution before analytical measurement increases the accurate measurement of the test material in solution because this removes the undissolved material in the solution. This remaining, soluble portion of the chemical is more biologically available to aquatic organisms and represents a more conservative estimate of the toxicity to these organisms. These filtered and measured " parent complexes", is the portion of the parent material that is available to aquatic organisms in the environment ( see Figure VI 1). The EPA's Rejection Rate Analysis determined that studies, testing materials having poor water solubility, were to use measured as opposed to nominal concentrations. Studies were to use measured concentrations for fixing aquatic toxicological endpoints for compounds with poor solubility ( US EPA. December, 1994). EFED believes filtered and measured samples provide a more conservative estimate of the EBDCs' toxicity to aquatic organisms. Also, EFED believes the filtered and measured samples 32 provide a more true estimate of aquatic organism exposure to the EBDC complexes in the environment.

Modeling estimates using PRZM EXAMS are also estimating EBDC complexes by predicting the EECs using the physicochemical properties of the EBDC, parent aerobic soil metabolism half lives and sorption coefficients. Appendix VI shows the toxicity to aquatic organisms found from the various EBDC aquatic toxicological studies. These endpoints are an estimate of the EBDC complex that fixes the toxicities ( that is, LC 50 s, EC 50 s, and NOAECs). The modeling EECs are also estimates. Influences such as particle size, conditions of storage, degree of decomposition, pH, and the presence of other cations ( see Figure VI 1) would always cause difficulty in providing definite aquatic toxicological endpoints for the EBDCs. 33 Table VI 1: Toxicological Endpoints Used to Determine Aquatic Risk Quotients ( RQs) for Mancozeb Type of Toxicity Organism Species Toxicological Endpoint Acute Freshwater fish rainbow trout ( Salmo gairdneri) LC 50 = 460 ppb Chronic fathead minnow ( Pimephales promelas) NOAEC = 2.19 ppb1 Acute Freshwater invertebrate waterflea ( Daphnia magna) LC 50 = 580 ppb Chronic waterflea ( Daphnia magna) NOAEC = 7.3 ppb2 Acute Estuarine/ marine fish sheepshead minnow ( Cyprinodon variegatus) LC 50 = 1,600 ppb Chronic no data no data Acute Estuarine/ marine invertebrate mysid shrimp ( Americamysis bahia) EC 50 = 10.5 ppb Chronic no data no data Acute Aquatic plant green algae ( Selenastrum capricornutum) EC 50 = 47 ppb 1 Due to survival and lack of growth effects. 2 Due to immobility, length and time until first brood.

b. Exposure and Risk Quotients EFED performed Tier II modeling ( PRZM/ EXAMS) for selected sites for which EFED currently has modeling scenarios. Below ( Figure VI 2) are graphs representing Mancozeb Complex' aquatic risks to non target organisms. EFED selected representative mancozeb use patterns at maximum application rates and minimum intervals between applications. For a more detailed listing and explanation of mancozeb's risk, see Appendix IV. EFED does not have a method to evaluate chronic risks to non target aquatic plants.

The results show: 1) The acute RQs exceed freshwater fish endangered species LOCs for all mancozeb uses ( acute RQ ranges from 0.1 to 0.46). The chronic RQs exceed LOCs for freshwater fish for all mancozeb's modeled uses ( chronic RQ ranges from 1.00 to 3.33). 2) The acute freshwater invertebrates' RQs exceed endangered species LOCs for all mancozeb uses except walnuts ( acute RQ ranges from 0.08 to 0.36). The chronic RQs exceed LOCs for freshwater invertebrates for mancozeb's use on sweet corn, tomatoes, and wheat ( chronic RQ ranges from 1.05 to 2.29). 3) The acute estuarine/ marine fish RQs exceed endangered species LOCs for mancozeb uses apples, tomatoes, and wheat ( acute RQ ranges from 0.05 to 0.13). 4) The results show estuarine/ marine invertebrate acute RQs exceed LOCs for all mancozeb uses ( acute RQ ranges from 4.46 to 20.08). There are currently no estuarine/ marine invertebrates listed as endangered species. 34 0.01 0.1 1 10 100 Risk Quotient Potato Corn ( Sweet) Apples Wheat Tomato Sites Estuarine/ Marine Fish Acute Freshwater Invertebrates Acute Freshwater Fish Acute Aquatic Non Vascular Plants Acute Estuarine/ Marine Invertebrates Acute Freshwater Invertebrates Chronic Freshwater Fish Chronic Mancozeb Aquatic Risks Based on PRZM EXAMS Modeling Figure VI 2 RQ greater or equal to 1.0 exceeds aquatic plant acute and acute endangered species LOCs. RQ greater or equal to 0.5 exceeds aquatic animal acute, acute restricted use and acute endangered species LOCs. RQ greater or equal to 0.1 exceeds aquatic animal acute restricted use and acute endangered species LOCs. RQ greater or equal to 0.05 exceeds aquatic animal acute endangered species LOCs. RQ greater or equal to 1 exceeds animal chronic LOCs. There are no estuarine/ marine invertebrates or non vascular aquatic plant species listed on the endangered species list. 5) Mancozeb's use patterns on all modeled uses exceed acute risk LOCs for nonvascular aquatic plants ( acute RQ ranges from 1.00 to 4.49). There are no nonvascular aquatic plants listed as endangered species. 18 Based on green algae, ( Pseudokirchneriella subcapitata) testing.

19The highest ETU RQ is 0.0005 ( see EFED's ETU chapter).

35 c. Aquatic Risk Assessment Dose/ response slope values for the toxicological endpoints ( see Table V 1) used to calculate aquatic animal RQs for mancozeb were not reported for freshwater fish, freshwater invertebrates, or estuarine/ marine fish, in the studies used to determine these endpoints. Lacking slope information, the likelihood of individual effects, from Mancozeb Complex exposure, to freshwater fish, freshwater invertebrates, and estuarine/ marine fish was not determined.

1) The estuarine/ marine invertebrate acute RQs exceed LOCs for all mancozeb uses ( acute RQ ranges from 4.46 to 20.08). There are currently no estuarine/ marine invertebrates listed as endangered species. At the peak Mancozeb Complex aquatic EEC expected from drift and runoff of 210.8 ppb, the likelihood of adverse Mancozeb Complex effects to individual estuarine/ marine invertebrate is 1 in 1 or 100%. EFED calculated this chance estimate using Equation V 1 with an estuarine/ marine invertebrate acute LC 50 = 10.5 ppb and a slope = 3.0 from MRID No. 41822901 and LC k = 210.8 ppb.

2) Mancozeb's use patterns on all modeled uses exceed acute risk LOCs for nonvascular aquatic plants ( acute RQ ranges from 1.00 to 4.49). There are no nonvascular aquatic plants listed as endangered species. At the peak Mancozeb Complex aquatic EEC expected from drift and runoff of 210.8 ppb, the likelihood of adverse Mancozeb Complex effects to individual nonvascular aquatic plants is 1 in 1 or 100%. EFED calculated this chance estimate using a nonvascular aquatic plants LC 50 = 47 ppb; LC k = 210.8 ppb; and slope = 4.1 from MRID No. 43664701.

Based on laboratory data and modeled EECs, the Mancozeb Complex are responsible for exceeding acute LOCs and not the degradate, ETU. The ETU acute RQs for nonvascular aquatic plants18, freshwater fish and freshwater invertebrates were well below19 the lowest LOC ( endangered species LOC = 0.05) for aquatic organisms. This means the Mancozeb Complex, other than ETU, is responsible for the acute toxicity to freshwater fish, freshwater invertebrates, and nonvascular aquatic plants. EFED does not know how acutely toxic ETU is to estuarine/ marine fish or invertebrates because no data has been reviewed for evaluating this hazard. Also EFED needs ETU data to evaluate fully the acute risks to aquatic plants ( vascular and nonvascular) and the chronic risks to freshwater and esturine/ marine organisms.

ETU is an important transformation product of all the EBDC complexes. These complexes are shortlived in aquatic media and ETU is persistent in this media unless ETU is subjected to rapid degradation by microbes and/ or indirect photolysis.. Because of this, EFED expects the acute toxicity to freshwater fish, freshwater invertebrates, estuarine/ marine fish and nonvascular aquatic plants, from exposure to the Mancozeb Complex, will not last long. The acute fish studies have a duration of 96 probit k = ( log LC  log LC ) * slope + probit 50%

k = new percentage mortality k 50 Equation VI 1 36 hours, while the acute invertebrate studies last 48 hours and the nonvascular aquatic plant studies are 120 hours in duration. Acceptable aquatic half life data is unavailable for most products of the Mancozeb Complex. EFED expects mancozeb to hydrolyze quickly ( that is, within hours) to its complex. Based on this information, EFED expects the Mancozeb Complex' acute toxicity to these aquatic organisms will last for 120 hours but suspects this toxicity will rapidly decline after this time period as this complex degrades to ETU. EFED suspects the Mancozeb Complex' acute toxicity will decrease after about 120 hours. However, EFED expects there will still be enough Mancozeb Complex to present an acute risk to estuarine/ marine invertebrates and a chronic risk to freshwater fish and freshwater invertebrates as mentioned in Section b., above. EFED expects the acute risk to estuarine/ marine invertebrates will persist because the Mancozeb Complex isvery highly toxic these organisms ( mysid shrimp EC50 = 10.5 ppb). Modeled Mancozeb Complex EECs for selected sites range from 2.3 to 14.4 ppb 21 days after mancozeb applications ( see Table V. 2). This combination of exposure and toxicity suggests acute LOCs could still be triggered for estuarine/ marine invertebrates 21 days after mancozeb is applied.

A registrant filed a draft mesocosm study to the Agency as MRID 44944401 under section 6( a)( 2). Section 6( a)( 2) of FIFRA requires pesticide product registrants to file adverse effects information about their products to the EPA. EFED believes the registrant submitted a completed study to OPP under MRID No. 45014901 but EFED has not reviewed this final study. The author conducted the study in Germany. EFED completed an abbreviated review of the draft study ( MRID 44944401) in February, 2000 and a provides the following synopsis of the abbreviated review.

This study followed the Society of Environmental Toxicology and Chemistry ( SETAC) " Guidance Document on Testing Procedures for Pesticides in Freshwater Mesocosms" ( July 1991). The field study lasted 2.5 months: preapplication ( three weeks); application ( seven weeks); and the postapplication period ( four weeks). The author used ten outdoor fiberglass tanks ( mesocosms) in this study  3 controls and 7 treatment tanks. Each mesocosm was about 2 m in diameter and 1.6 m deep with an estimated volume of 5 m3. The treatment tanks received eight simulated spray drift applications of Penncozeb 80 WP ( 80% mancozeb ai) each separated by one week using handheld sprayers. The seven treatment tanks' nominal concentrations of Penncozeb ® 80WP were: 1.25, 4.0, 12.5, 40.0, 125.0, 400.0, and 1250.0 ppb. The author based the results on nominal concentrations of the formulated product not measured concentrations of mancozeb in the treatment tanks. The author conducted the mesocosm study using nonreplicated treatments. Dose response values ( EC 20 and EC 50 ) were derived by employing nonlinear regression analysis. The EC 20 was regarded by the authors as the threshold level, below which no ecologically relevant effects occur. The following table provides the toxicity of Penncozeb 80 WP to various aquatic species in this study.

Table VI 2: Freshwater Organism Toxicity from MRID 44944401  A Draft Mesocosm Study Taxon Species Period EC20/ EC50 1 ( ppb Penncozeb 80 WP)

Zooplankton Cladocera Daphnia magna Application 252/ 408 Cladocera Daphnia longispina Application 332/ 398 Cladocera Scapholeberis mucronata Application 188/ 263 Cladocera Chydorus sphaericus Application 67/ 134 Copepoda Copepod nauplii Application 29/ 57 Table VI 2: Freshwater Organism Toxicity from MRID 44944401  A Draft Mesocosm Study Taxon Species Period EC20/ EC50 1 ( ppb Penncozeb 80 WP)

37 Rotifera Keratella quadrata Application 22/ 27 Rotifera Cephalodella sp. Application 15/ 31 Rotifera Brachionus leydigi Application 5.5/ 9.2 Phytoplankton Protista Volvox sp. Application 1.6/ 4.8 1 Based on reductions in individual species densities.

The EC 50 of 408 ppb for Daphnia magna determined in this mesocosm study ( see Table VI 2) compares closely to the laboratory determined Daphnia magna EC 50 of 580 ppb used for calculating mancozeb's acute aquatic invertebrate RQs in this assessment. Both toxicity values were based on nominal values of a 80% mancozeb formulation although the EC 50 of 580 ppb is based on mortality with replicated results. The author believed the rotifer component of zooplankton to be the most representative for direct sensitivity to the test material, since the EC 20 for Volvox sp. was based on highly variable counts of this species. Also, it was unknown whether the toxicity to Volvox sp. was a direct effect from the chemical, an indirect effect because of competition with other autotrophs, or a combination of the two effects. Based on this the author estimated a range from 4.0 to 5.5 ppb would be a safe level ( that is, a NOAEC) for all organisms identified in the study.

The EPA's " Aquatic Mesocosm Tests to Support Pesticide Registrations EPA 540/ 09 88 035" ( March 1988) requires three replicates at each treatment level, a mesocosm size of 300 m3 in volume and the inclusion of viable finfish in the study. These three major departures from EPA guideline requirements are noted at this time. Although EFED has not reviewed the final mesocosm study, a review of this draft study suggests the study is scientifically sound and useful in showing the sensitivity differences across freshwater invertebrate taxa from exposure to Mancozeb Complex.

i. Incidents EIIS reported mancozeb in three fish kill incidents ( see Table VI 3). One incident occurred in 1970, another in 1992 and the latest occurred in 1995. In the 1970 and 1992 incidents, mancozeb had been applied with insecticides highly toxic to fish ( thiodan and endosulfan) and, because of sample analysis, EFED classified mancozeb as unlikely to have been responsible for the these fish kills. The third incident in 1995 involved an accidental mancozeb spill into a stream that was the source water for a salmon hatchery which resulted in a fish kill at the salmon hatchery. Although no samples were analyzed ( fish or water), EFED considered mancozeb to be a probable cause to the kill.

Table VI 3: Mancozeb Incidents from EIIS Incident Number Pesticide( s) Involved Date ( month/ year) Adverse Effect Magnitude of Damage B0000 233 mancozeb, sulfur, & thiodan 7/ 1970 Fish kill thousands I000799 008 mancozeb, maneb, fenarimol, & endosulfan 4/ 1992 Fish kill > 600 fish Table VI 3: Mancozeb Incidents from EIIS Incident Number Pesticide( s) Involved Date ( month/ year) Adverse Effect Magnitude of Damage 38 I008745 004 mancozeb 7/ 1995 Fish kill 30,000 to 35,000 fish ii. Endocrine Disruptors Chronic testing in freshwater organisms showed immobility, length and time until first brood in daphnia and reduced survival and lack of growth effects in fathead minnow. See Appendix III for a detailed listing of the studies and results. These effects noted in freshwater species could be a result of hormonal disruptions and could suggest that mancozeb may be an possible disruptor. Based on these effects in freshwater fish and invertebrates, EFED recommends mancozeb be subjected to more definitive testing to better characterize effects related to its possible endocrine disruption. This testing should occur when EPA develops suitable screening and testing protocols, considered under the Agency's EDSP.

iii. Endangered Species Based on available screening level information, there is a potential concern for mancozeb's acute and chronic effects on listed Endangered and Threatened species of freshwater animals and acute effects on listed estuarine/ marine fish should exposure actually occur. There are no nonvascular aquatic plant or estuarine/ marine invertebrate species on the endangered species list. 39 VII. Terrestrial Exposure and Risk a. Hazards Summary ( Acute/ Chronic Toxicity)

Avian acute oral toxicity testing was conducted for mancozeb using the English sparrow, mallard duck and Japanese quail as test species. The acute oral LD 50 was determined to be ~ 1500 mg/ kg for the sparrow and > 6400 mg/ kg for the duck and quail. These studies were not the standard single oral dose studies but were multiple oral dose studies that were accepted as supplemental studies in lieu of the standard testing. Therefore, mancozeb is categorized as slightly to practically nontoxic to avian species on an acute oral basis. The requirement for avian subacute dietary testing was waived. In a memorandum dated, October 27, 1987, from EFED to RD, EFED waived the requirement for these studies because it was felt that the multiple dosing studies, mentioned above, exceeded the requirements for dietary testing and dietary testing that was attempted on mallard ducks and bobwhite quail indicated the birds had an aversion to test diet and would not consume the test material. Chronic avian reproduction testing was conducted for mancozeb on mallard ducks and bobwhite quails. The lowest NOAEC was determined to be 125 ppm on the ducks with a LOAEC of 1,000 ppm based upon reductions in: egg production; early and late embryo viability; hatchability; and offspring weight at hatch and 14 days of age. Two ( 2) studies on quails yielded NOAECs of 125 and 300 ppm. The LOAECs for both of these studies was 1000 ppm based upon reductions in the hatchlings' and 14 day old survivors' weights and the reduction in the number of 14 day old survivors.

Mancozeb is practically nontoxic to small mammals on an acute oral basis with LD 50 > 5,000 mg/ kg in tests done on laboratory rats. Results from chronic reproduction study for mancozeb indicate a parental toxicity at a LOAEL of 1,200 ppm ( NOAEL = 120 ppm) with parental body weight decrements, increased relative thyroid weights, and increased incidence of thyroid follicular cell hyperplasia being the endpoints affected.

Currently, EFED does not assess risk to non target insects using risk quotient methodology. Results of acceptable studies are used for recommending appropriate label precautions. Since mancozeb was determined to be practically nontoxic to honey bees ( LD 50 > 179 µ g/ bee) no bee precautionary labeling is required on mancozeb product labeling. A beneficial mite study ( MRID No. 45577201) determined that mancozeb's LR 50 ( residue concentration on foliage causing 50% lethality) for Typhlodromus pyri is 0.1 lb active ingredient/ A and the LOAEC which can potentially be expected to cause adverse reproductive effects is 0.02 lb active ingredient/ A ( lowest concentration tested).

Tier I seedling emergence and vegetative vigor studies for a TEP ( a 60% mancozeb and 9% dimethomorph mixture ) have been reviewed. Ten ( 10) different plant species were exposed to the TEP in each study which included representative plants from the dicotyledonous and monocotyledonous families. These studies indicated the TEP had less than a 25% inhibition on the various growth paramenters that were checked. To fully evaluate the risk to non target terrestrial plants and rule out any possible synergistic effects, EFED is recommending that Tier I seedling emergence and vegetative vigor studies for a single active ingredient ( mancozeb, only) TEP be submitted. For a more detailed listing and explanation of mancozeb's hazards to all terrestrial organisms, see Appendix III. 40 Table VII 1: Toxicological Endpoints Used to Determine Risk Quotients ( RQs) for Mancozeb Type of Toxicity Organism Species Toxicological Endpoint Acute oral Bird English sparrow ( Passer domesticus) LD 50

1,500 mg/ kg Chronic Bird mallard duck ( Anas platyrhynchos) NOAEC = 125 ppm1 Chronic Mammal laboratory rat ( Rattus norvegicus) NOAEL = 120 ppm2 1 Due to reductions in: egg production; early and late embryo viability; hatchability; and offspring weight at hatch and 14 days of age. 2 Reproductive study, due to parental body weight decrements, increased relative thyroid weights, and increased incidence of thyroid follicular cell hyperplasia.

b. Exposure Summary Terrestrial exposure was evaluated using estimated environmental concentrations generated from the FATE version 5.0 model that calculates the decay of a chemical applied to foliar surfaces for single or multiple applications. The model assumes initial concentrations on plant surfaces based on Kenaga predicted maximum and mean residues as modified by Fletcher et al. ( 1994) and assumes 1st order dissipation. Kenaga estimates and an explanation of the model with sample output are presented in Appendix II. EFED used a 35 day TFR half life value for estimating terrestrial EECs. Mancozeb is used on more than 20 crop grouping ( see Table II 1) or more than 40 crops. The DFR studies in Table II 2 provide half life information on 4 crops ( that is, grapes, apples, tomatoes, and turf) and TFR half life information on 2 crops ( that is, grapes and tomatoes). The upper limit on half life values listed in Table II 2 is 35.4 days. It is reasonable to use this high end estimate in Table II 2 ( that is, 35 days) in this screening level assessment. It is reasonable because it is the highest, worst case, half life value and the data available is limited.

c. Risk Quotients Chronic concerns to terrestrial animals are exceeded when the RQ reaches 1.0. Below are graphs ( figures VII 1 through VII 4) representing mancozeb's potential chronic risks to non target terrestrial animals. These graphs show the chronic RQs that can be expected from terrestrial animals feeding on the food items listed. These chronic RQs are derived from EECs based on the maximum and mean residue estimates ( see Appendix II) that are expected on these food items following mancozeb's applications to various sites shown. For example, the chronic RQ for birds feeding on short grass as a result of mancozeb being applied to turf is over 90 ( figure VII 1) at maximum residue levels and over 30 ( figure VII 1) at mean residue levels. As can be seen from these graphs, all mancozeb's uses exceed chronic LOCs for birds and mammals. The chronic exceedances to birds range from a high RQ of 91 ( figure VII 1) on turf to a low of 1 ( figure VII 2) on citrus. For mammals, the range of RQ exceedance is from a high of 94 ( figure VII 3) on turf to a low of 1 ( figure VII 4) on peanuts. These potential risks are based on mancozeb's current use patterns at maximum application rates and minimum intervals between applications. 41 1 10 100 Risk Quotient ( RQ)

Turfe Ornamentals ( pachysandra) Turf ( golf course) Papaya Apples, etc. Grapes ( E. of Rocky Mtns.) Onion, Garlic, & Shallot Cranberry Cucumber Melons/ Squash Tomato Corn ( E. of Miss. River)

Sites Mean for Fruits, Pods, Seeds, and Large Insects Max. for Fruits, Pods, Seeds, and Large Insects Mean for Tall grass Mean for Broadleaf/ Forage Plants & Small Insects Mean for Short grass Max. for Tall grass Max. for Broadleaf/ Forage Plants & Sm Max. for Short grass Mancozeb Avian Chronic Risk Maximum and Mean Risk Figure VII 1 42 1 10 100 Risk Quotient ( RQ)

Bananas/ Plantain Corn ( W. of Miss. River) Potato/ Sugar Beet Fennel Peanuts Forestry Tobacco Grapes ( W. of Rocky Mtns.) Asparagus Cotton Ornamentals Barley, etc. Vegetables Citrus Sites Mean for Fruits, Pods, Seeds, and Large Insects Max. for Fruits, Pods, Seeds, and Large Insects Mean for Tall grass Mean for Broadleaf/ Forage Plants & Small Insec Mean for Short grass Max. for Tall grass Max. for Broadleaf/ Forage Plants & Max. for Short grass Mancozeb Avian Chronic Risk Maximum and Mean Risk Figure VII 2 43 1 10 100 Risk Quotient ( RQ)

Turf Ornamentals ( pachysandra) Turf ( golf course) Papaya Apples, etc. Grapes ( E. of Rocky Mtns.) Onion, Garlic, & Shallot Cranberry Cucumber Melons/ Squash Tomato Corn ( E. of Miss. River)

Sites Mean for Fruits, Pods, Seeds, and Large Insects Max. for Fruits, Pods, Seeds, and Large Insects Mean for Tall grass Mean for Broadleaf/ Forage Plants & Small In Mean for Short grass Max. for Tall grass Max. for Broadleaf/ Forage Plant Max. for Short grass Mancozeb Mammalian Chronic Risk Maximum and Mean Risk Figure VII 3 It should also be noted that the applications of maneb to tobacco, vegetables, forestry, ornamentals and turf assumed 3 applications per crop cycle since the labeling did not indicate the number of applications that could be made. Even at this relatively low number of applications chronic LOC exceedances are high. 44 1 10 100 Risk Quotient ( RQ)

Bananas/ Plantain Corn ( W. of Miss. River) Potato/ Sugar Beet Fennel Peanuts ForestryTobacco Grapes ( W. of Rocky Mtns.) AsparagusCotton Ornamentals Barley, etc. Vegetables Citrus Sites Mean for Fruits, Pods, Seeds, and Large Insects Max. for Fruits, Pods, Seeds, and Large Insects Mean for Tall grass Mean for Broadleaf/ Forage Plants & Small In Mean for Short grass Max. for Tall grass Max. for Broadleaf/ Forage Plants Max. for Short grass Mancozeb Mammalian Chronic Risk Maximum and Mean Risk Figure VII 4 45 EFED expects the potential acute risk to terrestrial animals from mancozeb's use are a low risk concern since mancozeb is slightly to practically nontoxic to birds and practically nontoxic to mammals on an acute oral basis. Acute RQs were not generated for birds and mammals. Since mancozeb has numerous seed treatment uses, EFED calculated RQs for birds from several seed treatment uses. The acute RQs for applications of mancozeb treated seed are in Appendix IV, Table 5. Results showed no LOCs were exceeded. For a more detailed listing and explanation of mancozeb's risk to all terrestrial organisms, see Appendix IV. 46 Mancozeb's Residue from Tomato Use Based on Fate v. 5 Modeling 1 10 100 1000 10000 1 4 7 10 131619 22 252831 34 37 4043 4649 5255 5861 6467 7073 76 79 Day ppm Mancozeb's Avian NOAEC = 125 ppm Mancozeb's Mammalian NOAEL = 120 ppm Maximum Residue on Short Grass Maximum Residue on Broadleaf/ Forage Plants & Small Insects Maximum Residue on Tall grass Mean Residue on Short grass Mean Residue on Broadleaf/ Forage Plants & Small Insects Mean Residue on Tall grass Maximum Residue on Fruits, Pods, Seeds, and Large Insects Mean Residue on Fruits, Pods, Seeds, and Large Insects Figure VII 5 d. Terrestrial Risk Assessment The RQ values for mancozeb's use patterns show there is a low acute risk to birds from eating mancozeb treated seed with no LOCs exceeded ( Table 5, Appendix IV). EFED calculated the RQs using the LD 50 / sq. ft method for certain seed treatment uses to make this determination. Also EFED made the following estimate to compare an English house sparrow's seed consumption with the number of mancozeb treated seeds needed to reach a toxic dose ( Keehner D. July, 1999a). An English house sparrow's multiple dose acute oral LD 50 is about 1,500 mg ai/ kg for mancozeb ( MRID No. 00036094). Its food consumption is 19.0% of body wt/ day ( that is, 5 grams). Based on this, a 26 gram English house sparrow would need to consume 591 mancozeb treated rice seeds to reach its LD 50 ( see formula in Table 5, Appendix IV). 15,000 rice seeds per pound divided by 4.5359 x 102 grams per pound yields 33 rice seeds per gram. An English house sparrow, assuming it is consuming only mancozeb treated rice seeds, would consume 165 rice seeds each day ( 33 rice seeds each gram * 5 grams each day). This consumption rate would be roughly 4 times less than the expected multiple dose LD 50 of 591 rice seeds. Also, the assumption the sparrow would consume only rice seeds in a single day is unlikely.

Wildlife can be found in and around all of the sites mancozeb is currently labeled for. For example, tomatoes are widely grown across the U. S. on both a commercial and noncommercial basis. Approximately 975,000 lbs ai of mancozeb are applied annually to US fresh tomatoes with 56% of the total fresh tomato, U. S. planted, acres being treated with mancozeb ( EPA use data 1987 1996)( BEAD's Quantitative Usage Analysis for Mancozeb dated 11/ 24/ 1998). Currently, up to 7 20 Rate reductions determined by randomly inputing rates into ELL Fate spreadsheet program until the mammalian chronic risk from mancozeb residues on short grass is less than or equal to 1.

47 applications of mancozeb are allowed to be applied to tomatoes every 7 days during the growing season. Pheasants, cottontail rabbits, quail, blackbirds, deer, raccoons, opossums, skunks, songbirds, woodchucks, crows, muskrats, groundhogs, and wild turkeys all feed on tomato plants. In addition to feeding, some of these animals utilize areas in and around tomatoes for nesting, brood rearing, cover and loafing ( Gusey and Maturdo, 1973). The applications of mancozeb to tomatoes occur from seedling emergence ( spring) until 5 days prior to harvest ( late summer/ early fall) which coincides with the timing of the wildlife activities mentioned. Figure VII 5 shows the residue levels ( ppm) that can be expected on various avian and mammalian food items as a result of mancozeb's use on tomatoes. These mancozeb residues are based on mancozeb being applied 7 times every 7 days at a maximum application rates ( 2.4 lb ai/ A). This figure also shows the NOAEC ( 125 ppm) for birds and the NOAEL ( 120 ppm) for mammals as horizontal lines. Mancozeb residue levels above these lines pose a potential risk of adverse reproductive effects to the birds and/ or mammals feeding on these food items. For birds this potential risk begins on Day 1 when mancozeb residues range from 17 to 576 ppm for any and all food items the birds may ingest except for fruits, pods, seeds, and large insects. This potential risk continues throughout the tomato growing season for more than 79 days. On Day 79 the mancozeb residues would range from 40 ppm as the mean residue on fruit, pods, seeds, and large insects to 1,355 ppm as the maximum residue on short grass. Likewise, the potential reproductive risk to mammals from feeding on short grass ( at maximum or mean residue levels), broadleaf/ forage plants, small insects, and tall grass at maximum expected mancozeb residues would begin on Day 1 and continue throughout the tomato growing season for more than 79 days. From figure VII 5, the only food items that birds and mammals could feed on without a potential reproductive risk are fruit, pods, seeds and large insects and this assumes that only mean mancozeb residues would be expected on these food items.

In this screening level assessment, mancozeb's high application rates combined with repeat applications are a major reason why avian and mammalian LOCs are exceeded. Single application rates range from 0.9 lb ai/ A on citrus to 19 lb ai/ A on turf. Labeling allows repeat applications at these maximum rates for all mancozeb's uses. These high applications rates with repeat applications increases the exposure of mancozeb to nontarget organism. High exposure is the reason for high RQs. One way to grasp the impact of the high exposure is to use modeling to estimate the reductions needed to reduce the EECs below the LOCs. Using modeling to calculate EECs below LOCs is simply a rough estimate but does provide some insight into the extent mancozeb's application rates contributes to potential chronic risk to birds and mammals.

To reduce the exposure risk to birds and mammals from mancozebs's use on tomatoes, the maximum single application rate would need to be reduced from the current 2.4 lb ai/ A to 0.1 lb ai/ A ( see figure VII 6) 20. This calls for a 24 fold decrease in the maximum application rate of mancozeb to tomatoes. A combination of rate drops with a decrease in the number of applications per growing season, could also be used to lessen the EECs. However, to reduce the chronic EEC exposure risk, essentially only 1 mancozeb application could be made to tomatoes at a maximum application rate of 0.5 lb ai/ A ( see figure VII 7). This translates to a 5 fold application rate decrease and cuts out all multiples applications. Current labeling allows seven mancozeb applications to tomatoes. 48 Mancozeb Chemical Name: Tomatoes Use Non granular Formulation Inputs lbs a. i./ acre 0.1 Application Rate days 35 Half life days 7 Application Interval 7 Maximum # Apps./ Yea Outputs 56 Day Average Maximum Concentration Concentration ( PPM) ( PPM) 73.52 115.15 Short Grass 33.70 52.78 Tall Grass 41.36 64.77 Broadleaf plants/ Insec 4.60 7.20 Seeds 1600 Acute LC50 ( ppm) Avian 125 Chronic NOAEC ( pp Chronic RQ Acute RQ ( Max. res. mult. apps.) 0.92 0.0720 Short Grass 0.42 0.0330 Tall Grass 0.52 0.0405 Broadleaf plants/ Insec 0.06 0.0045 Seeds 5000 Acute LD50 ( mg/ kg) Mammalian 120 Chronic NOAEL ( mg 1000 g mammal 35 g mamma 15 g mammal Rat Chron Dietary Acute RQ Acute RQ Acute RQ RQ ( mult. apps) ( mult. apps) ( mult. apps) 0.96 0.00345 0.01520 0.02188 Short Grass 0.44 0.00158 0.00697 0.01003 Tall Grass 0.54 0.00194 0.00855 0.01231 Broadleaf plants/ Insec 0.06 0.00022 0.00095 0.00137 Seeds Figure VII 6: Mancozeb's Reduction in Application Rate to Tomatoes ( Libelo. 1999) 49 Mancozeb Chemical Name: Tomatoes Use Non granular Formulation Inputs lbs a. i./ acre 0.5 Application Rate days 35 Half life days 0 Application Interval 1 Maximum # Apps./ Yea Outputs 56 Day Average Maximum Concentration Concentration ( PPM) ( PPM) 73.23 120.00 Short Grass 33.56 55.00 Tall Grass 41.19 67.50 Broadleaf plants/ Insec 4.58 7.50 Seeds 1600 Acute LC50 ( ppm) Avian 125 Chronic NOAEC ( pp Chronic RQ Acute RQ ( Max. res. mult. apps.) 0.96 0.0750 Short Grass 0.44 0.0344 Tall Grass 0.54 0.0422 Broadleaf plants/ Insec 0.06 0.0047 Seeds 5000 Acute LD50 ( mg/ kg) Mammalian 120 Chronic NOAEL ( mg 1000 g mammal 35 g mamma 15 g mammal Rat Chron Dietary Acute RQ Acute RQ Acute RQ RQ ( mult. apps) ( mult. apps) ( mult. apps) 1.00 0.00360 0.01584 0.02280 Short Grass 0.46 0.00165 0.00726 0.01045 Tall Grass 0.56 0.00203 0.00891 0.01283 Broadleaf plants/ Insec 0.06 0.00023 0.00099 0.00143 Seeds Figure VII 7: Mancozeb's Reduction in Number of Applications to Tomatoes ( Libelo. 1999)

Excluding mancozeb's dip treatment and seed treatment uses, there are over twenty different crop groupings listed in Table II 1, above. Each of these groupings represent a unique use pattern based on rates of application, number of applications allowed per crop cycle or season, and minimum intervals between applications. The risk assessment, using tomatoes as an example, could be extended to each of these separate crop groupings with similar results. The potential temporal chronic risks to birds and mammals from mancozeb's current uses are provided in Table VII 2. As with the tomato use the potential chronic risks to birds and mammals begins with the first application of mancozeb to the crop and continues throughout the crop cycle. 50 Table VII 2. Temporal Chronic Risks as a Result of Mancozeb Residues on Avian/ Mammalian Food Items. 1 Crop Number of Days Mancozeb ResiduesExceed Birds' Chronic NOAEC ( 125 ppm) & Mammals' Chronic NOAEL ( 120 ppm) ( days) 7 Range of Average, Daily, Maximum Mancozeb Residues on Short Grass to Average, Daily, Mean Mancozeb Residues on Fruits, Pods, Seed & Large Insects ( ppm)

Apples, Cranapple, Pear, & Quince > 58 2,451 to 71 Asparagus > 70 733 to 21 Bananas & Plantain > 170 1,448 to 42 Barley, Oats, Rye, Triticale, & Wheat > 51 668 to 19 Citrus2 > 51 375 to 11 Corn ( unspecified) > 90 1,688 to 49 Cotton > 70 733 to 21 Cranberry > 50 2,001 to 58 Cucumber > 86 1,883 to 55 Fennel > 86 1,255 to 37 Garlic & Shallot > 86 647 to 19 Grapes > 72 2,123 to 62 Melons & Squash > 86 1,883 to 55 Onion > 100 2,119 to 62 Papaya > 65 3,275 to 96 Peanuts > 86 1,255 to 37 Potato & Sugar Beet > 65 1,310 to 38 Tobacco2 > 45 890 to 26 Tomato > 79 1,745 to 51 Vegetables2,3 > 51 625 to 18 Forestry ( Douglas Fir) 2 > 72 1,101 to 32 Ornamental Trees2,4 > 72 1,101 to 32 Ornamentals2,5 > 51 667 to 19 Turf2,6 > 45 7,747 to 226 1. Based on FATE v 5.0 modeling with a total foliar residue half life of 35 days. 2. Maximum number of applications/ year or crop cycle not specified on labeling. Assumed 3 applications per crop cycle. 3. Beets ( unspecified), Broccoli, Brussel sprouts, Cabbage, Carrots, Cauliflower, Chard ( Swiss), Collards, Coriander, Dill, Endive, Kale, Kohlrabi, Leeks, Lettuce, Mustard, Mustard Cabbage, Parsley, Parsnip, Radish, Rape, Roquette ( Arrugula), Rutabaga, Spinach, & Turnip 4. Christmas Tree Plantations 5. Trees, Herbaceous Plants, Non Flowering Plants, & Woody Shrubs and Vines 6. Commercial/ Industrial, Golf Course, Sod Farm & Residential 7. Maximum Number of Applications * Minimum Interval Between Applications + 30 days Table VII 2 lists the number of days mancozeb's potential chronic risks to birds and mammals extends. The third column of Table VII 2 shows range of average maximum residues to average mean residues for the days listed in the middle column. 51 i. Incidents The Ecological Incident Information System ( EIIS) showed mancozeb was connected to bird kill and plant damage incidents. The bird kill occurred in 1992 on an island near France. In this case, mancozeb had been applied with an insecticide ( methomyl) highly toxic [ methomyl mallard duck acute oral LD 50 = 15.9 mg/ kg ( US EPA. 1998)] to birds. The insecticide was confirmed through sampling and mancozeb was determined to be a possible contributory cause to the bird kill. The plant damage incident, reported mancozeb had been tanked mixed with benomyl and applied to apple trees. This application may have caused leaves and blossoms to drop from the trees. All US pesticide uses of benomyl were voluntarily canceled by the registrant, DuPont, in 2001 ( USEPA. 2001). According to the registrant, identical applications made by other growers in the area to apple orchards did not result in this damage and mancozeb was determined to be a possible contributory cause to the damage.

The acute toxicity data provided in this document for birds shows mancozeb is slightly to practically nontoxic to birds ( oral LD 50 ~ 1500 mg/ kg for the sparrow and > 6400 mg/ kg for the duck and quail). Methomyl is highly toxic to birds. It is unlikely mancozeb contributed to this bird kill and more likely methomyl caused the kill. Current toxicity data received on MAI nontarget plant testing with mancozeb does not show mancozeb should adversely affect terrestrial plants ( none of the ten terrestrial plant species tested displayed $ 25% inhibition to plant growth). However, SAI testing is being required for mancozeb to confirm the terrestrial plant toxicity status of mancozeb ( see Appendix III for details). At this point, it would appear the plant damage was not likely to have been caused from mancozeb exposure.

Even though mancozeb appears to pose a low acute risk to terrestrial animals and plants, the chronic LOCs to terrestrial animals ( birds and mammals) are exceeded for all mancozeb use patterns. The incident reports sent to EPA mainly deal with field mortality of wildlife and phytotoxicity issues. Chronic problems that affect wildlife from the use of mancozeb and it's degradate, ETU, would be expected to be largely unnoticed in the field and thus incident reports, from chronic problems in wildlife, would not be expected.

ii. Endocrine Disruptors EPA is required under the Federal Food, Drug, and Cosmetic Act ( FFDCA), as amended by the Food Quality Protection Act ( FQPA), to develop a screening program to determine whether certain substances ( including all pesticide active and other ingredients) " may have an effect in humans that is similar to an effect produced by a naturally occurring estrogen, or other such endocrine effects as the Administrator may designate." Following the recommendations of its Endocrine Disruptor Screening and Testing Advisory Committee( EDSTAC), EPA determined that there was scientific basis for including, as part of the program, the androgen and thyroid hormone systems, in addition to the estrogen hormone system. EPA also adopted EDSTAC's recommendation that the Program include evaluations of potential effects in wildlife. For pesticide chemicals, EPA will use FIFRA and, to the extent that effects in wildlife may help determine whether a substance may have an effect in humans, FFDCA authority to require the wildlife evaluations. As the science develops and resources allow, screening of additional hormone systems may be added to the Endocrine Disruptor Screening Program ( EDSP). 52 The avian reproductive studies reviewed by EFED noted reproductive effects such as reductions in: egg production; early and late embryo viability; hatchability; offspring weight at hatch and 14 days of age; and the number of 14 day old survivors. For mammals chronic effects were noted such as decreased serum thyroxine levels being the endpoints affected in females and body weight decrements, changes in thyroid hormones, changes in liver enzymes, microscopic changes in the liver and thyroids, increased absolute and relative thyroid weights, and increased relative liver weights being the endpoints affected in males. Some developmental effects noted in mammals were gross developmental defects, central nervous system defects, skeletal defects, cryptorchidism ( failure of one or more testes to descend into the scrotum) , abortions, etc. See Appendix III for a detailed listing of the studies and results. These effects noted in both birds and mammals could be a result of hormonal disruptions and may tend to support the concern that mancozeb may be an endocrine disruptor. Based on these effects in birds and mammals, EFED recommends that when appropriate screening and/ or testing protocols being considered under the Agency's EDSP have been developed, mancozeb be subjected to more definitive testing to better characterize effects related to its possible endocrine disruptor activity.

iii. Endangered Species Based on available screening level information, there is a potential concern for mancozeb's chronic effects on listed Endangered and Threatened species of birds and mammals should exposure actually occur. EFED is uncertain about mancozeb's risk to endangered/ threatened non target terrestrial plants and needs testing performed at mancozeb's maximum rate of application in the environment. 53 APPENDIX I: Notes on Fate Studies and Modeling & Additional Fate Data a. Notes on Fate Studies i. Aqueous medium studies Guidance for hydrolysis and aqueous photolysis require EBDC parent to be applied at concentrations within the solubility range. It was established that any part of EBDC parent that goes into solution will completely decompose, by hydrolytic reactions, into a suite of multi species; the EBDCs Complex. Reported levels of EBDC parents solubilities water were near 2 ppm for metiram and in the range of 6 22 ppm for mancozeb and 6 200 ppm for maneb; at these levels EBDC parents decompose or hydrolyze completely. Additionally, particle size reduction ( i. e. sonication) is believed to cause an increase in the level susceptibility of parent EBDCs to decomposition. In most studies, levels used in aqueous media studies were near this critical range of susceptibility, parent was determined by CS 2 and suspensions were prepared using ultrasonic. Therefore, calculated hydrolysis and/ or photolysis half lives are affected by:

( 1) Occurrence of hydrolytic decomposition during preparation of stock solution; indicated by the presence of high concentrations of transient species and degradates at time zero.

( 2) An increase of hydrolytic reactions caused by reduction of particle size by sonication; and ( 3) Nonspecificity of CS 2  determination for EBDC parent in the presence of its hydrolytic complex because it was experimentally proven that CS 2 evolves from at least one of its constituents; EBIS.

( 4) influence of the presence of metal ions on solubility of EBDC parent ( i. e decomposition to EBDCs Complex). These metal ions are introduced to the system from chemicals present in buffer solutions.

In studies were the solvent DMSO is used, no half life could be calculated for EBDCs because no EBDC parent would be present at time zero. This solvent appears to cause complete breakage of the EBDC complex into various transformation products dominated by ETU. This means that such studies can only be used to identify effects of pH or photon energy and aging on the suite of EBDCs Complex present at time zero.

ii. Soil/ sediment studies Problems associated with soil sediment/ studies include:

( 1) Degradation of EBDC parent, by decomposition in water, before time zero and when the application suspension is prepared. In most cases, resultant application suspensions were dominated by the EBDCs Complex. Analysis was not always performed for suspensions just before application.

( 2) Extraction systems ( i. e., acetonitrile/ water or methanol/ water) appear to affect the integrity of the parent. Therefore, resultant suite of EBDCs Complex ( in the extraction solution) was at least partly artificial and can not be used to represent the suite that might form in the environment. The use of different extraction systems made it difficult to compare results obtained from different soils. 54 0 7 14 21 28 Time ( days) 30 60 50 70 % of Applied Radioactivity SL ( Germany) Loam ( Germany) SiL ( Germany) SiL ( Germany) Approximation 0 50 100 Time ( days) 50 65 60 70 % of Applied Radioactivity SL ( Germany) Loam ( Germany) SiL ( Germany) SiL ( Germany) Approximation ( 3) EBDCs Complex has high affinity to soil and no characterization was conducted for the resultant bound species. Therefore, bound EBDC Complex is suspicious of containing active species that can be precursors for the degradate of concern ETU. For example, In mancozeb aerobic soil studies, Bound species degraded after reaching a plateau in the range of 55 70%. Production of degradates and CO 2 , increased after the Bound species reach the described plateau. Figure 1 shows bound radioactivity distribution with time as reported for soils in four aerobic soil studies.

( 4) Nonspecificity of CS 2  determination for EBDC parent in the presence of its hydrolytic complex because it was experimentally proven that CS 2 evolves from at least one of its constituent; EBIS.

( 5) Chromatographic separation between EBDC parent and various species in its complex was not conclusive and solvents used appear to affect the integrity of parent and some degradates and/ or transient species.

Figure 1. Change of bound radioactivity with time in four aerobic soils treated with mancozeb.

Therefore, the above mentioned difficulties should be taken in consideration in determining species present in fate studies and those expected to be present in the natural environment. For example, in mancozeb, it is expected that species present in fate studies are those shown in Figure 2 and those 55 in compartments of the natural environment are those shown in Figure 3. 56 0 7 14 21 28 35 42 Time ( days); Four Applications at days: 0, 7, 14 and 21 0 1 2 7 Expected Metiram Parent Concentration ( ppm)

Parent EECs based on Hydrolysis half life= 0.7 day) b. Notes on Modeling i. EECs for Parent mancozeb EECs for Parent mancozeb are presented in the Figure 4. Data for EECs were calculated using the slope of the line for 0.7 days ( Table IV. 2); the estimated hydrolysis half. Other assumptions included:

 Application rate of 4.8 lbs a. i/ Acre applied four times at 7 day intervals;

 All applied material reached the soil and mixed with top 2" giving a zero time concentration of 7.1 ppm.

 Enough moisture is present to complete hydrolytic reactions.

Data indicate that soil EECs of Parent mancozeb are expected to be below 1 ppm (. 14% of the applied) within 2 days of the first application and reach less than 0.01 ppm (< 1% of the applied) just before the second application. The same is repeated after each of the four application with negligible amounts being left within one week from the last application. This data are believed to represent concentrations in soil environments where most of the pesticide is applied. However, higher EECs is expected in dry conditions and in soils with very low water holding capacity.

Considering that only a small fraction of the applied material would reach water bodies by drift, Mancozeb Complex, not parent, is the species expected to be found in water bodies affected by drift.

Figure 4. EECs for Parent mancozeb following four applications of 4.8 lbs a. i/ acre applied four times at 7 day intervals. 57 ii. Background Information on the PRZM and EXAMS models & the Index Reservoir Scenario The linked PRZM and EXAMS models are used in this case as a second tier screen designed to estimate the pesticide concentrations found in water for use in drinking water assessments. They provide high end values on the concentrations that might be found in a small drinking water reservoir due to the use of pesticide. The Drinking Water Index Reservoir scenario includes a 427 acres field immediately adjacent to a 13 acres reservoir, 9 feet deep, with continuous site specific flow. This amount can be reduced due to degradation in field and the effect of binding to soil. Spray drift is equal to 6.4% of the applied concentration from the ground spray application and 16% for aerial applications.

The PRZM/ EXAMS modeling system with the Index Reservoir scenario also makes adjustments for the percent cropped area. While it is assumed that the entire watershed would not be treated, the use of a PCA is still a screen because it represents the highest percentage of crop cover of any large watershed in the US, and it assumes that the entire crop is being treated. Various other conservative assumptions of this scenario include the use of a small drinking water reservoir surrounded by a runoff prone watershed, the use of the maximum use rate and no buffer zone.

iii. Background Information on SCIGROW SCI GROW is a screening model which the Office of Pesticide Programs ( OPP) in EPA frequently uses to estimate pesticide concentrations in vulnerable ground water. The model provides an exposure value which is used to determine the potential risk to the environment and to human health from drinking water contaminated with the pesticide. The SCI GROW estimate is based on environmental fate properties of the pesticide ( aerobic soil degradation half life and linear adsorption coefficient normalized for soil organic carbon content), the maximum application rate, and existing data from small scale prospective ground water monitoring studies at sites with sandy soils and shallow ground water.

Pesticide concentrations estimated by SCI GROW represent conservative or high end exposure values because the model is based on ground water monitoring studies which were conducted by applying pesticides at maximum allowed rates and frequency to vulnerable sites ( i. e., shallow aquifers, sandy, permeable soils, and substantial rainfall and/ or irrigation to maximize leaching). In most cases, a large majority of the use areas will have ground water that is less vulnerable to contamination than the areas used to derive the SCI GROW estimate. SCIGROW provides a groundwater screening exposure value to be used in determining the potential risk to human health from drinking water contaminated with the pesticide. SCIGROW estimates likely groundwater concentrations if the pesticide is used at the maximum allowable rate in areas where groundwater is exceptionally vulnerable to contamination. In most cases, a large majority of the use area will have groundwater that is less vulnerable to contamination than the areas used to derive the SCIGROW estimate. 58 c. Additional Fate Data The following are additional fate data on mancozeb mobility:

Table 1. K ads and K oc and characteristics of the soils used in the adsorption/ desorption study ( MRID 00888 22)

Soil/ Sediment Type Solomon CL Virdan SiCL 1 Sassafras SL Hagerstown SiL Cecil Clay 2 Delaware River Sediment Textural class Clay Loam silty Clay loam Sandy Loam Silty Loam Clay Silt Clay (%) 32 18 6.0 28 54 8 pH ( water) 7.4 6.0 4.9 6.4 4.7 5.7 % Organic carbon 8.78 3.08 0.23 1.98 0.23 6.28 C. E. C ( meq/ 100g) 49.9 21.4 1.6 9.4 6.9 8.5 K ads 32 49 18 4 50 101 K oc 365 1,591 7,826 202 21,739 1,608 1 Montmorillonite Clay; 2 Kaolinite clay.

Table 2. K ads and K oc and characteristics of the soils used in the adsorption/ desorption study ( MRID402229 01)

State Georgia Georgia Pennsylvania Mississippi Textural class Sand ( GA) Sandy Loam Silty Loam Clay loam Clay (%) 4 12 20 28 pH ( water) 5.7 5.9 6.4 7.4 % Organic carbon 0.5 1.6 2.0 1.5 C. E. C ( meq/ 100g) 3.5 5.7 9.6 12.9 K ads 11.67 9.89 7.26 10.13 K oc 2,320 618 363 675 59 APPENDIX II: Hoerger Kenaga Estimates & Fate v. 5.0 Model a. Hoerger Kenaga Estimates EFED uses Hoerger and Kenaga estimates ( 1972) as changed by Fletcher and other researchers ( 1994) to estimate the residues on plants and insects. Hoerger Kenaga categories represent preferred foods of various terrestrial vertebrates. Upland game birds prefer fruits and bud and shoot tips of leafy crops. Hares and hoofed mammals consume leaves and stems of leafy crops. Rodents consume seeds, seedpods and grasses; and various birds, mammals, reptiles and terrestrial phase amphibians consume insects. Terrestrial vertebrates also may contact pesticides applied to soil by swallowing pesticide granules or pesticide laden soil when foraging. Rich in minerals, soil comprises 5 to 30% of dietary intake by many wildlife species ( Beyer and Conner).

Hoerger and Kenaga based pesticide environmental concentration estimates on residue data correlated from more than 20 pesticides on more than 60 crops. These estimates are representative of many geographic regions ( 7 states) and a wide array of cultural practices. Hoerger Kenaga estimates also considered differences in vegetative yield, surface to mass ratio and interception causes. In 1994, Fletcher, Nellessen and Pfleeger reexamined the Hoerger Kenaga simple linear model ( y= B1x, where x= application rate and y= pesticide residue in ppm) to decide whether the terrestrial EEC's were accurate. They compiled a data set of pesticide day 0 and residue decay data involving 121 pesticides ( 85 insecticides, 27 herbicides, and 9 fungicides from 17 different chemical classes) on 118 species of plants. After analysis, their conclusions were that Hoerger Kenaga estimates needed only minor changes to increase the predictive values. They recommended an increase for forage and fruit categories from 58 to 135 ppm and from 7 to 15 ppm, respectively. Otherwise, the Hoerger Kenaga estimates were accurate in predicting the maximum residue values after a 1 lb ai/ acre application. Mean values represent the arithmetic mean of values from samples collected the day of pesticide treatment. The values in the table below are the predicted 0 day maximum and mean residues of a pesticide that may occur on selected avian, mammalian, reptilian or terrestrial phase amphibian food items. These predicted residues occur immediately following a direct single application at a 1 lb ai/ acre application rate. For pesticides applied as a nongranular product ( for example, liquid or dust), EFED compared the estimated environmental concentrations ( EECs) on food items following product application to LC 50 values to assess risk. EFED based the estimated environmental concentrations of ETU on food items on Kenaga maximum and mean predicted values.

Estimated Environmental Concentrations on Avian and Mammalian Food Items ( ppm) Following a Single Application at 1 lb ai/ A)

Food Items EEC ( ppm) Predicted Maximum Residue1 EEC ( ppm) Predicted Mean Residue1 Short grass 240 85 Tall grass 110 36 Broadleaf/ forage plants and small insects 135 45 Fruits, pods, seeds, and large insects 15 7 1 Predicted maximum and mean residues are for a 1 lb ai/ a application rate and are based on Hoerger and Kenaga ( 1972) as modified by Fletcher et al. ( 1994). 60 b. Fate v. 5.0 Model Terrestrial Exposure Values The model assumes a first order decay to fix the concentration at each day after first application based on the concentration resulting from the first and more applications. The model calculates decay from the first order rate equation:

CT = Ci e kT or in integrated form: ln ( CT/ Ci) =  kT Where:

CT = concentration at time T on day zero Ci = concentration in parts per million ( ppm) present initially ( on day zero) on the surfaces. The model calculates Ci based on Kenaga and Fletcher by multiplying the application rate, in pounds active ingredient per acre. The model multiplies the application rate by 240 ( mean of 85) for short grass, 110 ( mean of 36) for tall grass, and 135 ( mean of 45) for broad leaf plants and insects and 15 ( mean of 7) for seeds. The model converts extra applications from pounds active ingredient per acre to PPM on the plant surface and the addition mass added to the mass of the chemical still present on the surfaces on the day of application.

k= degradation rate constant determined from studies of hydrolysis, photolysis, microbial degradation, etc. Since degradation rate is reported by half life, the model calculates the rate constant from the half life ( k = ln 2/ T1/ 2). Choosing the degradation rate and half life to use in terrestrial exposure calculations is open for debate and should be done by a qualified scientist.

T= time, in days, since the start of the simulation. The first application is on day 0. The simulation runs for the number of days entered by the modeler.

The program calculates concentration on each surface on a daily interval for the number of days entered by the modeler. The modeler chooses the days based on the guidance provided in Urban, 2000. The modeler uses the following formula with acute exposure addition of 30 days or the chronic exposure addition of 60 days:

maximum number of applications crop cycle or season minimum interval between applications ( days) + 30 or 60 days *

The model calculates maximum and mean EECs based on the maximum and mean Kenaga Fletcher values listed in Table 1 above. These EECs are the maximum amounts collecting on each day during the interval chosen. The model calculates these EECs for the different food item groupings.

c. Fate v. 5.0 Model Sample Output for Mancozeb RUN No. 1 FOR MANCOZEB ON APPLES, ETC *** INPUT VALUES ***  61 RATE(#/ AC) APPLICATIONS HALF LIFE AVIAN ( ppm) MAMMALIAN ( mg/ kg) ONE( MAX) NO. INTERVAL ( DAYS) LC50 NOAEC LD50 NOAEL  4.800( 15.783) 4 7 35.0 ******* ******* ******* *******

MAXIMUM & 58 DAY AVERAGE KENAGA/ FLETCHER RESIDUES: 95th% ( mean) in ppm  SHORT BROADLEAF TALL SEED GRASS & INSECTS GRASS FRUIT ____________________ ________________ ________________ ________________ MAX 3787.96( 1341.57) 2130.73( 710.24) 1736.15( 568.19) 236.75( 110.48)

RUN No. 2 FOR MANCOZEB ON ASPARAGUS *** INPUT VALUES ***  RATE(#/ AC) APPLICATIONS HALF LIFE AVIAN ( ppm) MAMMALIAN ( mg/ kg) ONE( MAX) NO. INTERVAL ( DAYS) LC50 NOAEC LD50 NOAEL  1.600( 4.873) 4 10 35.0 ******* ******* ******* *******

MAXIMUM & 70 DAY AVERAGE KENAGA/ FLETCHER RESIDUES: 95th% ( mean) in ppm  SHORT BROADLEAF TALL SEED GRASS & INSECTS GRASS FRUIT ____________________ ________________ ________________ ________________ MAX 1169.41( 414.16) 657.79( 219.26) 535.98( 175.41) 73.09( 34.11)

Below are lists of daily Kenaga Flether pesticide residue values for four avian/ mammalian food groupings for MANCOZEB use on TOMATO Values are in parts per million ( ppm).

SHORT BROADLEAF TALL SEED GRASS & INSECTS GRASS FRUIT DAILY DAILY DAILY DAILY VALUES VALUES VALUES VALUES DAY 95% MEAN 95% MEAN 95% MEAN 95% MEAN ___ _______________ _______________ _______________ _______________

1 576.00 204.00 324.00 108.00 264.00 86.40 36.00 16.80 2 564.71 200.00 317.65 105.88 258.82 84.71 35.29 16.47 3 553.63 196.08 311.42 103.81 253.75 83.04 34.60 16.15 4 542.78 192.23 305.31 101.77 248.77 81.42 33.92 15.83 5 532.13 188.46 299.32 99.77 243.89 79.82 33.26 15.52 6 521.70 184.77 293.45 97.82 239.11 78.25 32.61 15.22 7 511.47 181.14 287.70 95.90 234.42 76.72 31.97 14.92 8 1077.44 381.59 606.06 202.02 493.83 161.62 67.34 31.43 9 1056.31 374.11 594.17 198.06 484.14 158.45 66.02 30.81 10 1035.60 366.77 582.52 194.17 474.65 155.34 64.72 30.20 11 1015.29 359.58 571.10 190.37 465.34 152.29 63.46 29.61 12 995.38 352.53 559.90 186.63 456.22 149.31 62.21 29.03 13 975.86 345.62 548.92 182.97 447.27 146.38 60.99 28.46 14 956.72 338.84 538.16 179.39 438.50 143.51 59.80 27.90 15 1513.96 536.20 851.60 283.87 693.90 227.09 94.62 44.16 16 1484.28 525.68 834.91 278.30 680.29 222.64 92.77 43.29 17 1455.17 515.37 818.53 272.84 666.95 218.28 90.95 42.44 18 1426.63 505.27 802.48 267.49 653.87 214.00 89.16 41.61 19 1398.66 495.36 786.75 262.25 641.05 209.80 87.42 40.79 20 1371.23 485.64 771.32 257.11 628.48 205.68 85.70 39.99 21 1344.34 476.12 756.19 252.06 616.16 201.65 84.02 39.21 22 1893.98 670.79 1065.36 355.12 868.07 284.10 118.37 55.24 23 1856.84 657.63 1044.47 348.16 851.05 278.53 116.05 54.16 62 24 1820.43 644.74 1023.99 341.33 834.36 273.06 113.78 53.10 25 1784.73 632.09 1003.91 334.64 818.00 267.71 111.55 52.05 26 1749.74 619.70 984.23 328.08 801.96 262.46 109.36 51.03 27 1715.42 607.55 964.93 321.64 786.24 257.31 107.21 50.03 28 1681.79 595.63 946.00 315.33 770.82 252.27 105.11 49.05 29 2224.81 787.95 1251.45 417.15 1019.70 333.72 139.05 64.89 30 2181.18 772.50 1226.91 408.97 999.71 327.18 136.32 63.62 31 2138.41 757.35 1202.85 400.95 980.10 320.76 133.65 62.37 32 2096.48 742.50 1179.27 393.09 960.88 314.47 131.03 61.15 33 2055.36 727.94 1156.14 385.38 942.04 308.30 128.46 59.95 34 2015.06 713.67 1133.47 377.82 923.57 302.26 125.94 58.77 35 1975.55 699.67 1111.24 370.41 905.46 296.33 123.47 57.62 36 2512.81 889.95 1413.45 471.15 1151.70 376.92 157.05 73.29 37 2463.53 872.50 1385.74 461.91 1129.12 369.53 153.97 71.85 38 2415.22 855.39 1358.56 452.85 1106.98 362.28 150.95 70.44 39 2367.86 838.62 1331.92 443.97 1085.27 355.18 147.99 69.06 40 2321.43 822.17 1305.80 435.27 1063.99 348.21 145.09 67.71 41 2275.91 806.05 1280.20 426.73 1043.12 341.39 142.24 66.38 42 2231.28 790.24 1255.09 418.36 1022.67 334.69 139.45 65.08 43 2763.53 978.75 1554.48 518.16 1266.62 414.53 172.72 80.60 44 2709.33 959.56 1524.00 508.00 1241.78 406.40 169.33 79.02 45 2656.21 940.74 1494.12 498.04 1217.43 398.43 166.01 77.47 46 2604.12 922.29 1464.82 488.27 1193.55 390.62 162.76 75.95 47 2553.05 904.21 1436.09 478.70 1170.15 382.96 159.57 74.46 48 2502.99 886.48 1407.93 469.31 1147.20 375.45 156.44 73.00 49 2453.91 869.09 1380.32 460.11 1124.71 368.09 153.37 71.57 50 2405.79 852.05 1353.26 451.09 1102.65 360.87 150.36 70.17 51 2358.61 835.34 1326.72 442.24 1081.03 353.79 147.41 68.79 52 2312.36 818.96 1300.70 433.57 1059.83 346.85 144.52 67.44 53 2267.02 802.90 1275.20 425.07 1039.05 340.05 141.69 66.12 54 2222.56 787.16 1250.19 416.73 1018.67 333.38 138.91 64.82 55 2178.98 771.72 1225.68 408.56 998.70 326.85 136.19 63.55 56 2136.25 756.59 1201.64 400.55 979.12 320.44 133.52 62.31 57 2094.36 741.75 1178.08 392.69 959.92 314.15 130.90 61.09 58 2053.29 727.21 1154.98 384.99 941.09 307.99 128.33 59.89 59 2013.03 712.95 1132.33 377.44 922.64 301.95 125.81 58.71 60 1973.55 698.97 1110.12 370.04 904.55 296.03 123.35 57.56 61 1934.85 685.26 1088.35 362.78 886.81 290.23 120.93 56.43 62 1896.91 671.82 1067.01 355.67 869.42 284.54 118.56 55.33 63 1859.71 658.65 1046.09 348.70 852.37 278.96 116.23 54.24 64 1823.25 645.73 1025.58 341.86 835.65 273.49 113.95 53.18 65 1787.49 633.07 1005.47 335.16 819.27 268.12 111.72 52.14 66 1752.44 620.66 985.75 328.58 803.20 262.87 109.53 51.11 67 1718.08 608.49 966.42 322.14 787.45 257.71 107.38 50.11 68 1684.39 596.55 947.47 315.82 772.01 252.66 105.27 49.13 69 1651.36 584.86 928.89 309.63 756.87 247.70 103.21 48.16 70 1618.98 573.39 910.67 303.56 742.03 242.85 101.19 47.22 71 1587.23 562.14 892.82 297.61 727.48 238.08 99.20 46.29 72 1556.10 551.12 875.31 291.77 713.21 233.42 97.26 45.39 73 1525.59 540.31 858.14 286.05 699.23 228.84 95.35 44.50 74 1495.67 529.72 841.32 280.44 685.52 224.35 93.48 43.62 75 1466.34 519.33 824.82 274.94 672.07 219.95 91.65 42.77 76 1437.59 509.15 808.64 269.55 658.90 215.64 89.85 41.93 77 1409.40 499.16 792.79 264.26 645.97 211.41 88.09 41.11 78 1381.76 489.37 777.24 259.08 633.31 207.26 86.36 40.30 79 1354.67 479.78 762.00 254.00 620.89 203.20 84.67 39.51 80 1328.10 470.37 747.06 249.02 608.71 199.22 83.01 38.74 81 1302.06 461.15 732.41 244.14 596.78 195.31 81.38 37.98 82 1276.53 452.10 718.05 239.35 585.07 191.48 79.78 37.23 83 1251.49 443.24 703.97 234.66 573.60 187.72 78.22 36.50 84 1226.95 434.55 690.16 230.05 562.35 184.04 76.68 35.79 85 1202.89 426.02 676.63 225.54 551.33 180.43 75.18 35.08 86 1179.31 417.67 663.36 221.12 540.52 176.90 73.71 34.40 63 87 1156.18 409.48 650.35 216.78 529.92 173.43 72.26 33.72 88 1133.51 401.45 637.60 212.53 519.52 170.03 70.84 33.06 89 1111.28 393.58 625.10 208.37 509.34 166.69 69.46 32.41 90 1089.49 385.86 612.84 204.28 499.35 163.42 68.09 31.78 91 1068.13 378.29 600.82 200.27 489.56 160.22 66.76 31.15 92 1047.18 370.88 589.04 196.35 479.96 157.08 65.45 30.54 93 1026.65 363.60 577.49 192.50 470.55 154.00 64.17 29.94 94 1006.51 356.47 566.16 188.72 461.32 150.98 62.91 29.36 95 986.78 349.48 555.06 185.02 452.27 148.02 61.67 28.78 96 967.43 342.63 544.18 181.39 443.40 145.11 60.46 28.22 97 948.46 335.91 533.51 177.84 434.71 142.27 59.28 27.66 98 929.86 329.32 523.04 174.35 426.18 139.48 58.12 27.12 99 911.62 322.87 512.79 170.93 417.83 136.74 56.98 26.59 100 893.75 316.54 502.73 167.58 409.63 134.06 55.86 26.07 101 876.22 310.33 492.87 164.29 401.60 131.43 54.76 25.56 102 859.04 304.24 483.21 161.07 393.73 128.86 53.69 25.06 103 842.19 298.28 473.73 157.91 386.01 126.33 52.64 24.56 104 825.68 292.43 464.44 154.81 378.44 123.85 51.60 24.08 105 809.49 286.69 455.34 151.78 371.02 121.42 50.59 23.61 106 793.61 281.07 446.41 148.80 363.74 119.04 49.60 23.15 107 778.05 275.56 437.65 145.88 356.61 116.71 48.63 22.69 108 762.79 270.16 429.07 143.02 349.61 114.42 47.67 22.25 109 747.84 264.86 420.66 140.22 342.76 112.18 46.74 21.81 110 733.17 259.67 412.41 137.47 336.04 109.98 45.82 21.38 111 718.79 254.57 404.32 134.77 329.45 107.82 44.92 20.96 112 704.70 249.58 396.39 132.13 322.99 105.70 44.04 20.55 113 690.88 244.69 388.62 129.54 316.65 103.63 43.18 20.15 114 677.33 239.89 381.00 127.00 310.44 101.60 42.33 19.76 115 664.05 235.18 373.53 124.51 304.36 99.61 41.50 19.37 116 651.03 230.57 366.20 122.07 298.39 97.65 40.69 18.99 117 638.26 226.05 359.02 119.67 292.54 95.74 39.89 18.62 118 625.75 221.62 351.98 117.33 286.80 93.86 39.11 18.25 119 613.48 217.27 345.08 115.03 281.18 92.02 38.34 17.89 120 601.45 213.01 338.31 112.77 275.66 90.22 37.59 17.54 121 589.65 208.84 331.68 110.56 270.26 88.45 36.85 17.20 122 578.09 204.74 325.18 108.39 264.96 86.71 36.13 16.86 123 566.75 200.73 318.80 106.27 259.76 85.01 35.42 16.53 124 555.64 196.79 312.55 104.18 254.67 83.35 34.73 16.21 125 544.74 192.93 306.42 102.14 249.67 81.71 34.05 15.89 126 534.06 189.15 300.41 100.14 244.78 80.11 33.38 15.58 127 523.59 185.44 294.52 98.17 239.98 78.54 32.72 15.27 128 513.32 181.80 288.74 96.25 235.27 77.00 32.08 14.97 129 503.26 178.24 283.08 94.36 230.66 75.49 31.45 14.68 130 493.39 174.74 277.53 92.51 226.14 74.01 30.84 14.39 131 483.71 171.32 272.09 90.70 221.70 72.56 30.23 14.11 132 474.23 167.96 266.75 88.92 217.35 71.13 29.64 13.83 133 464.93 164.66 261.52 87.17 213.09 69.74 29.06 13.56 134 455.81 161.43 256.39 85.46 208.91 68.37 28.49 13.29 135 446.87 158.27 251.37 83.79 204.82 67.03 27.93 13.03 136 438.11 155.16 246.44 82.15 200.80 65.72 27.38 12.78 137 429.52 152.12 241.60 80.53 196.86 64.43 26.84 12.53 138 421.10 149.14 236.87 78.96 193.00 63.16 26.32 12.28 139 412.84 146.21 232.22 77.41 189.22 61.93 25.80 12.04 140 404.74 143.35 227.67 75.89 185.51 60.71 25.30 11.81 141 396.81 140.54 223.20 74.40 181.87 59.52 24.80 11.57 142 389.03 137.78 218.83 72.94 178.30 58.35 24.31 11.35 143 381.40 135.08 214.54 71.51 174.81 57.21 23.84 11.12 144 373.92 132.43 210.33 70.11 171.38 56.09 23.37 10.91 145 366.59 129.83 206.20 68.73 168.02 54.99 22.91 10.69 146 359.40 127.29 202.16 67.39 164.72 53.91 22.46 10.48 147 352.35 124.79 198.20 66.07 161.49 52.85 22.02 10.28 148 345.44 122.34 194.31 64.77 158.33 51.82 21.59 10.08 149 338.67 119.94 190.50 63.50 155.22 50.80 21.17 9.88 64 150 332.03 117.59 186.76 62.25 152.18 49.80 20.75 9.68 151 325.51 115.29 183.10 61.03 149.19 48.83 20.34 9.49 152 319.13 113.03 179.51 59.84 146.27 47.87 19.95 9.31 153 312.87 110.81 175.99 58.66 143.40 46.93 19.55 9.13 154 306.74 108.64 172.54 57.51 140.59 46.01 19.17 8.95 155 300.72 106.51 169.16 56.39 137.83 45.11 18.80 8.77 156 294.83 104.42 165.84 55.28 135.13 44.22 18.43 8.60 157 289.05 102.37 162.59 54.20 132.48 43.36 18.07 8.43 158 283.38 100.36 159.40 53.13 129.88 42.51 17.71 8.27 159 277.82 98.39 156.27 52.09 127.33 41.67 17.36 8.10 160 272.37 96.47 153.21 51.07 124.84 40.86 17.02 7.94 161 267.03 94.57 150.21 50.07 122.39 40.05 16.69 7.79 162 261.80 92.72 147.26 49.09 119.99 39.27 16.36 7.64 163 256.66 90.90 144.37 48.12 117.64 38.50 16.04 7.49 164 251.63 89.12 141.54 47.18 115.33 37.74 15.73 7.34 165 246.69 87.37 138.77 46.26 113.07 37.00 15.42 7.20 166 241.86 85.66 136.04 45.35 110.85 36.28 15.12 7.05 167 237.11 83.98 133.38 44.46 108.68 35.57 14.82 6.92 168 232.46 82.33 130.76 43.59 106.55 34.87 14.53 6.78 169 227.91 80.72 128.20 42.73 104.46 34.19 14.24 6.65 170 223.44 79.13 125.68 41.89 102.41 33.52 13.96 6.52 171 219.06 77.58 123.22 41.07 100.40 32.86 13.69 6.39 172 214.76 76.06 120.80 40.27 98.43 32.21 13.42 6.26 173 210.55 74.57 118.43 39.48 96.50 31.58 13.16 6.14 174 206.42 73.11 116.11 38.70 94.61 30.96 12.90 6.02 175 202.37 71.67 113.83 37.94 92.75 30.36 12.65 5.90 176 198.40 70.27 111.60 37.20 90.93 29.76 12.40 5.79 177 194.51 68.89 109.41 36.47 89.15 29.18 12.16 5.67 178 190.70 67.54 107.27 35.76 87.40 28.60 11.92 5.56 179 186.96 66.21 105.16 35.05 85.69 28.04 11.68 5.45 180 183.29 64.92 103.10 34.37 84.01 27.49 11.46 5.35 181 179.70 63.64 101.08 33.69 82.36 26.95 11.23 5.24 182 176.17 62.40 99.10 33.03 80.75 26.43 11.01 5.14 183 172.72 61.17 97.16 32.39 79.16 25.91 10.80 5.04 184 169.33 59.97 95.25 31.75 77.61 25.40 10.58 4.94 185 166.01 58.80 93.38 31.13 76.09 24.90 10.38 4.84 186 162.76 57.64 91.55 30.52 74.60 24.41 10.17 4.75 187 159.57 56.51 89.76 29.92 73.13 23.93 9.97 4.65 188 156.44 55.40 88.00 29.33 71.70 23.47 9.78 4.56 189 153.37 54.32 86.27 28.76 70.29 23.01 9.59 4.47 190 150.36 53.25 84.58 28.19 68.92 22.55 9.40 4.39 191 147.41 52.21 82.92 27.64 67.56 22.11 9.21 4.30 192 144.52 51.19 81.29 27.10 66.24 21.68 9.03 4.22 193 141.69 50.18 79.70 26.57 64.94 21.25 8.86 4.13 194 138.91 49.20 78.14 26.05 63.67 20.84 8.68 4.05 195 136.19 48.23 76.60 25.53 62.42 20.43 8.51 3.97 196 133.52 47.29 75.10 25.03 61.19 20.03 8.34 3.89 197 130.90 46.36 73.63 24.54 59.99 19.63 8.18 3.82 198 128.33 45.45 72.19 24.06 58.82 19.25 8.02 3.74 199 125.81 44.56 70.77 23.59 57.66 18.87 7.86 3.67 200 123.35 43.69 69.38 23.13 56.53 18.50 7.71 3.60 ___ _______________ _______________ _______________ _______________ SHORT BROADLEAF TALL SEED GRASS & INSECTS GRASS FRUIT AVERAGE AVERAGE AVERAGE AVERAGE VALUES VALUES VALUES VALUES DAY 95% MEAN 95% MEAN 95% MEAN 95% MEAN ___ _______________ _______________ _______________ _______________

997.24 353.19 560.95 186.98 457.07 149.59 62.33 29.09 65 APPENDIX III: Ecological Hazards Assessment a. Scope The toxicity testing required does not test all species of birds, fish, mammals, invertebrates, and plants. EFED uses only two surrogate species for birds ( Bobwhite quail and mallard ducks) to represent all bird species ( over 900 in the US). EFED uses three species of freshwater fish ( rainbow trout, bluegill sunfish and fathead minnow) to act as surrogate test species for all freshwater fish species ( over 900 in the US). One estuarine fish species ( sheepshead minnow) serves as surrogate for all estuarine and marine fish ( over 300 in the US). The surrogate species for terrestrial invertebrates is the honeybee. For freshwater invertebrates the surrogate species is usually the waterflea ( Daphnia magna). For estuarine and marine invertebrates the surrogate species are mysid shrimp and eastern oyster. EFED uses these four species to represent all invertebrates species ( over 10,000 in the US). For plants, there are ten surrogate species used for all terrestrial plants and five surrogate species used for all aquatic plants. There are over 20,000 plant species in the US which includes flowering plants, conifers, ferns, mosses, liverworts, hornworts and lichens. There are over 27,000 species of algae worldwide.

The surrogate species testing scheme used in this assessment assumes that a chemical's method of action and toxicity found for avian species is similar to that in all reptiles ( over 300 species in the US). The same assumption applies to amphibians ( over 200 species in the US) and fish. EFED assumes the tadpole stage of amphibians has the same sensitivity as a fish. Therefore, EFED considers the results from toxicity tests on surrogate species are applicable to other member species within their class and extrapolates this toxicity to reptiles and amphibians. EFED got the US species numbers noted in this section from: http:// www. natureserve. org/ summary ( NatureServe: An online encyclopedia of life [ web application]. 2000) and the worldwide species number from Ecological Planning and Toxicology, Inc. 1996.

b. Toxicity to Terrestrial Animals i. Birds, Acute, Subacute and Chronic An acute oral toxicity study using the technical grade of the active ingredient ( TGAI) is required to establish the toxicity of mancozeb to birds. The avian oral LD 50 is an acute, single dose laboratory study designed to estimate the quantity of toxicant required to cause 50% mortality in a test population of birds. The preferred test species is either the Mallard Duck, a waterfowl, or Bobwhite quail, an upland gamebird. The TGAI is administered by oral intubation to adult birds, and the results are expressed as LD 50 milligrams ( mg) active ingredient ( a. i.) per kilogram ( kg). Toxicity category descriptions are the following ( Brooks, 1973):

If the LD 50 is less than 10 mg a. i./ kg, then the test substance is very highly toxic. If the LD 50 is 10 to 50 mg a. i./ kg, then the test substance is highly toxic. If the LD 50 is 51 to 500 mg a. i./ kg, then the test substance is moderately toxic. If the LD 50 is 501 to 2,000 mg a. i./ kg, then the test substance is slightly toxic. If the LD 50 is greater than 2,000 mg a. i./ kg, then the test substance is practically nontoxic. 66 EFED did not receive a single oral dose study to fulfill this guideline but did review several multiple oral dose studies. The results of these studies are in Table 1, below. Since the LD 50 falls in the range of approximately 1,500 mg ai/ kg to greater than 6,400 mg ai/ kg, mancozeb is categorized as slightly to practically nontoxic to avian species on an acute oral basis. The guideline 71 1( a) is not fulfilled. A core study to fulfill this guideline is required to be submitted. The studies were categorized as supplemental because: the species tested were not preferred species; multiple dose as opposed to recommended single dose study was peformed; regurgitation made determination of toxicity dosages difficult; age and source of test animals was not provided; acclimation period, diet composition, or dose preparation was not provided; the number of test animals was below recommended levels; and/ or statistical analysis was unable to be performed. The toxicity value ( LD 50 ) appearing in the shaded area of the table will be used to calculate the acute avian risk quotients ( RQs).

Table 1: Avian ( also Reptilian and Terrestrial Phase Amphibian) Acute Oral Toxicity  Mancozeb Technical Species % ai LD 50 ( mg ai/ kg) Toxicity Category MRID No. Author/ year Classification1 English sparrow ( Passer domesticus)  10 day study duration 86.0 ~ 1500 ( Toxanal Approximate estimate) Probit LD 50 = 1833 95% CI = 863  8186 Probit slope = 4.24 95% CI = 0.44  8.03 slightly toxic 00036094/ Robinson, D. & K. Shillam/ 19663 Supplemental2 Mallard Duck ( Anas platyrhynchos) 86.0 > 6400 practically nontoxic 00080716/ Harper, K. & A. Palmer/ 1964 Supplemental2 Japanese Quail ( Coturnix japonica) 86.0 > 6400 practically nontoxic 00080717/ Harper, K. & A. Palmer/ 1965 Supplemental2 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline) 2 Cited in the 1987 Reregistration Standard as fulfilling data requirement. 3 Four birds were used in each of 5 dosage group.

Two dietary studies using the TGAI are required to establish the toxicity of mancozeb to birds. These avian dietary LC 50 tests, using the Mallard Duck and Bobwhite Quail, are acute, eight day dietary laboratory studies designed to estimate the quantities of toxicant required to cause 50% mortality in the two respective test populations of birds. The TGAI is administered by mixture to juvenile birds' diets for five days followed by three days of " clean" diet, and the results are expressed as LC 50 parts per million ( ppm) active ingredient ( a. i.) in the diet. Toxicity category descriptions are the following ( Brooks, 1973):

If the LC 50 is less than 50 ppm a. i., then the test substance is very highly toxic. If the LC 50 is 50 to 500 ppm a. i., then the test substance is highly toxic. If the LC 50 is 501 to 1,000 ppm a. i., then the test substance is moderately toxic. If the LC 50 is 1001 to 5,000 ppm a. i., then the test substance is slightly toxic. If the LC 50 is greater than 5,000 ppm a. i., then the test substance is practically nontoxic.

EFED has not received any studies to fulfill this requirement. In a memorandum dated, October 27, 1987, from EFED to RD, EFED waived the requirement for these studies because it was felt that the multiple dosing studies, mentioned above, exceeded the requirements for dietary testing and dietary testing that was attempted on mallard ducks and bobwhite quail indicated the birds had an aversion 67 to test diet and would not consume the test material. The requirement for submission of guidelines 71 2( a) and 71 2( b) is waived.

Avian reproduction studies using the Bobwhite Quail and Mallard Duck are laboratory tests designed to estimate the quantity of toxicant required to adversely affect the reproductive capabilities of a test population of birds. The TGAI is administered by mixture to breeding birds' diets throughout their breeding cycle. Test birds are approaching their first breeding season and, generally, are 18 to 23 weeks old. The onset of the exposure period is at least 10 weeks prior to egg laying. Exposure period during egg laying is generally 10 weeks with a withdrawal period of three additional weeks if reduced egg laying is noted. Results are expressed as No Observed Adverse Effect Concentration ( NOAEC) and various observable effect levels, such as the Lowest Observable Adverse Effect Concentration ( LOAEC), quantified in units of parts per million of active ingredient ( ppm a. i.) in the diet.

Avian reproduction studies using the TGAI are required for mancozeb because birds may be subject to repeated or continuous exposure to the pesticide, especially preceding or during the breeding season, the pesticide is stable in the environment to the extent that potentially toxic amounts may persist in animal feed and information derived from mammalian reproduction studies indicates reproduction in terrestrial vertebrates may be adversely affected by the anticipated use of the product. The preferred test species are mallard duck and bobwhite quail. Results of these tests are tabulated below ( Table 2). The toxicity value ( NOAEC) appearing in the shaded area of the table will be used to calculate the chronic avian risk quotients ( RQs).

Avian reproduction studies using bobwhite quail and mallard duck ( Guideline 71 4; resulted in LOAECs of 1000 ppm based on reductions in hatchling weight, 14 day old survivors weight, embryo viability, hatchability, and the percentage of 14 day old survivors when compared to the control ( Table 2). The NOAEC ranges from 125 to 300 ppm. Guidelines 71 4( a) and ( b) for the TGAI of mancozeb are fulfilled ( MRID Nos. 44159501, 41948401 and 44238001).

Table 2: Avian ( Reptilian & Terrestrial Phase Amphibian) Reproduction Chronic Toxicity  Mancozeb Technical Species/ Study Duration % ai NOAEC/ LOAEC ( ppm ai) LOAEC Endpoints MRID No. Author/ year Classification1 Northern bobwhite ( Colinus virginianus) / 22 weeks 81.9 125/ 1000 Hatchling wt., 14 day old survivor wt., & % of 14 day old survivors 44159501/ Mitchell L. et al./ 1996 Core Mallard Duck ( Anas platyrhynchos) / 22 weeks 80.1 125/ 1000 Reductions in: egg production; early and late embryo viability; hatchability; and offspring weight at hatch and 14 days of age. 41948401/ Beavers, J. et al./ 1991 Core Northern bobwhite ( Colinusvirginianus) / 22 weeks 86.2 88.5 300/ 1000 14 day old survivors wt. 44238001/ Johnson, A./ 1993 Core 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline) 2 Based on 2/ 9/ 95 review or D210278 memorandum dated 4/ 25/ 94 ii. Mammals, Acute and Chronic 68 1. Acute Oral Toxicity Testing Wild mammal testing is required on a case by case basis, depending on the results of lower tier laboratory mammalian studies, intended use pattern and pertinent environmental fate characteristics. In most cases, rat or mouse toxicity values obtained from the Agency's Health Effects Division ( HED) substitute for wild mammal testing. The toxicity values used in this assessment were taken from HED's Tox One Liner, preliminary draft HED reports received in October, 1999 and the final Hazard Identification Assessment Review Committee ( HIARC) report on mancozeb dated November 16, 1999. These toxicity values are reported below. The toxicity values ( LD 50 and NOAEL) appearing in the shaded areas of the tables will be used to calculate the acute and chronic mammalian risk quotients ( RQ's) in subsequent sections. Toxicity category descriptions are the following ( Brooks, 1973):

If the LD 50 is less than 10 mg a. i./ kg, then the test substance is very highly toxic. If the LD 50 is 10 to 50 mg a. i./ kg, then the test substance is highly toxic. If the LD 50 is 51 to 500 mg a. i./ kg, then the test substance is moderately toxic. If the LD 50 is 501 to 2,000 mg a. i./ kg, then the test substance is slightly toxic. If the LD 50 is greater than 2,000 mg a. i./ kg, then the test substance is practically nontoxic.

The results indicate that mancozeb is practically nontoxic to mammals on an acute oral basis ( Table 3).

Table 3: Mammalian Acute Oral Toxicity  Mancozeb Species % ai LD50 ( mg ai/ kg) Toxicity Category) Affected Endpoints MRID or Accession ( AC) No.

Technical laboratory rat ( Rattus norvegicus) laboratory mouse ( Mus musculus) l 80.0 > 5,000 ( male) practically nontoxic mortality AC259044 laboratory rat ( Rattus norvegicus) 72.6 > 5,000 ( male & female) Probit slope = 4.5 ( default) 1 practically nontoxic mortality 00142522 laboratory rat ( Rattus norvegicus) 70.0 & 75.0 > 5,000 practically nontoxic mortality AC254377 End Use Formulation  Mancozeb laboratory rat ( Rattus norvegicus) 36.0 > 5,000 ( male) practically nontoxic mortality AC238564 1 Raw data unavailable to estimate slope. Used default assumption cited in Urban and Cook ( 1986).

2. Acute Dermal and Inhalation Toxicity Testing In addition to acute oral routes of exposure, terrestrial vertebrates entering treatment area may be acutely exposed to mancozeb through other routes of exposure. Toxicity category descriptions associated with dermal routes of exposure include the following ( US EPA CFR. Part 156):

If the LD50 is less than or equal to 200 mg/ kg, then the test substance is in Toxicity Category I. If the LD50 is greater than 200 through 2,000 mg/ kg, then the test substance is in Toxicity Category II. If the LD50 is greater than 2,000 through 5,000 mg/ kg, then the test substance is in Toxicity Category III 69 If the LD50 is greater than 5,000 mg/ kg, then the test substance is in Toxicity Category IV.

The results indicate that mancozeb is a Category IV toxicant to mammals on an acute dermal basis. ( Table 4).

Table 4: Mammalian Acute Dermal Toxicity  Mancozeb Technical Surrogate Species % ai LD50 ( mg ai/ kg) Toxicity Category Affected Endpoints MRID or Accession ( AC) No.

laboratory rabbit ( Sylvilagus sp.) 70.0 & 75.0 > 5,000 Category IV not reported AC254377 laboratory rabbit ( Sylvilagus sp.) 72.6 > 5,000 Category IV not reported 00142522 The acute inhalation toxicity results for mancozeb are indicated in Table 5 below. Toxicity category descriptions associated with inhalation routes of exposure include the following ( US EPA CFR. Part 156):

If the LC50 is less than or equal to 0.05 mg/ liter, then the test substance is in Toxicity Category I. If the LC50 is greater than 0.05 mg/ liter through 0.5 mg/ liter, then the test substance is in Toxicity Category II. If the LC50 is greater than 0.5 mg/ liter through 2.0 mg/ liter, then the test substance is in Toxicity Category III If the LC50 is greater than 2.0 mg/ liter, then the test substance is in Toxicity Category IV.

Mancozeb is a Category IV toxicant to mammals based on acute inhalation exposure.

Table 5: Mammalian Acute Inhalation Toxicity  Mancozeb Technical Surrogate Species/ Formulation % A. I. LC50 ( mg/ liter) Toxicity Category Affected Endpoints MRID or Accession ( AC) No.

laboratory rat ( Rattus norvegicus) 80.0 > 5.14 Category IV not reported AC246662 laboratory rat ( Rattus norvegicus) 72.6 > 5.14 Category IV not reported 00142522 laboratory rat ( Rattus norvegicus) 70.0 & 75.0 > 5.14 Category IV not reported AC254377 3. Mammalian Sub chronic Toxicity Testing The submitted mammalian sub chronic feeding studies ( Table 6) indicate that extended exposure to Mancozeb Complex via the diet at levels of 250 ppm will cause decreased serum thyroxine levels in females and body weight decrements, changes in thyroid hormones, changes in liver enzymes, 70 microscopic changes in the liver and thyroids, increased absolute and relative thyroid weights, and increased relative liver weights in males.

Table 6: Mammalian Subchronic Toxicity  Mancozeb Surrogate Species/ % ai NOAEL/ LOAEL ( mg/ kg/ day) LOAEL Endpoints MRID or Accession ( AC) No.

Laboratory rat ( Rattus norvegicus)/ feeding 3 months 84.0 9.2417.82 ( 125/ 250 ppm) female 14.98/ 59.92 ( 250/ 1000 ppm) male female  decreased serum thyroxine levels male  body weight decrements, changes in thyroid hormones, changes in liver enzymes, microscopic changes in the liver and thyroids, increased absolute and relative thyroid weights, and increased relative liver weights 00261536 Laboratory mouse ( Mus musculus)/ feeding 3 months 83.1 18.13/ 166.9 ( 100/ 1000 ppm) microscopic lesions of thyroid follicular cell hypertrophy or hyperplasia in females and decreased liver MFO enzyme activity in males AC259888 4. Mammalian Feeding, Reproductive and Developmental Toxicity Testing As indicated in Table 7, treatment related developmental effects caused by mancozeb involved gross developmental defects, central nervous system defects, skeletal defects, cryptorchidism ( failure of one or more testes to descend into the scrotum) , abortions, and decreased fetal weight ( see MRID No. 00246663). This particular study is also listed as a study in the toxicological endpoints for mancozeb's metabolite, ETU ( see Appendix III of the ETU chapter). Although mancozeb and ETU caused many of the same developmental effects, ETU caused these effects at a much lower level ( 1000 ppm) as compared to mancozeb ( 10,240 ppm). Parental effects in the reproductive study on rats included body weight decrements, increased relative thyroid weights, and increased incidence of thyroid follicular cell hyperplasia ( see MRID No. 41365201) at the 1200 ppm level. There were no adverse offspring effects attributed to mancozeb in this study. A long term ( 1 year) feeding study on dogs resulted in decreased body weights in males and anemia in females at 200 ppm level for mancozeb.

Table 7: Mammalian Feeding, Developmental and Reproductive Chronic Toxicity  Mancozeb Technical Species/ Study Duration % ai Test Type NOAEL/ LOAEL Toxicity Value ( mg/ kg/ day) Affected Endpoints MRID or Accession ( AC) No.

Domestic dog ( Canis familiaris)/

1 year 80.6 Feeding 1.75/ 7.26 ( 50/ 200 ppm)

male 7.02/ 29.24 ( 200/ 800 ppm)

female male  decreased body weight gain female  anemia 41810501 Table 7: Mammalian Feeding, Developmental and Reproductive Chronic Toxicity  Mancozeb Technical Species/ Study Duration % ai Test Type NOAEL/ LOAEL Toxicity Value ( mg/ kg/ day) Affected Endpoints MRID or Accession ( AC) No.

71 laboratory rat ( Rattus norvegicus)

/ 2 year 83.8 Feeding 4.83/ 30.9 ( 125/ 750 ppm)

male 6.72/ 40.2 ( 125/ 750 ppm)

female thyroid toxicity and bilateral retinopathy 41903601 laboratory rat ( Rattus norvegicus) / not reported 83.0 Developmental 32/ 128 ( 640/ 2560 ppm) ( maternal) 128/ 512 ( 2560/ 10,240 ppm) ( developmental) mat.  decreased food consumptionn & body wt. gain dev.  gross developmental defects, central nervous system defects, skeletal defects, cryptorchidism, abortions, increased resorptions, and decreased fetal weight 00246663 laboratory rabbit ( Oryctolagus cuniculus)/ not reported 83.0 Developmental 30/ 80 ( 990/ 2,640 ppm) ( maternal & developmental) mat.  abortions, mortality, and clinical signs dev.  abortions 40433001 laboratory rat ( Rattus norvegicus)

/ 2 generation 84.0 Reproductive 6.95/ 68.9 ( male)

( 120/ 1200 ppm)

( parental)

$ 69.9/   69.9 ($ 1200/   1200 ppm)

( reproductive) parental  body weight decrements, increased relative thyroid weights, and increased incidence of thyroid follicular cell hyperplasia reproductive  No adverse offspring effects were attributed to mancozeb. Fecundity and gestation indices; litter sizes; and pup viability, survival,

and body weights were all similar among the groups 41365201 iii. Insect Acute Contact A honey bee acute contact study using the TGAI is required for mancozeb because its outdoor use will result in honey bee exposure. The acute contact LD 50 , using the honey bee, Apis mellifera, is an acute contact, single dose laboratory study designed to estimate the quantity of toxicant required to cause 50% mortality in a test population of bees. The TGAI is administered by one of two methods: whole body exposure to technical pesticide in a nontoxic dust diluent; or, topical exposure to technical pesticide via micro applicator. The median lethal dose ( LD 50 ) is expressed in micrograms of active ingredient per bee (: g a. i./ bee). Results of this test are tabulated below ( Table 8). Toxicity category descriptions are the following ( Atkins, 1981):

If the LD 50 is less than 2 : g a. i./ bee, then the test substance is highly toxic. If the LD 50 is 2 to less than 11 : g a. i./ bee, then the test substance is moderately toxic. If the LD 50 is 11 : g a. i./ bee or greater, then the test substance is practically nontoxic The LD 50 for mancozeb was greater than 178 : g per bee and it is, therefore, classified as practically nontoxic to bees. The guideline ( 141 1) is fulfilled ( MRID No. 00018842). 72 EFED reviewed a multiple active ingredient ( MAI) TEP study ( MRID No. 44950504) for a product containing mancozeb and the fungicide zoxamide. Table 8 includes the results from this study. EFED classified the acute oral toxicity portion of this study as supplemental because this study is not an OPP guideline required study. This acute oral bee study was scientifically sound. This MAI TEP is, acutely, practically nontoxic to honeybees. Table 8: Non target Insect Acute Toxicity  Mancozeb Species % ai LD 50 ( µ g a. i./ bee) Toxicity Category MRID/ Accession ( AC) No. Author/ Year Study Classification1 Technical Honey bee ( Apis mellifera) 72.0 > 178.87 ( contact) practically nontoxic 00018842/ Atkins, E. et al./ 1969 Core2 End Use Product Honey bee ( Apis mellifera) 8.3 ( zoxamide) 69.0 ( mancozeb) > 200 ( contact) practically nontoxic 44950504/ Engelhard, E./ 1997 Core Honey bee ( Apis mellifera) 8.3 ( zoxamide) 69.0 ( mancozeb) > 153 ( oral) Virtually nontoxic3 44950504/ Engelhard, E./ 1997 Supplemental 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline) 2 Study used in 1987 Reregistration Standard. 3 Toxicity category source: 1985. International Commission for Bee Botany Third Symposium on the " Harmonization of methods for testing the toxicity of pesticides to bees".

iv. Insect and Mite Residual Contact A honey bee toxicity of residues on foliage study is required on an end use product for any pesticide intended for outdoor application when the proposed use pattern indicates that honey bees may be exposed to the pesticide and when the formulation contains one or more active ingredients having an acute contact honey bee LD 50 which falls in the moderately toxic or highly toxic range. The purpose of this guideline study is to develop data on the residual toxicity to honey bees. Bee mortality determinations are made from bees exposed to treated foliage harvested at various time periods after treatment. Mancozeb, as indicated in the acute toxicity test in Table 8, above, is practically nontoxic to honey bees. Because of this, a honey bee toxicity of residues on foliage ( guideline 141 2) is not required for mancozeb. However, the information in Table 9 is included in this document because this study was cited in the 1987 Reregistration Standard for mancozeb. The residual toxicity of mancozeb to honey bees at an application rate of 0.27 lb ai/ A is low.

Table 9: Summary of Honey Bee Residue on Foliage  Mancozeb Species % ai LD50 ( µ g a. i./ bee) Toxicity Category MRID/ Accession ( AC) No. Author/ Year Study Classification1 Honey bee ( Apis mellifera) 72.0 At 0.27 lb ai/ A low toxicity from direct application or residue not applicable 00001949/ Johansen, C. and J. Eves/ 1969 Supplemental2 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline) 2 Study used in 1987 Reregistration Standard. 73 A predatory mite ( Typhlodromus pyri) study ( MRID No. 4577201) was submitted by Dow Agro Sciences on 12/ 14/ 01 in response to FIFRA 6 ( a)( 2) without concluding that this information should be regarded as an " unreasonable adverse effect on the environment." This study is not an Office of Pesticides ( OPP) guideline study. This study was generated to comply with European Council Directive ( ECD) 91/ 414/ EEC as amended by ECD 96/ 12/ EC. The results of this are listed in Table 9a below.

Table 9a: Summary of Residual and Reproductive Toxicity to Typhlodromus pyri  Mancozeb Species % ai LR50 a ( lb a. i./ A) Affected Endpoints NOAEC/ LOAE C Toxicity Value ( lb a. i./ A) Affected Endpoints MRID/ Accession ( AC) No. Author/ Year Study Classification1 Predatory or Beneficial Mite ( Typhlodromus pyri) 81.8 0.1 Mortality < 0.02/ 0.02 Reduction in mean number of eggs hatched per female. 45577201/ Nienstedt, K and S. Kollmann/ 2001 Supplemental a Residue concentration on foliage causing 50% lethality.

v. Terrestrial Field Testing No studies were submitted and no studies are required.

c. Aquatic Organism Toxicity i. Toxicity to Freshwater Animals 1. Freshwater Fish, Acute Two freshwater fish toxicity studies using the TGAI are required to establish the toxicity of mancozeb to fish. The preferred test species are rainbow trout ( a coldwater fish; Guideline 72 1c) and bluegill sunfish ( a warmwater fish; Guideline 72 1a). Results of these tests are tabulated below. The toxicity category descriptions for freshwater and estuarine/ marine fish and aquatic invertebrates, are defined below in parts per million ( ppm), the standard units of measure ( Brooks, 1973). The toxicity values ( LC 50 ) appearing in the shaded area of the tables will be used to calculate the acute aquatic risk quotients ( RQ's) in subsequent sections.

If the LC 50 is less than 0.1 ppm a. i., then the test substance is very highly toxic. If the LC 50 is 0.1 to 1.0 ppm a. i., then the test substance is highly toxic. If the LC 50 is greater than 1 and up through 10 ppm a. i., then the test substance is moderately toxic. If the LC 50 is greater than 10 and up through 100 ppm a. i., then the test substance is slightly toxic. If the LC 50 is greater than 100 ppm a. i., then the test substance is practically nontoxic.

Since the LC 50 falls in the range of 0.46 3.9 ppm, for the TGAI, mancozeb is categorized as highly to moderately toxic to freshwater fish on an acute basis ( see Table 10). The supplemental studies were not conducted according to acceptable protocols: the toxicity end points were not based on 74 measured concentrations; terminal wet weights of control fish were lower than the minimum required initial weight of test fish; the results are from measured but unfiltered samples; and/ or the information was provided as a reference source with no supporting data or statistical analysis. Guideline 72 1( c) for the TGAI of mancozeb is fulfilled ( MRID No. 40118502). Guideline 72 1( a) is not fulfilled for the TGAI. A core study is required to be submitted to fulfill this guideline requirement for acute toxicity to warmwater fish.

End use product testing was required to support the cranberry, wild rice and taro uses of mancozeb ( see Mancozeb 1987 Registration Standard). EFED subsequently allowed TEP testing ( with 80% WP) to fulfill TGAI testing requirements. Justification provided by the registrant was that the enduse product had greater solubility in water than the TGAI. Because of this, the requirement for submission of single active ingredient ( SAI) testing of a mancozeb TEP ( guideline 71b) can be fulfilled through the testing of the 80% WP formulation of mancozeb thus fulfilling both the TGAI and TEP testing requirement for the acute toxicity to warmwater fish. A study of rainbow trout was conducted using a mancozeb formulated product containing 37% active ingredient. This study ( MRID No. 40467501) was originally classified as core but is being downgraded to supplemental because the toxicity end point was not based on measured concentrations. However, this guideline requirement ( guideline 72 1d) has been fulfilled as a result of the core guideline 72 1( c) submission ( MRID No. 40118502) and no additional acute coldwater fish toxicity testing using a SAI mancozeb TEP is required.

Guidelines 72 1( d), the acute toxicity of mancozeb to rainbow trout using a single active TEP is fulfilled ( MRID No. 40467501).

Studies were also review for multiple active ingredient ( MAI) TEP products containing mancozeb and the fungicides dimethomorph and zoxamide. The results from these studies are also found in Table 10. The supplemental studies did not meet guideline requirements for one or more reasons: the study did not include an inert ingredient control, the test material at various concentrations was not measured, and/ or the range of test concentrations in the study was not appropriate for determining an LC 50 . Requirements for future MAI TEP testing of mancozeb is being reserved and may be required if these TEP formulations are identified as being a toxicological concern to freshwater organisms. 75 Table 10: Freshwater Fish 96 hr Acute Toxicity  Mancozeb.

Species/ Flow through or Static % ai LC 50 / ( C. I.) ( ppm ai)/ ( measured/ nominal) Toxicity Category MRID / Accession No./ Author/ Year Study Classification1 Technical Bluegill sunfish ( Lepomis macrochirus) / static ( 72 hour) 80.0 3.85/ ( 3.55 4.18) ( nominal) moderately toxic 00097147/ McCann, J./ 1967 Supplemental Bluegill sunfish ( Lepomis macrochirus) / static 80.0 1.35/ ( 0.6 2.9) ( not reported) moderately toxic 00097173/ McCann, J. & F. Pitcher/ 1973 Supplemental2 Bluegill sunfish ( Lepomis macrochirus) / static 80.0 1.54/ ( not reported) moderately toxic 40118501/ Terr.& Aquatic Bio. Lab., Beltsville, MD/ 1980 Supplemental2 Bluegill sunfish ( Lepomis macrochirus) / static 80.0 2.04/ ( 1.84 2.26) 3 ( measured) moderately toxic not reported/ Terr. & Aquatic Bio. Lab. Beltsville, MD/ 1980 Supplemental Bluegill sunfish ( Lepomis macrochirus) / flowthrough 81.3 > 3.6 ( highest dose tested) ( measured) moderately toxic 45934702/ Rhodes, J. E./ 2000 Supplemental Rainbow Trout ( Salmo gairdneri)/ static 80.0 0.64/ ( 0.46 0.89) 3 ( not reported) highly toxic not reported/ Animal Biology La. b./ 1977 Supplemental Rainbow Trout ( Salmo gairdneri)/ static 80.0 0.46/ ( 0.40 0.54) 3 ( measured) Probit slope = 4.5 ( default) 7 highly toxic 40118502/ Terr.& Aquatic Bio. Lab., Beltsville, MD/ 1980 Core2 Rainbow Trout ( Oncorhynchus mykiss)/ flowthrough 81.3 0.91/ ( 0.77 1.1) ( measured) slope = not reported highly toxic 45934701/ Rhodes, J. E./ 2000 Supplemental End Use Product Rainbow Trout ( Oncorhynchus mykiss) / static 37.0 1.1/ ( 0.85 1.4) 3 ( nominal) moderately toxic 40467501/ Bowman, J. H./ 1987 Supplemental Rainbow Trout ( Oncorhynchus mykiss) / static renewal 8.94/ 59.75 0.55/ ( 0.46 0.68) 3 ( nominal) highly toxic 43917218/ Toy, R. & A. Gray/ 1991 Supplemental Rainbow Trout ( Oncorhynchus mykiss) / static renewal 8.94/ 59.75 0.68/ ( 0.47 0.98) 3 ( nominal) highly toxic 43917216/ Toy, R. & A. Gray/ 1991 Supplemental Rainbow Trout ( Oncorhynchus mykiss) / static renewal 7.54/ 67.75 0.39/ ( 0.36 0.43) 3 ( nominal) highly toxic 43917217/ Toy, R. & A. Gray/ 1992 Supplemental Rainbow Trout 8.266/ 69.0 1.9/ moderately 44950503/ Rhodes, J. E. and Core 76 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline) 2 Study used in 1987 Reregistration Standard. 3 Based on total formulation. 4 Dimethomorph 5 Mancozeb 6 Zoxamide 7 Raw data unavailable to estimate slope. Used default assumption cited in Urban and Cook ( 1986).

2. Freshwater Fish, Chronic A freshwater fish early life stage test using the TGAI is required for mancozeb because the end use product is expected to be transported to water from the intended use site, and the following conditions are met: ( 1) the pesticide is intended for use such that its presence in water is likely to be continuous or recurrent, ( 2) an aquatic acute LC 50 or EC 50 is less than 1ppm, and ( 3) the EEC in water is equal to or greater than 0.01 of any acute LC 50 or EC 50 value. Acceptable freshwater test species are rainbow trout, brook trout, coho salmon, Chinook, bluegill, brown trout, lake trout, northern pike, fathead minnow, white sucker and channel catfish. The fish early life stage is a laboratory test designed to estimate the quantity of toxicant required to adversely effect the reproductive capabilities of a test population of fish. The test should be performed using flowthrough conditions. The TGAI is administered into water containing the test species, providing exposure throughout a critical life stage, and the results are expressed as a No Observed Adverse Effect Concentration ( NOAEC) and LOAEC ( Lowest Observed Adverse Effect Concentration) in parts per billion ( ppb) of active ingredient. The No Observed Adverse Effect Concentration represents an exposure concentration, at or below which biologically significant effects will not occur to species of similar sensitivities. Table 11 is a summary of a freshwater fish early life stage test ( Guideline 72 4a). The toxicity value ( NOAEC) appearing in the shaded area of the table will be used to calculate the chronic aquatic risk quotients ( RQ's) in subsequent sections. Guideline 72 4( a) for freshwater species is fulfilled ( MRID No. 43230701).

Table 11: Freshwater Fish Early Life Stage Toxicity Under Flow through Conditions  Mancozeb Technical Species/ Static or Flowthrough Study Duration % ai NOAEC/ LOAEC ( ppb ai)/ ( measured/ nominal) Endpoints Affected MRID/ Accession ( AC) No. Author/ Year Study1 Classification Fathead minnow ( Pimephales promelas) / flow through/ 35 days 79.3 2.19/ 4.56 ( measured) Survival and lack of growth effects 43230701/ Rhodes, et al./ 1994 Core 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline)

A freshwater fish life cycle test using the TGAI is required for mancozeb because the end use product is expected to be transported to water from the intended use site and any EEC is equal to or greater than one tenth of the NOAEC in the fish life stage or invertebrate life cycle test. The PRZM/ EXAMS modeled peak EECs for mancozeb's current use patterns range from 46.8 ppb for potato applications to 210.8 ppb for tomato applications. The preferred test species is fathead minnow. The freshwater fish life cycle test ( Guideline 72 5) has not been fulfilled. A core study for this guideline is required to be submitted.

3. Freshwater Invertebrates, Acute 77 A freshwater aquatic invertebrate toxicity test using the TGAI is required to establish the toxicity of mancozeb to aquatic invertebrates. The preferred test organism is Daphnia magna, but early instar amphipods, stoneflies, mayflies, or midges may also be used. Results of this test are tabulated below ( Table 12). The toxicity value ( EC 50 ) appearing in the shaded area of the table will be used to calculate the acute risk quotients ( RQ's) in subsequent sections. Since the LC 50 / EC 50 falls in the range of 0.58 to 1.0 ppb, mancozeb is categorized very highly toxic to freshwater aquatic invertebrates on an acute basis. Guideline 72 2( a) for the TGAI of mancozeb is fulfilled ( MRID Nos. 40118503 and 40467503).

Studies were also review for MAI TEP products containing mancozeb and dimethomorph. The results from these studies are also found in Table 12. The supplemental studies did not meet guideline requirements for one or more reasons: the study did not include an inert ingredient control, the test material at various concentrations was not measured, the results are from measured but unfiltered samples, and/ or the range of test concentrations in the study was not appropriate for determining an LC 50 . Requirements for future MAI TEP testing of mancozeb is being reserved and may be required if these TEP formulations are identified as being a toxicological concern to freshwater organisms. 78 Table 12: Freshwater Invertebrate Acute Toxicity  Mancozeb Technical Species/ Static or Flowthrough Duration % ai LC 50 /

EC 50 ( ppm)/( C. I.)/

( nominal/ measured) Toxicity Category MRID/ Accession ( AC)

No. Author/ Year Study Classification1 Technical Daphnid ( Daphnia magna)/ static ( 48 hr.) 80.0 0.58/

( 0.46 0.73) 3 ( nominal)

Probit slope = 4.5 ( default) 8 highly toxic 40118503/ Terr.&

Aquatic Bio.

Lab., Beltsville,

MD/ 1980 Core2 Daphnid ( Daphnia magna) static ( 48 hr.) 82.4 1.0/

( 0.87 1.30)

( nominal) highly toxic 40467503/ Forbis,

A./ 1987 Core End Use Product Daphnid ( Daphnia magna) static ( 48 hr.) 7.54/ 67.75 1.1/

( 0.48 2.3) 3 ( nominal) moderately toxic 43917217/ Toy, R. & A.

Gray/ 1992 Supplemental Daphnid ( Daphnia magna) static ( 48 hr.) 8.94/ 59.75 4.6/

( 0.41 2.8) 3 ( nominal) moderately toxic 43917216/ Toy, R. & A.

Gray/ 1991 Supplemental Daphnid ( Daphnia magna) static ( 48 hr.) 8.94/ 59.75 1.5/

( 1.1 2.2) 3 ( nominal) moderately toxic 43917215/ Toy, R. & A.

Gray/ 1991 Supplemental Daphnid ( Daphnia magna) flowthrough ( 48 hr.) 8.266/ 69.05 3.8/

( 3.0  5.0) 3 ( measured/ calculated)

slope = not reported moderately toxic 44950502/ Madsen, T. J & T. Leak/ 1998 Core Daphnid ( Daphnia magna) flowthrough ( 48 hr.) 4.097/ 66.66 5 1.8/

( 1.5  2.1) 3 ( measured)

slope = 4.6 moderately toxic 45934703/ Rhodes,

J./ 2001 Supplemental 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline) 2 Study used in 1987 Reregistration Standard. 3 Based on total formulation. 4 Dimethomorph 5 Mancozeb 6 Zoxamide 7 IR6141 ( Benalaxyl) 8 Raw data unavailable to estimate slope. Used default assumption cited in Urban and Cook ( 1986).

4. Freshwater Invertebrate, Chronic A freshwater aquatic invertebrate life cycle test using the TGAI is required for mancozeb since the end use product is expected to be transported to water from the intended use site, and the following conditions are met: ( 1) the pesticide is intended for use such that its presence in water is likely to be continuous or recurrent, ( 2) the aquatic acute LC 50 or EC 50 is less than 1.0 ppm, and ( 3) the EEC 79 in water is equal to or greater than 0.01 of any acute EC 50 or LC 50 value. The preferred test species is Daphnia magna. Results of this test are tabulated below. The toxicity value ( NOAEC) appearing in the shaded area of the table will be used to calculate the chronic risk quotients ( RQ's) in subsequent sections. Guideline 72 4( b) for mancozeb is fulfilled ( MRID No. 40953802).

Table 13: Freshwater Aquatic Invertebrate Life Cycle Toxicity  Mancozeb Technical Species/ Static Renewal or Flowthrough % ai 21 day NOAEC/ LOAEC ( ppb)/ ( measured/ nominal) Endpoints Affected MRID/ Accession ( AC) No. Author/ Year Study Classification1 Daphnid( Daphnia magna/ flowthrough 82.4 7.3/ 12.0 /( measured) immobility, length and time until first brood 40953802/ Burgess, D./ 1988 Core 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline)

5. Freshwater Field Studies A draft mesocosm study was performed and submitted to the Agency as MRID 44944401. An abbreviated review of this study was completed in February 2000 and a synopsis of the abbreviated review is submitted below.

This study followed the Society of Environmental Toxicology and Chemistry ( SETAC) " Guidance Document on Testing Procedures for Pesticides in Freshwater Mesocosms" ( July 1991) and employed the regression approach. Ten outdoor fiberglass tanks ( mesocosms) were used in this study  3 controls and 7 treatment tanks. Each mesocosm was approximately 2 m in diameter and 1.6 m deep with an approximate volume of 5 m3. The treatment tanks received eight simulated spray drift applications of Penncozeb 80 WP ( 80% mancozeb ai) each separated by one week. The nominal concentrations selected for each treatment tank were: 1.25, 4.0, 12.5, 40, 125, 400, and 1250 ppb of Penncozeb 80 WP. Since the half life of the parent material was reported to range from 2 hours for acidic pH to 14 hours for alkaline pH in an aquatic environment, mancozeb's degradate ( ETU) was assayed to confirm the presence of treatment material in the treatment tanks. The limit of determination in this study, for ETU, ranged from 1.7 to 3.4 ppb. Generally, all samples in which ETU was detected came from the 1250 ppb Penncozeb 80 WP treatment group and because of this the results were based upon nominal concentrations of the formulated product and not measured concentrations of the actual test material in the treatment tanks.

Since the mesocosm study was conducted using non replicated treatments, dose response values ( EC 20 and EC 50 ) were derived by employing non linear regression analysis. The EC 20 was regarded as the threshold level, below which no ecologically relevant effects occur. The following table provides the toxicity of Penncozeb 80 WP to various aquatic species in this study.

Species Period EC20/ EC50 ( ppb Penncozeb 80 WP)

Zooplankton Species Period EC20/ EC50 ( ppb Penncozeb 80 WP)

80 Daphnia magna Application 252/ 408 Daphnia longispina Application 332/ 398 Chydorus sphaericus Application 67/ 134 Scapholeberis mucronata Application 188/ 263 Copepod nauplii Application 29/ 57 Brachionus leydigi Application 5.5/ 9.2 Keratella quadrata Application 22/ 27 Hexarthra sp. Application Post Application 12/ 12 12/ 12 Cephalodella sp. Application 15/ 31 Phytoplankton Volvox sp. Application 1.6/ 4.8 The PRZM/ EXAMS modeled peak EECs for mancozeb's current use patterns range from 46.8 ppb for potato applications to 210.8 ppb for tomato applications ( see Table V. 2). The test levels used on this study were equivalent to: 1.0, 3.2, 10.0, 32.0, 100.0, 320.0, and 1000.0 ppb of mancozeb which indicates this study adequately covers the Mancozeb Complex that would currently be expected to occur in aquatic environments. It should be noted that EPA's " Aquatic Mesocosm Tests to Support Pesticide Registrations EPA 540/ 09 88 035" ( March 1988) requires three replicates per treatment level, a mesocosm size of 300 m3 in volume and the inclusion of viable finfish in the study. These three major departures from EPA guideline requirements are noted at this time. EFED has recently been made aware that the finalization of this study has been submitted to OPP under MRID No. 45014901. It is not anticipated that a review of the final study will be completed prior to the publication of the draft RED for mancozeb. However, since the RED process is rather lengthy it is anticipated that a review of MRID No. 45014901 will be completed and included in this chapter prior to publication of the final RED for mancozeb. At this time, until a review of the final document can be completed the study is categorized as supplemental.

ii. Toxicity to Estuarine and Marine Animals 1. Estuarine and Marine Fish, Acute Acute toxicity testing with estuarine and marine fish using the TGAI is required for mancozeb because the end use product is expected to reach the marine/ estuarine environment because of its use in coastal counties. The preferred test organisms are the sheepshead minnow. Results of these tests are tabulated in Table 14, below. The supplemental studies were not conducted according to acceptable protocols: there was precipitation in test vessels, concentrations were not measured, the size of the test fish was unknown, and/ or the weight of the test fish was unknown. Based on the 81 results of these tests, mancozeb is moderately toxic to estuarine fish. Guideline 72 3( a) is not fulfilled. A core study for determining the acute toxicity to estuarine/ marine fish must be submitted. The toxicity value ( LC 50 ) appearing in the shaded area of the table will be used to calculate the acute risk quotients ( RQ's) in subsequent sections.

The results for Guideline 72 3( d) studies for single active ingredient TEP formulations are also listed in Table 14. Requirements for future MAI TEP testing of mancozeb is being reserved and may be required if these TEP formulations are identified as being a toxicological concern to estuarine/ marine organisms.

Table 14: Summary of acute 96 hr toxicity tests for Estuarine/ Marine Fish with Mancozeb.

Species/ static or flowthrough % A. I. LC50/( C. I.)/ ppm ai/ ( measured/ nominal ) Toxicity Category MRID No. Author/ year Classification1 Technical Sheepshead Minnow/ ( Cyprinodon variegatus)/ static 82.4 4.2/ ( 2.3 6.5) /( nominal) moderately toxic 40586802/ Ward, G../ 1987 Supplemental Sheepshead Minnow/ ( Cyprinodon variegatus)/ flowthrough 82.4 1.6/ ( not reported)/ ( measured) Probit slope = 4.5 ( default) 4 moderately toxic 41844901/ Mmanning, C. et al./ 1990 Supplemental End Use Formulation Sheepshead Minnow/ ( Cyprinodon variegatus)/ flowthrough 37.0 2.72 ( 1.0) 3/ ( 2.2 3.8) /( nominal) moderately toxic 41844902/ Manning, C. et al./ 1990 Supplemental Sheepshead Minnow/ ( Cyprinodon variegatus)/ static 37.0 4.22/ ( 2.3 6.5) /( nominal) moderately toxic 40586804/ Ward, G./ 1988 Supplemental 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline) 2 Based on total formulation. 3 Based on active ingredient. 4 Raw data unavailable to estimate slope. Used default assumption cited in Urban and Cook ( 1986).

2. Estuarine and Marine Fish, Chronic An estuarine/ marine fish early life stage toxicity test using the TGAI is required for mancozeb because the end use product is expected to be transported to the estuarine/ marine environment from the intended use site, and the following conditions are met: the pesticide is intended for use such that its presence in water is likely to be continuous or recurrent and the EEC in water is equal to or greater than 0.01 of any acute LC 50 or EC 50 value. The preferred test species is sheepshead minnow. The guideline ( 72 4a) estuaine/ marine fish is not fulfilled. A core study is required to be submitted for this guideline.

3. Estuarine and Marine Invertebrates, Acute 82 Acute toxicity testing with estuarine/ marine invertebrates using the TGAI is required for mancozeb because the end use product is expected to reach the marine/ estuarine environment because of it use in coastal counties. The preferred test species are mysid shrimp and eastern oyster. Results of these tests are tabulated below. The toxicity value ( EC 50 ) appearing in the shaded area of the table will be used to calculate the acute risk quotients ( RQ's) in subsequent sections. Since the TGAI EC 50 ranges from 0.0105 to 1.6 ppm, the mancozeb is considered to be very highly toxic to moderately toxic to estuarine/ marine invertebrates on an acute exposure. However, there is a uncertainty is the supplemental study ( MRID No. 40586801) because the concentration of the test material was not measured after a substantial decrease in dissolved oxygen and subsequent aeration which may have altered the concentration of the test material in the solution. There is an uncertainty is the supplemental study ( MRID No. 41822901) because the shrimp tested were older than what was recommended and the control appeared to have been contaminated with the test material. Guideline 72 3( b) for the TGAI acute toxicity to estuarine/ marine organism mollusk is fulfilled ( MRID No. 40885102). Guideline 72 3( c) for the acute toxicity to estuarine/ marine organism shrimp is not fulfilled. A core study using the TGAI of mancozeb must be submitted for this guideline. Guideline 72 3( e), acute toxicity to estuarine/ marine mollusk for a single active ingredient mancozeb TEP, is fulfilled ( MRID No. 40885101). Guideline 72 3( f), acute toxicity to estuarine/ marine shrimp for a single active ingredient mancozeb TEP, is not fulfilled. A core study using a mancozeb TEP must be submitted for this guideline. Requirements for future MAI TEP testing of mancozeb is being reserved and may be required if these TEP formulations are identified as being a toxicological concern to estuarine/ marine organisms.

Table 15: Estuarine/ Marine Invertebrate Acute Toxicity  Mancozeb Species/ Static or Flow through % ai. 96 hour EC50 ( ppm ai)( C. I.)/ ( measured/ nominal) Toxicity Category MRID No./ Author/ Year Study Classification1 Technical Eastern oyster ( Crassostrea virginica)/ flowthrough ( shell deposition) 82.4 1.60/ ( 1.4 1.8) /( measured) moderately toxic 40885102/ Manning, C./ 1988 Core Mysid ( Americamysis bahia)/ flowthrough 82.4 0.0105/ ( 0.086 0.014) /( measured)

slope = 3.0 Probit LD 50 = 0.0106 95% CI = 0.0086

0.0142 Probit slope = 3.0 95% CI = 2.0  4.0 very highly toxic 41822901/ Ward,

G./ 1990 Supplemental Mysid ( Americamysis bahia)/ static ( 24 hr.) 82.4 0.067/

( 0.058 0.079)

/( nominal) very highly toxic 40586801/ Ward,

G./ 1988 Supplemental End Use Formulation Table 15: Estuarine/ Marine Invertebrate Acute Toxicity  Mancozeb Species/ Static or Flow through % ai. 96 hour EC50 ( ppm ai)( C. I.)/ ( measured/ nominal) Toxicity Category MRID No./ Author/ Year Study Classification1 83 Eastern oyster ( Crassostrea virginica)/

flowthrough ( shell deposition) 37.0 1.53/

( 0.4 3.4)

/( measured) moderately toxic 40885101/ Manning,

C./ 1988 Core Mysid ( Americamysis bahia)//

flowthrough 37.0 0.0095/

( 0.0083 0.0114)

/( measured) very highly toxic 41822902/ Ward, G.,

et. al/ 1990 Supplemental Mysid ( Americamysis bahia)/ static ( 24 hr.) 37.0 0.218/

( 0.185 0.265)

/( nominal) highly toxic 40586803/ Ward,

G./ 1988 Supplemental 1 Core ( study satisfies guideline). Supplemental ( study is scientifically sound, but does not satisfy guideline)

4. Estuarine and Marine Invertebrate, Chronic An estuarine/ marine invertebrate life cycle toxicity test ( Guideline 72 4b) using the TGAI is required for mancozeb because the end use product is expected to be transported to the estuarine/ marine environment from the intended use site, the pesticide is intended for use such that its presence in water is likely to be continuous or recurrent, any aquatic acute LC 50 or EC 50 is less than 1.0 ppm, and the EEC in water is equal to or greater than 0.01 of any acute LC 50 or EC 50 value. The preferred test species is mysid shrimp. This guideline has not been fulfilled and a core study for this guideline is required to be submitted.

5. Estuarine and Marine Field Studies No studies were submitted and no studies are required.

iii. Toxicity to Plants 1. Terrestrial Plants Terrestrial plant Tier I seedling emergence and vegetative vigor testing of a mancozeb TEP is currently recommended for all pesticides having outdoor uses. For seedling emergence and vegetative vigor testing the following plant species and groups should be tested: ( 1) six species of at least four dicotyledonous families, one species of which is soybean ( Glycine max) and the second is a root crop, and ( 2) four species of at least two monocotyledonous families, one of which is corn ( Zea mays). Tier I tests measure the response of plants, relative to a control, at a test level that is equal to the highest use rate ( expressed as lbs ai/ A). Tier II studies are required if the Tier I studies indicate any of the test species, when exposed to the test material, displayed a $ 25% inhibition of various growth parameters as compared to the control. 84 Tier I seedling emergence [ guideline 122 1( a)] and vegetative vigor [ guideline 122 1( b)] studies for the MAI TEP, Acrobat MZ, ( a mixture of mancozeb and dimethomorph) have been reviewed. Results of these studies are tabulated in Tables 16 and 17, below. For Tier I seedling emergence, soybean and tomato are the most sensitive dicots with 4% plant dry weight inhibition and onion is the most sensitive monocot with 12% plant dry weight inhibition when compared to the controls at the application rate of 1.38 and 0.20 lb ai/ A of mancozeb and dimethomorph, respectively. For Tier I vegetative vigor, tomato is the most sensitive dicot with a 4% plant dry weight inhibition and onion is the most sensitive monocot with 12% plant dry weight inhibition when compared to the controls at the application rate previously indicated.