Page 1 of 59 **UNITED STA TES ENVIRONMENTA**  **L PROTECTION A GENCY**  WA SHINGTON, D.C. 20460 **OFFICE OF CHEMICAL SAFETY AND**

**POLLUTION PREVENTION MEMORANDUM**  Date: 23 - October - 2014 Subject: **Metconazole** . Petition for the Establishment of Permanent Tolerances and

Registration for Use on the Pea and Bean , Dried Shelled, except Soy bean, Subgroup 6C and the Sunflower Subgroup 20B; Expansion of the Canola Tolerance to the Rapeseed Subgroup 20A ; and Conversion of the Establishe d Stone Fruit and Tree Nut Crop Groups to the Stone Fruit Group 12 - 12 and the Tree Nut Group 14 - 12. Summary of Anal ytical Chemistry and Residue Data. PC Code: 125619 DP Barcode: D 419223 Decision No.: 487580 Registration No. : 59639 - 147 Petition No.: 4E8244 Regulatory Action: Section 3 Registration Risk Assessment T ype: NA Case No.: NA T XR No.: NA CAS No.: 125116 - 23 - 6 MRID No.: See Below 40 CFR : 180.617 From: Nancy

Dodd, Chemist Risk Assessment Branch III (RAB3) Health Effects Division ( HED; 7509P) Through: Steve Funk, Senior Chemist

RAB3 /HED ( 7509P ) To: Barbara Madden, RM#05

Registration Division (7505P)Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 2 of 59 **Summary of Submitted Residue Chemistry Studies** O C S PP 860 Series Guideline MRID Number Title 860.1500 49297801 Corley, J. (2013) Metconazole: Magnitude of the Residue on Bean (Dry). Laboratory Project ID: 10388.10 - JRF02. Unpublished study prepared by IR- 4 Project. 201 p. 860.1500 49297802 Corley, J. (2013) Metconazole: Magnitude of the Residue on Pe a (Dry). Laboratory Project ID: 10389.10 - JRF03. Unpublished study prepared by IR- 4 Project. 173 p. 860.1500 860.1520 49297803 Corley, J. (2013) Metconazole: Magnitude of the Residue on Sunflower. Laboratory Project ID: 10390.10 - JRF01. Unpublished study prepared by IR- 4 Project. 237 p.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 3 of 59 **Table of Contents** 1.0 Executive Summary ................................ ................................ ................................ ............ 5 2.0 Regulatory

Recommendations ................................ ................................ ............................ 8 2.1 Data Deficiencies/Data Needs ................................ ................................ .......................... 9 2.2 Tolerance Considerations ................................ ................................ ................................ . 9 2.2.1 Enforcement Anal ytical Method ................................ ................................ ............... 9 2.2.2 Recommended Tolerances ................................ ................................ ........................ 9 2.2.3 Revisions to Petitioned - For Tolerances ................................ ................................ .. 10 2.2.4 International Harmonization ................................ ................................ ................... 10 3.0 Introduction ................................ ................................ ................................ ....................... 11 3.1 Chemical Identity ................................ ................................ ................................ ........... 12 3.2 Phy sical/Chemical Characteristics ................................ ................................ ................. 12 3.3 Pesticide Use Pattern/Directions for Use (860.1200) ................................ ..................... 14 4.0 Metabolite/Degradate Residue Profile ................................ ................................ .............. 19 4.1 Nature of the Residue ................................ ................................ ................................ ..... 19 4.1.1 Summary

of Plant Metabolism (860.1300) ................................ ............................. 19 4.1.2 Summary

of Livestock Metabolism (860.1300) ................................ ..................... 20 4.1.3 Summary

of Confined Rotational Crops (860.l850) ................................ ............... 20 4.1.4 Summary

of Metabolites and Degradates ................................ ............................... 21 4.2 Comparison of Metabolic Pathway s ................................ ................................ .............. 21 4.3 Residues of Concern Summary and Rationale ................................ ............................... 22 5.0 Residue Profile ................................ ................................ ................................ .................. 24 5.1 Resi due Anal ytical Methods (860.1340) ................................ ................................ ........ 24 5.1.1 Data Collection Methods ................................ ................................ ........................ 24 5.1.2 Multi - Residue Methods (860.1360) ................................ ................................ ........ 25 5.1.3 Tolerance Enforcement Methods ................................ ................................ ............ 26 5.1.4 Submittal of Analy tical Reference Standards (860.1650) ................................ ...... 28 5.2 Storage Stability

(860.1380) ................................ ................................ .......................... 29 5.3 Residue Data ................................ ................................ ................................ .................. 32 5.3.1 Crop F ield Trials (860.1500) ................................ ................................ .................. 32 5.3.2 Field Rotational Crops (860.1900) ................................ ................................ ......... 38 5.3.3 Processed Food and Feed (860.1520) ................................ ................................ ..... 39 5.3.4 Meat, Milk, Poultry and Eggs (860.1480) ................................ .............................. 42Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 4 of 59 5.3.4.1 Dietary

Burden ................................ ................................ ................................ 44 5.3.4.2 Estimated Secondary Residues in Livestock ................................ ................... 45 5.3.5 Food Handling (860.1460) ................................ ................................ ...................... 46 5.3.6 Water, Fish, and Irrigated Crops (860.1400) ................................ .......................... 46 5.4 Food Residue Profile ................................ ................................ ................................ ...... 46 6.0 Tolerance Derivation ................................ ................................ ................................ ........ 47 Appendix A. Tabular Summary of Metabolites ................................ ................................ ........... 50 Appendix B. Field Trial Geographic Distribution ................................ ................................ ....... 52 Appendix C. International Residue Limits Table ................................ ................................ ........ 53 Appendix D. OECD MRL Calculation Procedure Inputs/Outputs ................................ .............. 55Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 5 of 59 **1.0 Executive Summary**  Metconazole [ 5 - [(4 - chlorophenyl)methyl] - 2,2 - dimethyl - 1 - (1 H - 1,2,4 - triazol - 1 - yl methyl)cyclopentanol ] is a broad - spectrum triazole fungicide that works sy stemically by preventing spore formation and inhibiting mycelial growth. Metconazole acts primaril y as an inhibitor of ergosterol biosy nthesis, thereby

interfering with sy

nthesis of fungal cell membranes and providing s ys temic seed and seedling protection . The Interregional Research Project No. 4 ( IR - 4 ) , on behalf of the IR - 4 Project and the Agricultural Experiment Stations of Montana, South Dakota, North D akota , an d C olorado ( dry b ean) , M o ntan a , S o uth D akota , Idah o , an d N orth D akot a ( dry p e a) , an d Kan sas , M o ntan a , S o uth D akot a an d N orth D akot a (s un flo wer) , re qu est ed the establishment of permanent tolerances and registration for use on the pea and bean , dried shelled, except soy bean, subgroup 6C, and the sunflower subgroup 20B; expansion of the canola tolerance to the rapeseed subgroup 20A; and conversion of the established stone fruit crop group 12 and tree nut crop group 14 to the stone fruit crop group 12 - 12 and the tree nut crop group 14 - 12. Prop osed Uses : Metconazole 50 WDG Fungicide (EPA Reg. No. 59639 - 147) is a waterdispersible granule formulation containing 50% active ingredient (ai). It is to be applied to crops in the pea and bean , dried shelled, except soy bean, subgroup 6C; the sunflower subgroup 20B; the rapeseed subgroup 20A; the stone fruit crop group 12 - 12 , and the tree nut crop group 14 - 12. Applications are to be made as broadcast foliar spray s in sufficient water for thorough coverage using ground equipment (including chemigation) or aerial equipment. Depending on the crop and the targeted fungal disease, s ingle application rates range from 0.0 625 - 0.125 lb ai/A . Depending on the crop, a maximum of one to four applications can be made with minimum retreatment interval s (RTIs) ranging from 7 to 14 day s except for pecan (interval not specified) and pistachio (2 - 3 week interval) ; the yearl y application rates range from 0.125 to 0.500 lb ai/A. Preharvest intervals (PHIs) range from 14 - 35 day s. Immediate plant - back is all owed for barley , corn, cotton, oat, peanut, rye, soy bean, sugar beet, triticale, wheat, and those crops listed on the label. A 30 - day

plant - back interval (PBI) is required for Brassica leafy v egetables and leafy v egetables. A 120 - day

PBI applies to other crops. Nature of the Residue in Primary Plants : The nature of the residue in crops in the pea and bean , dried shelled, except so ybean, subgroup 6C ; the sunflower subgroup 20B , the rapeseed subgroup 20A , the stone fruit crop group 12 - 12 , and the tree nut crop group 14 - 12 is adequatel y understood based on m etabolism studies on banana, canola, mandarin, pea, and wheat . The m etabolism of metconazole was similar in all crops investigated. M etconazole (parent) is the residue of concern for the tolerance expre ssion for primary and rotational crops. Metconazole is the residue of concern for risk assessment purposes in primary and rotational crops except for cereal grains; the residues of concern for risk assessment in cereal grains (as both primary and rotation al crops) are metconazole and the metabolite M11 . (See Section 4.3 and Appendix A . ) HED also has concern for residues of free 1,2,4 - triazole and its conjugates, triazolylalanine (TA) and triazolylacetic acid (TAA), in plants as a result of the use of metconazole. However, because separate endpoints for these compounds have been established, exposure and risks from free triazole and its conjugates will be addressed separately .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 6 of 59 Nature of the Residue in Livestock : The nature of the residue in livestoc k (ruminants and poultry) is adequatel y understood. The residue of concern for the tolerance expression in livestock commodities is metconazole . The residues of concern in livestock for purposes of the risk assessment are metconazole and m etabolites M1 (free and its glucuronic acid conjugate), M12, and M31 (free and its glucuronic acid conjugate) . (See Section 4.3 and Appendix A . ) HED also has concern for residues of 1,2,4 - triazole, TA, and TAA in livestock as a result of the use of metco nazole. However, because separate endpoints for these compounds have been established, exposure and risks from free triazole and its conjugates will be addressed separatel y. Enforcement Method

s : An adequate gas chromatography method with nitrogen - phospho rus detection (GC/NPD), Valent M ethod RM - 41C - 1 - 1, is available for enforcement of tolerances for residues of metconazole ( cis - and trans - isomers ) in plant commodities from the pea and bean , dried shelled, except so ybean, subgroup 6C; the sunflower subgrou p 20B, the rapeseed subgroup 20A, the stone fruit crop group 12 - 12 , and tree nut crop group 14 - 12. A confirmatory liquid chromatography/tandem mass spectrometry ( LC/MS/MS ) method, Method RM - 41C - 4, is available. For both methods, the reported limit of quantitation ( LO Q ) is 0.02 ppm for each isomer in each matrix. An adequate GC/NPD method is available for enforcement of tolerances for residues of metconazole ( cis - and trans - isomers) in livestock c ommodities . The enforcement method is a modified vers ion of the German multiresidue method DFG S19. An acceptable confirmatory procedure , gas chromatography /mass spectrometry (GC/MS) , is included for the method . The LOQ is 0.01 ppm for each isomer in each matrix , for an LOQ of 0.02 ppm f or total metconazol e residues. Multiresidue Methods : Multiresidue methods data have been submitted for metconazole. The multiresidue methods are not adequate for determining residues of metconazole for dietary exposure assessment. The data (MRIDs 44721509 and 47790001) wi ll be forwarded to the US FDA. Storage Stability : Adequate s torage stability data for cis - and trans - metconazole were previously submitted to support the storage conditions and durations of samples of raw agricultural and processed commodities from the previously submitted crop field trials and processing studies on stone fruit, tree nuts, and canola. The currently submitted storage stability data for dry bean, dry pea, and sunflower are adequate to support the intervals of frozen storage from harvest to anal ys is for dry

bean, dry pea, and sunflower seed, meal, and oil. No corrections of residue values from the field trials or p rocessing studies for loss of metconazole or triazole residues (TA in sunflowers and dry

shelled beans/peas; 1,2,4 - triazole, TA, and TAA in canola) are necessary . Meat, Milk, Poultry, and Eggs : Based on the cattle feeding study and the calculated dietary burden based on the maximum reasonabl y balanced diet ( Table 1 Feedstuffs , June 2008), no change s are required in the established livestock tolerances as a result of the proposed/expanded uses. The established tolerances for meat by products of cattle, goat, horse, and sheep at 0.04Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 7 of 59 ppm and for egg at 0.04 ppm are adequate. No tolerances are established for milk; fat and meat of cattle, goat, hog, horse, poultry , and sheep; or meat by products of hog and poultry since residues are not expected to occur in those commodities . If additional uses increase the dairy cattle dietary

burden , additional ruminant feeding studies conducted at higher rates may be needed. Crop Field Trials : Adequate field trial data have been submitted for the pea and bean, dried shelled, except soy

bean, subgroup 6C and the sunflower subgroup 20B. Field trials were conducted on dry

beans, dry

peas, and sunflowers. The studies adequately reflect the proposed use patterns. The number of field trials and geogra phic representations are adequate. The residue data are supported by adequate storage stability data. The anal ytical methods (the GC/NPD method adapted from Valent Method RM - 41C - 1 for metconazole and the LC/MS/MS method adapted from Morse Laboratories Meth - 160 for TA) are adequate for anal ys is of the residues of concern. Although triazole fungicides are typicall y monitored for residues of all three triazole metabolites (i.e., 1,2,4 - triazole, TA, and TAA), HED previously concluded that only analysis for TA need be conducted in the subject studies (refer to HED’s Chemistry Science Advisory Council minutes, 8/11/2010 meeting). The previousl y submitted field trial data on canola, cherry, peach, plum, almond, and pecan are adequate to support the rapeseed sub group 20A, the stone fruit subgroup 12 - 12, and the tree nut group 14 - 12. The studies adequatel y reflect the proposed use patterns. The number of field trials and geographic representation are adequate . Adequate storage stability data are available to su pport the field trial data. An adequate data collection method, the GC/NPD method RM 41C - 1, was used to determine metconazole ( cis - and trans - isomers) in canola, stone fruit, and tree nuts. Residues of 1,2,4 - triazole, TA, and TAA were determined in cano la seed using an adequate LC/MS/MS method (Morse Laboratories Method 160). Although stone fruit and tree nut samples were not analy zed for the triazole metabolites, field trial data for triazoles are not required for those petitions submitted in 2006. Processing Studies : Adequate p rocessing studies have been conducted on canola, p lums , and sunflowers . Canola: M etconazole (the sum of cis - and trans - isomers) w as non - detectable in/on canola seed, meal and refined oil samples reflecting treatment at a 5x rate; therefore, separate tolerances are not required for canola meal and oil. Residues of 1 ,2,4 - triazole were also not detectable in canola seed, meal and refined oil reflecting treatment at 5x. Re sidues of TA and TAA do not concentrate in oil. Howe ver, residues of TA and TAA concentrated in canola meal by 2.1x and 1.4x, respectively . Plum: Metconazo le (the sum of cis - and trans - isomers) concentrate s 2.3x in prunes. Sunflower: M etconazole (the sum of cis - and trans - isomers) do es not concentrate in sunflower meal and oil. Residues of TA concentrate 2.9x in sunflower meal , but do not concentrate in oil. Confined Accumulation in Rotational Crops : The nature of the residue in rotational crops is adequatel y understood . The metab olism of metconazole appears to proceed in rotational cropsMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 8 of 59 via similar mechanisms as in primary crops and to be more extensive than that observed in primary crops (banana, canola, mandarin, pea, and wheat) . The residue of concern for the tolerance expres sion in rotational crops is metconazole. The residue of concern for the risk assessment in rotational crops except small grains is metconazole; the residues of concern for the risk assessment in small grains as rotational crops is metconazole and the metab olite M11 . Since the confined study indicated the potential for quantifiable metconazole residues in rotated crop commodities, limited field rotational crop trials were conducted. Field Accumulation in Rotational Crops : Adequate limited field rotational crop studies have previously

been submitted. Based on the limited field rotational crop trials, rotational crop restrictions are included on the registered Metconazole 50 WDG label s ( EPA Reg. No. 59639 - 147) . The same rotational crop restrictions on the proposed Metconazole 50 WDG label (as shown in Section 3.3) are adequate . International Tolerances : There are no Codex maximum residue limits (MRLs) established for metconazole. Residue definitions are harmonized with Canada. Tolerances in the US are established for residues of metconazole, including its metabolites and degradates. In both the US and Canada, compliance with the tolerance/MRL levels is determined by measuring only metconazole. The recommended toler ance levels are harmonized with Canada . A human health risk assessment is forthcoming. **2.0 R** **egulatory R ecommendations**  Provided the Section B/label is revised as requested, there are no residue chemistry considerations that would preclude granting the requested registration and establishing the recommended tolerances for metconazole on the pea and bean , dried shelled, except soy bean, subgroup 6C and the sunflower subgroup 20B; expansion of the canola tolerance to the rapeseed subgroup 20A; and conversion of the established tolerances and registrations for the stone fruit crop group 12 and tree nut crop group 14 to the stone fruit crop group 12 - 12 and the tree nut crop group 14 - 12. The specific tolerance recommendations are discussed in Section 2.2 , and label modifications are discussed in Section 2.3.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 9 of 59 **2.1 Data Deficiencies/Data Needs**  **Data gaps to be addressed prio r**  **to a tolerance being established /registration allowed**  Refer to Section 2.3 for label modificati ons . **Data that may be required for future uses** If additional uses increase the dairy cattle dietary

burden, additional ruminant feeding studies conducted at higher rates may be needed. **2.2 Tolerance Considerations**  **2.2.1 Enforcement**  **Analytical Method** An adequate G C/NPD method , Valent M ethod RM - 41C - 1 - 1, is available for enforcement of tolerances for residues of metconazole ( cis - and trans - isomers ) in plant commodities. A confirmatory LC/MS/MS method, Method RM - 41C - 4, is available. For both methods, the reported LOQ is 0.02 ppm for each isomer in each matrix. The method has been validated b y the ACB/BEAD and was found adequate for enforcing tolerances for residues of metconazole per s e in plant commodities. No radiovalidation data were submitted for method RM - 41C - 1 - 1; however, HED has concluded that because the extraction solvent used for the proposed enforcement method is similar to the aqueous organic solvent mixtures used in the pl ant metabolism studies, radiovalidation of the method is not required. An adequate GC/NPD method is available for enforcement of tolerances for residues of metconazole ( cis - and trans - isomers) in livestock c ommodities . The enforcement method is a modifie d version of the German multiresidue method DFG S19 . The LOQ is 0.01 ppm for each isomer in each matrix , for an LOQ of 0.02 ppm for total metconazole residues. An acceptable confirmatory

procedure (GC/MS) is included for the method . The method has been validated by ACB/BEAD and was found adequate for enforcing tolerances for residues of metconazole ( cis and trans - isomers) in/on livestock commodities. No radiovalidation data were submitted; however, because DFG S19 is an established multiresidue method, these data are not required. **2.2.2 Recommended Tolerances**  The petitioner’s proposed residue definition (tolerance expression) is adequate and is consistent with the S. Knizner memo dat ed 5/27/09. The petitioner re qu est ed th e esta b lis hment o f toleran ce s fo r resi du e s o f metco n azole , in cluding it s meta b olite s an d d egradates . C o m p lian c e with th e toleran c e level s sp ecifie d b elo w i s t o b e d eter min e d b y meas urin g o n l y metco n azol e [ 5 - [( 4 - chlorophenyl) methyl] - 2,2 - di methyl - 1 - ( 1 H - 1,2,4 -triazol - 1 - yl m ethyl)c yclo p e ntan ol] a s th e s um o f it s cis - an d trans - iso mer s .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 10 of 59 **Table 2.2.2**  **. Tolerance Summary for Metconazole.**  **Comm odity**  **Established/Proposed Tolerance (ppm)**  **HED**  

** Recommended** **Tolerance (ppm)**  **Comments**

**( correct commodity**  **definition )**  P e a and b ean , drie d s h elle d , e x cep t so y

b ean , s ub gro u

p 6 C 0.15 0.15 The 0.15 ppm level h armo niz e s with the C ana dian M RL. B ase d o n calc ulatio n s u si n g th e OEC D c alc ulator fo r dry p ea (0.08 ppm) and <0.04 ppm residues for dry bean , a toleranc e o f 0.0 8 pp m wo ul d h av e b ee n re commended . Sun flo we r s ub gro u

p 20 B 0.9 0.7 Rap esee d sub gro u

p 20 A 0.04 0.08 The 0.08 ppm level h armo niz es with the C ana dian M RL. F r uit , sto n e , gro u

p 1 2 - 1 2 0.2 0.2 Nut , tree , gro u

p 14 - 1 2 0.04 0.04 C anol a see d 0.04 None Remove upon establishment of rapeseed subgroup 20A tolerance. F r uit , sto n e , gro u

p 1 2 0.2 0 None Remove upon establishment of fruit, stone, group 12 - 12 tolerance. Nut , tree , gro u

p 1 4 0.04 None Remove upon establishment of nut, tree, group 14 - 12 tolerance P istac hi o 0.04 None Remove upon establishment of nut, tree, group 14 - 12 tolerance **2.2.3 Revisions to Petitioned**  **- For Tolerances**  The proposed tolerance on the sunflower subgroup 20B is 0.9 ppm; HED is recommending a de crease to 0.7 ppm based on the OECD tolerance calculation procedures with two studies combined as not independent. The proposed tolerance for the rapeseed subgroup 20A is 0.04 ppm. HED is recommending an increase to 0.08 ppm to harmonize with the C an adian M RL. B ase d o n calculatio n s u sing th e OEC D c alculato r fo r canola, a toleran c e o f 0.0 4 pp m wo ul d h av e b een recommended. **2.2.4 International Harmonization**  There are no Codex maximum residue limits (MRLs) established for metconazole. Residue definitions are harmonized with Canada. Tolerances in the US are established for residues of metconazole, including its metabolites and degradates. In both the US and Canada,Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 11 of 59 compliance with the tolerance/MRL levels is determined by measuring only metconazole. The recommended tolerance levels are harmonized with Canada . Refer to the International Residue Limits (IRL) table in Appendix C . **2.3 Label Recommendations**  860.1200 Directions for Use The Section B/label must be revised to include the follow ing statement for the dried shelled pea and bean, except soy

bean, subgroup 6C: “Do not apply to cowpea or field pea used for livestock feed.” The Section B/label should be revised to include the interval between applications for pecan and pistachio. **3.0 Introduction**  Metconazole is a broad - spectrum triazole fungicide that works s ys temicall y by preventing spore formation and inhibiting mycelial growth. Metconazole acts primaril y as an inhibitor of ergosterol bios ynthesis, thereb y interfering with sy nthesis of fungal cell membranes and providing s ys temic seed and seedling protection .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 12 of 59 **3.1 Chemical Identity**  **Table 3.1.**  **Metconazole Nomenclature.**  Chemical Structure

cis - isomer trans - isomer Common name Metconazole Com pany experimental name KNF - S - 474m (Kureha); BAS 555 F (BASF); V - 10116 (Valent) IUPAC name (1 RS,5 RS;1 RS,5 SR ) - 5 - (4 - chlorobenzyl) - 2,2 - dimethyl - 1 - (1 H - 1,2,4 - triazol - 1 - ylmethyl)cyclopentanol CAS name 5 - [(4 - chlorophenyl)methyl] - 2,2 - dimethyl - 1 - (1 H - 1,2,4 - triazol - 1 - ylmethyl)cyclopentanol CAS # 125116 - 23 - 6 ( cis - and trans - isomers) 115850 - 27 - 6 ( cis - isomer) 115850 - 28 - 7 ( trans - isomer) End - use product/EP Metconazole 50 WDG Fungicide (EPA Reg. No. 59639 - 147 ) , a water - dispersible granule formulation containing 50% active ingredient. Quash 50 WDG (EPA Reg. No. 59639 - 147 ) , also known as V - 10116 50 WDG **3.2 Physical/Chemical Characteristics**  Metconazole is a granule formulation with a low vapor pressure. It is more soluble in organic solvents than in water. The phy sicochemical properties are reported in Table 3.2 below. N N N

C H 3 C H 3 O H Cl N N N

C H 3 C H 3 O H ClMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 13 of 59 **Table 3.2. Physicochemical Properties of**  **the Technical Grade Metconazole**  Parameter Value Reference * (MRID) Molecular weight (g/mole) 319.8 -- Melting point/range ( °C) 100.0 - 108.4 ° C (using Electrothermal Digital Melting Point Apparatus) ( AC900,768 technical grade) 44721505 pH 5.81 at 25oC (1% aqueous suspension) 46808402 Relative d ensity (20°C) **Asked for Density (g/cm 3**  **)** 1.14 (relative density to water at 4 ° C , using capillary stoppered, density - specific gravity bottle) (Lot No. AC 8879 - 140B) 44721505 Water solubility ( mg/L at 20oC) Using shake - flask method: 18.7 ± 1.0 mg/L ( cis - isomer , WL148271, KNF - S - 474m) 13.6 ± 1.7 mg/L ( trans - isomer , WL148271, KNF - S 474m) 44721505 Solvent solubility ( g/L at 2 0oC ) Solvent Metconazole cis trans 44721505 acetone 363 251 117 methanol 403 294 117 dichloromethane 481 343 141 ethyl acetate 260 173 90.0 propanol 132 86.6 46.7 toluene 103 66.2 38.0 h exane 1.40 0.929 0.483 Vapor pressure at 20°C (Pa) Using gas - saturation method: < 1.23x10 - 5 Pa or 9.23 x 10 - 8 mm Hg (metconazole) < 1.04x10 - 5 Pa or 7.80 x 10 - 8 mm Hg ( cis - isomer) < 1.96x10 - 6 Pa or 1.47 x 10 - 8 mm Hg ( trans - isomer) 44721505

Dissociation constant (pKa) 11.38±0.03 and 1.06±0.03 (in water at 29.1°C using sp ectrophotometric method; Lot No. AC 8879 - 140B) 44721505 Octanol/water partition coefficient, Log(KOW) At 20 oC (using flask shaking method) : Kow (log Kow) = 7090±989 (3.85) (Lot No. AC 8879 - 140B) (TGAI) Kow (log Kow) = 7150±803 (3.85) ( cis - isomer , CL 354,801 ) Kow (log Kow) = 6800±1700 (3.8) ( trans - isomer , CL 354,802 ) 44721505

* DP #256877, Shyam Mathur, Ph. D . , 9/12/2000 and DP #329168, Shyam Mathur, Ph.D., 7/13/07 .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 14 of 59 **3.3 Pesticide Use Pattern/** **Directions for Use (860.1200)**  **Table 3.3.**  **Summ ary of**  **Proposed Directions for Use of**  **Me tconazole**  **.** Applic. Timing, Ty pe, and Equip. Form

ulation [EPA Reg. No.] Applic.

Rate (lb ai/A) Max.

No. Applic. per Year Max.

Yearly Applic. Rate (lb ai/A) PHI

(days) Use Directions and Limitations 1 **Dried Shelled Pea and Bean,**  **E xcept Soybean**  **, Subgroup 6C**  [D ried cultivars of bean ( Lupinus ); bean (Phaseolus ) (includes field bean, kidney bean, lima bean (dry), navy bean, pinto bean, tepary bean); bean ( Vigna ) (includes adzuki bean, blackeyed pea, catjang, cow pea, crowder pea, mo th bean, mung bean, rice bean, southern pea, urd bean); broad bean (dry); chickpea; guar; lablab bean; lentil; pea (Pisum ) (includes field pea); pigeon pea] Postemergence; Broadcast foliar spray s ; Ground or aerial equipment; Chemigati on 50% WDG

[59639 - 147] 0.08 -

0.125 2 0.25 21 Apply when conditions favor disease development and prior to infection. A second application may be made at a 7 - to 10 - day interval. Apply in sufficient water to obtain thorough coverage of the plant. Apply with ground equipment in a minimum of 20 gallons per acre (GPA) or by air in a minimum of 5 GPA. Two applications may be made sequentially. Use a non - group 3 fungicide in alternation with Metconazole 50 WDG Fungicide. **Rapeseed Subgroup 20A**  ( B orage; crambe; cuphea; ex c hium; flax seed; gold of pleasure; hare’s ear mustard; lesquerella; lunaria; meado w foam; milkweed; mustard seed; oil radish; poppy seed; rapeseed (canola varieties only); sesame; sweet rocket; cultivars, varieties and/or hybrids of these) B roadcast foliar spray during flowering ; ground or aerial equipment . 50% WDG

[59639 - 147] 0.0625 -

0.125 1 0.125 35 Make application between 20% and 50% bloom. Apply in sufficient water to obtain thorough coverage of the plant. Apply with ground equipment in 10 - 20 GPA or by **a** ir in a minimum of 5 GPA. **Stone Fruit, Crop**  **Group 12 -**  **12** ( B lack cherry; capulin; Chinese Jujube; Nanking cherry; sweet cherry; tart cherry; cultivars, varieties and/or hybrids of these) Broadcast foliar spray; ground or aerial equipment 50% WDG

[59639 - 147] 0.0 7 8 -

0.125 3 0.375 14 Timing: For brown rot/blossom blight, green fruit rot/jacket rot, or cherry leaf spot, begin applications at green tip. If conditions are favorable for disease development, make additional applications at full bloom and at petal fall. For fruit brown rot, makeMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 15 of 59 applications 14 to 21 days prior to harvest. For powdery

mildew, follow the brown rot/blossom blight schedule; make additional applications on a 10 - 14 day interval until terminal growth ceases; application can be made after harvest. Apply as a foliar spray in sufficient water to obtain thorough coverage of blossoms, foliage, and or fruit. Apply with ground equipment in 100 - 400 GPA or by air in a minimum of 20 GPA. Do not make more than 2 applications after petal fall. **Stone Fruit, Crop Group 12 -**  **12** (Apricot; Japanese apricot; nectarine and peach) Broadcast foliar spray s ; ground or aerial equipment 50% WDG

[59639 - 147] 0.078 -

0.125 3 0.375 14 Timing: For brown rot/blossom blight, green fruit rot/jacket rot, scab, or shot hole, begin applications at early pink bud stage before infection occurs. If conditions are favorable for disease development, make additional applications at full bloom and at petal fall. For fruit brown rot, make applications 14 - 21 days prior to harvest. For powdery

mildew , follow the brown rot/blossom blight schedule; make additional applications on a 10 - 14 day interval until terminal growth ceases. Begin applications prior to disease development and continue at a 7 - 10 day

interval. For rust, begin application when bud tissue is susceptible to disease development (i.e., pink, white, or red bud). If conditions are favorable for disease development, make a second application at full bloom or at petal fall.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 16 of 59 Apply as a foliar spray in sufficient water to obtain thorough coverage of blossoms, foliage, and or fruit. Apply with ground equipment in 100 - 400 GPA or by air in a minimum of 20 GPA. Do not make more than 2 applications after petal fall. **Stone Fruit, Crop Group 12 -**  **12** (American plum; beach plum; Canada plum; cherry plum; Chickasaw plum; Damson plum; Japanese plum; Klamath plum; plum; plumcot; prune plum; sloe) Broadcast foliar spray; ground or aerial equipment 50% WDG

[59639 - 147] 0.078 -

0.125 3 0.375 14 Timing: For brown rot/blossom blight and rust, begin applications at green tip. If conditions are favorable for disease development, make additional applications at full bloom and at petal fall. For powdery

mildew, follow the brown rot/blossom blight schedule; make additional applications on a 10 - 14 day interval until terminal growth ceases. Apply as a foliar spray in sufficient water to obtain thorough coverage of blossoms, foliage, and or fruit. Apply with ground equipment in 100 - 400 GPA or by air in a minimum of 20 GPA. Do not make more than 2 applications after petal fall Do not apply Metconazole 50 WDG Fungicide to “Stanley” ty pe plums.” **Sunflower Subgroup 20B** (C alendula; castor oil plant; Chinese tallowtree; euphorbia; evening primrose; jojoba; niger seed; rose hip; safflower; stokes aster; sunflower; tallowwood; tea oil plant; vernonia; cultivars, varieties, and/or hybrids of these) Postemergence; Broadcast foliar spray; Ground or aerial 50% WDG

[59639 - 147] 0.078 -

0.125 2 0.25 21 Apply when conditions favor disease development and prior to infection. A second application may be made on a 7 - to 14 - day

interval.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 17 of 59 equipment Apply as a foliar spray in sufficient water to obtain thorough coverage of leaves. Apply by ground in a minimum of 20 GP A or by air in a minimum of 5 GPA. T wo applications may be made sequentially. Use a non - group 3 fungicide in alternation with Metconazole 50 WDG Fungicide. **Tree Nuts, Crop Group 14 -**  **12, Except Filbert, Pecan, and Pistachio** (African nut - tree; almond; beechnut; black walnut; Brazil nut; Brazilian pine; bunya; bur oak; butternut; Cajou nut; candlenut; cashew; chestnut; chinquapin; coconut; coquito nut; dika nut; English walnut; ginkgo; Guiana chestnut; heartnut; hickory nut; Japanese horse - chestnut; maca damia nut; mongongo nut; monkey -pot; monkey puzzle nut; Okari nut; Pachira nut; peach palm nut; pequi; Pili nut; pine nut; Sapucaia nut; tropical almond; yellowhorn; cultivars, varieties and/or hybrids of these) Broadcast foliar spray; Ground or aerial equipment 50% WDG

[59639 - 147] 0.0 7 8 -

0.11 4 0.44 25 Begin applications prior to disease development and continue at a 7 to 14 day interval throughout the year. Apply as a foliar spray in sufficient water to obtain thorough coverage of blossoms, foliag e and/or fruit. Apply in 100 - 400 GPA with ground equipment or in a minimum of 20 GPA by air. Do not make more than 2 applications after petal fall. **Filbert (Hazelnut)**  Broadcast foliar spray; Ground or aerial equipment 50% WDG

[59639 - 147] 0.11 4 0.44 25 Begin applications starting at bud swell to bud break and continue at 10 or 14 - day intervals. Apply as a foliar spray in sufficient water to obtain thorough coverage of all branches. Apply in 100 - 400 GPA with ground equipment or in a minimum of 2 0 GPA by air. Do not make more than 2 sequenti al appl i c ati ons before switching to a non - Group 3 fungicide for resistance management. **Pecan** Broadcast foliar 50% WDG 0.0 7 8 - 4 0.44 25 Begin applications when leavesMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 18 of 59 spray; Ground or aerial equipment [59639 - 147] 0.11 reach one - half mature size. Continue to make scab applications if scab model predicts need. Apply as a foliar spray in sufficient water to obtain thorough coverage of blossoms, foliage and/or fruit. Apply in 100 - 400 GPA with ground equipment or in a minimum of 20 GPA by air. Do not make more than 2 sequential applications before switching to a non - Group 3 fungicide for resistance management. **Pistachio** Broadcast foliar spray; Ground or aerial equipment 50% WDG

[59639 - 147] 0.125 4 0.500 25 Apply prior to onset of disease development and continue on a 2 to 3 week interval. Apply as a foliar spray in sufficient water to obtain thorough coverage of blossoms, foliage and/or fruit. Apply in 100 - 400 GPA with ground equipment o r in a minimum of 20 GPA by air. Do not make more than 2 sequential applications before switching to a non - Group 3 fungicide for resistance management. 1 **Rotational Crop Restrictions** : Immediate plant -back is allowed for barley, corn, cotton, oat, peanut, rye, soybean, sugar beet, triticale, wheat, and those crops listed on the label. A 30 - day plant -back interval is required for Brassica Leafy Vegetables and Leafy Vegetables. Do not plant any crop, except barley, corn, cotton, oat, peanut, rye, soyb ean, sugar beet, triticale, wheat, Brassica Leafy Vegetables, Leafy Vegetables and those crops listed on the label , earlier than 120 days after applying Metconazole 50 WDG Fungicide. Conclusions . Metconazole 50 WDG Fungicide (EPA Reg. No. 59639 - 147) is t o be applied to crops in the pea and bean , dried shelled, except soy bean, subgroup 6C; the sunflower subgroup 20B; the rapeseed subgroup 20A; the stone fruit crop group 12 - 12 , and the tree nut crop group 14 - 12. Applications are to be made as broadcast fol iar spray s in sufficient water for thorough coverage using ground equipment (including chemigation) or aerial equipment. Depending on the crop and the targeted fungal disease, single application rates range from 0.0625 - 0.125 lb ai/A. Depending on the crop, a maximum of one to four applications can be made with minimum RTI s ranging from 7 to 14 days except for pecan (interval not specified) and pistachioMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 19 of 59 (2 - 3 week interval); the yearl y application rates range from 0.125 to 0.500 lb ai/A. P HI s range from 1 4 - 35 day s. Immediate plant - back is allowed for barley , corn, cotton, oat, peanut, rye, soy bean, sugar beet, triticale, wheat, and those crops listed on the label. A 30 - day plant - back interval (PBI) is required for Brassica leafy v egetables and leafy

v egetables. A 120 - day

PBI applies to other crops. Pending the following revision s , the Section B/label is adequate to allow evaluation of the residue data relative to the proposed use : The Section B/label must be revised to include the following statement f or the dried shelled pea and bean, except soy

bean, subgroup 6C: “Do not apply to cowpea or field pea used for livestock feed.” The Section B/label should be revised to include the interval between applications for pecan. **4.0 Metabolite/Degradate Residue**  **Profile 4.1**  **Nature of the Residue 4.1.1**  **Summary of Plant Metabolism (860.1300)** D P# 403859, S. Funk, 2/14/13 DP# 348168 , N. Dodd, 2/20/08 DP# 348234, C. Olinger, 2/11/08 ( Report of the Residues of Concern Knowledgebase Subcommittee; ROCKS memo) DP# 324541, N. Dodd, 12/14/05 No new metabolism data were submitted with the subject petition. Metabolism studies with banana, canola, mandarin, pea, and wheat were previously submitted. The metabolism of metconazole was found to be similar in all crops investigated . The main metabolic route of metconazole in crops is via oxidative hydroxylation of the methylene groups, the methyl groups on the cyclopentylring, and possibly the cyclopentyl ring. In addition, monohydrox yl ation may occur at the various pro - chiral carbons of metconazole, giving rise to chromatographicall y distinguishable stereoisomeric structures. The detection of TA and triazole conjugates in the canola, pea, and wheat studies indicates that the methylene group between the triazole and cyclopentylrings is susceptible to oxidative hydroxylation. HED determined that metconazole (parent) is the residue of concern for both the tolerance expression and risk assessment purposes in plants except for cereal grains; the residues of concern for risk assessment in cereal grains are metconazole and the metabolite M11. Conclusions. The nature of the residue in crops in the pea and bean , dried shelled, except soy bean, subgroup 6C ; the sunflower subgroup 20B , the rapeseed subgroup 20A , the stone fruit crop group 12 - 12 , and the tree nut crop group 14 - 12 is adequatel y understood based on m etabolism studies on banana, canola, mandarin, pea, and wheat . The m etabolism of metconazole was similar in all crops investigated. M etconazole (parent) is the residue of concern for the tolerance expression for primary and rotational crops. Metconazole is the residue of concern for risk assessment purposes in primary and rotational crops except for cereal grains;Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 20 of 59 the residues of concern for risk assess ment in cereal grains (as both primary and rotational crops) are metco nazole and the metabolite M11. HED also has concern for residues of 1,2,4 - triazole, TA, and TAA in plants as a result of the use of metconazole. However, because separate endpoints for these compounds have been established, exposure and risks from free triazole and its conjugates will be addressed separatel y. **4.1.2 Summary of Livestock Metabolism (860.1300)**  D P# 403859, S. Funk, 2/14/13 DP# 348234, C. Olinger, 2/11/08 (ROCKS memo) DP# 3 48168, N. Dodd, 2/20/08 No new metabolism data were submitted with the subject petition. Adequate ruminant and poultry metabolism studies are available . The data indicate that the metabolism of metconazole in ruminants and poultry is generall y similar. The major routes of metabolism involve oxidation and/or oxidative hydrox ylation of the methyl group at position 2 of the cyclopentyl ring and oxidative hydrox yl ation of the phenylring. Glucuronic acid conjugates were observed in the goat metabolism studies, and sulfate ester conjugates were observed in the hen metabolism study . In addition, in the hen metabolism study with triazole - labeled metconazole, C -N bond cleavage releasing 1,2,4 - T was observed. Based on the available data, HED determined that th e residue of concern for the tolerance expression in livestock commodities is metconazole (parent) . The residues of concern in livestock for purposes of the risk assessment are metconazole and metabolites M1 (free and conjugated), M12, and M31 (free and conjugated) . Conclusions. The nature of the residue in livestock (ruminants and poultry) is adequatel y understood. The residue of concern for the tolerance expression in livestock commodities is metconazole . The residues of concern in livestock for purposes of the risk assessment are metconazole and m etabolites M1 (free and its glucuronic acid conjugate), M12, and M31 (free and its glucuronic acid conjugate). HED also has concern for residues of 1,2,4 - triazole, TA, and TAA in livestock as a result of the use of metconazole. However, because separate endpoints for these compounds have been established, exposure and risks from free triazole and its conjugates will be addressed separatel y. **4.1.3 Summary of Confined Rotational Crops (860.l850)**  D P# 40385 9 , S. Funk, 2/14/13 DP# 348168, N. Dodd, 2/20/08 DP# 348234, C. Olinger, 2/11/08 (ROCKS memo) The nature of the residue in rotational crops is adequately defined. The metabolism of metconazole appears to proceed in rotational crops via similar mechanisms as in primary crops and to be more extensive than that observed in primary crops (banana, cano la, mandarin, pea, and wheat). Two metabolites were identified in rotational crops that were not identified in primary crops, the stereoisomers M12 and M13. HED noted that these metabolites reflect further oxidation of the methyl groups on the cyclopentyl ring of metconazole. HED determined that the residues of concern for rotational crops are the same as for primary crops. The residue of concern for the tolerance expression in rotational crops is metconazole. The residue of concern for the risk assessm ent in rotational crops except small grains is metconazole; the residues ofMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 21 of 59 concern for the risk assessment in small grains as rotational crops is metconazole and the metabolite M11 . The confined study indicated the potential for quantifiable metconazole residues in rotated crop commodities at 30 - and 120 - day plant - back intervals based on total radioactive resi due (TRR) levels. Metconazole was quantifiable (>0.01 ppm) at both PBIs in all rotational crop matrices except wheat grain. Therefore, limited fie ld rotational crop trials were conducted. Conclusions. The nature of the residue in rotational crops is adequatel y understood . The metabolism of metconazole appears to proceed in rotational crops via similar mechanisms as in primary crops and to be more extensive than that observed in primary crops (banana, canola, mandarin, pea, and wheat) . The residue of concern for the tolerance expression in rotational crops is metconazole. The residue of concern for the risk assessment in rotational crops except sm all grains is metconazole; the residues of concern for the risk assessment in small grains as rotational crops is metconazole and the metabolite M11 . Since the confined study indicated the potential for quantifiable metconazole residues in rotated crop co mmodities, limited field rotation al crop trials were conducted. HED also has concern for residues of 1,2,4 - triazole, TA, and TAA in rotational crops as a result of the use of metconazole. However, because separate endpoints for these compounds have been established, exposure and risks from free triazole and its conjugates will be addressed separatel y. **4.1.4 Summary of Metabolites and Degradates**  Refer to Appendix A for the summary table of chemical names and structures of parent and metabolites. **4. 2**  **Comparison of Metabolic Pathways** D P# 441926, Y. Donovan, 3/12/08 The metabolism of metconazole was found to be similar in all crops investigated. The main metabolic route of metconazole in crops is via oxidative hydroxylation of the methylene groups, the methyl groups on the cyclopentylring, and possibly of the cyclopentylring. In addition, monohydrox yl ation may

occur at the various pro - chiral carbons of metconazole, giving rise to chromatographicall y distinguishable stereoisomeric structures. Further oxidation of the hydrox yl ated metabolites to form dihydrox yl ated or carboxylated derivatives was also observed in the mandarin study . Finally glucose conjugation of the mono - and/or dihydrox yl ated metabolites was observed in all crops, yielding glucoside s as terminal residues. The detection of TA and triazole conjugates in the canola, pea, and wheat studies indicates that the methylene group between the triazole and cyclopentylrings is susceptible to oxidative hydrox yl ation . The metabolism of metconaz ole appears to proceed in rotational crops via similar mechanisms as in primary

crops and to be more extensive than that observed in primary crops (banana, canola, mandarin, pea, and wheat).Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 22 of 59 The metabolism of metconazole in ruminants and poultry was generally

similar. The major routes of metabolism involved oxidation and/or oxidative hydrox yl ation of the methyl group at position 2 of the cyclopentyl ring and oxidative hydroxylation of the phenyl ring. Glucuronic acid conjugates were observed in the goat metabolism studies, and sulfate ester conjugates were observed in the hen metabolism study . In addition, in the hen metabolism study with triazole labeled metconazole, C - N bond cleavage releasing 1,2,4 - T was observed. Based on the above descriptions , it is concluded that there are significant similarities in plant and livestock metabolism. M etconazole was metabolized primarily through oxidative hydrox yl ation of the benzylic methylene and the methylgroups on the cyclopentylring, followed by conjugati on with glucose. The triazole metabolites (1,2,4 - triazole , TA, and TAA) are also residues of concern. **4.3 Residues of Concern Summary and Rationale**  DP# 348234, C. Olinger, 2/11/08 (ROCKS memo) A summary

of the metabolites and degradates to be included in the risk assessment and tolerance expression are presented below in Table 4.3 , followed by the rationale. **Table 4.3. Summary of Metabolites and Degradates to be included in th**  **e Risk Assessment and**  **Tolerance Expression** Matrix Residues Included In Risk Assessment Residues Included In Tolerance Expression Plants Primary and Rotational

Crops, except Cereal Grains Metconazole Metconazole Primary and Rotational Crops, Cereal Grains only Metconazole and M11 Metconazole Livestock Ruminant Metconazole; M1 and its glucuronic acid conjugate; M12; M31 and its glucuronic acid conjugate Metconazole Poultry Drinking Water Metconazole Not Applicable Note: For all triazole - containing pesticides, the triazole - containing metabolites 1,2,4 - T, TA, and TAA should also be included as residues of concern for risk assessment purposes only for plant and livestock commodities. Since these metabolites are common to the entire class of triazole - derivative fungicides and because of differential toxicity between the metabolites and the various parent compounds, risks associated with exposure to 1,2,4 - T and to TA/TAA are addressed in separate risk assessment documents. M1 = 5 - [(4 - chlorophenyl)methyl] - 2 - methoxyl - 2 - methyl - 1 - (1 H - 1,2,4 - triazol - 1 - ylmethyl) - 1 - cyclopentanol; M11 = 5 - [(4 - chlorophenyl)methoxyl] - 2,2 - dimethyl - 1 - (1 H - 1,2,4 - triazol - 1 - ylmethyl) - 1 - cyclopentanol; M12 = 5 - [(4 - chlorophenyl)methyl] - 2 - carboxyl - 2 - me thyl - 1 - (1 H - 1,2, 4 - triazol - 1 - ylmethyl) - 1 - cyclopentanol; M31 = (1S*,3R*,5S*) - 3 - hydroxy - cis - metconazole; 1,2,4 - T = 1 H - 1,2,4 - triazole; TAA = 1 H - 1,2,4 - triazol - 1 - yl acetic acid; TA = 2 - amino - 3 - (1 H

- 1,2,4 - triazol - 1 - yl)propanoic acid . (See Appendix A . ) Rationale:Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 23 of 59 Plants Metconazole is the major residue in plant commodities based on the nature of the residue and magnitude of residue studies in numerous crops, and is , therefore, a residue of concern for both tolerance expression and risk assessment purposes. The registrant anal yz ed for residues of three metabolites, M11, M21, and M30, in cereal grain magnitude of residue studies. M11 was found at levels exceeding 1 ppm in oat and wheat straw at the proposed application rate, and at higher relative amounts than observed in the nature of the residue studies. Toxicity data are not available for M11, but it has a very similar chemical structure to the parent compound; therefore, without empirical data, it is assumed to have equal toxicity to the parent. M11 need s to be included as a residue of concern for risk assessment purposes in cereal grains only . M12 was a major residue in one of the rotational crop studies. For any future uses with higher application rates that result in the need for rotational crop tolerances, HED sh ould consider inclusion of the M12 metabolite for risk assessment purposes. Livestock The major residues observed in the ruminant and poultry metabolism studies were metconazole, M1, M12, and the glucuronic acid conjugates of M1 and M31. Since the parent compound is the major residue in many of the livestock commodities , it is the only residue that needs to be included in the tolerance expression. M1 is very similar to the parent with an additional hydrox ylgroup in the cyclopentanol ring, and M12 has a carbox yl ic acid group in the same ring. The anal ytical method used in the feeding study is able to quantify

the parent compound, M12, M1, and the glucuronic acid conjugate of M1. Due to the chemical structural similarity to the parent and assumed equival ent toxicity, they should be included in the risk assessment. The conjugated nature of the M31 metabolite mitigates the hazard concern to some extent; however, in the absence of toxicity data for the M31 metabolite, and the chemical structural similarity to the parent and assumed equivalent toxicity to the parent compound, HED recommends that M31 be included in the risk assessment only . Triazoles Metconazole is a member of the triazole - containing class of pesticides. HED generally includes 1,2,4 - T, TA, and TAA as residues of concern for risk assessment purposes for most triazole containing pesticides. 1,2,4 - T was a major residue found in some livestock commodities, and TA and TAA were significant residues in some plant metabolism studies. Since these m etabolites are common to the entire class of triazole - derivative fungicides and because of differential toxicity

between the metabolites and the various parent compounds, risks associated with exposure to 1,2,4 - T and to TA/TAA are addressed in separate ris k assessment document s . Water In addition to the parent compound, three degradates were observed at greater than 10% of the applied dose in laboratory fate studies: M30, hydroxy metconazole, and M13. Metconazole is generall y slow to degrade in the enviro nment, and the environmental fate data suggest that microbial - mediated degradation is likely the major degradation pathway for the proposed terrestrial agricultural uses. Although M30 was a major soil aerobic transformation product inMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 24 of 59 laboratory

studies (approximately

13% of the applied dose), it was a not a significant degradation product in field dissipation studies (approximately 5% of the applied dose). Hydroxy metconazole was a major photoly sis product, but photolysis would not be a significant rout e of dissipation in the environment for the existing and proposed uses. In addition, the loss of the chlorine in hydroxymetconazole lessens the hazard concern for the degradate. M13 was observed in onl y one water soil system of the two tested and at a level barely over 10%, and is , therefore, not considered to be a significant degradate. HED recommends only the parent compound be included in the drinking water exposure and risk assessments since exposure is not likely to be significantl y different if the major degradates were included in the assessment. **5.0 Residue Profile**  **5.1 Residue Analytical Methods (860.1340)**  **5.1 .1**  **Data Collection Methods** 49297801.der (dry bean) 49297802.der (dry pea) 49297803.de1 (sunflower) 49297803.de2 (sunflower processed commodities) Dry Shelled Beans, Dry Shelled Peas, and Sunflower Seeds Dry beans , dry

peas , sunflower seeds , and sunflower processed commodities (meal and oil) were anal yz ed for residues of metconazole, determined as cis - and trans - metconazole, using a GC /NPD method adapted from Valent Method RM - 4 1 C - 1 (dated 11/13/03) . For determination of cis - and trans - metconazole, samples were extracted with acetonitrile (ACN):water (70:30, v:v), filtered, and concentrated to remove the ACN. Residues were partitioned into hexane and then into ACN. The resulting ACN phases were combined with ethyl acetate, concentrated to dry ness, and redissolved in methanol (MeOH):water (1:1, v:v), then subjected to solid phase extraction (SPE) through a C 18 cartridge. Residues were eluted with MeOH:water (5:1, v:v). The eluate was evaporated to an aqueous remainder, combined with ethylacetate, and evaporated to dry

ness. Residues were then redissolved in toluene for GC/NPD analy sis. The validated LOQ is 0.02 ppm for each isomer. Samples were anal yz ed for residues of the triazole metabolite triazole alanine (TA) using an LC/MS/MS method adapted from Morse Laboratories Meth - 160 (dated 6/27/03) . For determination of TA , samples were extracted with methanol:water (80:20, v:v). Follo wing the addition of Celite, the extracts were vacuum filtered, rinsed, and brought to volume with methanol : water (80:20, v:v) . The resulting extract was purified b y elution through a Bond Elut Certify I I SPE cartridge. The resulting eluate was reduced to dry ness then subjected to two derivatizations: an esterification using hydrochloric acid ( HCl ) /butanol and an acylation using heptafluorobutyric anhydride (HFBA). The resulting extract w as evaporated to dry ness, and redissolved in ACN/water for analy si s by LC/MS/MS. The L OQ (determined as the LLMV) was 0.02 ppm. The limits of detection (LODs) were not reported. Acceptable method validation and concurrent recovery data were reported for dry bean , dry pea , sunflower, and sunflower processed commodities at fortification levels of 0.02 and 0.2 ppm, thusMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 25 of 59 validating the method s . The fortification levels were adequate to bracket expected residue levels. Although triazole fungicides are ty picall y monitored for residues of all three triazole metabolites (i.e. , 1,2,4 - triazole, TA, and TAA ), HED previousl y concluded that only analysis for TA need be conducted in the subject study (refer to HED’s Chemistry Science Advisory

Council minutes, 8/11/2010 meeting). Canola Samples of canola seed , meal, and oil were an al yzed for residues of cis - and trans - metconazole using an adequate GC/NPD method (RM - 41C - 1). The validated LOQ is 0.02 ppm for each metconazole isomer ; the LOQ for total metconazole residues ( cis - + trans - isomers) is 0.04 ppm. Residues of 1,2,4 - triazole, TA, and TAA were determined in canola seed , meal, and oil using an adequate LC/MS/MS method (Morse Laboratories Method 160). The validated LOQ of the LC/MS/MS method in canola matrices was 0.01 ppm for triazole and TAA and 0. 03 ppm for TA . Almond, Pecan, Cherry , Peach, and P lum Samples were anal yz ed for residues of cis - and trans - metconazole using an adequate GC/NPD method (RM - 41C - 1). The validated LOQ is 0.02 ppm for each metconazole isomer ; the LOQ for total metconazole residues ( cis - + trans - isomers) is 0.04 ppm. Conclusions. An acceptable data collection method was used for determination of metconazole. The method used for determination of metconazole (as cis - and trans - metconazole) in dry beans, dry peas, sunflower seeds, sunflower processed commodities (meal and refined oil) , canola seed, canola processed commodities (meal and refined oil), almond nutmeat and hulls, cherries, peaches, plums, and prunes is a GC/NPD meth od adapted from Valent Method RM - 4 1 C - 1 . The method has been adequately validated as a data collection method based on acceptable method validation and concurrent recovery data. The LOQ of the method is 0.02 ppm for each anal yt e ( cis - and trans - metconazol e) in each matrix . An acceptable data collection method was used for determination of triazoles. Samples of dry beans, dry

peas, sunflower seeds , and sunflower processed commodities (meal and oil) were anal yz ed for residues of TA using an LC /MS/MS method adapted from Morse Laboratories Meth - 160 (dated 6/27/03). Residues of 1,2,4 - triazole, TA, and TAA were determined in canola seed using Method 160. The method has been adequately validated as a data collection method based on acceptable concurrent recovery data. The validated LOQ for dry beans, dry

peas, and sunflower seeds, meal, and oil is 0.02 ppm. The validated LOQ of the L C/MS/MS method in canola matrices was 0.01 ppm for triazole and TAA and 0.03 ppm for TA . **5.1.2 Multi**  **- Residue Methods (**  **860.1360)** DP# 361110, D. Soderberg, 2/26/10 (MRID 47790001) DP# 3 24541 , N. Dodd, 12/14/05 (MRID 44721509) The Agency

previousl y reviewed multiresidue methods data for metconazole. Based on its chemical structure, metconazole was not tested using FDA Mu ltiresidue Method Protocols A, B, and G. Testing of metconazole through protocols A, B and G is unnecessaryMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 26 of 59 because metconazole is not naturally fluorescent, is neither an N - methyl carbamate nor a substituted urea, nor does it pos s ess a phenol or carbox yl ic acid group . An acceptable GC response (Protocol C) was obtained under Level I conditions using Module DG5, with a DB - 1 ( 100% methyl siloxane) GC column . Metconazole in peach (a non - fatty food) was tested through Protocol D using electron capture detection ( EC D) . Metconazole could not be seen in the extract when tested using ECD without a cleanup step. When tested through Fluorisil cleanup protocols C1 and C5 , the residues appeared to be poorly

recoverable through a Fluorisil column, but the recovery was largel y obscured when residues were determined by ECD. Thus , protocol D cannot be used with EC D , but a more selective NPD was not tried, so results were equivocal for possibilities with that or other more selective detectors. Metconazo l e in peach was also tested through Protocol E without cleanup. Results again showed that a cleanup was needed when using an ECD. Because of the previous results using protocol D, no attempt was made to try the Protocol E extract through a Fluorisil cleanup. Because of these poor results, no attempt was made to test metconazole through Protocol F (for fatty foods). Conclusions . Multiresidue methods data have been submitted for metconazole. The multiresidue methods are not adequate for determining re sidues of metconazole for dietary exposure assessment. The data (MRIDs 44721509 and 47790001) will be forwarded to the US FDA. **5.1 .3**  **Tolerance Enforcement Methods** D P# 348168, N Dodd, 2/20/08 DP# 350367, N. Dodd, 9/18/08 D P# 389556, N. Dodd, 9/29/11 Plants An adequate GC/NPD method , Valent M ethod RM - 41C - 1 - 1, is available for enforcement of tolerances for residues of metconazole parent isomers ( cis - and trans - metconazole) in plant commodities from dry

bean, dry pea, sunflower, canola, stone fruit and tree nuts . A confirmatory

L C/MS/MS method, M ethod RM - 41C - 4, is available. In M ethod RM - 41C - 1 - 1, homogenized samples are extracted with ACN:water (70:30, v:v) and filtered. The extract is concentrated to remove ACN and partitioned with hexane (2x). Th e resulting hexane phases are combined and partitioned with ACN (2x), and the ACN phases are combined with ethyl acetate, concentrated to dry ne ss, and redissolved in MeOH:water (1:1, v:v). The reconstituted extract is applied to a C18 SPE cartridge, and residues are eluted with MeOH:water (5:1, v:v). The eluate is evaporated to aqueous, combined with ethyl acetate, evaporated to dry

ness, and then redissolved in toluene for GC/NPD anal ys is. The reported LOQ is 0.02 ppm for each isomer. In the confirmatory m ethod RM - 41C - 4, homogenized samples are extracted with ACN/water, filtered, and concentrated to aqueous as above, then partitioned with hexane:ethyl acetate (9:1,Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 27 of 59 v:v; 2x). The resulting hexane/ethyl acetate phase is partitioned with ACN (2x) and the combined ACN phases are concentrated, mixed with ethyl acetate, and evaporated to dry ness. The residues are dissolved in MeOH: water (1:1, v:v) and subjected to C18 SPE cleanup as described above. The resulting eluate is diluted with aque ous formic acid for L C/MS/MS anal ys is. The LOQ, based on the submitted method validation data, is 0.02 ppm for metconazole (total of cis and trans - isomers). Method RM - 41C - 1 - 1 has undergone an acceptable independent laboratory validation ( ILV) with almond nutmeat fortified at 0.02 - 0.2 ppm. Adequate recoveries were obtained for almond nutmeat, ranging from 93.5 to 111% for cis - metconazole and from 88.6 to 112% for trans metconazole. No radiovalidation data were submitted for method RM - 41C - 1 - 1; however, HED has concluded that because the extraction solvent used for the proposed enforcement method is similar to the aqueous organic solvent mixtures used in the plant metabolism studies, radiovalidation of the method is not required. Method RM - 41C - 1 - 1 was fo rwarded to ACB/BEAD for petition method review (DP #339994, N. Dodd, 5/29/07) . ACB/BEAD (DP# 339995, Paul Golden, ACB Project #B07 - 19, 2/15/08) reviewed the method and found it adequate as an enforcement method for determination of resid ues of metconazole ( cis - and trans - isomers) . Livestock An adequate method is available for enforcement of tolerances for residues of metconazole ( cis and trans - isomers ) in livestock c ommodities . The enforcement method is a modified version of the German multiresidue method DFG S19 . The LOQ is 0.01 ppm for each isomer, for an LOQ of 0.02 ppm for total metconazole residues. The method has been validated by ACB/BEAD and was found adequate for enforcement. For milk, bovine muscle, and egg, samples are homogenized with water:acetone (1:2, v:v), then combined with ethyl acetate:cyclohexane (1:1, v:v), and sodium chloride. An aliquot of the resulting organic phase is filtered through sodium sulfate and concentrated by evaporation, then reconstituted in ethylacetate. Sodium sulfate:sodium chloride (1:1, w:w) and cyclohexane are added, and the salts are allowed to precipitate. For fat, samples are blended with ACN:acetone (9:1, v:v) and Calflo E and Celite as adsorbents, filtered, and combined with isooctane. The extract is concentrated and redissolved in ethyl acetate:cyclohexane (1:1, v:v) as above. For all matrices, the resulting ethyl acetate/cyclohexane fractions are subjected to sequential cleanup on a GPC column (residues eluted with ethyl acetate/cyclohexane ) and a silica gel mini - column (residues eluted with acetone ) . The resulting eluate is con centrated b y rotary evaporation and reconstituted in ethylacetate for GC/NPD or GC/MS (confirmatory procedure) anal ys is. The method L OQ is 0.01 ppm for each isomer. Method DFG S19 with modified extraction has undergone an acceptable ILV with grape, pea, wheat grain, rapeseed, milk, bovine muscle, egg, and bovine fat fortified with each isomer atMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 28 of 59 0.01 and 0.10 ppm. Adequate recoveries, generally within the acceptable range of 70 - 120%, were obtained for all matrices at both fortification levels. An acceptable confirmatory procedure (GC/MS) was included for the method. No radiovalidation data were submitted; however, because DFG S19 is an established multiresidue method, these data are not required. The method based on the German multiresidue method DFG S19 was forwarded to ACB/BEAD for a petition method review (DP #339992, N. Dodd, 5/29/07). ACB/BEAD (Paul Golden, ACB Project #B07 - 18, 2/ 8 /08) conducted a successful petition method review , indicating that the method is adequate for enforcing tolerances for residues of metconazole ( cis - and trans - isomers) in/on livestock commodities. Conclusions. An GC/NPD method , Valent M ethod RM - 41C - 1 - 1, is available for enforcement of tolerances for residues of metconazole ( cis - and trans - isomers ) in plant commodities from the pea and bean , dried shelled, except soy bean, subgroup 6C; the sunflower subgroup 20B, the rapeseed subgroup 20A, the stone fruit crop group 12 - 12 , and tree nut crop group 14 - 12. A confirmatory

L C/MS/MS method, Method RM - 41C - 4, is available. For both methods, the reported LOQ is 0.02 ppm for each isomer in each matrix. The method has been validated b y ACB/BEAD and was found adequate for enforcing tolerances for residues of metconazole per se in plant commodities. No radiovalidation data were submitted for method RM - 41C - 1 - 1; however, HED has concluded that because the extraction solvent used for the proposed enforcement method is similar to the aqueous organic solvent mixtures used in the plant metabolism studies, radiovalidation of the method is not required. An adequate GC/NPD method is available for enforcement of tolerances for residues of metconazole ( cis - and trans - isomers) in livestock c ommo dities . An acceptable confirmatory procedure , GC/MS , is included for the method . The enforcement method is a modified version of the German multiresidue method DFG S19 . The LOQ is 0.01 ppm for each isomer in each matrix , for an L OQ of 0.02 ppm for total metconazole residues. The method has been validated by ACB/BEAD and was found adequate for enforcing tolerances for residues of metconazole ( cis - and trans - isomers) in/on livestock commodities. No radiovalidation data were submitted; however, because DF G S19 is an established multiresidue method, these data are not required. **5.1.4 Submittal of**  **Analytical Reference Standards (860. 1650)**  D P# 386784, A. Acierto, 7/27/11 An anal ytical reference standard for metconazole, with an expiration date of 9/1/2015, is available in the EPA National Pesticide Standards Repository (personal communication between T. Cole, ACB, and Versar, e - mail 1/25/11).Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 29 of 59 **5.2 Storage Stability (860.1380)**  D P# 403859, S. Funk, 2/14/13 D P# 363016, D. Drew , 1/12/12 (47606601.der). D P# 3503 67, N. Dodd, 9/18/08 D P# 348168, N. Dodd, 2/20/08. 49297801.der (dry bean) 49297802.der (dry pea) 49297803.de1 (sunflower) 49297803.de2 (sunflower processed commodities) Ra peseed Subgroup 20A , Stone Fruit, and Tree Nuts The previousl y submitted storage stability data for cis - and trans - metconazole are adequate to support the storage conditions and durations of samples of raw agricultural and processed commodities from the previously submitted crop field trials and process ing studies on stone fruit and tree nuts (DP# 348168, N. Dodd, 2/2/08) and canola (DP# 350367, N. Dodd, 9/18/08). Dry Bean, Dry

Pea , and Sunflower Storage stability

data su bmitted for dry

peas and sunflower meal and oil are reported in Table 5.2.1 belo w. **T able**  **5.2.1. Stability of Metconazole in Frozen Dry Peas and Sunflower Meal and Oil.**  Analyte Spike

Level (ppm) Storage interval 1 (days) Fre sh

Fortification Recoveries (%) Recovered Residues (ppm) Mean

Recovered Residues (ppm) Mean

Recovery (%) Corrected %

recovery

2 **Dry Peas** cis - metconazole 0.2 419 83 NR3 NR 88 106 trans - metconazole 0.2 419 92 NR NR 79 86 **Sunflow er Meal**  cis - metconazole 0.2 306 72.5 0.1791, 0.1494, 0.1545 0.1610 80.5 111 trans - metconazole 0.2 306 70.5 0.1507, 0.1406, 0.1459 0.1457 72.8 103 **Sunflow er Oil**  cis - metconazole 0.2 305 117 0.2347, 0.1972, 0.2233 0.2184 109 93.2 trans - metconazole 0.2 305 89.7 0.1951, 0.2060, 0.2437 0.2149 107 119 1 Interval from fortification to extraction. 2 Corrected for recovery of freshly fortified samples . 3 NR = not reported. The storage durations and conditions of samples from the crop field trials and sunflower processing study are presented in Table 5.2 . 2. Dry bean s amples were stored frozen from harvest to extraction for a maximum of 258 day s (8.5 months) prior to anal ys is for cis - and trans - metconazole and for a maximum of 192 days (6.3 months) prior to anal ys is for TA (Table 5.2.2 ). Samples were anal yz ed within 1 - 5 days of extraction. The available freezer storage stability data indicate that residues of cis - and trans metconazole were stable when stored frozen at ≤ - 20 °C in/on dry pea f or up to 419 day s (13.8 months), and residues of TA were stable when stored frozen in/on canola seed and wheat grain for up to 4 years .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 30 of 59 Dry pea s amples were stored frozen from harvest to extraction for a maximum of 376 days (12.4 months) prior to anal ys is for cis - and trans - metconazole and for a maximum of 417 days (13.7 months) prior to anal ys is for TA (Table 5.2.2 ). Samples were anal yz ed within 2 - 14 days of extraction. The available freezer storage stability data indicate that residues of cis - and trans metconazole were stable when stored frozen at ≤ - 20 °C in/on dry pea for up to 419 day s (13.8 months), and residues of TA were stable when stored frozen in/on canola seed and wheat grain for up to 4 years. Sunflower seed s amples were stored frozen from harvest to extraction for a maximum of 423 day s (13.9 months) prior to analy sis for cis - and trans - metconazole and for a maximum of 472 day s ( 15.5 months) prior to analy sis for TA (Table 5.2.2 ). Samples were analyzed with 1 - 18 day s of extraction. The available storage stability data indicate that residues of cis - and trans metconazole were stable und er frozen storage conditions for up to 26 months in/on soy bean seed . Residues of TA have been shown to be stable in/on canola seed and wheat grain under frozen conditions for up to 4 years. In the sunflower processing study, s amples were stored frozen from harvest/processing to extraction for 389 - 403 day s ( 12.8 - 13.2 months) for sunflower seed (RAC) and 1 41 - 1 49 day s (4. 6 - 4.9 months) for meal and oil (Table 5.2.2) . Samples were anal yz ed within 1 - 14 day s of extraction. Processing took place within 290 - 293 day s (9.5 - 9.6 months) of harvest. The available storage stability data indicate that residues of cis - and trans - metconazole were stable under frozen storage conditions for up to 26 months in/on soy bean seed. To support the sample storage intervals for sunflower meal and oil , a concurrent storage stability study was conducted with the field trial study ; the results are presented in Table 5.2.1 . The data demonstrate that residues of metconazole , determined as cis - and trans - metc onazole , were stable in/on samples of sunflower meal and oil stored frozen for up to 306 and 305 day s; no 0 - day data were provided. These data are acceptable to support the storage conditions and durations of samples from the submitted field trials; howev er, storage stability studies should alway s include a 0 - day sampling interval to establish the residue levels present at the time samples are placed into storage [see OCSPP 860.1380(d)(6)(i)]. Residues of TA have been shown to be stable in/on canola seed , meal, and wheat grain under frozen conditions for up to 4 years and up to 8 months in canola oil .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 31 of 59 **Table 5.2. 2.**  **Summary of Storage Conditions.** Matrix Analyte Storage Tem perature (°C) Actual Storage Duration 1

(days/months) Interval of Demonstrated Storage Stability Bean, dry Metconazole ~ - 20 148 - 258 days (4.9 - 8.5 months) Residues are stable for up to 419 days

(13.8 months) in dry pea. 2 TA 88 - 192 days (2.9 - 6.3 months) Residues are stable for up to 4 years

in/on canola seed and wheat grain . 3 Pea, dry Metconazole ~ - 20 312 - 376 days (10.3 - 12.4 months) Residues are stable for up to 419 days

(13.8 months) in dry pea. 2 TA 350 - 417 days (11.5 - 13.7 months) Residues are stable for up to 4 years

in/on canola seed and wheat grain . 3 Sunflower seed Metconazole ~ - 20 355 - 423 days (11.7 - 13.9 months) Residues of cis - and trans - metconazole

were stable under frozen storage conditions for up to 2 2 mo nths in/on almond nutmeat . 4 TA ~ - 20 388 - 472 days (12.8 - 15.5 months) Residues are stable for up to 4 years

in/on canola seed and wheat grain . 3 Sunflower, seed (for processing) Metconazole ~ - 20 389 days (12.8 months) Residues of cis - and trans metconazole were stable under frozen storage conditions for up to 2 2 mo nths in/on almond nutmeat . 4 Sunflower, meal 142 days (4.7 months) 306 days (10.1 months) 5 Sunflower, oil 141 days (4.6 months) 305 days (10.0 months) 5 Sunflower, seed TA ~ - 20 403 days (13.2 months) Residues of TA are stable for up to 4

years in/on canola seed , meal, and wheat grain . 3 Sunflower, meal 149 days (4.9 months) Sunflower, oil 148 days (4.9 months) Residues of TA are stable for up to 8 mo nths in canola oil. 3 1 Field trial studies: Interval from harvest to extraction. Dry bean samples were analyzed within 1 - 5 days of extraction. Dry pea samples were analyzed within 2 - 14 days of extraction. Sunflower seed samples were analyzed within 1 - 18 day s of extraction. Sunflower processing study: Interval from harvest/processing to extraction. In the processing study, sampl es were analyzed within 1 - 14 day s of extraction. Processing took place within 290 - 293 days (9.5 - 9.6 months) of harvest. 2 Based on concurrent dry pea storage stability study ( MRID 49 29780) . 3 DP# 363016, D. Drew , 1/12/12 (47606601.der) . 4 DP# 348168, N. Dodd, 2/20/08 . 5 Based on concurrent sunflower storage stability study (MRID 49297803) . Conclusions : The currently submitted storage stability data are adequate to support the intervals of frozen storage from harvest to anal ys is for dry bean, dry pea, and sunflower seed, meal, and oil. The previously

submitted storage stability data for cis - and trans - metconazole are adequate to support the storage conditions and durations of samples of raw agricultural and processed commodities from the previously submitted crop field trials and processing studies on stone fruit , tree nuts, and canola. No corrections of residue values from the field trials or p rocessing studies for loss of metconazole residues are necessary .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 32 of 59 **5.3 Residue Data**  **5.3.1 Crop Field Trials**  **(860.1500)** D P# 350367, N. Dodd, 9/18/08 ; 47287801.de1 (Rapeseed subgroup 20A: canola) DP# 371571, A. Acierto, 8/20/10 (Rapeseed subgroup 20A: canola) D P# 348168, N. Dodd, 2/20/08 (stone fruits: cherry, peach, and plum ; and tree nuts: almond and pecan) DP# 361110, D. Soderberg, 2/26/10 (stone fruits: cherry, peach, and plum; and tree nuts: almond and pecan) 49297801.der (dry bean) 49297802.der (dry pea) 49297803.de1 (sunflower) Shelled Dry B ean, Shelled Dry Pea , and Sunflower As shown in Table 5.3.1, field trials were conducted on dry beans, dry

peas, and sunflowers. Refer to the geographic distribution tables in Appendix B . As discussed in Section 5.1 .1 , s amples from all field trials were anal yz ed for residues of metconazole, determined as cis - and trans - metconazole, using a GC/NPD method adapted from Valent Method RM - 4 1 C - 1 (dated 11/13/03) . Samples were anal yz ed for residues of the triazole metabolite TA using an LC/MS/MS method adapted from Morse Laboratories Meth - 160 (dated 6/27/03) . The LOQ ( determined as the lowest level of method validation, LLMV) was 0.02 ppm for each analy

te. Acceptable method validation and concurrent recovery data (with recoveries generall y within the acceptable range of 70 - 120%) were reported for dry bean , dry pea, and sunflower samples at fortification levels of 0.02 and 0.2 ppm, thus validating the method s as adequate data collection method s . The fortification levels were adequate to bracket expected residue levels. Although triazole fungicides are typically monitored for residues of all three triazole metabolites (i.e., 1,2,4 - triazole, TA, and TAA) , HED previously concluded that only anal ys is for TA need be conducted in the subject studies (refer to HED’s Chemistry Science Advisory Council minutes, 8/11/2010 meeting). As discussed in Section 5.2, the available storage stability data are adequate to support the storage conditions and intervals of samples from the field trials. All samples were maintained frozen at the testing facility , during shipping to the laborato ry , and were stored frozen until anal ys is. Dry Bean IR - 4 has submitted field trial data for metconazole on dry beans. Thirteen field trials were conducted in the United States during the 2010 growing season in the North American Free Trade Agreement (NAFTA) Growing Zones 1 (NY; 1 trial), 5 ( MI , NE, OH and WI ; 6 trials), 7 (ND; 1 trial), 8 ( KS ; 1 trial), 9 (NM ; 1 trial), 10 (CA; 1 trial) and 11 ( ID and WA ; 2 trial s ). Each trial consisted of one untreated plot and one treated plot. Each treated plot received two foliar broadcast applications of the 50% water dispersible granule (WG) formulation of metconazole (Quash 50 WDG) at 0.119 - 0.133 lb ai/A/application for a total seasonal rate of 0.245 - 0.259 lb ai/A. Applications were made at RTI s of 6 - 8 day s using ground equipment in spray volumes of 15 - 51 gal/A. A nonionic surfactant (NIS) was included in the spray mixturesMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 33 of 59 for all applications. Samples of dry bean were harvested at PHIs of 19 - 23 day s. At seven trials, samples were allowed to dry in the field for 3 - 12 day s between harvest and collection. No residue decline trials were conducted. Individual sample (and per- trial average) total res idues of metconazole (determined as the sum of cis - and trans - metconazole) were below the LOQ (<0.04 ppm) in/on all samples. Corresponding residues of TA were <0.02 - 0.348 ppm (<0.02 - 0.346 ppm). Dry Pea IR - 4 has submitted field trial data for metconazo le on dry peas. Five field trials were conducted in the United States during the 2010 growing season in the NAFTA Growing Zones 5 (NE ; 1 trial ), 7 (ND; 1 trial), 10 (AZ; 1 trial) and 11 ( ID and WA ; 2 trial s ). One pair of trials conducted in Velva, ND (Zo ne 7 ) are separated b y <20 miles and have been assessed for independence; HED h as concluded that these trials should be considered replicates . The above field trial distribution incorporates this conclusion. Each trial consisted of one untreated plot and one treated plot. Each treated plot received two foliar broadcast applications of the 50% WG formulation of metconazole (Quash 50 WDG) at 0.124 - 0.131 lb ai/A/application for a total seasonal rate of 0.250 - 0.258 lb ai/A. Applications were made at RTIs of 7 - 8 day s using ground equipment in spray volumes of 15 - 31 gal/A. An NI S was included in the spray mixtures for all applications. Samples of dry pea were harvested at PHI s of 20 - 22 day s. At two trials, samples were allowed to dry in the field for 2 - 8 day s between harvest and collection. At one trial, additional samples were collected to assess residue decline at PHIs of 9, 14, and 28 day s. Individual sample (and per- trial average) total residues of metconazole (determined as the sum of cis - and trans - metconazole) were <0.04 - <0.062 ppm (<0.04 - <0.0562 ppm). Corresponding residues of TA were 0. 15 5 - 3.16 ppm (0.187 - 2.38 ppm). Inthe residue decline trial , average total residues of metconazole (determined as the sum of cis - and trans - metconazole) were below the LOQ at the 9 - day

PHI, increased at the 14 - day PHI (<0.0546 ppm), and then decreases to at or below the LOQ with increasing PHIs. Corresponding average residues of TA were constant (0.172 - 0.202 ppm) at all sampling intervals. Sunflower IR - 4 has submitted field trial data for metconazole on sunflowers. Ten field trials were conducted in Canada and the United States during the 2010 growing season in the NAFTA Growing Zones 5 (ND and SD ; 3 trials ), 7 (ND and NE; 3 trials), 8 (NM; 1 trial) and 14 ( SK ; 3 trial s ). One pair of trials conducted in Velva, ND were treated with the same spray solution, and, therefore, have been assessed for independence; it w as concluded that these trials should be considered replicates . The above field trial distribution incorporates this conclusion. Each trial consisted of one untreated plot and one treated plo t. Each treated plot received two foliar broadcast applications of the 50% WG formulation of metconazole (Quash 50 WDG) at 0.121 - 0.130 lb ai/A/application for a total seasonal rate of 0.245 - 0.259 lb ai/A. ApplicationsMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 34 of 59 were made at RTI s of 7 - 8 day s using ground equipment in spray volumes of 10 - 35 gal/A. An NI S was included in the spray mixtures for all applications. Samples of sunflower were harvested at PHI s of 20 - 21 day s. At three trials, samples were allowed to dry in the field or were bagged and hun g to dry for 6 - 17 day s between harvest and collection. At one trial, additional samples were collected to assess residue decline at PHI s of 7, 14 and 27 day s. Individual sample (and per- trial average) total residues of metconazole (determined as the sum of cis - and trans - metconazole) were <0.04 - 0.968 ppm (<0.04 - 0. 440 ppm). Corresponding residues of TA were <0.02 - 0.252 ppm (<0.02 - 0. 148 ppm). In the residue decline trial , total residues of metconazole (determined as the sum of cis - and trans - metconazole) and corresponding residues of TA in seed were at or below the LOQ in/on all samples; therefore, residue decline could not be determined. **Table 5.3.1**  **. Summary of Residues from Field Trials with**  **Metconazole .**  Crop Matrix Analyte Total Application Rate (lb ai/A) PHI

(days) n 1 Residues (ppm)

Min. 2 Max. 2 LAFT 3 HAFT 3 Median 3 Mean 3 SD 3 **BEAN, DRY (**  **Proposed Use = 0.25**  **lb ai/acre total application rate, 21**  **- day PHI** **)** Bean, dry Metconazole (sum of

cis - and trans - isomers) 0.245 - 0.259 19 - 23 13 <0.04 <0.04 <0.04 <0.04 0.04 0.04 N/A TA 0.245 - 0.259 19 - 23 13 <0.02 0.348 <0.02 0.346 0.021 0.048 0.090

**PEA, DRY (**  **Proposed Use = 0.25**  **lb ai/acre total application rate, 21**  **- day PHI** **)** Pea, dry Metconazole (sum of

cis - and trans - isomers) 0.250 - 0.258 20 - 22 5 <0.04 <0.0620 < 0.04 <0.0562 0.040 0.043 0.007 Pea, dry TA 0.250 - 0.258 20 - 22 5 0.155 3.16 0.187 2.38 0.591 0.864 0.869

**SUNFLOWER** ( **Proposed Use = 0.25**  **lb ai/acre total application rate, 21**  **- day PHI** **)** Sunflower seed Metconazole (sum of

cis - and trans - isomers) 0.245 - 0.259 20 - 21 10 <0.04 0.968 <0.04 0.440 0.067 0.127 0.131 Sunflower seed TA 0.245 - 0.259 20 - 21 10 <0.02 0.252 <0.02 0.148 0.049 0.054 0.039 1 n = number of field trials. 2 Values based on total number of samples. 3 Values based on per - trial averages. LAFT = lowest average field trial, HAFT = highest average field trial, SD = standard deviation. For computation of the LAFT, HAFT, median, mean, and standard deviation, values <LOQ are assumed to be at the LOQ ( 0.04 p pm for total metconazole and 0.02 ppm for TA). N/A = Not applicable. Rapeseed Subgroup 20A Valent previousl y submitted field trial data for canola, the representative crop for the rapeseed subgroup 20A . The field trials are adequate in number and geographic representation. Samples of canola seed were analyzed for residues of cis - and trans - metconazole using an adequate GC/NPD method (RM - 41C - 1). The validated LOQ is 0.02 ppm for each metconazole isomer ; the L OQ for total metconazole residues ( cis - + trans - isomers) is 0.04 ppm. Residues of 1,2,4 - triazole, TA, and TAA were determined in canola seed using an adequate LC/MS/MS method (Morse Laboratories Method 160) . The validated LOQ of the LC/MS/MS method in canola matrices was 0.01 ppm for triazole an d TAA and 0.03 ppm for TA . Adequate storage stability data are available supporting the storage duration prior to anal ys is of metconazole (parent) and triazole metabolites (1,2,4 - triazole, TA, and TAA) in canola seed. The field trial residues for metconazole and the triazoles are summarized below in Table s 5.3.2 and 5.3.3, respectivel y.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 35 of 59 **Table 5.3.2**  **. Summary of Residue Data from** **Crop Field Trials with Me** **tconazole (WDG) .**  Crop matrix Total Applic.

Rate (lb ai/A) PHI

(days) Residue Levels (ppm) 1

n Min. Max. HAFT 2 Median Mean Std. Dev. **Canola (proposed use =**  **0.125 lb ai/A total application rate,**  **35 -**  **day PHI)** Canola seed 0.124 - 0.130 35 - 49 14 <0.04 <0.04 <0.04 0.04 0.04 NA

0.245 - 0.250 37 - 49 4 <0.04 <0.04 <0.04 0.04 0.04 NA 0.632 35 3 <0.04 <0.04 <0.04 0.04 0.04 NA 1 The LOQ is 0.02 ppm for each isomer, for a combined LOQ of 0.04 ppm. For calculation of the median, mean, and standard deviation, the LOQ was used for samples with residues <LOQ. 2 HAFT = Highest Average Field Trial. **Table 5.3.3**  **. Summary of Residue Data for the Triazole Metabolites from** **Canola Field Trials with**

**Me tconazole (WDG).**  Commodity Total

Applic. Rate (lb ai/A) PHI

(days) Analyte Residue Levels (ppm) 1 n 2 Min. Max. HAFT 3 Median Mean Std. Dev. **Canola (proposed use =**  **0.125 lb ai/A total application rate,**  **35 -**  **day PHI)** Canola seed 0.124 - 0.130 35 - 49 1,2,4 - T 6 <0.01 <0.01 <0.01 0.01 0.01 NA TA 4 6 0.18 0.50 0.49 0.28 0.31 0.14 TAA 6 <0.01 <0.01 <0.01 0.01 0.01 NA 1 The LOQ is 0.01 ppm for each triazole analyte. For calculation of the median, mean, and standard deviation, the LOQ was used for samples with residues <LOQ. 2 For triazole analysis, seed samples were pooled by growing region to yield 3 pooled samples t hat were each analyzed in duplicate. Seeds from Trial F were not included in the pool samples as they were not of commercial quality. 3 HAFT = highest average residues from pooled regional samples. 4 TA residues were found in all control samples at 0.22 - 0.27 ppm and averaged 0.24 ppm. Stone Fruit Crop Group 12 - 12 Valent previousl y submitted field trials on ch e rries, peaches, and plums, which are the representative crops of the stone fruit crop group 12 - 12. The field trials are adequate in number and geographic representation. Samples of stone fruit were anal yz ed for residues of cis - and trans - metconazole using an adequate GC/NPD method (RM - 41C - 1). The validated LOQ is 0.02 ppm for each metconazole isomer ; the LOQ for total metconazole residues ( c is - + trans - isomers) is 0.04 ppm. Adequate storage stability data are available supporting the storage duration prior to analysis of metconazole (parent) in stone fruit. The field trial residues are summarized in Table 5.3.4 below. **Table 5.3.4**  **. Summary**  **of Residue Data from Stone Fruit Crop Field Trials with Metconazole**  Crop matrix Total Applic.

Rate (lb ai/A) PHI

(days) Analyte Residue Levels (ppm) 1 n Min. Max. HAFT 2 Median Mean Std. Dev. **STONE FRUIT (proposed use = 0.375 lb ai/A total application rate, 14**  **- day PHI)**  **1.81 lb/gal FlC form ulation**  Cherry 0.405 - 0.416

0.538 (1 trial) 13 - 14 cis - Metconazole 16 <0.02 0.134 0.119 0.041 0.048 0.032

trans - Metconazole 16 <0.02 0.028 0.025 0.020 0.021 0.002 **Me tconazole**  **16 <0.04**  **0.162 0.143**  **0.061 0.068**  **0.033**Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 36 of 59 **Table 5.3.4**  **. Summary**  **of Residue Data from Stone Fruit Crop Field Trials with Metconazole**  Crop matrix Total Applic.

Rate (lb ai/A) PHI

(days) Analyte Residue Levels (ppm) 1 n Min. Max. HAFT 2 Median Mean Std. Dev. Peach 0.403 - 0.417

0.545 (1 trial) 13 - 14 cis - Metconazole 18 <0.020 0.073 0.066 0.027 0.030 0.015

trans - Metconazole 18 <0.020 <0.020 0.020 <0.020 <0.020 0.00 **Me tconazole**  **18 <0.040**  **< 0.093**  **0.086 0.047**  **0.050 0.015**  Plum 0.40 5 - 0.412

0.538 (1 trial) 13 - 14 cis - Metconazole 12 <0.020 0.04 0.06 0.020 0.024 0.008

trans - Metconazole 12 <0.020 <0.020 <0.020 <0.020 <0.020 -- **Me tconazole**  **12 <0.040**  **< 0.060**  **0.060 0.040**  **0.044 0.008** 

**50% WDG formulation** Cherry 0.407 - 0.410 14 cis - Metconazole 4 0.027 0.056 0.052 0.039 0.040 0.014 trans - Metconazole 4 <0.02 <0.02 0.02 0.020 0.020 0.020 **Me tconazole**  **4 0.049**  **< 0.076**  **0.076 0.068**  **0.065 0.011**  Peach 0.418 14 cis - Metconazole 2 <0.02 0.020 0.02 0.02 0.02 -- trans - Metconazole 2 <0.02 <0.02 0.02 0.02 0.02 -- **Me tconazole**  **2 <0.04**  **< 0.040**  **0.04 0.04**  **0.04 --**  Plum 0.408 14 cis - Metconazole 2 <0.02 0.020 0.02 0.02 0.02 -- trans - Metconazole 2 <0.02 <0.02 0.02 0.02 0.02 -- **Me tconazole**  **2 <0.04**  **< 0.040**  **0.04 0.04**  **0.04 --**  1 Values for “Metconazole” and “Total Residues” are reported on a sample basis and are therefore not summations of tabulated data. 2 HAFT = Highest average field trial result. Tree Nut Group 14 - 12 D348168, N. Dodd, 2/20/08 (almonds and pecans) Valent previousl y submitted field trial s for metconazole on almonds and pecans, the representative commodities of the tree nut crop group 14 - 12. The field trials are adequate in number and geographic representation. Samples of stone fruit were analyzed for resi dues of cis and trans - metconazole using an adequate GC/NPD method (RM - 41C - 1). The validated LOQ is 0.02 ppm for each metconazole isomer ; the L OQ for total metconazole residues ( cis - + trans isomers) is 0.04 ppm. Adequate storage stability data are avail able supporting the storage duration prior to anal ys is of metconazole (parent) in stone fruit. The field trial residues are summarized in Table 5.3.5 below.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 37 of 59 **Table 5.3.5**  **. Summary of Residue Data from** **Tree Nut Crop Field Trials with Metconazole 1**  Crop matrix Total

Applic. Rate (lb ai/A) PHI

(days) Analyte Residue Levels (ppm) n Min. Max. HAFT 2 Median Mean Std. Dev. **TREE NUTS (proposed use = 0.44 or**  **0.50 lb ai/A total application rate, 25**  **- day PHI)**  **1.81 lb/gal FlC form ulation**  Almond, hulls 0.543 - 0.570 25 cis - Metconazole 10 0.42 3.04 2.49 0.65 1.05 0.84 trans - Metconazole 10 0.08 0.65 0.50 0.13 0.22 0.19 **Me tconazole**  **10 0.50**  **3.69 2.82**  **0.78 1.27**  **1.03** 0.394 - 0.408 25 cis - Metconazole 4 0.30 0.62 0.62 0.48 0.47 0.17

trans - Metconazole 4 0.07 0.15 0.14 0.11 0.11 0.04 **Me tconazole**  **4 0.37**  **0.76 0.76**  **0.59 0.58**  **0.21** Almond, nutmeat 0.543 - 0.570 25 cis - Metconazole 10 <0.02 <0.02 <0.02 0.02 0.02 -- trans - Metconazole 10 <0.02 <0.02 <0.02 0.02 0.02 -- **Me tconazole**  **10 <0.04**  **<0.04 <0.04**  **0.04 0.04**  **--** 0.394 - 0.408 25 cis - Metconazole 4 <0.02 <0.02 <0.02 0.02 0.02 --

trans - Metconazole 4 <0.02 <0.02 <0.02 0.02 0.02 -- **Me tconazole**  **4 <0.04**  **<0.04 <0.04**  **0.04 0.04**  **--** Pecan, nutmeat 0.502 - 0.537 25 - 32 cis - Metconazole 4 <0.02 <0.02 <0.02 0.02 0.02 -- trans - Metconazole 4 <0.02 <0.02 <0.02 0.02 0.02 -- **Me tconazole**  **6 <0.04**  **<0.04 <0.04**  **0.04 0.04**  **--**

**50% WDG formulation** Almond, hulls 0.402 - 0.407 25 cis - Metconazole 4 <0.02 1.69 1.51 0.68 0.77 0.87 trans - Metconazole 4 <0.02 0.33 0.31 0.15 0.16 0.17 **Me tconazole**  **4 <0.04**  **2.02 1.82**  **0.83 0.93**  **1.04** Almond, nutmeat 0.402 - 0.407 25 cis - Metconazole 4 <0.02 <0.02 <0.02 0.02 0.02 -- trans - Metconazole 4 <0.02 <0.02 <0.02 0.02 0.02 -- **Me tconazole**  **4 <0.04**  **<0.04 <0.04**  **0.04 0.04**  **--** Pecan, nutmeat 0.529 26 cis - Metconazole 2 <0.02 <0.02 <0.02 0.02 0.02 -- trans - Metconazole 2 <0.02 <0.02 <0.02 0.02 0.02 -- **Me tconazole**  **2 <0.04**  **<0.04 <0.04**  **0.04 0.04**  **--** 1 Values for “Metconazole” and “Total Residues” are reported on a sample basis and are therefore not summations of tabulated data. 2 HAFT = Highest average field trial result. Conclusions . Adequate field trial data have been submitted for the pea and bean , dried shelled, except soy

bean, subgroup 6C and the sunflower subgroup 20B . Field trials were conducted on dry beans, dry

peas, and sunflowers. The studies adequatel y reflect the proposed use patterns. The number of field trials and geographic representations are adequate. The residue data are supported by

adequate storage stability data. The anal ytical methods (the GC/NPD method adapted from Valent Method RM - 41C - 1 f or metconazole and the L C/MS/MS method adapted from Morse Laboratories Meth - 160 for TA) are adequate for anal ys is of the residues of concern. In samples of dry

bean harvested 19 - 23 day s after two applications of the 50% WG formulation of metconazole at a seasonal rate of 0.245 - 0.259 lb ai/A, individual sample (and per- trialMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 38 of 59 average) residues of total metconazole (determined the sum of cis - and trans - metconazole) were below the LOQ (<0.04 ppm) in/on all samples. Corresponding residues of TA were <0.02 - 0. 348 ppm (<0.02 - 0.34 6 ppm). In samples of dry

pea harvested 20 - 22 day s after two applications of the 50% WG formulation of metconazole at a seasonal rate of 0.250 - 0.258 lb ai/A, individual sample (and per- trial average) residues of total metconazole (determined as the sum of cis - and trans - metconazole) were <0.04 - <0.0620 ppm (<0.04 - <0.0562 ppm). Corresponding residues of TA were 0.155 - 3.16 ppm (0.187 - 2.38 ppm). In the residue de cline trial , average total residues of metconazole (determined as the sum of cis - and trans - metconazole) were below the LOQ at the 9 - day PHI , increased at the 14 - day PHI (<0.0546 ppm), and then decreased to at or below the LOQ with increasing PHIs. Corresponding average residues of TA were constant (0.172 - 0.202 ppm) at all sampling intervals. In samples of sunflower seed harvested 20 - 21 day s after two applications of the 50% WG formulation of metconazole at a seasonal rate of 0.245 - 0.259 lb ai/A, individu al sample (and pertrial average) residues of total metconazole (determined as the sum of cis - and trans metconazole ) were <0.04 - 0.968 ppm (<0.04 - 0. 440 ppm). Corresponding residues of TA were <0.02 - 0.252 ppm (<0.02 - 0. 148 ppm). Inthe residue decline trial , total residues of metconazole (determined as the sum of cis - and trans - metconazole) and corresponding residues of TA in seed were at or below the LOQ in/on all samples; therefore, residue decline could not be determined. Th e previousl y submitted field trial data on canola, cherry, peach, plum, almond, and pecan are adequate to support the rapeseed subgroup 20A, the stone fruit subgroup 12 - 12, and the tree nut group 14 - 12. The number of field trials and geographic representations are adequate. Adequate storage stability

data are available to support the field trial data. An adequate data collection method, the GC/NPD method RM - 41C - 1, was used to determine metconazole ( cis - and trans isomers) in canola, stone fruit, and tre e nuts. Residues of 1,2,4 - triazole, TA, and TAA were determined in canola seed using an adequate LC /MS/MS method (Morse Laboratories Method 160). Although stone fruit and tree nut samples were not analyzed for the triazole metabolites, field trial data f

or triazoles are not required for those petitions submitted in 2006. **5.3.2 Field**  **Rotational Crops (860.1900 )**  DP# 380990, 3/24/11, A. Acierto DP# 361110, 2/26/10, D. Soderberg DP# 348168 , 2/20/08, N. Dodd No new field rotational crop studies have been submitted. Limited field rotational crop studies were previousl y submitted for the rotational crops radish, spinach, wheat, and lettuce after seasonal application rates of approximately 0.50 lb ai/A to soy beans , tomatoes , or wheat . Based on th at data, HED required that end - use labels include plant - back restrictions of 30 days for leafy vegetables and Brassica leafy vegetables and 120 day s for all remaining crops other than those with labeled uses. Rotational crop restrictions on both the current label dated 8/12/13 and the proposed label ( Metconazole 50 WDG Fungicide, EPA Reg. No. 59639 - 147) are shown below:Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 39 of 59 ● Immediate plant - back is allowed for barley , corn, cotton, oat, peanut, rye, soy bean, sugar beet, triticale, wheat, and those crops list ed on the label. [Note: Peanut is included on the Metcon azole 50 WDG label; barley , corn, cotton, oat, rye, so yb ean, sugar beet, triticale, and wheat are on the Caramba® Fungicide label (EPA Reg. No. 7969 - 246, dated 6/13/13)]. ● A 30 - day

plant - back interval is required for Brassica Leafy Vegetables and L eafy

Vegetables. ● Do not plant any

crop, except barley , corn, cotton, oat, peanut, rye, so yb ean, sugar beet, triticale, wheat, Brassica Leafy Vegetables, Leafy

Vegetables and those crops listed on the label , earlier than 120 days after applying Metconazole 50 WDG Fungicide. Conclusions . Adequate limited field rotational crop studies have previously been submitted. The rotational crop restrictions on the proposed label (Metconazole 50 WDG Fungicide, EPA Reg. No. 59639 - 147) are adequate. Note: T o support the field rotational crop studies , additional storage stability data were requested for cis - and trans - metconazole reflecting storage for up to 18 months for wheat grain and straw, 19 months for lettuce and wheat hay , and 21 months for radish roots and tops and wheat forage (DP# 348168 (N. Dodd, 2/20/08). This deficiency

has been resolved. HED has accepted the available storage stability data, including data showin g storage stability data for potato for 31.5 months (DP# 380990, A. Acierto, 3/24/11); almond nutmeat for 22 months and almond hulls for 26 months (DP# 348168, N. Dodd, 2/20/08 ) ; and radish root, wheat hay , and soy bean seed for 26 months ( DP# 361110, D. So derberg, 2/26/10) . **5.3.3 Processed Food and Feed (860.1520)**  DP# 350367, N. Dodd, 9/18/08 (canola) DP# 348168, N. Dodd, 2/20/08 (plum) 49297803.de2 (sunflower) Canola A processing study on canola was previously submitted . M etconazole (50% WDG) was appl ied to canola as a single broadcast foliar application during flowering at 0.632 lb ai/A (5x rate the proposed rate). Samples of canola seed, meal and oil were analyzed for residues of cis - and trans - metconazole using an adequate GC/NPD method (RM - 41C - 1). Residues of 1,2,4 - triazole, TA, and TAA were determined using an adequate LC/MS/MS method (Morse Laboratories Method 160). Adequate storage stability data are available supporting the storage durati on prior to analysis of metconazole (parent) and triazole metabolites (1,2,4 - triazole, TA, and TAA) in canola seed, meal, and oil. The processing factors for metconazole and the triazole - related residues are discussed in Table 5.3.3 .1 below. Plum A proc essing study

on plum was previousl y submitted. Metconazole (1 .81 lb ai/gal FlC formulation) was applied three times for a total application rate of 2.04 lb ai/A/season ( 5.4 x the maximum proposed seasonal application rate for stone fruits ) . Residues of metconazole in/onMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 40 of 59 plum samples were quantitated using GC/NPD method RM - 41C - 1 . The method was adequate for data collection based on acceptable method validation and concurrent method recoveries. Adequate storage stability data on cherries are available to support the storage conditions and durations of samples from the plum processing study . The processing factor for metconazole was determined to be 2.3x as shown in Table 5.3.3 .1 below. Sunflower IR - 4 submitted a processing study for metconazole on sunflo wer seed. The processed commodities of sunflower seed are meal and refined oil. In one trial conducted in ND during the 2010 growing season , a 50% WG formulation of metconazole (Quash 50 WDG) was applied as two foliar broadcast applications to sunflower at an exaggerated rate of 0.630 - 0.635 lb ai/A/application for a total seasonal rate of 1.265 lb ai/A ( 5.1x the proposed total application rate) . Applications were made at a 7 - day RTI using ground equipment in spray

volumes of 1 2 gal/A. An NIS was added to the spray mixture for each of the applications. S amples of sunflower seed were harvested at a PHI of 21 days and processed into meal and oil by

GLP Technologies (Navasota, TX) using simulated commercial procedures. Adequate descriptions were provided of the processing procedures, including material balance summaries. As discussed in Section 5.2, the available storage stability data are adequate to support the storage conditions and intervals of samples from the processing study. All samples were frozen at the testing facility

and remained frozen during shipping and st orage prior to processing and anal ys is . Samples were anal yz ed for residues of metconazole, determined as cis - and trans - metconazole, using a GC/NPD method adapted from Valent Method RM - 41C - 1 (dated 11/13/03). Samples were anal yz ed for residues of the tri azole metabolit e triazole alanine (TA) using an LC/MS/MS method adapted from Morse Laboratories Meth - 160 (dated 6/27/03). The LOQ ( determined as the lowest level of method validation, LLMV) was 0.02 ppm for each anal yt e. Acceptable method validation and concurrent recovery data were reported for sunflower samples at fortification levels of 0.02 - 0.2 ppm , thus validating the method s . The fortification levels were adequate to bracket expected residue levels. A lthough triazole fungicides are typicall y monit ored for residues of all three triazole metabolites (i.e., 1,2,4 - triazole, TA, and TAA) , HED previously

concluded that only

anal ys is for TA need be conducted in the subject study (refer to HED’s Chemistry

Science Advisory

Council minutes, 8/11/2010 meeting). Following two foliar broadcast applications of the 50% WG formulation at total application rates of 1.265 lb ai/A, quantifiable residues of total metconazole (determined as the sum of cis - and trans - metconazole) were observed in/on sunflower seed (RAC) , but were below the combined LOQ (<0.04 ppm) in meal and oil. Corresponding residues of TA were 0.0200 ppm in/on sunflower seed, 0.0580 ppm in meal, and below the LOQ (<0.0 2 ppm) in oil . A comparison of the residues in sunflower seed (RAC) with those in each processed sunflower fraction indicated that total residues of metconazole (determined as the sum of cis - and trans metconazole) do not concentrate (processing factors <1x) in meal and oil. Residues of TAMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 41 of 59 concentrate in sunflower meal (processing fac tor of 2.9x), but do not concentrate in oil . These processing factors are less than or close to the theoretical concentration factors. The theoretical concentration factors for sunflower are 4.5x for meal and 2.5x for oil (Table 3, OCSPP 860.1520). Resid ues found in samples and processing factors are given in Table 5.3.3 .2 below . **Table 5.3.3.**  **1. Summary of Processing Factors for Metconazole**  **( cis**  **- and**  **trans -**  **isomers) in Canola**  **.** RAC Processed Commodity Processing Factor s 1 Metconazole 1,2,4 - triazole TA TAA Canola seed Meal NC NC 2.07x 1.43x

Refined oil NC NC 0.005x 1.0x Plum Pr

une 2.3x NA2 NA NA 1 NC = Not calculated; residues were below the LOQ in the RAC and the processed commodity. 2 NA = Not analyzed since analysis is not required for data submitted in 2006. **Table 5.3.3. 2.**  **Residue Data from Sunflower Processing Study with**  **cis -**  **and trans**  **- Me** **tconazole and TA.** RAC/Processed Commodity Total

Rate lb ai/A PHI

(day) Analyte Residues (ppm) 1 Processing

Factor Median

Processing Factor Sunflower, seed 1.265 21 cis - metconazole 0.170 -- -- trans - metconazole 0.0362 -- -- Total metconazole 0.206 -- -- TA 0.0200 -- -- Sunflower, meal cis - metconazole <0.02 <0.1x -- trans - metconazole <0.02 <0.6x -- Total metconazole <0.04 <0.2x -- TA 0.0580 2.9x -- Sunflower, oil cis - metconazole <0.02 <0.1x -- trans - metconazole <0.02 <0.6x -- Total metconazole <0.04 <0.2x -- TA ND <1.0x -- 1 ND = Not detected (< LOD). For seed, meal, and oil, respectively, the LODs were 0.00601, 0.00615, and 0.01330 ppm for cis - metconazole and 0.00864, 0.01533, and 0.00589 ppm for trans - me tconazole, and the LOQ was 0.02 ppm for each analyte, for a combined LOQ of 0.04 ppm. For T A, the LODs were 0.00356, 0.02229, and 0.01207 ppm for seed, meal, and oil, respectively, and the LOQ was 0.02 ppm. Combined residues and per trial averages were calculated by the study reviewer using the LOQ for all residues reported as <LOQ. Conclusions . Adequate processing studies have been submitted on canola, plum, and sunflower. (Refer to Section 6.0 for a discussion of recommended tolerances for processed commodities.) Canola: M etconazole residues ( cis - and trans - metconazole) were non - detectable in/on seed, meal and refined oil samples from a field trial treated at an exaggerated 5x rate. Residues of 1,2,4 - triazole were also not detectable in the RAC treated at 5x and processed commodities (meal and refined oil). The data indicate that residue s of TA and TAA do not concentrate in oil. However, residues of TA and TAA concentrated in canola meal by 2.1x and 1.4x, respectively .Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 42 of 59 Plum: The process ing study on plums treated at a 5.4x rate indicate that m etconazole residues ( cis - and trans - metcon az ole) concentrate 2.3x in prunes. S unflower : Following two foliar broadcast applications of the 50% WG formulation at total application rates of 1.265 lb ai/A (5 .1 x the proposed total application rate) , quantifiable residues of metconazole ( cis - and trans - metconazole) were observed in/on sunflower seed (RAC) . Metconazole residues ( cis - and trans - metconazole ) were below the combined LOQ (<0.04 ppm) in sunflower meal and oil , indicating that metconazole residues do not concentrate (processing factors <1x) in meal and oil. Corresponding residues of TA were 0.0200 ppm in/on sunflower seed, 0.0580 ppm in meal, and below the LOQ (<0.0 2 ppm) in oil ; these data indicate that residues of TA concentrate in sunflower meal (processing factor of 2.9x), but do not concentrate in oil. Adequate storage stability data are available to support sample storage durations and conditions for these processing studies . The data collection methods (the GC/NPD method adapted from Valent Method RM - 41C - 1 for metconazole and the L C/MS/MS method adapted from Morse Laboratories Meth - 160 for 1,2,4 - triazole, TA, and TAA) are adequate for analysis of the residues of concern. The observed processing factors in these processing studie s are less than the theoretical concentration factors . The theoretical processing factor is 3.5x for prunes (OCSPP 860.1520, Table 1). The theoretical processing factors are 1.9x for canola meal, 3.0x for canola oil, 4.5x for sunflower meal , and 2.5x for sunflower oil (based on separation into components; OCSPP 860.1520, Table 3). **5.3.4 Meat, Milk, Poultry and Eggs**  **(860.1480)** D P# 348168, N. Dodd, 2/20/08 (cattle feeding study) D P# 350367, N. Dodd, 9/18/08 (poultry feeding study) D P# 399057, N. Dodd, 7/19/12 Adequate c attle and poultry feeding studies were previously submitted and are summarized below . Maximum residues of metconazole (sum of cis - and trans - isomers) and 1,2,4 - triazole are reported below in Tables 5.3.4.1 and 5.3.4.2, respectively . Cattle In the cattle feeding study (MRID 46901914), cattle were dosed orall y with metconazole at 4.73, 14.6, and 45.7 ppm (low, mid, and high dose) in the diet via capsules for 28 consecutive day s. These dose levels are respectivel y equivalent to 2.0x, 6.1 x, and 19x the dietary burden for beef cattle and 0.56x, 1.7x, and 5.4x the dietary burden for dairy

cattle. Residues of cis - and trans metconazole were determined in milk using method RM - 41M - 1 (GC/NPD) and in tissues using method RM - 41M - 2 (L C/MS/MS). Th e validated LOQs for RM - 41M - 1 were 0.02 ppm for each anal yt e in milk and 0.04 ppm for each anal yt e in cream. The validated LOQ for RM - 41M - 2 was 0.02 ppm for each anal yt e in tissues. L ow - and mid - dose samples were not anal yz ed for cis - and trans - metconazo le except for mid - dose liver, which had residues of <0.02 ppm for each isomer. In high - dose liver, residues of cis - and trans - metconazole were <0.02 - 0.021 ppm and <0.02 ppm, respectivel y; maximum total metconazole residues (sum of cis - and trans - isomers) were <0.041Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 43 of 59 ppm in liver. Residues of cis - and trans - metconazole were <LOQ in all samples of whole milk, skim milk, cream, fat, muscle, and kidney from the high - dose group. The triazole metabolites ( 1,2,4 - triazole, TA, and TAA) were not determined in the cattle feeding study . Poultry In the poultry

feeding study

(MRID 47406901), layinghens were dosed orally with metconazole at 2.05, 6.24, and 20.3 ppm (low, mid, and high dose) in the diet via capsules for 28 consecutive day s. The dose levels are respectivel y equivalent to 5.4x, 16x, and 53x the dietary burden for poultry . Residues of cis - and trans - metconazole were separatel y determined in e ggs and tissues using the LC/MS/MS method RM - 41M - 2. The validated L OQ for RM - 41M - 2 is 0.02 ppm for each anal yt e in eggs and tissues. Residues of cis - and trans - metconazole were <LOQ in eggs from the low - and mid - dose groups, but quantifiable metconazole residues were found in eggs from the high - dose group, with total residues of cis - and trans - metconazole in eggs ranging from <0.04 - < 0.085 ppm. Residues of cis - and trans - metconazole were <LOQ in all samples of muscle, fat, and liver from all three dose groups. Residues of 1,2,4 - triazole in egg and poultry tissue samples were determined using the LC/MS/MS method (Morse Laboratories Method 160, Revision 2). The validated L OQ is 0.01 ppm for triazole in eggs and tissues. Triazole residues were <LOQ (<0.0 1 ppm) in selected egg samples from the 1x and 3x group s , with the exception of one sample from the 3x group on Day 28, which had triazole residues of 0.011 ppm. Inthe 10x dose group, triazole residues were quantifiable in all anal yz ed egg samples . Triazole residues plateaued in eggs b y Day 7 and were 0.015 - 0.026 ppm between Day s 7 - 28 and averag ed 0.02 ppm. Inpoultry tissues, triazole residues were <LOQ in fat from the 10x dose group and in muscle and liver from the 1x dose groups; however, triazole re sidues were quantifiable in muscle and liver from the 3x and 10x dose groups and increased with dose level. For both muscle and liver, triazole residues averaged 0.01 ppm for the 3x dose group and 0.029 ppm for the 10x dose group. TA and TAA were not det ermined in eggs and poultry tissues . **Table 5.3.4.**  **1. Summ**  **ary of Livestock Feeding Studies with Me** **tconazole** Commodity Feeding Level, ppm Residue in Tissue, ppm 1 Tissue - to - Feed Ratio 2 Milk (whole and skim) 45.7 <0.04 (<LOQ) -- Cream 45.7 <0.08 (<LOQ) -- Muscle (cattle) 45.7 <0.04 -- Fat (cattle) 45.7 <0.04 -- Liver (cattle) 14.6 <0.04 -- 45.7 < 0.041 0.00090 Kidney (cattle) 45.7 <0.04 -- Eggs 2.05 <0.04 -- 6.24 <0.04 -- 20.3 < 0.085 0.0042 Muscle (poultry) 2.05 <0.04 -- 6.24 <0.04 - 20.3 < 0.04 -- Fat (poultry) 2.05 <0.04 -- 6.24 <0.04 -- 20.3 <0.04 --Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 44 of 59 Liver (poultry) 2.05 <0.04 -- 6.24 <0.04 -- 20.3 <0.04 -- 1 M aximum residues of metconazole (sum of cis - and trans - isomers). are reported . The LOQ is 0.04 ppm (0.02 ppm for each isomer) in all commodities except cream. The LOQ in cream is 0.08 ppm . Tissue - to - feed ratios were not calculated for matrices with residues of <LOQ. 2 Tissue - to - feed ratios were not calculated for matrices with re sidues of <LOQ. **Table 5.3.4. 2**  **. Summ ary of**  **1,2,4 -**  **Triazole Residues from Poultry**  **Feeding Studies with Metconazole**  Commodity Feeding Level, ppm Residue in Tissue, ppm 1 Tissue - to - Feed Ratio 2 Eggs 2.05 <0.01 -- 6.24 0.011 0.0018 20.3 0.026 0.0013 Muscle (poultry) 2.05 <0.01 -- 6.24 0.011 0.0018 20.3 0.031 0.0015 Fat (poultry) 20.3 <0.01 -- Liver (poultry) 2.05 <0.01 -- 6.24 0.011 0.0018 20.3 0.032 0.0016 1 M aximum residues of 1 , 2 , 4 - triazole , expressed as 1,2,4 - triazole, are reported . The LOQ is 0.01 ppm. 2 Tissue - to - feed ratios were not calculated for matrices with residues of <LOQ. **5.3. 4.1**  **Dietary Burden** Livestock feed items associated with the proposed /expanded uses are sunflower meal, safflower meal, canola meal, flax meal, and almond hulls. There are no livestock feed items associated with stone fruits or tree nuts other than almonds. There are no livestock feed items associated with dried shelled peas and beans except for cowpeas (seed, forage, and hay) and field peas (seed, vines/silage, and hay) ( Table 1 Feedstuffs , June 2008). To avoid the need for residue data on livestock feed items of cowpea and field pea, the label should be revised to include the following statement for the dried shelled pea and bean, except soy

bean, subgroup 6C: “Do not apply to cowpea or field pea used for livestock feed.” 

### The dietary

burdens for metconazole residues are based on the maximum reasonabl y balanced diets ( Table 1 Feedstuffs , June 2008) . The dietary burdens for metconazole residues are calculated to be 2.4 ppm for beef cattle, 8.5 ppm for dairy cattle, 0. 38 ppm for poultry , and 0. 14 ppm for swine. **Table 5.**  **3. 4.1**  **. Calculation of Dietary Burdens of**  **Me tconazole R** **esidues to Livestock.** Feedstuff Ty pe 1 % Dry Matter2 % Diet2 HAFT 4 or Median 5,6 ,7 Residue Level

(ppm) Dietary

Contribution (ppm) 3 **Beef Cattle (R = 15%; CC = 80%; PC = 5%)**  Wheat hay R 88 15 HAFT 12.6 2.15 Barley grain CC 88 50 Median 0.48 0.27Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 45 of 59 **Table 5.**  **3. 4.1**  **. Calculation of Dietary Burdens of**  **Me tconazole R** **esidues to Livestock.** Feedstuff Ty pe 1 % Dry Matter2 % Diet2 HAFT 4 or Median 5,6 ,7 Residue Level

(ppm) Dietary

Contribution (ppm) 3 Wheat, milled byproducts CC 88 30 Median x PF 0.063 0.021 Sunflower meal PC 92 5 Median 0. 067 0 .0036

TO TAL BURDEN -- -- 100 -- -- **2.4 Dairy Cattle**  **(R = 45%; CC = 45%; PC = 10%)** Oat hay R 90 10 HAFT 11.24 1.25 Wheat hay R 88 20 HAFT 12.6 2.86 Corn, sweet, stover R 83 15 HAFT 22.7 4.10 Barley grain CC 88 4 5 Median 0.48 0.25 Sunflower meal PC 92 10 Median 0. 067 0.0073

TO TAL BURDEN -- -- 100 -- -- **8.5 Swine**  **(CC = 85%; PC = 15%)** Barley grain CC 88 20 Median 0.48 0.096 Wheat, milled byproducts CC 88 50 Median x PF 0.063 0.032 Corn, field, grain CC 88 1 5 Median 0.01 0.0015 Sunflower meal PC 92 15 Median 0 .067 0.010

TO TAL BURDEN -- -- 100 -- -- **0.14 Poultry**  **(CC = 75%; PC = 25%)**  Barley grain CC 88 75 Median 0.48 0.36 Sunflower meal PC 92 25 Median 0. 067 0 .017

TO TAL BURDEN -- -- 100 -- -- **0.38** 1 R: Roughage; CC: Carbohydrate concentrate; PC: Protein concentrate. 2 Table 1 Feedstuffs (June 2008). 3 Contribution = ([tolerance /% DM] X % diet) for beef and dairy cattle; contribution = ([tolerance] X % diet) for poultry and swine. 4 The HAFT (highest average field trial) was used for sweet corn stover , oat hay, and wheat hay. 5 The median was used for the blended commodities field corn grain and barley grain. 6 The median times the processing factor (PF) was used for wheat milled by products ( PF = 2.1x based on shorts, which had the highest PF considering bran, middlings, s horts). 7 The median was used for sunflower meal (OECD’s “Guidance on Residues in Livestock,” ENV/JM/MONO(2013)8, 9/4/13 ) . **5.3. 4.2**  **Estimated Secondary Residues in Livestock**  The secondary

residue levels of metconazole in livestock commodities in Table 5.3.4.2 below were estimated using tissue - to - feed ratios from Table 5.3.4 above and the calculated dietary burden from Table 5.3.4.1 above. **Table 5.3.**  **4.2 .**  **Estim ation of Secondary Residues from** **Use of Me** **tconazole (sum of**  **cis -**  **and trans**  **- isomers)**  **.** Commodity Tissue - to - Feed Ratio Dietary Burden (ppm) Expected Residue Liver (cattle) 0.00 090 8.5 0.0076 Eggs 0.0042 0.38 0.0016Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 46 of 59 Tolerances for metconazole are established in 40 CFR §180.617 at 0.04 ppm for meat b yproducts of cattle, goat, horse, and sheep. No tolerances are established for milk, meat, or fat of cattle, goat, horse, and sheep. A tolerance of 0.04 ppm is establishe d in egg; no other tolerances are established for poultry . No tolerances are established for swine. Conclusions. Based on the cattle feeding study and the calculated dietary burden based on the maximum reasonably

balanced diet ( Table 1 Feedstuffs , June 2008), no change s are required in the established livestock tolerances as a result of the proposed/expanded uses. The established tolerances for meat by

products of cattle, goat, horse, and sheep at 0.04 ppm and for egg at 0.04 ppm are adequate. No tolerances are established for milk; fat and meat of cattle, goat, hog, horse, poultry , and sheep; or meat by products of hog and poultry since residues are not expected to occur in those commodities. If additional uses increase the dairy cattle dietary

burden, additional ruminant feeding studies conducted at higher rates may be needed. **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**  Crop Field Trials : Adequate field trial data have been sub mitted on dry beans, dry

peas, sunflowers , canola, almonds, pecans, cherries, peaches, and plums . The studies adequatel y reflect the proposed use patterns. The number of field trials and geographic representations are adequate. The residue data are supported b y adequate storage stability data. The anal ytical methods (the GC/NPD method adapted from Valent Method RM - 41C - 1 for metconazole and the LC/MS/MS method adapted from Morse Laboratories Meth - 160 for triazoles ) are adequate for anal ys is of the residues of concern. The residue data on canola, almonds, pecans , cherries, peaches, and plums support the established tolerance levels. Metconazole residues (the sum of cis - and trans - isomers) in dry beans were all below the LOQ (<0.04 ppm) . Metconazole residues in dry pea were generall y <LOQ. Metconazole residues sunflower seeds were generall y quantifiable but low. Residues of TA were quantifiable (>0.02 ppm) in 54% of the dry

bean samples. TA was generall y quantifiable in dry pea and sunflower seeds . In the dry pea residue decline trial , av erage total residues of metconazole were below the LOQ at the 9 - day PHI, increased at the 14 - day PHI (<0.0546 ppm), and then decreased to at or below the LOQ with increasing PHIs. Corresponding average residues of TA were constant (0.172 - 0.202 ppm) at all sampling intervals.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 47 of 59 In the sunflower residue decline trial , residue decline could not be determined because all residues were ≤L OQ. Processing Studies : Adequate processing studies have been conducted on canola, plums, and sunflowers. Canola: Metconaz ole (the sum of cis - and trans - isomers) was non - detectable in/on canola seed, meal and refined oil samples reflecting treatment at a 5x rate; therefore, separate tolerances are not required for canola meal and oil. Residues of 1,2,4 - triazole were also not detectable in canola seed, meal and refined oil reflecting treatment at 5x. Re sidues of TA and TAA do not concentrate in oil. However, residues of TA and TAA concentrated in canola meal by 2.1x and 1.4x, respectively . Plum: Metconazole (the sum of cis - and trans - isomers) concentrates 2.3x in prunes. Sunflower: M etconazole (the sum of cis - and trans - isomers) do es not concentrate in sunflower meal and oil. Residues of TA concentrate 2.9x in sunflower meal , but do not concentrate in oil. Storage Stability : The storage stability data are adequate to support the intervals of frozen storage from harvest to analysis for dry bean, dry pea, sunflower (seed, meal, and refined oil), canola (seed, meal and refined oil), cherry , peach, plum, and prune. No corrections of residue values from the field trials or p rocessing studies for loss of metconazole or TA residues are necessary . Meat, Milk, Poultry, and Eggs : Based on the cattle feeding study and the calculated dietary burden based on the maximum reasonabl y balanced diet ( Table 1 Feedstuffs , June 2008), no change s are required in the established livestock tolerances as a result of the proposed/expanded uses. No residues are expected to occur in milk, fat, and meat, and residues in liver are not expected to exceed the established tolerance of 0.04 ppm. Rotational Crops : Since the confined study indicated the potential for quantifiable metconazole residues in rotated crop commodities, limited field rotational crop trials were conducted. Based on the limited field rotational crop trials, rotational crop restrictions are included on the registered label (Metconazole 50 WDG Fungicide, EPA Reg. No. 59639 - 147) . The same rotational crop restrictions on the proposed label are adequate . **6.0 Tolerance**  **Derivation** The established tolerances for canola, the stone fruit crop group 12, and the tree nut crop group 14 are adequate for the rapeseed subgroup 20A, the stone fruit crop group 12 - 12, an d the tree nut crop group 14 - 12, respectively . However, to harmonize with Canada, HED is recommending a tolerance of 0.08 ppm for the rapeseed subgroup 20A. As shown in Appendix D , the Office of Economic Cooperation and Development (OECD) tolerance calculation procedures were used for calculating a tolerance for metconazole in sunflower. The statistical goal of the tolerance calculation procedures is to produce a maximumMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 48 of 59 residue limit MRL) proposal in the region of the 95 th percentile of the underlying residues distribution. The OECD tolerance procedures were use d for calculating a tolerance for dry pea. However, to harmonize with Canada, HED is recommending a tolerance of 0.15 ppm on the pea and bean, dried shelled, except so ybean, subgroup 6C. The OECD tolerance calculation procedures were not used for metconazole in dry beans since all residues of metconazole (MRID 49297801) were <LOQ (<0.04 ppm) in dry beans. Separate tolerances are not required for canola meal and oil since metconazole residues were non - detectable in/on seed, meal and refined oil samples from a field trial treated at an exaggerated 5x rate . Residues of 1,2,4 - triazole were also not detectable in canola seed treated at 5x and processed commodities (meal and refined oil). The data indicate that residues of TA and TAA do not concentrate in oil. However, residues of TA and TAA concentrated in canola meal by 2.1x and 1.4x, respectively . Residues of metconazole concentrate 2.3x in prunes. Based on the HAFT residues in plum (0.06 ppm) and the processing factor (2.3x), expected residues in p rune would be 0.14 ppm. This value is less than the established/recommended 0.20 ppm tolerance for the stone fruit group; therefore, a separate tolerance for prune is not required. Residues of metconazole do not concentrate in sunflower meal and oil ; there fore, separate tolerances are not needed for sunflower meal and oil . Residues of TA concentrate in sunflower meal (processing factor of 2.9x), but do not concentrate in oil. Dry Pea (MRID 49 297802 ) The dataset for metconazole on dry pea c onsisted of data from five field trials representing foliar broadcast application s at the rate of 0. 250 - 0.258 lb ai/A/ season with PHI s of 2 0 - 22 day s . The field trial application rates are within 25% of the maximum label application rate. The average fiel d trial residue values used to calculate the tolerance are provided in Appendix D . Residues of metconazole were quantifiable in only one of five f

ield trials. Using the OECD tolerance calculation procedures, the tolerance for the residues of metconazole in dry bean would be 0.0 8 ppm, which is the higher result of dry bean (0.04 ppm) and dry pea (0.08 ppm). However, t o harmonize with Canada, HED is recommending a tolerance of 0.15 ppm for the pea and bean, dried shelled, except so ybean, subgroup 6C. Sunflower (MRID 49297803) The dataset used to determine a tolerance for metconazole on sunflower c onsisted of data from ten field trials representing foliar broadcast application s at the rate of 0.245 - 0.259 lb ai/A/ season with PHI s of 20 - 21 day s . The fie ld trial application rates are within 25% of the maximum label application rate. The average field trial residue values used to calculate the tolerance are provided in Appendix D . Residues of metconazole were quantifiable in eight of ten field trials.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 49 of 59 U sing the OECD tolerance calculation procedures, the recommended tolerance for the residues of metconazole in sunflower is 0.7 ppm.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 50 of 59 **Appendix A. Tabular**  **Summary of Metabolites Table A.1. Structures and Names of Metconazole and Metabolites**  Common name/code ID No. Chemical name Chemical structure Metconazole (AC 900768) (CL 900768) 5 - [(4 - chlorophenyl)methyl] - 2,2 - dimethyl - 1 - (1 H

- 1,2,4 - triazol - 1 - ylmethyl)cyclopentanol Cis - isomer

Trans - isomer

M1 (CL 359451) 5 - [(4 - chlorophenyl)methyl] - 2 - methoxyl - 2 - methyl - 1 - (1 H - 1,2,4 - triazol - 1 - ylmethyl) - 1 - cyclopentanol

M11 (CL 382390) 5 - [(4 - chlorophenyl)methoxyl] - 2,2 - dimethyl - 1 - (1 H

- 1,2,4 - triazol - 1 - yl methyl) - 1 - cyclopentanol

M12 (CL 359138) 5 - [(4 - chlorophenyl)methyl] - 2 - carboxyl 2 - methyl - 1 - (1 H

- 1,2,4 - triazol - 1 - yl methyl) - 1 - cyclopentanol

M13 (CL359139) 3 - (4 - chlorobenzyl) - 2 - hydroxy- 1 - methyl - 2 - [1,2,4]triazol - 1 - ylmethyl cyclopentanecarboxylic acid N N N

C H 3 C H 3 O H Cl

N N N

C H 3 C H 3 O H Cl

N N N

Cl H

H C H 2 O H C H 3 O H

N N N

Cl O

H H C H 2 O H C H 3

C H 3 N N N

C H 3 O H Cl H O O C

O

H N N N

Cl O H OMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 51 of 59 **Table A.1. Structures and Names of Metconazole and Metabolites** Common name/code ID No. Chemical name Chemical structure M21 (CL 382391) 5 - [(4 - chlorophenyl)methoxyl] - 2,2 - dimethyl - 1 - (1 H

- 1,2,4 - triazol - 1 - yl methyl) - 1 - cyclopentanol

M30 (CL 382389) 5 - [(4 - chlorophenyl)keto] - 2,2 - dimethyl 1 - (1 H - 1,2,4 - triazol - 1 - yl methyl) - 1 - cyclopentanol

M31 (CL 359139) (1S*,3R*,5S*) - 3 - hydroxy - cis metconazole

1,2,4 - Triazole (1,2,4 - T; free triazole) 1 H - 1,2,4 - triazole N H N N Triazolylalanine (Triazole alanine) (TA) (M35) (CL 147267) 2 - amino - 3 - (1 H - 1,2,4 - triazol - 1 - yl)propanoic acid

Triazolylacetic acid (Triazole acetic acid) (TAA) 1 H - 1,2,4 - triazol - 1 - yl acetic acid Hydroxymetconazole (1RS,5RS,1RS,5SR) - 5 - (4 - hydroxybenzyl) - 2,2 - dimethyl - 1 - (1H 1,2,4 - triazol - 1 - yl methyl)cyclopentanol O H N N N

Cl C H 3 C H 3 O

N N N

C H 3 O H Cl C H 3 O H

N N N NH 2 C O O H

N N N C O O H

N N N

O H O HMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 52 of 59 **Appendix B**  **. Field Trial Geographic Distribution**  **Table C.1**  **. Dry Bean**  **Trial Numbers and Geographical Locations.** Crop No.

Trials NAFTA Growing Zone Total

1 2 3 4 5 6 7 8 9 10 11 12 Bean, dried Sub. 1 -- -- -- 6 -- 1 1 1 1 2 -- 13

Req. 1 1/0 -- -- -- 5/4 -- 2/1 1/1 1/1 1/1 1/1 -- 12/9 1 As per Table 5 of 860.1500 for bean, dried; the second number reflects a 25% reduction in the number of field trials allowed for the crop as a representative commodity in support of a crop group/subgroup tolerance or when application results in no quantif iable residues. **Table C.**  **2. Dry Pea**  **Trial Numbers and Geographical Locations.** Crop No.

Trials NAFTA Growing Zone Total

1 2 3 4 5 6 7 8 9 10 11 12 Pea, dried Sub. -- -- -- -- 1 -- 1 2

-- -- 1 2 -- 5

Req. 1

-- -- -- -- -- -- -- -- -- -- -- -- 5 1 As per Table 1 of OCSPP 860.1500 for peas (dried shelled) ; requested 5 trials, regions are not specified. 2 HED has concluded that two trials conducted in ND (Zone 7 ) are replicate trials for purposes of OCSPP 860.1500 data requirements. **Table C**  **. 3**  **. Sunflower**  **Trial Numbers and Geographical Locations.** Crop No.

Trials NAFTA Growing Zone Total 1 2 3 4 5 6 7 8 9 10 11 12 **13 14**  Sunflower Sub. -- -- -- -- 3 -- 3 3 1 -- -- -- -- -- 3 1 0

Req. 1

-- -- -- -- 3/2 -- 4/3 1/1 -- -- -- -- -- -- 8 /6 Req. 2

-- -- -- -- 2 -- 1 -- -- -- -- -- -- 2 5 1 As per Table 5 of 860.1500 for sunflower ; the second number reflects a 25% reduction in the number of field trials allowed for the crop as a representative commodity in support of a crop group/subgroup tolerance or when application results in no quantifiable residues. 2 As per Table 1.2 of PMRA Directive DIR98 - 02 for sunflower . 3 HED has concluded that two trials conducted in Velva, ND (Zone 7 ) are replicate trials for purposes of OCSPP 860.1500 data requirements.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 53 of 59 **Appendix C**  **. International Residue Limits Table**



### Metconazole ( 125619 ; 0 8/27/20 14 ) Summary of US and International Tolerances and Maximum Residue Limits Residue Definition : US Canada Mexico 2 Codex 40 CFR §180.617 Metconazole [5 - [(4 - chlorophenyl)methyl] - 2,2 - dimethyl - 1 - (1 H

- 1,2,4 - triazol - 1 - ylmethyl)cyclopentanol] 5 - [(4 - chlorophenyl)methyl] - 2,2 - dimethyl - 1 - (1 H

- 1,2,4 - triazol - 1 - ylmethyl) cyclopentanol None Commodity 1 Tolerance (ppm) /Maximum Residue Limit (mg/kg) US Canada Mexico 2 Codex

F r uit , sto n e , gro u

p 1 2 - 1 2 0.2 0.2 American plums, apricots, beach plums, black cherries, Canada plums, capulins, cherry plums, chicksaw plums, damson plums, fresh prune plums, Japanese apricots, Japanese plums, klamath plums, nanking cherries, nectarines, peaches, plumcots, plums, sloes, sweet cherries, tart cherries

Nut , tree , gro u

p 14 - 1 2 0.04 0.04 African tree nuts, almond nuts, beechnuts, black walnuts, Brazil nuts, Brazilian pine nuts, bunya nuts, bur oak nuts, butternuts, Cajou nuts, candlenuts, cashew nuts, chestnuts, chinquapin nuts, coconuts, coquito nuts, dika nuts, English walnuts, ginkgo nuts, Guiana chestnuts, hazelnuts (filbert), heartnuts, hickory nuts, Japanese horse - chestnuts, macadamia nuts, mongongo nuts, mo nkey -pot nuts, mo nkey puzzle nuts, Okari nuts, Pachira nuts, peach palm nuts, peanuts, pecan nuts, pequi nuts, Pili nuts, pine nuts, pistachio nuts, Sapucaia nuts, tropical almond nuts, yellow horn nuts

P e a and b ean , drie d s h elle d , e x cep t so y

b ean , s ub gro u

p 6 C 0.15 0.15 Dry (adzuki beans, beans,

blackeyed peas, broad beans, catjang seeds, chickpeas, cow

pea seeds, field peas, guar seeds, kidney beans, lablab beans, lentils, lima beans, mo th beans, mung beans, navy beans, pigeon peas, pink beans, pinto beans, rice be ans, southern peas, tepary beans, urd beans, grain lupin 0.05 dry soybeansMetconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 54 of 59 Summary of US and International Tolerances and Maximum Residue Limits Residue Definition : US Canada Mexico 2 Codex 40 CFR §180.617 Metconazole [5 - [(4 - chlorophenyl)methyl] - 2,2 - dimethyl - 1 - (1 H

- 1,2,4 - triazol - 1 - ylmethyl)cyclopentanol] 5 - [(4 - chlorophenyl)methyl] - 2,2 - dimethyl - 1 - (1 H

- 1,2,4 - triazol - 1 - ylmethyl) cyclopentanol None

Rap esee d sub gro u

p 20 A 0.08 0.08 Seeds (borage, cuphea, echium, flax, gold of pleasure, hare's ear mustard, milkweed, mustard (oilseed type), oil radish, poppy, rapeseed (canola), sesame, sweet rocket Sun flo we r s ub gro u

p 20 B 0.7 Com pleted: M. Negussie; 08/27/2014 1 Includes only commodities of interest for this action. Tolerance values should be the HED recommendations and not those proposed by the applicant. 2 Mexico adopts US tolerances and/or Codex MRLs for its export purposes.Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 55 of 59 **A ppendix**  **D .**  **OECD MRL Calcu lation Procedure**  **Inputs/Outputs** Sunflower Seeds (MRID 49297803) - Metco nazole 0.245 - 0.259 lb ai/A ; 20 - 21 day PHI **Residues (mg/kg) n**  < 0.04 2 0.0402 1 0.043 1 0.045 1 0.0883 1 0.0957 1 0.196 1 0.237 1 0.44 1 **Metconazole Sunflower**  **S eeds**  **USA, Canada 0.245**  **- 0.259 lb ai/A;**  **20 -**  **21 day PHI Total number of data (n)**  10 **Percentage of censored data** 20% **Number of non -**  **censored data** 8 **Lowest residue** 0.040 **Highest residue** 0.440 **Median residue** 0.067 **Mean** 0.127 **Standard deviation (SD)** 0.131 **Correction factor for censoring (CF)** 0.867 **Proposed MRL estimate**

**- Highest residue**  0.440

**- Mean + 4 SD**  0.649

**- CF x 3 Mean**  0.329 **Unrounded MRL** 0.649 **Rounded MRL 0.7** Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 56 of 59 Sunflower (MRID 49297803)

– TA 0.245 - 0.259 lb ai/A ; 20 - 21 day PHI **Residues (mg/kg) n**  < 0.02 1 0.0213 1 0.0243 1 0.0253 1 0.042 1 0.0562 1 0.0654 1 0.0663 1 0.073 1 0.148 1

**TA**

**Sunflower Seeds USA, Canada**  **0.245 -**  **0.259 lb ai/A; 20**  **- 21 day PHI**  **Total number of data (n)** 10 **Percentage of censored data**  10% **Number of non -**  **censored data** 9 **Lowest residue** 0.020 **Highest residue** 0.148 **Median residue** 0.049 **Mean** 0.054 **Standard deviation (SD)** 0.039 **Correction factor for censoring (CF)** 0.933 **Proposed MRL estimate**

**- Highest**  **residue** 0.148

**- Mean + 4 SD**  0.209

**- CF x 3 Mean**  0.152 **Unrounded MRL** 0.209 **Rounded MRL 0.2** Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 57 of 59 D ry Bean (MRID 49297801)

– TA 0.245 - 0.259 lb ai/A; 19 - 23 day PHI **Residues (mg/kg) n**  < 0.02 6 0.0208 1 0.0218 1 0.0236 1 0.0242 1 0.0275 1 0.0369 1 0.346 1 **TA Dry bean**  **USA 0.245**  **- 0.259 lb ai/A**  **; 19**  **- 23 day PHI**  **Total number of data (n)** 13 **Percentage of censored data** 46% **Number of non -**  **censored data** 7 **Lowest residue** 0.020 **Highest residue** 0.346 **Median residue** 0.021 **Mean** 0.048 **Standard deviation (SD)** 0.090 **Correction factor for censoring (CF)** 0.692 **Proposed MRL estimate**

**- Highest residue**  0.346

**- Mean + 4 SD**  0.407

**- CF x 3 Mean**  0.099 **Unrounded MRL** 0.407 **Rounded MRL 0.4** Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 58 of 59 Dry Pea (MRID 49297802)

– Metconazole 0.250 - 0.258 lb ai/A; 20 - 22 day PHI **Residues (mg/kg) n**  < 0.04 4 0.0562 1 **Metconazole Dry Pea**  **USA 0.250**  **- 0.258 lb ai/A;**  **20 -**  **22 day PHI Total number of data (n)**  5 **Percentage of censored data** 80% **Number of non -**  **censored data**  1 **Lowest residue** 0.040 **Highest residue** 0.056 **Median residue** 0.040 **Mean** 0.043 **Standard deviation (SD)** 0.007 **Correction factor for censoring (CF)** 0.467 **Proposed MRL estimate**

**- Highest residue**  0.056

**- Mean + 4 SD**  0.072

**- CF x 3 Mean**  0.061 **Unrounded MRL** 0.072 **Rounded MRL 0.08**  High uncertainty of MRL estimate. [Small dataset and high level of censoring]Metconazole Summary of Analytical Chemistry and Residue Data Barcode D 419223

Page 59 of 59 Dry Pea (MRID 49297802) - TA 0.250 - 0.258 lb ai/A; 20 - 22 day PHI **Residues (mg/kg) n**  0.187 1 0.459 1 0.591 1 0.701 1 2.38 1 **TA Dry Pea**  **USA 0.250**  **- 0.258 lb ai/A;**  **20 -**  **22 day PHI Total number of data (n)**  5 **Percentage of censored data** 0% **Number of non -**  **censored data** 5 **Lowest residue** 0.187 **Highest residue** 2.380 **Median residue** 0.591 **Mean** 0.864 **Standard deviation (SD)**  0.869 **Correction factor for censoring (CF)** 1.000 **Proposed MRL estimate**

**- Highest residue**  2.380

**- Mean + 4 SD**  4.340

**- CF x 3 Mean**  2.591 **Unrounded MRL** 4.340 **Rounded MRL 5**  High uncertainty of MRL estimate. [Small dataset]