M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 1 of 38 **UNITED STATES ENVIRONMENTAL PROTECTION AGENCY**

**WASHINGTON, DC 20460 OFFICE OF CHEMICAL S**  **AFETY AND POLLUTION PREVENTION**  **MEMORANDUM DATE**  **: 27 August 2013**  **SUBJECT: Mandipropamid**  **.** Petition to Establish Permanent Tolerances ( and Section 3

Registration) for Residues Resulting from Use of the Fung icide on Basil , Succulent Beans, Cowpea Forage , Ginseng and Greenhouse Tomatoes ; to Update Fruiting Vegetables Group 8 to Group 8 - 10; to Extend the Tolerance in Grapes to S ubgroup 13 - 07F, the Tolerance in Dry Bulb Onions to Subgroup 3 - 07 A , and the Tolerance in Green Onions to Subgroup 3 - 07B . Summary of Anal ytical Chemistry

and Residue Data. **PC Code:** 036602 **DP Barcode :**  D40 9363 **Decision N umber**  **:** 4 72 7 4 7 **Registration Number**  **:** 100 - 1254 **P etition**  **:** 2 E 8 1 26 **Regulatory Action:** Section 3 **Risk Assessment Type:** NA **Case Number**  **:** 7 058 **T XR**  **Number :**  NA **CAS Number**  **:** 374726 - 62 - 2 **MRID Numbers**  **:** 4899 20 01 - 04 **40 CFR:** § 180. 637 **FROM:** William T. Drew, Chemist

Risk Assessment Branch II (RAB2) Health Effects Division ( HED), 7509P **THR U:**  Dennis McNeill y , Chem ist

Michael A. Doherty, PhD, Senior Chemist RAB2/HED , 7509P **TO:** Barbara Madden and Laura Nollen , RM Team 5

Risk Integration, Minor Use, and Emergency Response Branch (RIMUERB) Registration Division ( RD), 7505PM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 2 of 38 **Table of Contents** 1.0 Executive Summary ................................ ................................ ................................ .............. 4 2.0 Regulatory

Recommendations ................................ ................................ .............................. 7 2.1 Data Deficiencies/Data Needs ................................ ................................ .......................... 8 2.2 Tolerance Considerations ................................ ................................ ................................ .. 8 2.2.1 Enforcement Analy tical Method/Multiresidue Methods ................................ .......... 8 2.2.2 Recommended Tolerances ................................ ................................ ........................ 9 2.2.3 Revisions to Petitioned - For Tolerances ................................ ................................ .... 9 2.2.4 International Harmonization ................................ ................................ ..................... 9 2.3 L abel Recommendations ................................ ................................ ................................ 10 2.4 Submittal of Analy tical Reference Standards (860.1650) ................................ ............. 10 3.0 Chemical Identity ................................ ................................ ................................ ............... 11 3.1 Nomenclature ................................ ................................ ................................ ................. 11 3.2 Phy sic o c hemical Characteristics ................................ ................................ .................... 12 3.3 Pesticide Use Pattern/Directions for Use (860.1200) ................................ .................... 12 4.0 Metabolite/Degradate Residue Profile ................................ ................................ ............... 13 4.1 Nature of the Residue ................................ ................................ ................................ ..... 13 4.1.1 Summary

of Plant and

/or Li vestock Metabolism (860.1300) ................................ . 14 4.1.2 Summary

of Confined Rotational Crops (860.l850) ................................ ............... 14 4.1.3 Summary

of Rat Metabolism ................................ ................................ .................. 15 4.1. 4 Summary

of Environmental Degradation ................................ ............................... 15 5.0 Residue Profile ................................ ................................ ................................ ................... 16 5.1 Residue Anal ytical Methods (860.1340) ................................ ................................ ...... 16 5.1.1 Data Collection Methods ................................ ................................ ........................ 16 5.1.2 Multi - Residue Methods (860.1360) ................................ ................................ ........ 21 5.1.3 Tolerance Enforcement Methods ................................ ................................ ............ 21 5.2 Storage Stability

(860.1380) ................................ ................................ .......................... 21 5.3 Residue Data ................................ ................................ ................................ .................. 24 5.3.1 Crop Field Trials (860.1500) ................................ ................................ .................. 24 5.3.2 Field Rotational Crops (860.1900) ................................ ................................ ......... 27 5.3.3 Processed Food and Feed (860.1520) ................................ ................................ ..... 27M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 3 of 38 5.3.4 Meat, Milk, Poultry and Eggs (860.1480) ................................ .............................. 28 5.3.5. Food Handling (860.1460) ................................ ................................ ...................... 28 5.3.6 Water, Fish and Irrigated Crops (860.1400) ................................ ........................... 28 5.4 Food Residue Profile ................................ ................................ ................................ ...... 28 6.0 Tolerance Derivation ................................ ................................ ................................ ......... 29 References ................................ ................................ ................................ ................................ ..... 30 Attachment 1: International Residue Limit Statu s ................................ ................................ ....... 32 Attachment 2: OECD MRL(Tolerance) Assessment Calculations ................................ ............. 33M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 4 of 38 **1.0 Executive Summary**  Mandipropamid (with CAS name 4 - chloro -N - [2 - [3 - methoxy- 4 - (2 - prop ynylox y) phenyl]ethyl] - α - (2 - prop ynyl oxy)benzeneacetamide , and CAS number 374726 - 62 - 2 ) is a fungicide in the mandelamide class developed by S yn genta Crop Protection for the control of foliar oomycet e pathogens in a range of crops including Plasmopara viticola in grapes, Phytophthora infestans in potatoes and tomatoes, and Pseudoperonospora cubensis in cucurbits. The previous residue chemistry summary document for man dipropamid was completed in conjunction with its registration for use on hops and tobacco ( D 348229 , D352322 ; D. Rate; 11 December 2008 ). Permanent tolerances are established for residues of mandipropamid in or on a variety of plant commodities, at level s ranging from 0.0 3 ppm in wet potato peel s, to 5 0 ppm in dried hops c on e s (40CFR §180. 637 [a]). Time - limited tolerances (associated with Section 18 emergency exemptions) are established for residues of mandipropamid in fresh and dried basil (40CFR §180. 6 37[b]); these tolerances expire on 31 December 2015 . The Interregional Research Project Number 4 (IR- 4) has submitted a petition requesting new use s on basil , ginseng, succulent beans, and greenhouse tomatoes. In conjunction with the requested new uses, IR- 4 has proposed the establishment of permanent tolerance s for residues of mandipropamid in/on the following raw agricultural commodities (RAC s ) and dried basil , at the tolerance levels listed : Basil, fresh..................................... . ......... . ............ 30 ppm Basil, dried.................................... . ......... . ..........200 ppm Bean, succulent.................................... . ...... . .......0.90 ppm Ginseng ............ .......................................... . ...... 0.3 ppm Cowpea, forage................................. . ......... . .........15 ppm Vegetable, fruiting, group 8 - 10........................ .. .........1.0 ppm Fruit, small, vine climbing, subgroup 13 - 07F, except fuzzy

kiwifruit.................................... . ... .. ....2.0 ppm Onion, bulb, subgroup 3 - 07A.................. . ............ .. ....0.1 ppm Onion, green, subgroup 3 - 07B.................. . ... . ... . .........7.0 ppm The proposed tolerances in fresh and dried basil, succulent beans, ginseng, and cowpea forage are based on crop field trial data entered into the Organization f or Economic Development and Cooperation’s (OECD’s) tolerance calculation procedure . Upon establishment of the permanent tolerance s in fresh and dried basil (40CFR §180.637[a]), the time - limited tolerances in fresh and dried basil (40CFR §180.637[ b ]) would be remov ed. The proposed tolerance in fruiting v egetable s ( group 8 - 10 ) is b ased on u pd ating the current tolerance in fruiting vegetables ( group 8 ) . The tolerance of 1.0 ppm would match the existing Codex (bell and non - bell peppers) and Canadian (tomatoes, okra, eggplant and peppers)M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 5 of 38 maximum residue limits (MRL s ) . Upon establishment of the tolerance in group 8 - 10 , the existing tolerance s in group 8 and okra would be removed . The proposed tolerance in small vine climbing f ruit s except fuzzy

kiwifruit ( subgroup 13 - 07F ) is b ased up on existing data for grapes (the representative commodity for the subgroup), and increas in g the current tolerance (1.4 ppm) to harmonize with the existing Codex MRL in grape s . Upon establishment of the tolerance in subgroup 13 - 07F , the existing tolerance in grape s would be removed . The proposed tolerance in bulb onion s (subgroup 3 - 07 A) is b ased up on existing data for dry bulb onion s (the representative commodity for the subgroup), and increasing the current tolerance ( 0.05 ppm) to harmonize with the existing Codex MRL in bulb onions . Upon establishment of the tolerance in subgroup 3 - 07 A , the existing tolerance in dry bulb onion s would be removed . The proposed tolerance in green onion s (subgroup 3 - 07 B ) is based up on existing data for green onions (the representative commodity for the subgroup), and increasing the current tolerance (4 ppm) to harmonize with the existing Codex MRLin spring onions . Upon establishment of the tolerance in subgroup 3 - 07 B , the existing tolerance in green onion s would be removed . This summary

document addresses the data submitted in support of the proposed tolerances for residues of mandipropamid in the various commodities listed above. Crop Field Trials : To support the requested use s , field trials were conducted on basil (along with 2 greenhouse trials) , ginseng, and sn ap beans, and greenhouse trials were conducted on tomatoes . IR - 4 has submitted basil field and greenhouse trial data with mandipropamid. Four field trials were conducted in Canada and the US in North American Free Trade Agreement (NAFTA) Growing Zones 2 (1 trial in NC), 5A (1 trial in WI), 10 (1 trial in CA) and 11 (1 trial in BC) during the 2009 growing season, and two greenhouse trials were conducted in the US in Zones 2 (1 trial in MD) and 3 (1 trial in FL) during the 2009 and 2010 growing seasons. Fo llowing 4 foliar directed applications of the Revus 2.08SC formulation , containing 2.08 pounds of active ingredient per gallon (lb ai/gal), at a total seasonal rate of 0.520 - 0.528 lb ai per acre (lb ai/A), to basil plants (stems and leaves) harvested at a pre - harvest interval ( PHI) of 1 day , mandipropamid residues ranged from 3.5 ppm to 19 ppm in fresh basil , and 36 ppm to 91 ppm in dried basil grown in the field and greenhouse . The ad equate basil field trial data support a tolerance of 3 0 ppm in fresh bas il , and a tolerance of 2 00 ppm in dried basil . Four ginseng field trials were conducted in Canada and the US in NAFTA Growing Zones 5A (3 trials in WI) and 11 (1 trial in BC) during the 2008 growing season. Following 4 foliar broadcast applications of the Revus 2.08SC formulation, at a total seasonal rate of 0.521 - 0.547 lb ai/A , to ginseng plants harvested at a PHI of 2 day s , mandipropamid residues ranged from 0.0222 ppm to 0.167 ppm in dried ginseng roots . There were no quantifiable residues (< 0.005 ppm) ofM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 6 of 38 metabolite SYN500003 in any of the dried root sample s. The adequate ginseng field trial data support a tolerance of 0. 30 ppm in dried ginseng roots . Ten snap bean field trials were conducted in the US in NAFTA Growing Zones 1 (1 trial in NY), 2 (1 trial in MD and 1 trial in GA), 3 (1 trial in FL), 5 (1 trial in OH), 5A (1 trial in MIand 1 trial in WI), 10 (2 trials in CA) and 11 (1 trial in WA) during the 2010 growing season. Following 4 foliar broadcast or directed applications of the Revus 2.08SC formulation, at a total seasonal rate of 0.490 - 0.540 lb ai/A, to snap bean plants harvested at a PHI of 1 day , mandipropamid residues ranged from 0.0858 ppm to 0.761 ppm in pods with seed, and 1.24 ppm to 9.84 ppm in plants with pods . The adequate snap bean field trial data support a tolerance of 0.90 ppm in sn ap beans. The submitted snap bean data do not support the proposed tolerances in all succulent beans or cowpea forage (see Section 2.1, below) . Four tomato greenhouse trials were co nducted in the US in NAFTA Growing Zones 2 ( 1 trial in MD ) , 4 (1 trial in AR), 5 (1 trial in WI) and 1 0 (1 trial in C A) during the 20 1 0 growing season. Following 4 (5 at trial site 10 - AR05) foliar broadcast or directed applications of the Revus 2.08SC for

mulation, at a total seasonal rate of 0. 480 - 0. 6 5 1 lb ai/A, to tomato plants harvested at a PHI of 1 day , mandipropamid residues ranged from 0.0 45 ppm to 0. 339 ppm in tomato fruit . The adequate greenhouse trial data support the proposed use on greenhouse tomatoes , at a tolerance of 0 .60 ppm (based on the OECD tolerance calculation procedure), which is covered b y the proposed tolerance of 1.0 ppm in fruiting vegetables group 8 - 10 . Processing Studies : Because there are no processed commodities for ginseng or succulent beans , processing studies are not required for these RACs. The processed commodity for basil is dried basil, samples of which were produced at the field trial sites, and subsequently anal yz ed along with the fresh basil samples. A processin g study i s not needed for tomatoes, as this requirement was addressed in a previous summary document ( D328534, D337543; D. McNeilly ; 28 August 2007 ). Residue Analytical Methods : There is an adequate enforcement method available for the quantitation of mandipropamid in plant commodities. The Food and Drug Administration ( FDA) multiresidue methods are not adequate for determining residues of mandipropamid. Storage Stability : Adequate storage stability data are available to support the storage durations and conditions of samples from the submitted field trial studies . Meat, Milk, Poultry and Eggs: Because the proposed tolerance in cowpea forage cannot be established at this time, the current action for the proposed new use s will not result in the need for tolerances in livestock commodities (see Section 2.1, below) . MRL Harmonization : Neither Codex nor Canada’s Pest Management Regulatory Agency (PMRA) have established MRL s for mandipropamid in any of the commodities associated with the proposed new uses . As such, there are no harmonization issues associated with Codex for theM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 7 of 38 proposed new uses in the current action. However, PMRA and EPA are jointly reviewing the basil , ginseng and snap bean data in the current action; EPA and PMRA are harmonize d on the recommended tolerances/MRL s in fresh basil, dried basil, and ginseng. PMRA is establishing an MRL in edible - podded beans at 0.9 ppm, while HED is recommending for a tolerance in snap beans at 0.90 ppm. A lthough the tolerance/MRL level is harmonized, HED cannot harmonize with PMRA on the commodity definition, as the submitted snap bean data do not support use on all succulent beans, since no data were submitted for a succulent shelled bean, and do not meet the requirements of subgroup 6A, since no data were submitted for an edible - podded pea. Both the current tolerance in group 8 (1 .0 ppm) and the proposed tolerance in group 8 - 10 (1 .0 ppm) are harmonized with the Codex (bell and non - bell peppers) an d PMRA (tomatoes , okra , eggplant and peppers ) MRL s . The proposed tolerance of 2 .0 ppm in subgroup 13 - 07F , translated from grape data, would be harmonize d with the Codex MRL in grapes , but would no longer be harmonized with PMRA ’s MRL of 1.4 mg/kg in grapes . The proposed tolerance of 0 .1 ppm in subgroup 3 - 07A , translated from dry bulb onion data , would be harmonized with the Codex MRLin bulb onions , but would no longer be harmonized with PMRA ’s MRL of 0.05 ppm in various bulb onions . The proposed tolerance of 7. 0 ppm in subgroup 3 - 07 B , translated from green onion data , would be harmonized with the Codex MRLin spring onions, but would no longer be harmonized with PMRA ’s MRL of 4 ppm in various green onions . **2.0 Regulatory Recom**  **m endations**  HED has examined the residue chemistry database for mandipropamid . Pending submission of a revised Section F (to propose tolerance levels in accordance with those recommended by HED , and to correct some of the commodity definitions ) , there are no residue chemistry issues that would preclude establish ing tolerance s in the requested basil and ginseng commodities , and in the updated/expanded crop groups and subgroups . However, the submitted snap bean data do not support the proposed to lerances in succulent beans or cowpea forage (see Section 2.1, below) . The recommended tolerance s are listed in Table 2.2.2 , below . **Note to RD:** Concurrent with the establishment of permanent tolerances in fresh and dried basil (40CFR §180.637[a]), the paragraph referring to, and the table containing, the time - limited tolerances in fresh and dried basil ( 40CFR §180.637[b ]) sh ould be removed , and replaced with “ [Reserved] ” . Concurrent with the establishment of the tolerance in group 8 - 10, the existing tolerances in group 8 and okra sh ould be removed (40CFR §180.637[a]) . Concurrent with the establishment of the tolerance in subgroup 13 - 07F, the existing tolerance in grapes sh ould be removed (40CFR §180.637[a]) .M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 8 of 38 Concurrent with the establis hment of the tolerance in subgroup 3 - 07A, the existing tolerance in dry bulb onions sh ould be removed (40CFR §180.637[a]) . Concurrent with the establishment of the tolerance in subgroup 3 - 07B, the existing tolerance in green onions sh ould be removed (40 CFR §180.637[a]) . **Note to RD:** According to HED’s Interim Guidance on Tolerance Expressions (S. Knizner; 27 May 2009), the tolerance expression for mandipropamid cited in 40CFR §180.6 37 [a] should be revised to state: Tolerances are established for re sidues of mandipropamid, including its metabolites and degradates, in or on the commodities listed in the table below. Compliance with the tolerance levels specified below is to be determined by measuring only mandipropamid ( 4 - chloro -N - [2 - [3 - methoxy- 4 - (2 - propy nyloxy)phenyl]ethyl] - α - (2 - prop ynyl oxy)benzeneacetamide ) in or on the commodity . **2.1 Data Deficiencies/Data Needs**  HED’s Chemistry

Science Advisory

Council (ChemSAC ) has determined that the submitted snap bean data do not support the proposed tolerances in succulent beans and cowpea forage (ChemSAC meeting; 17 July 2013) . Additional field trial data on a succulent shelled bean cultivar (such as lima beans) would be necessary in order to establish a tolerance in all succulent bean s . Because of the possibility of detectable residues occurring in dairy cattle commodities ( fat, milk and liver) arising from the feeding of treated cowpea forage, the concurrent establishment of mandipropamid tolerances at the limit of quantitation ( LOQ ) in those commodities would be necessary . However, with no validated anal ytical method for enforcing tolerances in livestock commodities, it is not possible to establish tolerances in them. Ergo, the proposed tolerance in cowpea forage cannot be establis h ed until a validated method for determining mandipropamid residues in livestock (cattle) commodities is available . Also, if uses on additional significant livestock feed items are requested in any future petition, a livestock feeding study will be required. **2.2 Tolerance Con**  **sid erations**  **2.2.1 Enforcement Analytical Method** **/Multiresidue Methods** There is an adequate enforcement method available for the quantitation of mandipropamid in plant commodities. M ethod RAM 415/01 , using h igh performance l iquid chromatography with tandem mass spectrometric detection (LC/MS/MS) , has been adequatel y validated by an independent laboratory . It has a validated LOQ of 0.01 ppm. An acceptable confirmatory method is also available.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 9 of 38 The FDA Multiresidue methods are n ot adequate for determining residues of mandipropamid. **2.2.2 Recommended Tolerances**  **TABLE 2.2.2**  **Tolerance Summary for Ma**  **ndipropamid .**  **Comm odity as Proposed by**  **Registrant Proposed**  **Tolerance (ppm) Recommended** 

**Tolerance (ppm) Comments;**  **Correct Commodity Definition**  Basil, fresh 30 30 Basil, fresh leaves Basil, dried 200 200 Basil, dried leaves Bean, succulent 0.90 None Field trial data on a succulent shelled bean cultivar is needed. Bean, snap None 0.90 The snap bean field trials support the establishment of this tolerance. Ginseng 0.3 0.30 Cow pea, forage 15 None A validated method for residues in cattle commodities is needed. Vegetable, fruiting, group 8 - 10 1.0 1.0 Fruit, small, vine climbing, subgroup 13 - 07F, except fuzzy kiwifruit 2.0 2.0 Fruit, small, vine climbing, except fuzzy kiwifruit, subgroup 13
- 07F Onion, bulb, subgroup 3 - 07A 0.1 0.10 Onion, green, subgroup 3 - 07B 7.0 7.0 **2.2.3 Revisions to Petitioned**  **- For Tolerances**  Instead of the proposed tolerance in ginseng (0.3 ppm), HED recommends establishing the tolerance at 0.30 ppm, in order to avoid the situation where a field sample containing residues significantl y above the tolerance (0.34 ppm, for example) would be consi dered non - violative. For the same reason, HED recommends that the proposed tolerance of 0.1 ppm in bulb onions ( subgroup 3 - 07A) be revised to 0. 1 0 ppm . For the reasons discussed in Section 2.1 (above) , the proposed tolerances in succulent beans and cowpea forage cannot be established . However, the s nap b e an field trials support a tolerance of 0.90 ppm in snap beans. **2.2.4 International Harmonization**  Neither Codex nor PMRA have established MRLs for mandipropamid in any of the commodities associated with the proposed new uses. As such, there are no harmonization issues associated with Codex for the proposed new uses in the current action. However, PMRA and EPA are jointly reviewing the basil, ginseng and snap bean data in the current action; EPA and PMRA are harmonized on the recommended tolerances/MRLs in fresh basil, dried basil, and ginseng. PMRA is establishing an MRL in edible - podded beans at 0.9 ppm, while HED is rec ommending for a tolerance in snap beans at 0.90 ppm. Although the tolerance/MRLlevel is harmonized, HED cannot harmonize with PMRA on the commodity definition, as the submitted snap bean data do not support use on all succulent beans, since no data were submitted for a succulentM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 10 of 38 shelled bean, and do not meet the requirements of subgroup 6A, since no data were submitted for an edible - podded pea. Both the current tolerance in group 8 (1.0 ppm) and the proposed tolerance in group 8 - 10 (1.0 ppm) are harmonized with the Codex (bell and non - bell peppers) and PMRA (tomatoes, okras and peppers) MRL s. The proposed tolerance of 2.0 ppm in subgroup 13 - 07F, translated from grape data, would be harmonized with the Codex MRL in grapes, but would no longer be harmoni zed with PMRA’s MRLof 1.4 mg/kg in grapes. The proposed tolerance of 0.1 ppm in subgroup 3 - 07A, translated from dry bulb onion data, would be harmonized with the Codex MRLin bulb onions, but would no longer be harmonized with PMRA’s MRLof 0.05 ppm in v arious bulb onions. The proposed tolerance of 7.0 ppm in subgroup 3 - 07B, translated from green onion data, would be harmonized with the Codex MRL in spring onions, but would no longer be harmonized with PMRA’s MRLof 4 ppm in various green onions. **2.3 Label Recommendations**  Because the submitted snap bean data do not support the proposed use on all succulent beans, the label section containing directions for the requested use on succulent beans ( “ Bean, succulent”) should instead refer only to snap beans (“Bean, sn ap ”) , and the listing of all other succulent bean commodities should be deleted from the proposed label . The requested use on greenhouse tomatoes listed in the proposed label is supported by the submitted greenhouse trial data . **2.4 Submittal**  **of Analytical Reference Standards (**  **860.1650 )**  The anal ytical standard for mandipropamid , with an expiration date of 30 July 201 6 , is currently available in the EPA’s National Pesticide Standards Repository (NPSR) , per Email communication from Theresa Cole of the Biological and Economic Analy sis Division’s (BEAD’s) Analy

tical Chemistry

Branch (ACB ) o n 25 June 201 3 . The registrant is required to maintain reasonable amount s of the anal ytical reference standard for mandipropamid . The mandipropamid metabolite , SYN 500003 , is not in stock. However, as this metabolite is not included in the tolerance expression , it is not required to be stocked in the NPSR. When necessary , a n ew reference standard , or updated certificate of anal ys is (COA) , should be sent to th e ACB, which is located at Fort Meade, MD. It should be sent to the attention of either Theresa Cole or Thuy Nguyen at the address listed below, along with a letter of transmittal. **Please note that the full 9 -**  **digit Z IP**  **Code is required**  **, or the mail will be returned to the**  **registrant. USEPA** 

**National Pesticide Standards Repository Analytical Chemistry Branch/BEAD/OPP**  **701 Mapes Road Fort George G. Meade, MD**  **20755 -**  **5350**M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 11 of 38 The letter of transmittal should include the assay of the standard, name of the anal ytical method used, a statement of principal impurities, purification procedures employed, storage requirements, and special precautions for safe handling. Replacement of standards may be required periodicall y if supplies are exhausted, if the standards expire, or if decomposition occurs during storage. Material Safety Data Sheets (MSDSs) must accompany all anal ytical standards as specified b y the Occupational Safety and Health Administration (OSHA) in 29CFR§1910.1200. **3. 0**  **Chemical Identity** Mandipropamid is a mandelamide and belongs to the chemical family of the carbox yl ic acid amides (CAA) or , more specificall y, the mandelic acid amides. It was developed by S yn genta for the control of foliar oomycete pathogens in a range of crops including Plasmopara viticola in grapes, Phytophthora infestans in potatoes and tomatoes, and Pseudoperonospora cubensis in cucurbits. Mandipropamid is also used on leafy vegetables to control downy mildew ( Bremia lactucae) and blue mold ( Peronospora effuse). The biochemical mode of action of mandipropamid is not fully known. However, preliminary results indicate that it inhibits the biosy nthesis of phospholipids (phosphatidyl choline, lecithin). Based on a review of its chemistry , resistance profile , and toxicol ogical attributes, mandipropamid is mechanisticall y unique , and its mode of action is different from other fungicides , including those within the CAA group. The chemical structure and nomenclature of mandipropamid are listed in Table 3 .1, and its physicoc hemical properties are presented in Table 3 .2 (below). **3.1 Nomenclature**  **TABLE 3.1 Mandipropamid Nomenclature.**  Com pound

Common name Mandipropamid Com pany experimental name NOA 446510 Molecular formula C 23 H 22 ClNO 4 Molecular weight 411.88 IUPAC name (RS ) - 2 - (4 - chloro -phenyl) -N

- [2 - (3 - methoxy - 4 -prop - 2 - ynyloxy -phenyl) - ethyl] - 2 - prop - 2 - ynyloxy - acetamide CAS name 4 - chloro -N - [2 - [3 - methoxy - 4 - (2 -propynyloxy)phenyl]ethyl] - α - (2 -propynyloxy) - benzeneacetamide Cl O C H

O N

H O C H 3 O C HM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 12 of 38 **TABLE 3.1 Mandipropamid Nomenclature.**  CAS registry number 374726 - 62 - 2 End - use product (EP) Revus 2.08SC Fungicide (2.08 lb ai/gal; EPA Reg istration # 100 - 1254) **3.2 Physic**  **oc hemical Characteristics**  **TABLE 3**  **.2 Physicochemical Properties of**  **Mandipropam id**  **.**

**Param eter**  **Value Reference**  Melting point/range (oC) 96.4 - 97.3 MRID # 46800006 (100 - REIR.doc ; S. Mathur; 22 M ay 2 007) pH ( at 25oC in a 1% aqueous dispersion) 6 - 8 Density (g/cm 3 at 22oC ) 1.24 Water solubility (mg/L at 25 oC) 4.2 Solvent solubility (g/L at 2 5 oC ) n - hexane 0.0 42 n - octanol 4.8 toluene 29 methanol 66 ethyl acetate 120 acetone 300 dichloromethane 400 Vapor pressure (Pa [ mm Hg ] at 25oC) <9.4 x 10 - 7 [ <7.1 x 10 - 9 ] Dissociation constant, pKa No dissociation in the pH range of 1 to 12 Octanol/water partition coefficient ( Lo g [ KOW ] at 25oC ) 3.3 UV/visible absorption spectrum Molar absorption coefficients for the absorbance maximums were: Neutral solution 20,144 L/mol cm at 223 nm 2,724 L/mol cm at 276 nm Acidic solution 20,313 L/mol cm at 223 nm 2,845 L/mol cm at 276 nm Basic solution 19,414 L/mol cm at 223 nm 2,864 L/mol cm at 276 nm Mandipropamid is a solid under ambient conditions , and has very low volatility . The compound has a relatively low solubility in water, and moderate to high solubility in organic solvents . Its octanol/water p artition coefficient suggests that accumulation of mandipropamid in fatty tissues is possible . **3.3 Pesticide Use Pattern/Directions for Use (860.1200)**  IR - 4 has requested that new Section 3 uses of the fungicide mandipropamid be added to the label for Revus 2.08SC ( EPA Reg istration # 100 - 1254 ). The proposed new uses would be for the treatment of basil, ginseng, succulent beans, and greenhouse tomatoes . Revus 2.08SC is a suspension concentrate (SC) formulation containing 2 3.3 % ai by weight, which is equivalent toM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 13 of 38 2 .08 lb ai/gal . An example of the proposed label for Revus 2.08SC w as provided, and the proposed use directions therein are summarized in Table 3.3 , below . **TABLE 3.3**  **Summary of Proposed**  **Directions for Use of Mandipropamid**  **. Application**  **Type; Equipment**  **1 Use** 

**Rate (lb ai/A)**  **Max. Uses**

**P er Season**  **Max. Seasonal** 

**Use Rate (lb ai/A)**  **PHI 2** 

**(Days) Use Directions**  **, Application Timing,** 

**and Limitations 3**  **Basil** Foliar; any ground or a erial equipment . 0.09 -

0.13 4 0.52 1 RTI **4** of 7 - 10 days. **Ginseng** Foliar; any ground or aerial equipment. 0.09 -

0.13 4 0.52 2 RTI of 7 - 10 days.

**S ucculent**  **B eans**  Foliar; any ground or aerial equipment. 0.09 -

0.13 4 0.52 1 RTI of 7 - 10 days.

**G reenhouse**  **T om**  **atoes** Foliar; any ground or aerial equipment. 0.09 -

0.13 4 0.52 1 RTI of 7 - 10 days. May be applied via chemigation . 1 . For ground application, apply in a minimum of 10 gallons of water per acre (GPA), unless specified otherwise on the label. Do not apply through any ultra - low volume (ULV) spray system. For a erial application, u se only on crops w

here aerial applications are indicated. Apply in a minimum of 5 GPA, unless specified otherwise on this label. Do not apply through any ULV spray system. For c hemigation, u se only on crops where chemig ation is specified on the label. Apply no more than 2 sequential applications unless otherwise stated in the crop - specific section. Do not use in transplant production. 2. PHI = Pre - Harvest Interval. 3. Begin applications prior to disease development. Use the shorter interval and/or higher rates under high pressure, or when conditions are conducive to disease. The addition of a spreading/penetrating type adjuvant such as a non - ionic based surfactant (NIS) or crop oil concentrate (COC) or blend is rec ommended. 4. RTI = Re - Treatment Interval. Conclusions: The proposed u se directions for application to basil, ginseng, succulent beans, and greenhouse tomatoes are sufficient to allow for evaluation of the submitted residue data relative to the proposed use pattern s . However, as the submitted snap bean data do not support the proposed use o n succulent beans , the label section containing directions for use on succulent beans (“ Bean, succulent”) should instead refer to snap beans (“Bean, snap”), and the listing of all other succulent bean commodities in that section should be deleted . **4.0 Metabolite/Degradate Residue Profile**  **4.1 Nature of the Residue**  **D328534, D337543; D. McNeilly; 28 August 2007** The nature of the residue in plants, rotational crops, and ruminants is adequately understood. For the purposes of tolerance enforcement and risk assessment, the terminal residue of concern (ROC) in primary crops, rotational crops, and ruminants is the parent mandipropamid , with theM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 14 of 38 exception of root and tuber vegetables , where the metabolite SYN 500003 is included for risk assessment. **4.1.1 Summary of Plant**  **and /** **or Livestock**  **Metabolism (860.1300)** Data have been submitted and reviewed depicting the metabolism/degradation of mandipropamid in numerous crops and the environment. HED has determined the plant and livestock ROCs for purposes of tolerance enforcement and risk assessment ; see Table 4.1.1 , below . **Table 4.1.1 Summary of**  **Mandipropamid Metabolites and Degradates to be included in**  **the Risk**

**Assessment and Tolerance Expression. Matrix**  **Residues Included in Risk Assessment**  **Residues Included in Tolerance Expression**  Plants Primary crops (except root and tuber

vegetables) Mandipropamid Mandipropamid Root and tuber vegetables Mandipropamid and SYN 500003 Mandipropamid Rotational crops Not applicable Mandipropamid * Livestock Ruminants Not applicable Not applicable

Poultry Not applicable Not applicable Drinking water Mandipropamid , SYN 504851 and SYN 500003 Not applicable *Although the parent compound is a ROC in rotational crops, tolerances are not needed for the present uses, based on the absence of residues in the field rotational crop study following the 30 day plant -back interval (PBI) stipulated on the label . Conclusions : The nature of the residue in plants and animals has been adequately delineated. **4.1. 2**  **Summary of Confined Rotational Crops (860.l850) D328534, D337543; D. McNeilly; 28 August 2007**  An acceptable confined rotational crop study was reviewed in P etition s # 6F7057 and # 7F7184. In this study, the extent and nature of the residue uptake b y crops planted 29, 58, 120, and/or 365 day s post - application in soil treated with [chlorophenyl 14 C] - mandipropamid or [methoxy phenyl 14 C] - mandipropamid at 0.806 - 0.8 32 lb ai/A was determined. Total radioactive residues accumulated at ≥0.01 ppm in all rotated crop matrices except radish roots and tops planted at the 120 - day PBI, and lettuce, wheat forage , and wheat grain (chlorophenyllabel only) planted at the 365 - day PBI. The distribution and nature of the residue in the rotated crops was similar between the two radio labels. The parent mandipropamid was identified at low levels. Unchanged parent was detected at a level greater than 0.01 ppm onl y in wheat straw (≤0 .023 ppm) , but was less than 0.01 ppm in lettuce, radish root, radish top, wheat forage, and wheat grain. Two other residue components, CGA 380778 and NOA 458422, were also detected at low levels. Metabolite CGA 380778 was identified at ≤0.006 ppm in lettuce, radish roots and tops, wheat forage, and wheat straw. Metabolite NOA 458422 was identified onl y in wheat straw at 0.008 - 0.016 ppm.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 15 of 38 The study results show ed that mandipropamid is extensively metabolized in rotational crops via pathway s similar to that in primary crops. The principal metabo lic routes include the removal of either or both of the propargyl side chains to generate the corresponding alcohol or phenol functionalities. Extensive metabolism may occur , yi elding small carbon units , followe d by incorporation into natural plant constituents ( such as cellulose, glucose, proteins, pectins and lignin) or , alternativel y , some radioactive components may become covalently

bound to macromolecules in the plant. **4.1. 3**  **Summary of Rat Metabolism Risk Assessment Document**  **D 365918**  **; D**  **. Rate**  **; 8**  **June 2009 (PP#**  **8F7342 )**  In rat metabolism studies, [ 14 C] - mandipropamid, as single oral or repeated oral methoxy or methoxy /chloro radiolabels, was administered to Wistar- derived rats. To examine biliary excretion, bile duct cannulation was performed. After 48 hours, absorption was 67 - 74% at 3 mg/kg, and 30 - 45% at 300 mg/kg. Blood T max at 3 mg/kg was 8.5 hours for males, and 4.5 hours for females; at 300 mg/kg it was 24 hours for males, and 10 hours for females. The rate of resorption was greater in females; the extent and rate of absorption was greater in the low dose animals. Recoveries at 168 hours were 88 - 99%, with most being eliminated by 48 hours. Excluding the females dosed at 3 mg/kg , most of the radioactivity was excreted in the feces; in the 3 - mg/kg females, feces and urine were similar. Elimination after 48 hours in bile was high at 3 mg/kg (55 - 73%), but was 22 - 28% at 300 mg/kg. Liver had the highest concentration at all measurements. More radioactivity was found in plasma than in whole blood. I dentified compounds were 66 - 94% of the administered dose in each group (168 hours). The parent and the following metabolites were ≥ 5% at 3 and/or 300 mg/kg: NOA 458422, NOA 458422 glucuronide, SYN 534133 and CGA 380778. Differences in metabolic profile were due to sex, dose and radiolabel position. Each unknown compound was less than 5%. Major metabolic transformations involved loss of one or both propargyl groups, followed by glucuronidation and O - demethyl ation. **4.1. 4**  **Summary of Environmental Degradation EFED**  **Mem o;**  **D382369 ;**  **C .**  **Wendel ;**  **26 July 2011**  The major route of dissipation is degradation under aerobic aquatic conditions. Mandipropamid appears to be stable to hydrolysis in the environmental pH range of 5 - 9, but is susceptible to photoly sis in soil and water. The environmental photoly sis half - l ives of mandipropamid at pH 7 in aqueous solutions were estimated at 0.63 - 1.1 day s. The soil photoly sis half - life of mandipropamid was estimated at 16.4 - 23.9 day s. Based on its vapor pressure and Henry ’s Law constant, volatilization from water and soil a re not expected to be important environmental fate processes. The linear biodegradation half - life of mandipropamid in six European soils , and one US soil, ranged from approximately 26 to 103 day s under aerobic conditions. Under anaerobic conditions , th e rate of biodegradation appears to be much slower. Mandipropamid degradedM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 16 of 38 with a linear half

- life of 151 days in a silt loam soil from Switzerland maintained under anaerobic conditions. The aerobic aquatic degradation half - lives of mandipropamid were 17 .8 - 18.5 day s in two river water/silt loam sediment systems from England and Germany . Acceptable anaerobic aquatic degradation data have not been submitted. Terrestrial field dissipation studies on mandipropamid were conducted in California (sandy loam soil), New York (loamy

sandy soil), and Georgia (sandy loam soil). The field dissipation halflives of mandipropamid were 75.3 days (California site) , l00.5 day s (New York), and 81.5 day s (Georgia). These studies confirm the persistence of mandipropamid in the environment. Mandipropamid is moderately mobile , and some of its metabolites are mobile to highl y mobile in soils, and therefore have the potential to leach into ground water. Mandipropamid can reach surface waters via spray

drift and rainfall events that cause runoff. **5.0 Residue Profile**  **5.1 Residue Analytical Methods (860.1340)**  **5.1.1 Data Collection Methods**  **MRID s**  **# 4899**  **20 01**  **to -**  **04** Basil : Residues of mandipropamid in treated and control samples of basil were determined using a working method derived from reference method RAM 415/01, titled NOA446510: Validation of Residue Analytical Method RAM 415/01 for the Determination of Residue in Crops . Method RAM 415/01 was previously reviewed , and deemed acceptab le for both data collection and tolerance enforcement. The modifications included a change in the volume of the subsample from 10 mLto 5 mL, which was diluted to 10 mLwith acetonitrile (ACN)/water (1:4 , v/v). F urther dilutions were made with ACN/water (1:1, v/v), and the SPE cleanup step was replaced with an on - line cleanup step. Briefl y, samples were extracted b y homogenization with ACN/water. Extracts were centrifuged, and aliquots were diluted with ACN/water. Residues of mandipropamid were determined via LC/MS/MS coupled with on - line cleanup. The reported limit of detection ( LOD ) and limit of LOQ were 0.0013 ppm and 0.0038 ppm, respectivel y, for fresh basil, and 0.0028 ppm and 0.0085 ppm, respectivel y, for dried basil . The lowest level o f method validation ( LLM V) was 0.01 ppm for fresh and dried basil. Given that the LLMV was 0.01 ppm for mandipropamid, the LOQ of the method will be set at 0.01 ppm for mandipropamid in fresh and dried basil. The analy tical method was validated prior to sample anal ys is. The method validation recoveries at spiking levels of 0.01 ppm (LOQ), 0.10 ppm ( 10X LOQ), 1.0 ppm ( 100X LOQ) and 20 ppm ( 2000X LO Q) mandipropamid ranged from 92 - 102%, 91 - 98%, 96 - 100% and 100 - 105%, respectivel y from fresh basil . The metho d validationM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 17 of 38 recoveries at spiking levels of 0.01 ppm (L OQ) and 0.10 ppm ( 10X LOQ), 1.0 ppm ( 100X LOQ) and 100 ppm ( 10000X LOQ) mandipropamid ranged from 83 - 104%, 93 - 106%, 95 - 100% and 98 - 100%, respectively from dried basil. The method suitability was also verified concurrentl y with sample anal ys is. Concurrent recoveries ranged from 93 - 103% and 95 - 116% from fresh basil spiked with 1.0 ppm ( 100X LOQ) and 10 ppm ( 1000X LOQ) mandipropamid, respectivel y, and ranged from 88 - 112% and 97 - 103% from dried basil spi ked with 1.0 ppm ( 100X LOQ) and 10 ppm ( 1000X LOQ) mandipropamid, respectivel y. All recoveries were within the generally recognized acceptable range of 70 to 120%. Therefore, the working method is adequate for the determination of residues of mandipropamid in fresh and dried basil samples (see Table s 5.1.1.1 and 5.1.1.2 ) . **TABLE 5.1.1.1 Summary of Method Validation Recoveries of Mandipropamid from** **Basil Matrix**  **Spike L**  **evel (ppm) Sample**  **S ize (n)**  **Recoveries (%) Me**  **an ± Std. Dev. (%)** Fresh basil 0.01 6 94, 94, 95, 92, 92, 102 95 ± 4

0.10 3 91, 98, 96 95 ± 4 1.0 3 96, 96, 100 97 ± 2 20 3 105, 100, 100 102 ± 3 Dried basil 0.01 6 98, 104, 98, 83, 85, 88 93 ± 8

0.10 3 93, 106, 103 101 ± 7 1.0 3 97, 95, 100 97 ± 3 100 3 100, 100, 98 99 ± 1 **TABLE 5.1.1.2**  **Summary of Concurrent Recoveries of Mandipropamid from Basil**  **Matrix Spike**  **L evel (ppm)**  **Sample S**  **ize (n) Recoveries (%)**  **Me an ± Std**  **. Dev**  **. (%)**  Fresh basil 1.0 4 103, 97, 94, 93 97 ± 5

10 3 116, 95, 108 106 ± 11 Dried basil 1.0 4 105, 112, 95, 88 100 ± 11

10 2 97, 103 100 Ginseng : Residues of mandipropamid and metabolite SYN500003 in treated and control samples of ginseng were determined using a working method derived from method RAM 415/01 , titled NOA446510: Validation of Residue Analytical Method RAM 415/01 for the Determination of Residue in Crops , and GRM001.01A , titled Mandipropamid (NOA446510): Method for the Determination of Residues of SYN500003 in Potato Tubers and Process Potato Commodities. Final Determination by LC
- MS/MS. Method RAM 415/01 was previousl y reviewed, and deemed acceptable as a data gathering and enforcement method. Method GRM001.01A was not previously reviewed , but is similar to method GRM001.01B , which was previously deemed adequate for data gathering purposes. The modifications include a change in the volume of the subsample from 10 mLto 5 mL , which was diluted to 10 mLwith ACN/water ( 1:4 , v/v) . F urther dilutions were made with ACN/water (1:1, v/v) , and the SPE cleanup step was replaced with an on - line cleanup s tep for the anal ys is of parent only . Briefl y, residues of mandipropamid and metabolite SYN500003 were extracted with ACN/water in a tissumizer. Extracts were anal yz ed for mandipropamid residues b y LC - MS/MS coupledM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 18 of 38 with online cleanup. For the anal ys is of residues of metabolite SYN500003, an aliquot was cleaned up b y SPE prior to analysis b y LC /MS/MS in combination with online cleanup. The reported LOD and LOQ were 0.0072 ppm and 0.022 ppm, respectively , for mandipropamid, and 0.0019 ppm and 0.0056 ppm, respectivel y, for metabolite SYN500003 . The LLMV was 0.01 ppm for mandipropamid , and 0.005 ppm for metabolite SYN500003. Given that the LLMV was 0.01 ppm for mandipropamid , and 0.005 ppm for metabolite SYN500003, the LOQ of the method will be set at 0.01 ppm for mandipropamid , and 0.005 ppm for metabolite SYN500003. The anal ytical method was validated prior to sample anal ys is. The method validation recoveries at spiking levels of 0.01 ppm (L OQ), 0.10 ppm ( 10X LOQ) and 1.0 ppm ( 100X LOQ) mandipropamid ranged from 72 - 113%, 89 - 98% and 95 - 99%, respectivel y . The method validation recoveries at spiking levels of 0.005 ppm (LOQ) and 0.10 ppm (20 X LOQ) metabolite SYN500003 ranged from 84 - 116% and 85 - 97%, respectivel y. The method suitabili ty was also verified concurrently

with sample anal ys is. Concurrent recoveries ranged from 103 - 108% from ginseng roots spiked with 0.10 ppm mandipropamid , and ranged from 102 - 127% from ginseng roots spiked with 0.10 ppm of metabolite SYN500003. All recoveries were within the generall y recognized acceptable range of 70 to 120% , with the exception of two concurrent recoveries of 121% and 127% from gi nseng roots spiked with 0.10 ppm of metabolite SYN500003. Therefore, the working method is adequate for the determination of residues of mandipropamid and metabolite SYN500003 in ginseng roots (see Table s 5.1.1. 3 and 5.1.1.4 ) . **TABLE 5.1.1.3 Summary of Method Validation Recoveries of Mandipropamid from** **Ginseng. Matrix**  **Spike Level (ppm)**  **Sample Size (n)**  **Recoveries (%)**  **Me an ± Std. Dev.**  **(%) Mandipropamid**  Ginseng roots 0.01 6 73, 74, 72, 113, 112, 112 93 ± 22

0.10 3 98, 96, 89 94 ± 5 1.0 3 99, 97, 95 97 ± 2

**Me tabolite SYN500003**  Ginseng roots 0.005 6 107, 116, 99, 108, 99, 84 102 ± 11

0.10 3 97, 85, 90 91 ± 6 **TABLE 5.1.1.4 Summary of Concurrent Recoveries of Mandipropamid from** **Ginseng. Matrix**  **Spike L**  **evel (ppm)**  **Sample S**  **ize (n)**  **Recoveries (%)**  **Me an ± S**  **td .**  **D ev**  **. (%)**  **Mandipropamid** Ginseng roots 0.10 4 104, 103, 105, 108 105 ± 2 **Me tabolite SYN500003**  Ginseng roots 0.10 4 116, 127, 102, 121 117 ± 11 S nap beans : Residues of mandipropamid in treated and control samples of snap bean s were determined using a working method based on method RAM 415 /01 , titled NOA446510: Validation of Residue Analytical Method RAM 415/01 for the Determination of Residue in Crops . The modifications included a change in the volume of the subsample from 10 mLto 5 mL , which was diluted to 10 mLwith ACN/water ( 1:4 , v/v) . F urther dilutions were made with ACN/water (1:1, v/v) , and the SPE cleanup step was replaced with an on - line cleanup step . ThisM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 19 of 38 method was previousl y reviewed , and deemed acceptable for data gathering and enforcement purposes. Briefl y, samples are extracted b y homogenization with ACN/water. Extracts are centrifuged and aliquots are diluted with ACN/water. Residues of mandipropamid are determined by high performance liquid chromatography with tandem quadrupole mass spectrometric detection (L C/MS/MS) coupled with on - line cleanup. The reported LOD and LO Q were 0.00165 ppm and 0.00495 ppm, respectively , for pods with seeds, and 0.00122 ppm and 0.00365 ppm, respectively , for plants with pods . The LLMV was 0.01 ppm for pods with seeds and plants with pods. Given that the LLMV was 0.01 ppm for mandipropamid in pods with seeds and plants with pods, the L OQ of the method will be set at 0.01 ppm. The anal ytical method was validated prior to sample anal ys is. The method validation mean recoveries at spiking levels of 0.01 ppm (LOQ), 0.10 ppm ( 10X LOQ) and 1.0 ppm ( 100X LOQ) mandipropamid were 102 ± 5% (n = 6), 102 ± 4% (n = 3) and 101 ± 3% (n = 3), respectivel y, from pods with seeds . The method validation mean recoveries at spiking levels of 0.01 ppm (L OQ), 0.10 ppm ( 10X LOQ), 1.0 ppm ( 100X LOQ) and 20 ppm ( 200 0X LOQ) mandipropamid were 102 ± 4% (n = 4), 99 ± 3% (n = 3), 94 ± 1% (n = 3) and 101 ± 4% (n = 3), respectivel y, from plants with pods. The method suitability was also verified concurrently with sample anal ys is. Concurrent mean recoveries were 94 ± 9% (n = 10) from pods with seeds spiked at 0.10 ppm, and were 99% (n = 2) and 104 ± 12% (n = 8) from plants with pods spiked at 0.10 ppm and 1 .0 ppm, respectivel y. All method validation and concurrent recoveries were within the generall y recognized acceptable range (70 to 120%) with the exception of one concurrent recovery

of 124% from plants with pods at a spiking level of 1.0 ppm. As such, m ethod RAM 415/01 is adequate for the determination of residues of mandipropamid in snap beans (see Table s 5.1.1. 5 and 5.1.1.6 ) . **TABLE 5.1.1.5 Summary of Method Validation Recoveries of Mandipropamid from** **Snap Beans. Matrix**  **Spike L**  **evel (ppm)**  **Sample S**  **ize (n)**  **Recoveries (%)**  **Me an ±**  **S td**  **. D ev**  **. (%)**  Pods with seed 0.01 6 99, 104, 110, 98, 98, 100 102 ± 5 0.10 3 106, 102, 99 102 ± 4 1.0 3 99, 105, 100 101 ± 3 Plants with pods 0.01 6 103, 103, 107, 100, 99, 97 102 ± 4 0.10 3 97, 102, 99 99 ± 3 1.0 3 95, 95, 93 94 ± 1 20 3 105, 101, 98 101 ± 4 **TABLE 5.1.1.6 Summary of Concurrent Recoveries of Mandipropamid from** **Snap Beans. Matrix**  **Spike L**  **evel**

**(ppm) Sample** 

**S ize**  **(n) Recoveries**  **(%) Me**  **an ± S td**  **. D**  **ev .**  **(%)** Pods with seed 0.10 10 102, 94, 79, 101, 84, 85, 100, 107, 93, 91 94 ± 9 Plants with pods 0.10 2 103, 95 99 1.0 8 104, 124, 98, 101, 111, 102, 83, 107 104 ± 12M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 20 of 38 Greenhouse tomatoes : Residues of mandipropamid in treated and control samples of tomatoes were determined using a working method derived from reference method RAM 415/01, titled NOA446510: Validation of Residue Analytical Method RAM 415/01 for the Determination of Residue in C

rops . Method RAM 415/01 was previously reviewed, and deemed acceptable for both data collection and tolerance enforcement. The modifications included a change in the volume of the subsample from 10 mLto 5 mL, which was diluted to 10 mLwith acetonitrile (ACN)/water (1:4, v/v). Further dilutions were made with ACN/water (1:1, v/v), and the SPE cleanup step was replaced with an on - line cleanup step. Briefl y, samples were extracted b y homogenization with ACN/water. Extracts were centrifuged, and aliquo ts were diluted with ACN/water. Residues of mandipropamid were determined via LC/MS/MS coupled with on - line cleanup. The reported LOD and limit of L OQ were 0.019 ppm and 0.056 ppm, respectively , for tomatoes . The LLMV was 0.01 ppm for tomatoes. Given that the LLMV was 0.01 ppm for mandipropamid, the LOQ of the method will be set at 0.01 ppm for mandipropamid in tomatoes. The anal ytical method was validated prior to sample anal ys is. The method validation recoveries at spiking levels of 0.01 ppm (L OQ) , 0.10 ppm (10X LOQ) and 1.0 ppm (100X LOQ) mandipropamid ranged from 9 4 - 10 7 %, 8 9 - 9 4 %, and 86 - 9 1%, respectivel y , from tomatoes . The method suitability

was also verified concurrently with sample anal ys is. Concurrent recoveries ranged from 87 - 10 1 % from tom atoes spiked with 0. 1 0 ppm (10 X LOQ) mandipropamid. All recoveries were within the generally recognized acceptable range of 70 to 120%. Therefore, the working method is adequate for the determination of residues of mandipropamid in tomatoes (see Table s 5 .1.1. 7 and 5.1.1.8 ) . **TABLE 5.1.1.7 Summary of Method Validation Recoveries of Mandipropamid from** **Tomat oes.**  **Matrix Spike L**  **evel (ppm) Sample**  **S ize (n)**  **Recoveries (%) Me**  **an ± Std. Dev. (%)** Tomato fruit 0.01 6 102, 96, 94, 106, 104, 107 101 ± 6

0.10 3 89, 89, 94 9 0 ± 3 1.0 3 88, 91, 86 88 ± 3 **TABL E 5.1.1.8**  **Summary of Concurrent Recoveries of Mandipropamid from Tomatoes.**  **Matrix Spike**  **L evel (ppm)**  **Sample S**  **ize (n) Recoveries (%)**  **Me an ± Std**  **. Dev**  **. (%)**  Tomato fruit 0.10 5 101, 87, 94, 87 9 2 ± 7 Conclusions: Adequate method validation data have been submitted o n the LC /MS/MS method used for the determination of mandipropamid residues in the various commodities . No additional data are required in support of this data collection method.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 21 of 38 **5.1.2 M**  **ulti -**  **Residue Methods (860.1360) D328534, D337543; D. McNeilly; 28 August 2007**  Multiresidue method testing data for mandipropamid were submitted. The study was performed according to the FDA Multi - Residue Method Test guidelines in PAM Vol. I. Mandipropamid was tested onl y through Protocol C (Section 302). It was not tested under Protocols A, B, D, E, F or G. The petitioner simply stated these protocols were not applicable without further explanation. Mandipropamid was tested according to Protocol C using GL C sy stems DG5, DG13, DG17 and DG 18. No significant responses were obtained with GL C systems DG5 and DG17, and low or multiple peak responses were achieved with GL C sy stems DG13 and DG18. Further testing with mandipropamid was therefor e terminated. Conclusions: Mandipropamid was tested under Protocol C which appears to be the only appropriate protocol to evaluate given the results achieved using that protocol. The FDA Multiresidue methods do not appear to be adequate for determining residues of mandipropamid. These data w er e forwarded to the US FDA for further evaluation. **5.1.3 Tolerance Enforcement Methods**  **D328534, D337543; D. McNeilly; 28 August 2007 D**  **348229, D352322 ,**  **D. Rate; 11 Decem** **ber 2008** There is an adequate enforcement method for determination of mandipropamid in plant commodities. L C/MS/MS m ethod RAM 415/01, which was previously submitted under P etition s # 6F7057 and # 7F7184, has a validated method L OQ of 0.01 ppm. Method 415/01 has been adequatel y validated by an independent laboratory and was forwarded to ACB/BEAD for a petition method validation. The ACB concluded (D336257 ; C. Stafford ; 15 August 2007) , without conducting a laboratory trial, that the method appears to meet O CS PP Residue Chemistry

Test Guideline 860.1340 for an acceptable tolerance enforcement method, with the exception o f the general requirement for a confirmatory method since onl y one MS/MS ion transition was documented. The ACB recommended that the petitioner provide an alternate chromatographic column and/or mobile - phase combination to add an additional degree of specificity , and further reduce the possibility of false positive residues. An acceptable confirmatory

method is available. **5.2 Storage Stability (860.1380)**  **MRIDs #48992001 to -**  **0 4**  Basil: Sample storage conditions and durations are reported in Table 5.2.1 , below . Treated fresh and dried basil samples were stored frozen ( < - 20oC/< - 4oF) for up to 723 day s and 671 day s, respectivel y, from harvest to extraction. All samples were analyzed within 9 days of extraction. The freezer storage stability of residues of mandipropamid fresh and dried basil samples fromM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 22 of 38 this study was demonstrated concurrentl y with the sample anal ys is (see Table 5.2.2.). Untreated fresh and dried basil were sp iked with 1.0 ppm of mandipropamid. The corrected mean recovery of mandipropamid from fresh and dried basil samples stored frozen for 700 day s was 87 ± 8% and 115 ± 0%, respectively . The concurrent recoveries of mandipropamid from freshl y fortified sampl e s of fresh and dried basil spiked at 1.0 ppm w ere 105% and 85%, respectivel y. The demonstrated storage stability interval of mandipropamid in dried basil covers the actual storage duration, and is only slightly shorter than the actual storage duration for fresh basil. As such, there are no concerns with the stability of mandipropamid residues in fresh and dried basil samples from this study . **TABLE 5.2.1 Summary of Storage Conditions.**  **Matrix Storage Tem** **perature (°C/** **° F)**  **Actual Storage**

**Duration ( D**  **ays)*** **Interval of Dem onstrated**  **Storage Stability ( D**  **ays)** Fresh basil < - 20/< - 4 723 700 Dried basil < - 20/< - 4 671 700 * Storage duration between harvest and extraction. Samples were analyzed within 9 days of extraction. **TABLE 5.2.2 Stability of Residues**  **of Mandipropamid Following Frozen Storage. Matrix**  **Storage**

**Temperature (°C/** **° F)**  **Spiking**

**Level (ppm)**  **Storage**

**Interval (D**  **ays) Concurrent** 

**R ecovery**  **(%) Recoveries** 

**(%) Me**  **an**

**Recovery ± S**  **td . D**  **ev .**  **(%) Corrected**  *****

**Me an Recovery**  **± S**  **td .**  **D ev**  **. (%)**  Fresh basil < - 20/< - 4 1.0 700 105 82, 95, 98 92 ± 9 87 ± 8 Dried basil < - 20/< - 4 1.0 700 85 98, 98, 98 98 ± 0 115 ± 0 * Corrected for concurrent recovery. Mean of recoveries from three stored samples, divided by the recovery from the freshly fortified sample, multiplied by 100%. Ginseng: Treated ginseng root samples were stored frozen ( < - 20oC/< - 4oF) for up to 939 days from harvest to extraction (see Table 5 .2. 3 ). All samples were anal yz ed within 11 day s of extraction. The freezer storage stability of residues of mandipropamid and metabolite SYN500003 in ginseng root samples from this study was demonstrated concurrentl y with the sample anal ys is (see Table 5 .2. 4 ). Untreated ginseng root samples were spiked with 0.10 ppm of mandipropamid and metabolite SYN500003. The corrected mean recoveries of mandipropamid and metabolite SYN500003 from ginsen g root samples stored frozen for 922 days w ere 107 ± 12% and 119 ± 10%, respec tivel y. The concurrent recoveries of mandipropamid and metabolite SYN500003 from a freshly fortified sample spiked at 0.10 ppm w ere 99% and 84%, respectivel y. The demonstrated storage stability interval of mandipropamid in ginseng is similar to the actual storage duration. Therefore, there are no concerns with the stability of mandipropamid residues in ginseng root sample s from this study . **TABLE 5.2.3 Summary of Storage Cond**  **itions. Matrix**  **Storage Tem perature**  **(°C/° F)**  **Actual Storage Duration (Days)** * **Interval of Dem onstrated** 

**Storage Stability (Days)** Ginseng roots < - 20/< - 4 939 922 * Storage duration between harvest and extraction. Samples were analyzed within 11 days of extraction.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 23 of 38 **TABLE 5**  **.2. 4**  **Stability of Residues of Mandipropamid and Metabolite SYN500003 in Ginseng Roots**

**Following Frozen Storage. Matrix**  **Storage Temperature**  **(°C/ °**  **F) Spiking** 

**Level (ppm)**  **Storage**

**Interval (** **D ays)**  **Concurrent**

**R ecovery**  **(%) Recoveries** 

**(%) Me**  **an**

**Recovery ± S**  **td .**  **D ev**  **. (%)**  **Corrected** *****

**Me an Recovery**  **± S**  **td . D**  **ev .**  **(%) Mandipropamid**  Ginseng roots < - 20/< - 4 0.10 922 99 96, 102, 119 106 ± 12 107 ± 12 **Me tabolite SYN500003**  Ginseng roots < - 20/< - 4 0.10 922 84 90, 105, 105 100 ± 9 119 ± 10 * Corrected for concurrent recovery. Mean of recoveries from three stored samples, divided by the recovery from the freshly fortified sample, multiplied by 100%. Snap beans : Treated snap bean samples were stored frozen (< - 20oC/< - 4oF) for up to 359 day s from harvest to extraction (see Table 5 .2. 5 ). All samples were anal yz ed within 21 day s of extraction. The freezer storage stability of residues in snap bean samples from this study was demonstrated concurrently with the sample analy sis. Untreated snap bean samples (pods with seed and plants with pods) were spiked with 0.10 ppm of mandipropamid (see Table 5 .2. 6 ). The corrected mean recoveries from pods with seed and plants with pod samples stored frozen for 357 day s w ere 86 ± 3% and 92 ± 2%, respectively . The concurrent recoveries of mandipropamid from freshl y fortified sample s spiked at 0.10 ppm w ere 107% from pods with seed, and 103% from plants with pods. The demonstrated storage stability interval of mandipropamid in snap beans is almost the same (2 day s shorter) as the actual storage duration. Therefore, there are no concerns with the stability of mandipropamid residues in snap bean s ample s from this study . **TABLE 5.2.5 Summary of Storage Conditions.**  **Matri x**  **Storage Tem perature**  **(°C/°F) Actual Storage Duration**  **( D**  **ays)*** **Interval of Dem onstrated** 

**Storage Stability ( D**  **ays)** Pods with seed < - 20/< - 4 359 357 Plants with pods * Storage duration between harvest and extraction. Samples were analyzed within 21 days of extraction. **TABLE 5**  **.2. 6**  **Stability of Mandipropamid Residues in Snap Beans Following Frozen Storage. Matrix**  **Storage**

**Temperature (°C/** **° F)**  **Spiking**

**Level (ppm)**  **Storage Interval**  **( D**  **ays) Concurrent** 

**R ecovery**  **(%) Recoveries** 

**(%) Me**  **an**

**Recovery ± S**  **td .**  **D ev**  **. (%)**  **Corrected** *****

**Me an**  **Recovery ± S**  **td .**  **D ev**  **. (%)**  Pods with seed < - 20/< - 4 0.1 357 107 91, 90, 95 92 ± 3 86 ± 3 Plants with pods 103 94, 93, 97 95 ± 2 92 ± 2 * Corrected for concurrent recovery. Mean of recoveries f rom three stored samples , divided by the recovery f rom the freshly fortified sample, multiplied by 100 % . Greenhouse tomatoes: Treated t omato fruit samples were stored frozen ( < - 20oC/< - 4oF) for up to 35 2 day s from harvest to extraction (see Table 5.2. 7 ). All samples were analy zed within 4 daysM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 24 of 38 of extraction. The freezer storage stability of residues in tomato samples from this study was demonstrated concurrently with the sample anal ys is. Untreat ed tomato samples were spiked with 0.10 3 ppm of mandipropamid (see Table 5.2. 8 ). The corrected mean recovery from tomato fruit stored frozen for 35 8 day s w as 91 ± 4 %. The concurrent recovery of mandipropamid from a freshl y fortified tomato sample spiked at 0.10 ppm w as 9 0%. The demonstrated storage stability interval of mandipropamid in tomato fruit covers the actual storage duration. Therefore, there are no concerns with the stability of mandipropamid residues in tomato fruit samples from this study . **TABLE 5.2.3 Summary of Storage Conditions.**  **Matrix Storage Tem** **perature (°C/°F)**  **Actual Storage Duration (Days)** * **Interval of Dem onstrated** 

**Storage Stability (Days)** Tomato fruit < - 20/< - 4 352 358 * Storage duration between harvest and extraction. Samples were analyzed within 4 days of extraction. **TABLE 5.2.4 Stability of Residues of Mandipropamid in**  **Tomato F**  **ruit Following Frozen Storage.**  **Matrix Storage**  **Temperature (°C/°F)**  **Spiking**

**Level (ppm)**  **Storage**

**Interval (Days)**  **Concurrent**

**Recovery (%)**  **Recoveries**

**(%) Me**  **an**

**Recovery ± Std. Dev. (%)**  **Corrected** *****

**Me an Recovery**  **± Std. Dev. (%)** Tomato fruit < - 20/< - 4 0.10 3 358 9 0 83, 85, 78 82 ± 4 9 1 ± 4 * Corrected for concurrent recovery. Mean of recoveries from three stored samples, divided by the recovery from the freshly fortified sample, multiplied by 100%. Conclusions : There are no storage stability issues associated with any of the field trial studies. Therefore, no corrections for potential decline during storage are needed in reviewing the residue studies submitted for the various commodities . **5.3 Residue Data**  **5.3.1 Crop Field Trials (860.1500)**  **MRIDs #48992001 to -**  **04** Basil: IR - 4 submitted field and greenhouse trial data for mandipropamid in basil (fresh and dried). A total of 4 field trials were conducted in Canada and the US in Zones 2 (1 trial in NC), 5A (1 trial in WI), 10 (1 trial in CA) and 11 (1 trial in BC) during the 2009 growing season, and a total of 2 greenhouse trials were conducted in the US in Zones 2 (1 trial in MD) and 3 (1 trial in FL) during the 2009 and 2010 growing seasons. Two trials ( in 2 separate greenhouses ) were required to support the proposed use expans ion to greenhouse basil ; the growing regions in which these were conducted were not specified by OCSPP Residue Chemistry Test Guideline 860.1 50 0 . At each trial site, mandipropamid formulated as Revus 2.08SC was applied as 4 foliar directed applications at a rate of 0.128 - 0.139 lb ai/A, with re - treatment intervals ( RTIs) of 6 to 8 day s, for a total seasonal rate of 0.520 - 0.528 lb ai/A. All applicati ons included a non - ionic surfactantM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 25 of 38 (NI S) in the spray

mixture. Fresh basil (stems and leaves) was harvested at a PHI of 1 day . At one trial site, fresh basil samples (stems and leaves) were harvested at PHIs of 3, 7 and 11 day s to assess residue decline . Samples of fresh basil (stems and leaves) used for drying were also collected at a PHI of 1 day, and dried for up to 3 days according to local commercial practices. The results from this study indicated that mandipropamid residues ranged from 3.5 ppm to 19 ppm in fresh basil , and ranged from 36 ppm to 91 ppm in dried basil , grown in the field and greenhouse (see Table 5.3.1.1, below) . The residue decline data indicate d that residues of mandipropamid in fresh basil decreased with increasing PHIs. **T ABLE 5.3.1.1**  **Summary of Residue Data from Basil Field**  **and Greenhouse Trials with Mandipropamid**  **. Basil**  **Comm odity**  **Total Use**

**Rate (lb ai/A)**  **PHI**

**(Days) Residue Levels**  **(ppm)**

**n Min.**  **Max. LAFT**  ***** **HAFT** ***** **Median Me**  **an Std. Dev.**  Fresh stems and leaves 0.520 -

0.528 1 12 **1** 3.5 19 - - 9.0 9.3 4.8

6 **2**

- - 3.6 19 8.8 9.4 5 .0 Dried stems and leaves 0.520 -

0.528 1 6 **1,2** 36 91 - - 63 63 20 * LAFT = Lowest Average Field Trial; HAFT = Highest Average Field Trial. 1. n = total number of samples. 2. n = total number of field trials. Ginseng : IR - 4 submitted field trial data for mandipropamid in ginseng. A total of 4 trials were conducted in Canada and the US in Zones 5A (3 trials in WI) and 11 (1 trial in BC) during the 2008 growing season. At e ach trial site, mandipropamid formulated as Revus 2.08SC was applied as 4 foliar broadcast application s at a rate of 0.129 - 0.141 lb ai/A, with RTI s of 6 to 9 day s, for a total seasonal rate of 0.521 - 0.547 lb ai/A. All applications included an NI S in the spray mixture. Ginseng roots were harvested at a PHIof 2 day s. At one trial site, additional samples of ginseng roots were harvested at PHIs of 0, 7, 15 and 21 day s to assess residue decline. The roots were dried for up to 19 days in commercial faciliti es simulating commercial practices. The results from this study indicated that mandipropamid residues ranged from 0.0222 ppm to 0.167 ppm in dried ginseng root samples (see Table 5.3.1. 2 , below) . Results also showed that there were no quantifiable resi dues (<0.005 ppm) of metabolite SYN500003 in dried roots. The residue decline data indicate d that residues of mandipropamid in dried roots remained fairl y stable between PHIs of 0 and 21 day s.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 26 of 38 **TABLE 5.3.1.2 Summary of Residue Data from**  **Ginseng Field**  **Trials with Mandipropam id**  **. Comm**  **odity Total** 

**Use Rate**  **(lb ai/A) PHI** 

**(D ays)**  **Residue Levels (ppm)** 

**n Min.**  **Max. LAFT**  ***** **HAFT** ***** **Median Me**  **an Std. Dev.** 

**Mandipropamid** Ginseng roots 0.521 -

0.547 2 8 **1** 0.0222 0.167 - - 0.0586 0.07 17 0.0 551

4 **2**

- - 0.0271 0.119 0.0705 0.0718 0.0 47 5 **Me tabolite SYN500003**  Ginseng roots 0.521 -

0.547 2 8 **1** <0.005 <0.005 - - <0.005 <0.005 -

4 **2**

- - <0.005 <0.005 <0.005 <0.005 - * LAFT = Lowest Average Field Trial; HAFT = Highest Average Field Trial. 1. n = total number of samples. 2. n = total number of field trials. Snap beans : IR - 4 submitted field trial data for mandipropamid in snap beans. A total of 10 trials were conducted in the US in Zones 1 (1 trial in NY), 2 (1 trial in MD and 1 trial in GA), 3 (1 trial in FL), 5 (1 trial in OH), 5A (1 trial in MIand 1 trial in WI), 10 (2 trials in CA) and 11 (1 trial in WA) during the 2010 growing season. At each trial site, mandipropamid formulated as Revus 2.08 SC was applied as 4 foliar (broadcast or directed) applications at a rate of 0.094 - 0.138 lb ai/A , with RTI s of 6 to 8 days, for a total seasonal rate of 0.490 - 0.540 lb ai/A . All applications included an NI S or a crop oil concentrate (COC) in the spray mixture. Snap beans (pods with seed and plants with pods) were harvested at a PHI of 1 day . At one trial site, snap beans were harvested at PHI s of 3, 7 and 10 day s to assess residue decline. The results from this study indicated that mandipropamid residues ranged from 0.0858 ppm to 0.761 ppm in pods with seed, and 1.24 ppm to 9.84 ppm in plants with pods (see Table 5.3.1. 3 , below) . Results from the residue decline study indicated that residues decreased over time. **TABLE 5.3.1.3 Summary of Residue Data from**  **Snap Bean Field Trials with Ma**  **ndipropam id**  **. Comm**  **odity Total** 

**Use Rate (lb ai/A)**  **PHI**

**(Days) Residue Levels**  **(ppm)**

**n Min.**  **Max. LAFT**  ***** **HAFT** ***** **Median Me**  **an Std. Dev.**  Pods with seed 0.490 -

0.540 1 20 **1** 0.0858 0.761 - - 0.210 0.256 0. 175

10 **2**

- - 0.10 0.58 0.220 0.256 0. 164 Plants with pods 0.490 -

0.540 1 20 **1** 1.24 9.84 - - 4.15 4.14 2 .34

10 **2**

- - 1.27 9.27 4.35 4.14 2 .36 * LAFT = Lowest Average Field Trial; HAFT = Highest Average Field Trial. 1. n = total number of samples. 2. n = total number of field trials. Greenhouse tomatoes: IR - 4 submitted greenhouse trial data for mandipropamid in tomatoes grown in greenhouses . A total of 4 greenhouse trials were conducted in the US in Zones 2 (1 trial in MD ), 4 (1 trial in AR), 5 (1 trial in WI) and 10 (1 trial in CA), during the 2010 growing season. At each trial site, mandipropamid formulated as Revus 2.08 SC was applied as 4 foliar (broadcast or directed) applications (5 at trial site 10 - AR05) at a rate of 0.120 - 0.13 6 lb ai/A , with RTI s of 6 to 8 days, for a total seasonal rate of 0.480 - 0.651 lb ai/A . The fifth application wasM andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 27 of 38 made at trial site 10 - AR05 in order to obtain commercial - size tomatoes at the proposed 1 - day PHI . All applications included an NIS in the spray mixture. The applications were made starting 2 2 day s befor e harvest , except at trial site 10 - AR05 , where the first application was made 30 day s prior to harvest. C ommercially mature tomatoes (large and small - sized varieties) were harvested at a PHI of 1 day . The results from this study indicated that mandipropamid residues ranged from 0. 04 5 ppm to 0. 339 ppm in tomato fruit (see Table 5. 3.1.4 , below) . **TABLE 5.3.1.4**  **Summary of Residue Data from Tom**  **ato Greenhouse Trials with Mandipropam** **id .**  **Comm odity**  **Total**

**Use Rate (lb ai/A)**  **PHI**

**(Days) Residue Levels (ppm)** 

**n Min.**  **Max. LAFT**  ***** **HAFT** ***** **Median Me**  **an Std. Dev.**  T omato fruit 0.480 -

0.651 1 8 **1** 0.045 0.339 - - 0.147 0.168 0.101

4 **2**

- - 0.059 0.289 0.115 0.168 0.105 * LAFT = Lowest Average Field Trial; HAFT = Highest Average Field Trial. 1. n = total number of samples. 2. n = total number of field trials. Conclusions : The submitted crop field trial data are adequate , and support the establ ishment of permanent tolerance s in basil (field and greenhouse) , ginseng and sn ap bean s , as list ed in Table 6.0 (see Section 6.0 , below) . The submitted greenhouse trial data are adequate to support the requested use on greenhouse tomatoes . Additional field trial data on a succulent shelled bean cultivar (such as lima beans) would be necessary in order to establish the proposed tolerance in all succulent beans. **5.3.2 Field Rotational Crops (860.1900)**  **D328534, D337543; D. McNeilly; 28 August 2007**  An adequate limited field rotational crop study was reviewed in P etition s # 6F7057 and # 7F7184. Mandipropamid residues were below the LOQ (<0.01 ppm) in all samples of rotated radish roots, radish tops, spinach leaves, fall wheat forage, spring wheat forage, wheat hay , wheat grain, and wheat straw planted at the 28/31 - day and 61 - day PBI s. HED has determined that the rotational crop restriction on the label which states “ [d] o not plant any crop which is not registered for use with mandipropamid for a period of 30 day s after the last application” is appropriate . Given the label restriction , tolerances in rotational crop s are not needed. **5.3.3 Processed Food and Feed (860.1520)**  Because there are no processed commodities for ginseng or succulent beans, processing studies are not required for these RACs. The processed commodity for basil is dried basil, samples of which were produced at the field trial sites, and subsequently anal yz ed along with the fresh basil samples. A processing study is n ot needed for tomatoes, as this requirement was addressed in a previous summary

document (D328534, D337543; D. McNeilly ; 28 August 2007).M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 28 of 38 **5.3.4 Meat, Milk, Poultry and Eggs (860.1480)**  **D328534, D337543; D. McNeilly; 28 August 2007** The only significant livestock feed item associated with the proposed new uses is cowpea forage, which is not fed to beef cattle, swine nor poultry . It is fed to dairy cattle at up to 20% of the diet in select locations, or as seasonall y available. At th e proposed tolerance level of 15 ppm, the calculated dietary

burden to dairy

cattle is 10 ppm (the contribution to dietary burden from the only current feed items, potato culls and processed waste , is negligible at 0.025 ppm). No livestock feeding studi es were submitted with this petition. An acceptable ruminant metabolism study

is available. Goats were dosed with radiolabeled mandipropamid at 30 - 36 ppm (3 - 3.6X the dietary

burden to dairy

cattle) in the feed for 7 consecutive day s . The parent compound was identified only in fat (0.013 - 0.019 ppm), milk (0.013 ppm), and liver (0.004 - 0.007 ppm). Based on the highest detected residue of 0.019 ppm in goat fat, anticipated residues from feeding cowpea forage containing mandipropamid at the recommended tolerance level of 15 ppm would be roughly 0.006 ppm. HED’s ChemSAC determined that it is not possible to establish a tolerance in cowpea forage, as the potential for finite residues in cattle commodities (fat, milk and liver) exists. E stablish ing a tolerance in cowpea forage would necessitate the concurrent establishment of tolerances at the LOQ in cattle fat, milk and liver , which would require a suitable method for the enforcement of tolerances in these commodities . However, with no validated method for en forcing tolerances in cattle commodities, it is not possible to establish tolerances in them (m inutes from ChemSAC meeting of 17 July 2013) . Conclusions: The proposed t olerance in cowpea forage cannot be establish ed until a validated method for determining mandipropamid residues in livestock (cattle) commodities is available . Also, if uses on additional significant livestock feed items are requested in any future petition, a livestock feeding study will be required. **5.3. 5**  **Food Handling (860.1460)** There are no proposed uses that are relevant to this guideline topic. **5.3. 6**  **Water, Fish and Irrigated Crops (860.1400)**  There are no proposed uses that are relevant to this guideline topic **5.4 Food Residue Profile**  Residue s of mandipropamid are expected to occur at low (up to 0 .10 ppm in bulb onions ) to high levels (up to 2 00 ppm in dried basil ) from the new uses proposed in the current action .M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 29 of 38 **6.0 Tolerance Derivation**  Instead of the proposed tolerance in ginseng (0.3 ppm), HED recommends establishing the tolerance at 0.30 ppm, in order to avoid the situation where a field sample containing residues significantl y above the tolerance (0.34 ppm, for example) would be considered non - violative. For the same reason, HED recommends that the proposed tolerance of 0.1 ppm in bulb onions (subgroup 3 - 07A) be revised to 0.10 ppm. The recommended tolerances in fresh and dried basil, sn ap beans, and ginseng are based on crop field trial data entered into OECD’s tolerance calculation procedure. Upon establishment of the permanent tolerances in fresh and dried basil (40CFR §180.637[a]), the time - limited tolerances in fresh and dried basil (40CFR §180.637[b]) sh ould be removed. The recommended tolerance in fruiting vegetables (group 8 - 10) is based on updating the current tolerance in fruiting vegetables (group 8). The tolerance of 1.0 ppm would match the existing Codex (bell and non - bell peppers) and PMRA (tomatoes, okras and peppers) MRL s . Up on establishment of the tolerance in group 8 - 10, the tolerances in group 8 and okra sh ould be removed. The recommended tolerance in small vine climbing fruits except fuzzy kiwifruit (subgroup 13 - 07F) is based upon expanding the current tolerance in grap e s (1.4 ppm), and raising the US tolerance to harmonize with the existing Codex MRL in grapes . Upon establishment of the tolerance in subgroup 13 - 07F, the tolerance in grapes sh ould be removed. The recommended tolerance in bulb onions (subgroup 3 - 07A) is based upon expanding the current tolerance in dry

bulb onions (0.05 ppm), and raising the US tolerance to harmonize with the existing Codex MRL in bulb onions . Upon establishment of the tolerance in subgroup 3 - 07A, the tolerance in dry

bulb onions sh ould be removed. The recommended tolerance in green onions (subgroup 3 - 07B) is based upon expanding the current tolerance in green onions (4 ppm), and raising the US tolerance to harmonize with the existing Codex MRL in spring onions . Upon establishment of the tolerance in subgroup 3 - 07B, the tolerance in green onions sh ould be removed. The rationales for the establishment (or not) and concurrent removal of tolerances associated with the current action are listed in Table 6.0, bel ow. An International Residue Limit Status s heet is appended as Attachment 1 . Data sets and results from the OECD tolerance calculation procedure for the various commodities are appended as Attachment 2.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 3 0 of 38 **TABLE 6.0**  **Tolerance Recommendations**  **for Mandipropam id.**  **Comm odity**  **Existing**

**Tolerance (ppm) Recommended** 

**Tolerance (ppm) Rationale**  **40CFR §180.637[a]** Basil, fresh leaves None 30 Based on submitted crop field trial data. Basil, dried leaves None 200 Bean, succulent None None Field trial data on a succulent shelled bean cultivar is needed. Bean, s nap None 0.90 Based on submitted crop field trial data. Ginseng None 0.30 Cow pea, forage None None A validated method for residues in cattle commodities is needed. Vegetable, fruiting, group 8 - 10 None 1.0 Updated from fruiting vegetables group 8. Fruit, small, vine climbing, except fuzzy kiwifruit, subgroup 13 - 07F None 2.0 Translated from grape data, and harmonized with Codex MRL in grapes. Onion, bulb, subgroup 3 - 07A None 0.10 Translated from bulb onion data, and harmonized with Codex MRL in bulb onions. Onion, green, subgroup 3 - 07B None 7.0 Translated from green onion data, and harmonized with Codex MRL in spring onions. Vegetable, fruiting, group 8 1.0 None Remove ; updated to group 8 - 10 tolerance. Okra 1.0 None Remove ; covered by group 8 - 10 tolerance. Grape 1.4 None Remove ; covered by sub group 1 3 - 07 F tolerance. Onion, dry bulb 0.05 None Remove ; updated to sub group 3 - 07A tolerance. Onion, green 4 None Remove ; updated to sub group 3 - 07 B tolerance. **40CFR §180.637[b]** Basil, dried 240 None Remove time - limited tolerances, establish permanent tolerances under 180.637[a]. Basil, fresh 20 None **References** Mandipropamid. Section 3 Registration Request to Register New Uses on Hops and Tobacco and Confirmatory Residue Analytical Method for Determination of Residues in Crop Matrices. Summary of Analytical Chemistry and Residue Data. ; D 348229, D352322 , D. Rate; 11 December 2008.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 31 of 38 Mandipropamid. Request to Register New Food/Feed Uses on Head and Stem Brassica, Leafy Brassica Greens, Cucurbit Vegetables, Fruiting Vegetables, Leafy Vegetables (except Brassica), Tuberous and Corm Vegetables, Grapes, and Onions (Dry Bulb and Green). Summary of Analytical Chemistry and Residue Data. Petition Numbers 6F7057 and 7F7184. ; D328534, D337543; D. McNeill y; 28 August 2007. Ecological Risk Assessment for the Mandipropamid Section 3 New Use on Outdoor/Non
- food Ornamentals and Listed Vegetables Grown for Transplant and Retail Sale to Consumers ; D382369; C. Wendel; 26 July 2011 . Minutes from ChemSAC meeting ; 17 July 2013 . **Attachments** Attachment 1: International Residue Limit Status sheet . Attachment 2: OECD MRL(t olerance) a ssessment c alculations.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 32 of 38 **Attachment 1: International Residue Limit**  **Statu s**  **. M**  **andipropamid (PC Code**  **0 3660**  **2 )**  **Summary of US Tolerances and International Maxim um Residue Limits.**  **Residue Definitions US (40CFR §180.**  **637 )**  **Canada Codex**  **Plants:** Mandipropamid ( 4 - chloro -N - [2 - [3 - methoxy - 4 - (2 - propynyloxy)phenyl] ethyl] - α - (2 - propynyloxy) - benzeneacetamide ). Mandipropamid (4 - chloro -N - [2 - [3 - methoxy - 4 - (2 -propynyloxy) phenyl]ethyl] - α - (2 -propynyloxy) - benzeneacetamide). Mandipropamid . **Comm odity**  **2 Tolerance** 

**(ppm) 3**  **Comm odity**  **MRL (m**  **g/kg) Comm**  **odity MRL**  **4 (m**  **g/kg)** Basil, fresh leaves 30 Basil, dried leaves 200 Bean, succulent 0.90 Ginseng 0.30 Cow pea, forage 15 Vegetable, fruiting, group 8 - 10 1.0 Bell peppers, eggplants, ground cherries, non -bell peppers, okras, pepinos, pepper hybrids, tomatillos, tomatoes 1 Bell peppers, non -bell peppers 1 Dried chili peppers 10 Tomatoes 0.3 Fruit, small, vine climbing , except fuzzy kiwifruit , subgroup 13 - 07F 2.0 Grapes 1.4 Grapes 2 Onion, bulb, subgroup 3 - 07A 0.10 Chinese onions, daylilies, dry bulb onions, fritillaria, bulbs, garlic, great - headed garlic, lilies, pearl onions, potato onions, serpent garlic, shallot bulbs 0.05 Bulb onions 0.1
Onion, green, subgroup 3 - 07B 7.0 Beltsville bunching onions, elegans hosta, fresh Chinese chive leaves, fresh chive leaves), fresh onions, fritillaria leaves, green onions, kurrats, lady's leek, leeks, macrostem onions, shallot leaves, tree onion tops, Welsh onion tops, wild leeks 4 Spring onions 7

**Completed:** M. Negussie, 27 June 2013. 1. Mexico adopts US tolerances, and/or Codex MRLs, for its export purposes. 2. Includes only commodities of interest for this action. 3. Tolerance values are those recommended by HED, not those proposed by the petitioner. 4. * = absent at the LOQ . Po = post - harvest treatment , such as treatment of stored grains . PoP = processed post harvest treated commodity , such as a process ed commodity of post - harvest treated stored wheat . ( Fat) = to be measured in the fat portion of the sample. MRLs indicated as “proposed ” have not been finalized by the CCPR and the CAC.M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 33 of 38 **Attachment 2: OECD MRL (Tolerance) Assessment Calculations. Basil**  **, Dried**  **Residues ( ppm**  **)** 63.000 36.000 62.000 91.000 48.000 78.000 **Mandipropamid Basil, dried**  **Canada/US A**  **0.52 lb ai/A Total number of data (n)**  6 **Percentage of censored data** 0% **Number of non -**  **censored data** 6 **Lowest residue** 36.000 **Highest residue** 91.000 **Median residue** 62.500 **Mean** 63.000 **Standard deviation (SD)** 19.819 **Correction factor for censoring (CF)** 1.000 **Proposed MRL estimate**

**- Highest residue**  91.000

**- Mean + 4 SD**  142.277

**- CF x 3 Mean**  189.000 **Unrounded MRL** 189.000 **Rounded MRL 200** M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 34 of 38 **Basil ,**  **Fresh Residues**  **( ppm**  **)** 6.500 19.000 8.500 9.000 3.600 9.600 **Mandipropamid Basil, fresh**  **Canada/US A**  **0.52 lb ai/A Total number of data (n)**  6 **Percentage of censored data** 0% **Number of non**  **- censored data**  6 **Lowest residue** 3.600 **Highest residue** 19.000 **Median residue** 8.750 **Mean** 9.367 **Standard deviation (SD)** 5.200 **Correction factor for censoring (CF)** 1.000 **Proposed MRL estimate**

**- Highest residue**  19.000

**- Mean + 4 SD**  30.168

**- CF x 3 Mean**  28.100 **Unrounded MRL** 30.168 **Rounded MRL 30** M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 35 of 38 **Ginseng Residues (**  **ppm )**  0.119 0.106 0.035 0.027 **Mandipropamid Ginseng**  **Canada/US A**  **0.52 lb ai/A Total number of data (n)**  4 **Percentage of censored data** 0% **Number of non -**  **censored data** 4 **Lowest residue** 0.027 **Highest residue** 0.119 **Median residue** 0.070 **Mean** 0.072 **Standard deviation (SD)** 0.047 **Correction factor for censoring (CF)** 1.000 **Proposed MRL estimate**

**- Highest residue**  0.119

**- Mean + 4**  **SD** 0.262

**- CF x 3 Mean**  0.215 **Unrounded MRL** 0.262 **Rounded MRL 0.3** M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 36 of 38 **S nap Bean**  **, Pods with Seed (for Succulent Bean) Residues (**  **ppm )**  0.100 0.191 0.114 0.248 0.399 0.130 0.113 0.580 0.429 0.254 **Mandipropamid Snap beans**  **(pods with seed)**

**US A**  **0.52 lb ai/A Total number of data (n)**  10 **Percentage of censored data** 0% **Number of non -**  **censored data** 10 **Lowest residue** 0.100 **Highest residue** 0.580 **Median residue** 0.220 **Mean** 0.256 **Standard deviation (SD)** 0.163 **Correction factor for censoring (CF)** 1.000 **Proposed MRL estimate**

**- Highest residue**  0.580

**- Mean + 4 SD**  0.910

**- CF x 3 Mean**  0.767 **Unrounded MRL** 0.910 **Rounded MRL**  **0.9**M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 37 of 38 **Snap Bean ,**  **Plants with Pods (for**  **Cowpea Forage )**  **Residues ( pp** **m)** 1.360 3.320 4.200 4.490 9.270 2.210 1.270 5.030 5.740 4.540 **Mandipropamid Snap beans (**  **plants with pods)** 

**USA 0.52 lb ai/A**  **Total number of data (n)** 10 **Percentage of censored data** 0% **Number of non -**  **censored data** 10 **Lowest residue** 1.270 **Highest residue** 9.270 **Median residue** 4.345 **Mean** 4.143 **Standard deviation (SD)** 2.364 **Correction factor for censoring (CF)**  1.000 **Proposed MRL estimate**

**- Highest residue**  9.270

**- Mean + 4 SD**  13.601

**- CF x 3 Mean**  12.429 **Unrounded MRL** 13.601 **Rounded MRL 15** M andipropamid Summary of Analytical Chemistry and Residue Data DP Barcode D 40 9363

Page 38 of 38 **Greenhouse Tomato**  **Residues ( pp** **m)** 0.059 0.289 0.219 0.104 **Mandipropamid Greenhouse**  **Tomato**

**USA 0.52 lb ai/A**  **Total number of data (n)** 4 **Percentage of censored data** 0% **Number of non -**  **censored data** 4 **Lowest residue** 0.059 **Highest residue** 0.289 **Median residue** 0.162 **Mean** 0.168 **Standard deviation (SD)** 0.105 **Correction factor for censoring (CF)** 1.000 **Proposed MRL estimate**

**- Highest residue**  0.289

**- Mean + 4 SD**  0.589

**- CF x 3 Mean**  0.503 **Unrounded MRL** 0.589 **Rounded MRL 0.6**