Page 1 of 52 UNITED STA

TES ENVIRONMENTA L PROTECTION AGENCY WASHINGTON, D.C. 20460 OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVENTON MEMORANDUM Date: June 15 , 2010 SUBJECT: S - Metolachlor. Petition for the Establishment of Permanent Tolerances for New

Us es on Bushberry

Subgroup 13 - 07B; Caneberry Subgroup 13 - 07A; Carrot; Cucumber; L eafy

Brassica Greens Subgroup 5B; Melon Subgroup 9A; Okra; Bulb Onion Subgroup 3 - 07A; Green Onion Subgroup 3 - 07B; Sesame Seed; Sorghum; and Turnip Greens. Summary of Analy tical Chemistry

and Residue Data . PC Code: 108800 DP Barcode: D369005, D375955 Decision No.: 418569 Registration No. : 100 - 816 and 100 - 818 Petition No.: 9E7607 Regulatory Action: Section 3 Registration Risk Assessment Type: NA Case No.: 0001 T XR No. : NA CAS No.: 87392 - 12 - 9 MRID No.: See MRID Summary Table 40 CFR: 180.368 (a)(2) FROM: Susan V. Hummel, Chemist

Risk Assessment Branch 4, Health Effects Division, 7509P THROUGH: Ray Kent, Chief

Risk Assessment Branch 4, Health Effects Division , 7509P TO: Rebecca Daiss, Risk Assessor

Risk Assessment Branch 4, Health Effects Division, 7509P And Sidney Jackson, PM#5 Risk Integration, Minor Use & Emergency Response Branch Registration Division MRID Sum ma ry Table MRID No. Study Type Com me nts 47829401 860.1500 Sesame New DER; 47829401.de1.doc 860.1520 Sesame New DER; 47829401.de2.doc 47829402 860.1500 Cantaloupe New DER; 47829402.der.doc 47829403 860.1500 Caneberry New DER; 47829403.der.doc 47829404 860.1500 Blueberry New DER; 47 829404.der.doc 47829405 860.1500 Sweet sorghum New DER; 47829405.de1.doc 860.1520 Sweet sorghum New DER; 47829405.de2.doc 47829406 860.1500 Mustard greens New DER; 47829406.der.doc 47829407 860.1500 Cucumber New DER; 47829407.der.doc 47829408 860.150 0 Carrot New DER; 47829408.der.doc 48020601 Addendum to 47829401 thru - 08 Included in above DERsPage 2 of 52

This document was originally prepared under contract by Dy namac Corporation (1901 Research Boulevard, Suite 220; Rockville, MD 20850). Dy namac QC Review er: Date: 01/28/2010

Kelly Luck Dy namac Program Manager: Date: 01/28/2010

Danilo Martinez The document has been reviewed by the Health Effects Division (HED) and revised to reflect current Office of Pesticide Programs (OPP) policies.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 3 of 52 Exec utive Summary S - Metolachlor (an isomer enriched form of metolachlor) is a selective, chloroacetanilide herbicide that is applied to a variety of crops as a preplant, preplant incorporated, preemergence, or postemergence application, primarily for the control of grass weeds. S - Metolachlor is registered to Sy

ngenta Crop Protection, Inc. for use on a wide variety of crops including: corn, cotton, grasses grown for seed, legume vegetables, peanuts, potatoes, safflower, sorghum, sunflower, and tomatoes. Und er PP#9E7607, Interregional Research Project No. 4 (IR - 4) is proposing , in Section F of the petition, the establishment of tolerances for combined residues of the herbicide S - metolachlor, acetamide, 2 - chloro - N - (2 - ethyl - 6 - methylphenyl) - N - (2 - methoxy- 1 - methyl ethyl) - , (S) and its metabolites, determined as the derivatives, 2 - (2 - ethyl - 6 - methylphenyl)amino - 1 - propanol and 4 - (2 - ethyl - 6 - methylphenyl) - 2 - hydroxy- 5 - methyl - 3 - morpholinone, each expressed as the parent compound S - metolachlor in/on the following raw agricu ltural commodities:

Blueberry , lowbush ................................ ....................... 1.4 ppm Bushberry

subgroup 13 - 07B ................................ ....... 0.15 ppm Caneberry , Subgroup 13 - 07A ................................ ..... 0.08 ppm Carrot ................................ ................................ ............ 0.3 ppm Cucumber ................................ ................................ ...... 0.1 ppm Leafy Brassica Greens, Subgroup 5 - B .......................... 1.2 ppm Melon subgroup 9A ................................ .................... 0.08 ppm Okra ................................ ................................ ............... 0.1 ppm Onion, Bulb, Subgroup 3 - 07A ................................ ...... 0.1 ppm Onion, Green, Subgroup 3 - 07B ................................ .... 2.0 ppm Sesame, seed ................................ ................................ . 0.1 ppm Sorghum, sweet ................................ ............................. 0.1 ppm Turnip greens ................................ ................................ 1.2 ppm Higher tolerances reflecting total metolachlor residues for the above commodities were proposed in an addendum to the MRIDs submitted in support of this petition, but the proposals were not submitted as a revised Section F. Upon establishment of the above tolerances, IR - 4 requests the removal of tolerances established under 180.368(a)(2) for S - metolachlor and its metabolites in/on bulb oni on (0.1 ppm) and green onion (2.0 ppm) as the proposed tolerances for the onion subgroups 3 - 07A and 3 - 07B will cover bulb and green onion, respectively . The proposed tolerances are requested on behalf of the Agricultural Experiment Station of the IR - 4 Pro ject and the Agricultural Experiment Stations of:  OK and TX (sesame requests);  MD, MS, TN, AR, NC, SC, GA, CO, TX, DE, FL , NY, NJ, OK, and CA (cantaloupe requests);  MD, MS, TN, and CA (watermelon requests);  OR, OK, MN, NY, NJ, MI , MO, AR, NC, VA, and TN (caneberry requests),S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 4 of 52  OR, VA, OK, AR, NY, SC, NC, WA, and MO (blueberry requests);  NC and TN (sweet sorghum requests);  OR, NJ, TX, TN, CO, FL , OK, GA, SC, and MO (mustard greens requests);  GA, DE, MO, TN, NC, SC, FL , AL , NY, and NJ (cucumber requests);  AR and NY (carrot request);  NC, FL, and KY (okra requests);  CA and OR (dry

bulb onion requests);  NJ, OH, and MI(green onion requests);  AR, OR, TX, TN, CO, MD, and OK (turnip greens requests) Inconjunction with this petition, IR - 4 is requesting amen ded registration of two products, a 7.62 lb/gal emulsifiable concentrate (EC) formulation of S - metolachlor, Dual Magnum® Herbicide (EPA Reg. No. 100 - 816) and a 7.64 lb/gal EC formulation, Dual II Magnum® (EPA Reg. No. 100 - 818), to add uses on the bulb onio n subgroup (3 - 07A), bushberry subgroup (13 - 07B), the caneberry subgroup (13 - 07A), carrot, cucumber, the green onion subgroup (3 - 07B), the leafy Brassica greens subgroup (5B, including turnip greens), the melon subgroup (9A), okra, sesame, and sweet sorghum . The products are proposed for postemergence application to the bushberry subgroup, the caneberry

subgroup, okra, the bulb onion subgroup, and the green onion subgroup at maximum application rates ranging 1.3 - 3.8 lb ai/A; preharvest intervals (PHI s) of 2 1 days for the green onion subgroup, 28 days for the bushberry and caneberry

subgroup, and 60 days for okra and the bulb onion subgroup are proposed. Preemergence, pre - transplant, and/or postemergence applications are proposed for carrot, cucumber, leafy Brassica greens, the melon subgroup, and sweet sorghum at maximum application rates ranging 1.2 - 1.9 lb ai/A; PHI s of 64 day s for carrot, 30 days for cucumber and leafy Brassica greens, 60 days for melons, and 90 days for sweet sorghum are proposed. In add ition, the 7.62 lb/gal EC formulation is proposed for preemergence application to sesame at up to 1.9 lb ai/A with a proposed PHI of 100 days. The nature of S - metolachlor residues in crops and livestock is understood based on adequate crop and livestock metabolism studies with metolachlor and S - metolachlor. For both S - metolachlor and metolachlor, the residues of concern in crop and livestock commodities include the parent compound (both R and S - enantiomers) and its metabolites, determined as the derivat ives CGA 37913 and CGA - 49751. Following recommendations made in the revised Tolerance Reassessment Eligibility

Decision (TRED) for Metolachlor and S - Metolachlor (DP# 292881, 8/15/03, S. Kinard), tolerances for metolachlor and S - metolachlor have been separ ated. Permanent tolerances for combined S - metolachlor residues have been established for crop commodities ranging from 0.10 ppm in/on a variety of crop commodities to 20 ppm in/on peanut hay [40 CFR §180.368(a)(2)]. Permanent tolerances for indirect or i nadvertent residues of S metolachlor have also been established for non - grass animal feeds (Group 18), and the forage, hay , grain and straw of small cereal grains (barley, buckwheat, millet, oats, rice, rye and wheat), at levels ranging 0.10 ppm in/on grai ns to 1.0 ppm in/on non - grass animal feeds [40 CFR §180.368(d)(2)]. Adequate methodology

is available for enforcing the current tolerances. The Pesticide Analy tical Manual (PAM), Vol. I I, lists a gas chromatography method with nitrogen phosphorus detecti on (GC/NPD) for determining residues in/on crop commodities (Method I) and a GC method with mass selective detection (GC/MSD) for determining residues in livestock commodities (MethodS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 5 of 52 II). These methods determine residues of metolachlor and its metabolite s as either CGA - 37913 or CGA - 49751 following acid hydrolysis. IR - 4 and Sy ngenta have proposed an enantiomer specific high performance liquid chromatography method with triple quadrupole mass spectrometric detection (L C/MS/MS) for the enforcement of the proposed tolerances, Method 1848 - 01, which has been previously reviewed by

HED (DP# 296904, 4/17/06, R. L oranger). The method uses a chiral HPL C column to separate out the S - enantiomers (SYN506357 and SYN508500) of the hydrolysis products CGA - 37913 and CGA - 49751. HED concludes that the method is not appropriate for enforcement purposes because it does not determine residues of the R - isomers of metolachlor and its metabolites, which are included in the tolerance expression. The S:R ratio in the active ingre dient is 88:12; therefore, there is potential for residues of the R isomers of metolachlor and its metabolites in crop commodities. The method could be adapted for enforcement by

measuring both the S - and the R - enantiomers. Residue data from the current field trial and processing studies were obtained using GC/NPD or GC/MS methods derived from the tolerance enforcement method, or using a modified version of LC /MS/MS Method No. 1848 - 01, in which a chiral column was not used for L C analyses. In three of th e field trial and processing study submissions, the petitioner stated that combined residues were reported in parent equivalents; however, the study reviewer could not verify this statement. In the remaining submissions, no information was provided indicating whether derivative and/or total residues were reported in terms of the analy te or in terms of parent metolachlor. In an update to the submitted MRIDs, the petitioner recalculated total metolachlor residues, so that the residues are now reported in terms of parent metolachlor equivalents. Adequate data are available on the recovery of metolachlor through Multiresidue Method Testing Protocols. The FDA PESTDATA database indicates that metolachlor is completely recovered through Method 302, PAM Vol. I (3rd ed., revised 10/97). Adequate concurrent storage stability data were submitted to support the sample storage conditions and durations from the submitted field trial and processing studies, other than blueberry , and adequate storage stability data ar e available to support the blueberry field trial study . These data indicate that the metolachlor derivatives CGA - 49751 and CGA - 37913 and/or S - metolachlor derivatives SYN506357 and SYN508500 are stable during frozen storage for at least 17 - 49 months in/on caneberry , cantaloupe, carrot root, cucumber, mustard greens, sesame seed, sweet sorghum stalks, and tomato; 28 months in sesame meal and oil; and 11 months in sweet sorghum sy

rup. Although there is one livestock feedstuff associated with the proposed u ses, carrot culls, the proposed uses have no impact on the dietary burden of S - metolachlor to livestock. Therefore, no changes to the existing tolerances for livestock commodities are needed. The proposed tolerances are not adequate for bushberry, subgro up 13 - 07B, caneberry , subgroup 13 - 07A; carrot; cucumber; leafy Brassica greens, subgroup 5B; melon subgroup 9A; sesame seed; and turnip greens. The tolerance proposals were updated in an addendum to the submitted MRIDs, but not formatted as a revised Sect ion F. A revised Section F is needed, expressing the tolerance proposals in terms of total metolachlor equivalents. The tolerance for bushberry , subgroup 13 - 07B can only be established at the level needed for the banded, soil directedS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 6 of 52 application. A tol erance currently exists for residues of S - metolachlor in/on the root vegetable, except sugar beet, subgroup, 1B. When the requested tolerance for carrot is established, the existing tolerance for subgroup 1B must be revised to “vegetable, root, except car rot and sugar beet, subgroup 1B.” The submitted broadcast foliar data for blueberries are not adequate to support the requested tolerances for lowbush blueberry . In addition, the proposed use patterns differ significantly . The submitted banded, soil dir ected application data for highbush blueberry would support a tolerance for bushberry , subgroup 13 - 07B (with use on lowbush blueberry and other low bush varieties of berries prohibited on the label), at 0.20 ppm, expressed as total metolachlor equivalents. Additional crop field trial data must be submitted before a tolerance may be established to cover broadcast foliar use on lowbush blueberry

– one additional trial in Region 1, one additional trial in Region 5; alternatively , with the additional field tri al data reflecting broadcast foliar use, the petitioner may wish to submit data and propose a tolerance for the low growing berry , except strawberry , subgroup 13 - 07H. The available field trial data for fruiting vegetables may be translated to support th e requested tolerance for okra; these data support the proposed 0.10 ppm tolerance. Adequate data have been submitted previously to support the requested tolerances for the bulb onion and green onion subgroups; the proposed tolerance levels of 0.10 ppm an d 2.0 ppm are appropriate. Concomitant with the establishment of tolerances for bulb onion subgroup 3 - 07A and green onion subgroup 3 - 07B, the established tolerances for S - metolachlor and its metabolites in/on bulb garlic, bulb onion, bulb shallot, and gre en onion under 180.368(a)(2) should be removed. The requested tolerance for sweet sorghum is not needed; the existing tolerance for S metolachlor residues in/on sorghum grain is adequate to cover residues in/on sweet sorghum commodities. The submitted pr ocessing data indicate that no tolerances are needed for S - metolachlor residues in the processed commodities of sesame or sweet sorghum. An adequate confined rotational crop study is available, although additional information pertaining to the study

remai ns outstanding. The residues of concern in rotated crops are the same as in the primary

crops, S - metolachlor, its R - enantiomer, and its metabolites determined as CGA - 37913 and CGA - 49751. Adequate field rotational crop data have been submitted previously which support the existing rotational crop restrictions on the labels for EPA Reg. Nos. 100 - 816 and 100 - 818, provided that the label for EPA Reg. No. 100 - 816 is amended as recommended below. Regulatory Recommendations and Residue Chemistry Deficiencies HED has examined the residue chemistry database for S - metolachlor. Pending submission of a revised Section B (see requirements under Directions for Use) and revised Section F (see requirements under Proposed Tolerances), there are no residue chemistry is sues that wouldS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 7 of 52 preclude granting a conditional registration for the requested u ses of S - metolachlor on Bushberry subgroup 13 - 07B, Caneberry , Subgroup 13 - 07A, Carrot, Cucumber, L eafy Brassica Greens, Subgroup 5B, Melon subgroup 9A, Okra, Onion, Bulb, Subgroup 3 - 07A, Onion, Green, Subgroup 3 - 07B, Sesame, seed, Sorghum, sweet, and Turnip greens, or establishment of tolerances for residues of S - metolachlor and its R - enantiomer, including its metabolites and degradates, in or on the commodities in the table bel ow. Compliance with the tolerance levels specified below is to be determined by measuring only

the sum of free and bound S - metolachlor, S - 2 - chloro - N - (2 - ethyl - 6 - methylphenyl) - N - (2 - methoxy- 1 - methylethyl)acetamide, its R enantiomer, and its metabolites, dete rmined as the derivatives, 2 - (2 - ethyl - 6 - methylphenyl)amino 1 - propanol and 4 - (2 - ethyl - 6 - methylphenyl) - 2 - hydroxy- 5 - methyl - 3 - morpholinone, calculated as the stoichiometric equivalent of S - metolachlor:

Bushberry , subgroup 13 - 07B ................................ ...... 0.15 ppm Caneberry , s ubgroup 13 - 07A ................................ ...... 0.10 ppm Carrot ................................ ................................ .......... 0.40 ppm Cucumber ................................ ................................ .... 0.13 ppm Le afy Brassica Greens, s ubgroup 5 B ............................ 1.8 ppm Melon subgroup 9 B ................................ ..................... 0.10 ppm Okra ................................ ................................ ............. 0.10 ppm Onion, Bulb, s ubgroup 3 - 07A ................................ ..... 0.10 ppm Onion, Green, s ubgroup 3 - 07B ................................ ..... 2.0 ppm Sesame, seed ................................ ............................... 0.13 ppm Sorghum, sweet, stalk ................................ ................... 4.0 ppm Turnip greens ................................ ................................ 1.8 ppm Note to PM: Concomitant with the establishment of tolerances for bulb onion subgroup 3 - 07A and green onion subgroup 3 - 07B, the established tolerances for S - metolachlor and its metabolites in/on garlic, bulb (0.10 ppm), onion, bu lb (0.10 ppm), shallot, bulb (0.10 ppm), and onion, green (2.0 ppm) under 180.368(a)(2) should be removed. Concomitant with the establishment of a tolerance for carrot, the existing tolerance for subgroup 1B must be revised to “vegetable, root, except car rot and sugar beet, subgroup 1B.” HED cannot recommend in favor of granting a conditional registration for the requested broadcast foliar use of S - metolachlor on lowbush blueberry , due to insufficient residue data (see requirements under Directions for Us e). A human health risk assessment is forthcoming. 860.1200 Directions for Use For EPA Reg. No. 100 - 816, the following amendments to the proposed uses are needed:  The proposed use should be amended to specify that postemergence application to sweet sorghum may

be made to crops up to 5 inches in height.  For postemergence applications, the label states that use of an adjuvant may increase risk to the crop. Since the field trials were conducted without the use of an adjuvant, the label must state that us e of adjuvants is prohibited.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 8 of 52  Rotational crop directions for crops with a 60 - day plantback interval must be amended to prohibit a second application of S - metolachlor to any of these crops replanted within 60 day s of the original application.  Bushberry

subgroup 13 - 07B: The petitioner must revi se the proposed use to delete the broadcast foliar use on lowbush varieties of berry . Use must be limited to banded, soil directed application. The proposed use on highbush blueberry may be expanded to include currant, elderberry , gooseberry , and huckleberry . The proposed uses must be amended to specify

that only one application may

be made.  Carrot: The proposed maximum single and seasonal application rate of 1.9 lb ai/A for postemergence application to carrots grown in muck soils must be removed from the label; no data have been submitted supporting postemergence application rates >1.27 lb ai/A to carrot. Adequate data are available to support the proposed preemergence application to carrots grown in muck soils at up to 1.9 lb ai/A.  Carrot: The proposed use must be amended to specify that postemergence applications may be made up to the 5 - leaf growth stage. No PHI is needed if postemergence application to carrot is defined by crop growth stage.  Cucumber: The prop osed use must be amended to specify that postemergence applications may

be made up to the 2 - leaf growth stage. No PHI is needed if postemergence application to cucumber is defined by crop growth stage.  Leafy Brassica greens: The proposed use must be ame nded to specify that postemergence applications may

be made up to the 2 - leaf growth stage. No PHI is needed if postemergence application to leafy Brassica greens is defined by crop growth stage.  Melon: The proposed use on melons not grown in plastic mulc h must be amended to specify that banded applications are to be made between rows. For EPA Reg. No. 100 - 818, the following amendments to the proposed uses are needed:  The proposed use must be amended to specify that postemergence application to sweet sorghum may

be made to crops up to 5 inches in height and that postemergence application may

not be made if preemergence application was made; a maximum of one application must be specified.  For postemergence applications, the label states that use of an adj uvant may increase risk to the crop. Since the field trials were conducted without the use of an adjuvant, the label must state that use of adjuvants is prohibited.  Bushberry

subgroup 13 - 07B: The petitioner must revise the proposed use to delete the broa dcast foliar use on lowbush varieties of berry . Use must be limited to banded, soil directed application. The proposed use on highbush blueberry may be expanded to include currant, elderberry , gooseberry , and huckleberry . The proposed uses must be amend ed to specify

that only one application may

be made.  Carrot: The proposed use must be amended to specify that only one application may

be made and that postemergence applications may be made up to the 5 - leaf growth stage.  Cucumber: The proposed use must be amended to specify that only one application may be made and that postemergence applications may be made up to the 2 - leaf growth stage.  Leafy Brassica greens: The proposed use must be amended to specify that only one application may

be made and that postemergence applications may be made up to the 2 - leaf growth stage.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 9 of 52  Melons: The proposed uses must be amended to specify that only one application may

be made. In addition, the proposed use on melons not grown in plastic mulch must be amended to specif

y that banded applications are to be made between rows. The following additional data are required to support the requested use on lowbush blueberry . 860.1500 Crop Field Trials

 If the petitioner wishes to support use on lowbush blueberry, two additional field trials representing broadcast application would be required , one in Region 1 and one in Region 5 . Alternatively , the petitioner may wish to submit data and propose a tolerance for the low growing berry , except strawberry , subgroup, 13 - 07H. Four ad ditional field trials, conducted on lowbush blueberry or cranberry , would be required. 860.1550 Proposed Tolerances

 The tolerances proposed by IR - 4 do not include the R - enantiomer. The tolerance expression in Section F of the submitted petition should b e revised to include the R enantiomer of metolachlor and to conform with current HED guidance, as follows: Tolerances are established for residues of S - metolachlor, including its R enantiomer, metabolites and degradates, in or on the commodities in the t able below. Compliance with the tolerance levels specified below is to be determined by

measuring only

the sum of free and bound S - metolachlor, S - 2 - chloro - N - (2 - ethyl - 6 - methylphenyl) - N - (2 - methoxy- 1 - methylethyl)acetamide, its R - enantiomer, and its metabolit es, determined as the derivatives, 2 - (2 - ethyl - 6 - methylphenyl)amino - 1 - propanol and 4 - (2 - ethyl - 6 - methylphenyl) - 2 - hydroxy- 5 - methyl - 3 - morpholinone, calculated as the stoichiometric equivalent of S - metolachlor, in or on the commodity .  A revised Section F is ne eded, correcting the proposed tolerance levels, as specified in Table 8, to be in terms of total metolachlor, on bushberry subgroup 13 - 07B; caneberry , Subgroup 13 - 07A; carrot; cucumber; leafy Brassica greens, subgroup 5B; melon subgroup 9A; sesame, seed; and turnip greens.

 HED now considers turnip greens to be a member of the leafy Brassica greens subgroup. Pending revision of 40 CFR §180.41, a separate tolerance must be established for turnip greens, at the same level as the tolerance for leafy Brassic a greens.  The proposed tolerance for sweet sorghum is not needed as residues in sweet sorghum commodities are covered by the exist ing tolerance for sorghum grain commodities. HED recommends that conversion of conditional registration to unconditional r egistration for the requested uses may be considered upon submission of the following outstanding residue chemistry data pertaining to confined accumulation in rotational crops.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 10 of 52 860.1850 Confined Accumulation in Rotational Crops

 To support the confined rotational crop study submitted under MRID 41470601, the additional data required by HED (DP# 207842, 10/12/94, S. Hummel) must be submitted; additional data were required characterizing the 14 C - residues in plants, along with information on the percentage of the 14 C - residues measured by the current enforcement method; sample storage conditions and intervals and supporting storage stability data were also required. These data requirements were reiterated in the Metolachlor TRED (DP# 292881, 8/15/03, S. Kinard). Background The chemical structure and nomenclature of S - metolachlor and its regulated hydroly tic derivatives are presented in Table 1, and the physicochemical properties of S - metolachlor are presented in Table 2. Table 1. Nom enclature of S - Metol achlor and its Regulated Hydrolytic Derivatives. Parent compound C H3

C H3

N O C H3

Cl C H3

O Common name 1 S - Metolachlor Company experimental name CGA - 77102 IUPAC name (S) - 2 - chloro -N - (2 - ethyl - 6 - methyl - phenyl) -N - (2 - metonym - 1 - methyl - ethyl) - acetamide CAS name 2 - chloro -N - (2 - ethyl - 6 - methylphenyl) -N - [(1S)2 - methoxy - 1 - methylethyl] - acetamide CAS registry number 87392 - 12 - 9 End - use product (EP) Dual Magnum® Herbicide (7.62 lb/gal EC; EPA Reg. No. 100 - 816) and Dual II Magnum® Herbicide (7.64 lb/gal EC; EPA Reg. No. 100 - 818) Regulated residue

C H 3 N H C H3 O H C H 3 Common name None Company experimental names CGA - 37913 SYN506357 (S - enantiomer of CGA 37913) Chemical name 2 - [(2 - ethyl - 6 - methylphenyl) amino] - 1 - propanol CAS registry number 61520 - 53 - 4 82508 - 08 - 5 (S - enantiomer)S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 11 of 52 Table 1. Nom enclature of S - Metol achlor and its Regulated Hydrolytic Derivatives. Regulat ed residue

C H3 C H 3 N O O O H C H3

Common name None Company experimental names CGA - 49751 SYN508500 (S - enantiomer of CGA 49751) Chemical name 4 - (2 - ethyl - 6 - methylphenyl) - 2 - hydroxy - 5 - methyl - 3 - mo rpholi no ne CAS registry number 61520 - 54 - 5 Table 2. Physicochemical Properties of S - Metolachlor. Parameter Value Reference Melting point/range Not applicable, liquid at room temperature MRID 47121701 (DP#s 332846, etc., 10/21/08, D. McNeilly) pH 7.8 at 25 oC (1% aqueous dispersion) Density 1.117 g/cm3 at 20 oC Water solubility (2 5°C) 0.48 g/L Solvent solubility (mg/L at 25°C) Completely miscible with methanol, acetone, toluene, n - octanol, n - hexane, ethyl acetate, and dichloromethane. Vapor pressure at 25°C 2.8 x 10 - 5 mm Hg Dissociation constant (pKa) No dissociation constant in pH range 2 - 12 Octanol/water partition coefficient Log(KOW ) 3.05 at 25 oC UV/visible absorption spectrum Neutral: 534 L/mol•cm @ 266.4 nm 443 L/mol•cm @ 274.4 nm Acidic: 534 L/mol•cm @ 266.4 nm

444 L/mol•cm @ 274.4 nm Basic: 531 L/mol•cm @ 266.4 nm

411 L/mol•cm @ 274.4 nm 860.1200 Directions for Use The petitioner provided a text listing of proposed uses in Section B of the petition; these included proposed uses for Dual Magnum® (EPA Reg. No. 100 - 816), a 7.62 lb/gal EC formulation, and Dual I I Magnum® (EPA Reg. No. 100 - 818), a 7.64 lb/gal EC formulation. In addition, the petitioner submitted two versions of a proposed label for Dual Magnum® Herbicide (EPA Reg. No. 100 - 816): one, dated 9/30/08, included only use directions for the crops propos ed in this petition (i.e., it did not include any previously

registered uses); and the second (which was submitted in both highlighted and unhighlighted forms), also dated 9/30/08, included existing uses for Dual Magnum Herbicide as well as proposed uses f or sweet sorghum. The proposed uses are presented below in Table 3.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 12 of 52 Table 3. Summary of Proposed Directions for Use of S - Metolachlor. 1 Applic. Timing; Ty pe; and Equip. (minimum volume) Formulation

[EPA Reg. No.] Applic.

Rate (lb ai/A) Max. No.

Appli c. per Season Max. Seasonal

Applic. Rate (lb ai/A) PHI

(days) Use Directions and

Limitations Bulb Onion Subgroup 3 - 07A (Daylily, bulb; fritillaria, bulb; bulb, garlic; great - headed, bulb; garlic, serpent, bulb; lily, bulb; onion, bulb; onion, Chinese, bulb; onion, pearl; onion, potato, bulb; shallot, bulb; cultivars, varieties, and/or hybrids of these) Postemergence; Broadcast; Ground (5 GPA) or aerial (2 GPA) 7.62 lb/gal EC [100 - 816] 0.60 -

1.27 2 2 2.54 60 Application to be made to plants at the 2 true l eaf stage and a second application may be made 21 days later. The harvest of green onions and the grazing of animals on green forage or stubble are prohibited. Bushberry Subgroup 13 - 07B and Low bush Blueberry (Bushberries including Aronia berry; bluebe rry, lowbush; blueberry, highbush; Buffalo currant; Chilean guava; currant, red; currant, black; elderberry; European barberry; gooseberry; highbush cranberry; honeysuckle; jostaberry; juneberry including Saskatoon berry; lingonberry; native currant; salal ; Sea buckthorn) Postemergence; Banded; Ground (10 GPA) 7.62 lb/gal EC [100 - 816] 0.64 - 1.26 1 1.27 28 Applications to highbush blueberry, currant, elderberry, gooseberry, and huckleberry to be made to soil surface on each side of the crop row . Postemergen ce; Broadcast; Ground (5 GPA) or aerial (2 GPA) Applications to low bush blueberry to be made as a broadcast spray. Postemergence; Banded; Ground (20 GPA) 7.64 lb/gal EC [100 - 818] 0.64 -

1.26 2 NS NS 30 ± 3 Applications to highbush blueberry to be made t o soil surface of both sides of the row . Postemergence; Broadcast; Ground (20 GPA) Applications to low bush blueberry to be made as a broadcast spray. Caneberry Subgroup 13 - 07A (Caneberries including blackberry; loganberry; red and black raspberry; c ultivars and/or hybrids of these) Postemergence; Banded to the soil surface on both sides of the cane; Ground (10 GPA) 7.62 lb/gal EC [100 - 816] 1.90 -

3.81 2 1 3.8 28 Application is to be directed to the soil surface.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 13 of 52 Table 3. Summary of Proposed Directions for Use of S - Metolachlor. 1 Applic. Timing; Ty pe; and Equip. (minimum volume) Formulation

[EPA Reg. No.] Applic.

Rate (lb ai/A) Max. No.

Appli c. per Season Max. Seasonal

Applic. Rate (lb ai/A) PHI

(days) Use Directions and

Limitations Carrot Preemergence; Broadcast or banded; Ground (5 GPA broadcast, 10 GPA banded) or aerial (2 GPA) 7.62 lb/gal EC [100 - 816] 0.64 - 1.27

mineral soils; 1.27 - 1.9 muck soil 3 1 1.27 mineral soils; 1.9 muck soils 64 Preemergence application is to be made after planting. Postemergence; Broadcast or banded; Ground (5 GPA broadcast, 10 GPA banded) or aerial (2 GPA) Postemergence application is to be made to plants with at least 3 - 5 true leaves. Postemergence; Broadcast; Ground (10 GPA) 7.64 lb/gal EC [100 - 818] 0.63 -

1.26 2 NS NS NS Foliar appl ication to be made after last cultivation, to plants at 3 - 5 true leaf stage. Cucumber Preemergence; Broadcast; Ground (5 GPA) or aerial (2 GPA) 7.62 lb/gal EC [100 - 816] 0.64 -

1.27 2 1 1.27 30 Preemergence application is to be made after planting. Posteme rgence; Broadcast; Ground (5 GPA) or aerial (2 GPA) Postemergence application is to be made to plants with at least 1 true leaf. Preemergence; Broadcast; Ground (10 GPA) 7.64 lb/gal EC [100 - 818] 0.95 -

1.27 2 NS NS NS Preemergence soil application to be made after planting. Postemergence; Broadcast; Ground (10 GPA) One postemergence foliar application to be made to plants at the 1 - 2 true leaf stage. Green Onion Subgroup 3 - 07B (Chive, fresh leaves; chive, Chinese, fresh leaves; elegans hosta; fritillaria, leaves; kurrat; lady’s leek; leek; leek, wild; Onion, Beltsville bunching; onion, fresh; onion, green; onion, macrostem; onion, tree, tops; onion, Welsh, tops; shallot, fresh leaves; cultivars, varieties, and/or hybrids of these) Postemergenc e; Broadcast; Ground (5 GPA) or aerial (2 GPA) 7.62 lb/gal EC [100 - 816] 0.64 -

1.27 2 1 1.27 21 Application to be made to plants at the 2 true leaf stage.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 14 of 52 Table 3. Summary of Proposed Directions for Use of S - Metolachlor. 1 Applic. Timing; Ty pe; and Equip. (minimum volume) Formulation

[EPA Reg. No.] Applic.

Rate (lb ai/A) Max. No.

Appli c. per Season Max. Seasonal

Applic. Rate (lb ai/A) PHI

(days) Use Directions and

Limitations Leafy Brassica Greens Subgroup 5 - B (Broccoli raab; cabbage, Chinese (bok choy); collards; kale; mizun a; mustard greens; mustard spinach; rape greens; turnip greens) Preemergence; Broadcast; Ground (5 GPA) or aerial (2 GPA) 7.62 lb/gal

[100 - 816] 0.64 -

1.27 2 1 1.27 30 Preemergence application is to be made after planting. Postemergence; Broadcast; Ground (5 GPA) or aerial (2 GPA) Postemergence application is to be made to plants with at least 1 true leaf. Preemergence; Broadcast; Ground (10 GPA) 7.64 lb/gal EC [100 - 818] 0.63 -

1.26 2 NS NS NS Preemergence soil application to be made after planting. Postemergence; Broadcast; Ground (10 GPA) One postemergence foliar application to be made to plants at the 1 - 2 true leaf stage. Melon Subgroup 9A (Including cantaloupe; citron melon; muskmelon; watermelon)

Preemergence or pre - transplant; Broadcast or banded; Ground (5 GPA broadcast, 10 GPA banded) or aerial (2 GPA) 7.62 lb/gal EC [100 - 816] 0.64 -

1.21 2 1 1.21 60 For melons grown in plastic mulch, broadcast application is to be made before laying of mulch and banded application is to be made after laying mulch; banded application is to be made between row s and may not be made if broadcast application was made before laying of mulch. For melons not grown in plastic mulch, banded application is to be banded over the crop row . Preemergence or pre - transp lant; Broadcast or banded; Ground (20 GPA) 7.64 lb/gal EC [100 - 818] 0.64 -

1.21 2 NS NS NS For melons grown in plastic mulch, banded application is to be made between row s. For melons not grown in plastic mulch, banded application is to be banded over the cr op row .S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 15 of 52 Table 3. Summary of Proposed Directions for Use of S - Metolachlor. 1 Applic. Timing; Ty pe; and Equip. (minimum volume) Formulation

[EPA Reg. No.] Applic.

Rate (lb ai/A) Max. No.

Appli c. per Season Max. Seasonal

Applic. Rate (lb ai/A) PHI

(days) Use Directions and

Limitations Okra Postemergence; Directed spray; Ground (10 GPA) 7.62 lb/gal EC [100 - 816] 0.95 -

1.90 2 1 1.9 60 Application to be made to plants at least 4 inches tall, directed to the soil (or row middle) to minimize contact to crop foliage. Sesame Preemerge nce; Broadcast or banded; Ground (5 GPA broadcast, 10 GPA banded) or aerial (2 GPA) 7.62 lb/gal EC [100 - 816] 0.95 - 1.9 2 1 1.9 100 Application to be made to soil surface after planting. Sweet Sorghum Preplant surface, preplant incorporated, or preemergence ; Broadcast; Ground (5 GPA) 7.62 lb/gal EC [100 - 816] 1.0 - 1.59 2 1 NS 90 Application may be made up to 45 days prior to planting. Preplant or preemergence applications are only to be made to seed treated with Concep herbicide safener. Postemergence; Broadc ast; Ground (5 GPA) 0.95 - 1.27 2 Postemergence application may not be made if preplant or preemergence application was made. Preemergence; Broadcast; Ground (10 GPA) 7.64 lb/gal EC [100 - 818] 1.0 - 1.67 2 NS NS NS Application to be made to soil surface afte r planting. Postemergence; Broadcast; Ground (10 GPA) 0.64 - 1.27 2 One foliar application to be made early postemergence. 1 NS = Not specified. GPA = Gallons per acre. 2 The lower rates are to be used on soils that are relatively coarse textured and the higher rates are to be used on fine - textured soils. 3 Muck soils defined as soils with >20% organic matter. All proposed uses specify that lower rates should be used on relatively coarse textured soils and higher rates should be used on fine textured soils. For onions, the proposed uses specify that lower rates are to be used on light sandy soils and higher rates are to be used on silt, clay , or muck soils or where weed pressure is heavy . For all crops with postemergence uses, it is stated that u se of an adjuvant may increase risk to the crop.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 16 of 52 HED notes that for caneberry subgroup 13 - 07A, okra, and sesame, the use directions provided in Section B of the petition differed slightly from those provided on the proposed amended label for EPA Reg. No. 100 - 816. For these crops, the proposed amended label specified a maximum seasonal rate and a maximum number of applications; no maximum seasonal rate or maximum number of applications were specified for these crops in Section B. In addition, no PHIwas s pecified in Section B for application to okra and sesame; the proposed amended label specified a PHIfor both these crops. In all cases, the proposed amended label for EPA Reg. No. 100 - 816 was considered to reflect the actual proposed uses. The propose d amended label for EPA Reg. No. 100 - 816 with uses on bulb vegetables, bushberries, caneberries, carrot, cucumber, leafy Brassica greens, melon, okra, and sesame did not include any

information about application equipment, minimum application volume, or ro tational crop restrictions. The study reviewer has assumed that the general application instructions and rotational crop restrictions on the parent label for EPA Reg. No. 100 - 816 are intended to be applied to the proposed uses. Plantback restrictions f

or the proposed uses in Section B refer to the master label. A master label was provided in Section A of the petition for Dual Magnum Herbicide (EPA Reg. No. 100 - 816); however, no master label for Dual II Magnum Herbicide (EPA Reg. No. 100 - 818) was provid ed. The following crop rotation restrictions are specified for EPA Reg. No. 100 - 816:

 a 0 - day

plantback interval (PBI) for any crop on the Dual Magnum label, or on a supplemental Dual Magnum label, provided that the rate of Dual Magnum applied to the pr evious crop was not greater than the labeled rate for the crop to be replanted;  a 4 - month PBIfor alfalfa (provided no more than 1.9 lb ai/A was applied to the previous crop);  a 41⁄2 - month PBIfor barley , oats, rye, and wheat;  a 9 - month PBIfor clover (provi ded no more than 1.9 lb ai/A was applied to the previous crop);  a 60 - day

PBIfor the crops and/or crop groups listed in the table below, depending on the amount of S - metolachlor applied to the previous crop;  tobacco, buckwheat, and rice may be planted the next spring;  a 12 - month PBIfor all other food or feed crops. Crops/crop groups allowed for rotation 60 days after application of S - me tolachlor. Crop group/subgroup/crop Am ount of S - me tolachlor previously applied to field 1 ≤1.3 lb ai/A ≤1.6 lb ai/A ≤1.9 lb ai/A Root vegetables (subgroup 1B) yes no no Bulb vegetables (group 3), green plants yes no no Winter squash, including pumpkins yes no no Fruiting vegetables, except cucurbits (group 8) yes yes no Tuberous and corm v egetables (subgroup 1C) yes yes yes Bulb vegetables (group 3), dry bulbs yes yes yesS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 17 of 52 Crops/crop groups allowed for rotation 60 days after application of S - me tolachlor. Crop group/subgroup/crop Am ount of S - me tolachlor previously applied to field 1 ≤1.3 lb ai/A ≤1.6 lb ai/A ≤1.9 lb ai/A Leaf petiole vegetables (subgroup 4B) yes yes yes Head and stem Brassica vegetables (subgroup 5A) yes yes yes 1 If the rate of S - metolachlor applied to the previous c rop was greater than the rate listed here, crops from the various groups cannot be planted until the following spring. The following rotational crop restrictions are specified for EPA Reg. No. 100 - 818 (PPL S label accepted 2/19/04):

 a 0 - day

PBIfor any

cr op on the label [corn, cotton, peanuts, pod crops (garbanzo, great northern beans, kidney

beans, lima beans, mung beans, navy beans, peas (English, southern peas, such as blackeye, pinkeye, crowder, etc.), pinto beans, snap beans (green, wax, string), and lupines (sweet, white, white sweet, and grain), potatoes, safflowers, grain or forage sorghum, and soy beans];  a 4 - month PBIfor alfalfa;  a 41⁄2 - month PBIfor barley , oats, rye, and wheat;  a 6 - month PBIfor tomato;  a 9 - month PBIfor clover;  any crop on the la

bel, as well as root crops, tobacco, barley , buckwheat, milo, oats, rice, rye, wheat, cabbage, and pepper, may be planted in the spring following treatment;  following a lay- by

treatment or multiple treatments applied the previous season, any crop on the la bel, in addition to tobacco, cabbage, peppers, stone fruits, or tree nuts, may be planted in the spring. Conclusions . The proposed use directions are adequate to allow for evaluation of the submitted residue data relative to the proposed uses. With the exception of the proposed use on lowbush blueberry , the proposed uses are generally supported by

the submitted field trial data. Several label amendments are required to modify the proposed use to reflect the use patterns of the crop field trials. The proposed broadcast foliar uses on lowbush blueberry are not supported by

the available field trial data. Adequate field trial data have been submitted to support banded (soil directed) application to highbush blueberry . No data are available to support pos temergence applications to carrots at rates >1.3 lb ai/A; adequate field trial data have been submitted previously to support preemergence applications to carrots grown in muck soils at up to 3.0 lb ai/A. The proposed uses for the melon subgroup specify that banded applications to melons not grown in plastic mulch be made over the crop row. The submitted field trial data only support banded applications made between crop rows.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 18 of 52 The petitioner proposed PHI s for several crops which are not needed, provide d the proposed use is amended to specify

that applications may

only be made up to a certain growth stage, which is the growth stage that applications were made at in the submitted field trials. No PHI is needed for sesame because applications are to be ma de prior to crop emergence. HED notes that application rate was not related to soil ty pe in any of the crop field trials studies submitted with this petition. For EPA Reg. No. 100 - 816, the following amendments to the proposed uses are needed:  The propo sed use should be amended to specify that postemergence application to sweet sorghum may

be made to crops up to 5 inches in height.  Rotational crop directions for crops with a 60 - day PBImust be amended to prohibit a second application of S - metolachlor t o any of these crops replanted within 60 days of the original application.  Bushberry

subgroup 13 - 07B: The petitioner must delete the broadcast foliar use on lowbush varieties in the bushberry subgroup from the proposed amended label. The proposed banded, soil directed uses on highbush blueberry , currant, elderberry , gooseberry , and huckleberry are supported by

the available data and may remain on the proposed amended label. The proposed uses must be amended to specify that only one application may

be made .  Carrot: The proposed maximum single and seasonal application rate of 1.9 lb ai/A for postemergence application to carrots grown in muck soils must be removed from the label; no data have been submitted supporting postemergence application rates >1.27 lb ai/A to carrot. Adequate data are available to support the proposed preemergence application to carrots grown in muck soils at up to 1.9 lb ai/A.  Carrot: The proposed use must be amended to specify that postemergence applications may be made up to the 5 - leaf growth stage. No PHI is needed if postemergence application to carrot is defined by crop growth stage.  Cucumber: The proposed use must be amended to specify that postemergence applications may

be made up to the 2 - leaf growth stage. No PHI is neede d if postemergence application to cucumber is defined by crop growth stage.  Leafy Brassica greens: The proposed use must be amended to specify that postemergence applications may

be made up to the 2 - leaf growth stage. No PHI is needed if postemergence a

pplication to leafy

Brassica greens is defined by crop growth stage.  Melon: The proposed use on melons not grown in plastic mulch must be amended to specify that banded applications are to be made between rows.  Sesame: The proposed use must be amended to specify that application may

only be made to sesame grown in OK and TX. In addition, because application is to be made preemergence, no PHI

is needed; the proposed 100 - day PHIshould be removed. For EPA Reg. No. 100 - 818, the following amendments to the proposed uses are needed:  The proposed use must be amended to specify that postemergence application to sweet sorghum may

be made to crops up to 5 inches in height and that postemergence application may

not be made if preemergence application was made; a maximum of one application must be specified.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 19 of 52  Bushberry

subgroup 13 - 07B: The petitioner must delete the broadcast foliar use on lowbush varieties in the bushberry subgroup from the proposed amended label. The proposed banded, soil directed uses on hi ghbush blueberry , currant, elderberry , gooseberry , and huckleberry are supported by

the available data and may remain on the proposed amended label. The proposed uses must be amended to specify that only one application may

be made.  Carrot: The proposed u se must be amended to specify that only one application may

be made and that postemergence applications may be made up to the 5 - leaf growth stage.  Cucumber: The proposed use must be amended to specify that only one application may be made and that postem ergence applications may be made up to the 2 - leaf growth stage.  Leafy Brassica greens: The proposed use must be amended to specify that only one application may

be made and that postemergence applications may be made up to the 2 - leaf growth stage.  Melons : The proposed uses must be amended to specify that only one application may

be made. In addition, the proposed use on melons not grown in plastic mulch must be amended to specify

that banded applications are to be made between rows. The rotational crop restrictions on the label for EPA Reg. No. 100 - 816 have been evaluated previously

(DP#s 332846, etc., 10/21/08, D. McNeilly ). It was concluded that the proposed restrictions are supported by the available data, provided that that rotational crop directio ns for crops with a 60 - day

PBIbe amended to prohibit a second application of S - metolachlor to any of these crops replanted within 60 days of the original application. This label amendment has not been made. The rotational crop restrictions on the label for EPA Reg. No. 100 - 818 are supported by the available field rotational crop data. 860.1300 Nature of the Residue - Plants The qualitative nature of metolachlor residues in plants is adequately understood based upon the adequate corn, potato, and soy bean metabolism studies. The metabolism of metolachlor involves conjugation with glutathione, breakage of this bond to form the mercaptan, conjugation of the mercaptan with glucuronic acid, O - demethylation of the methyl ether, and conjugation of the resultant alcohol with a neutral sugar. A minor pathway may involve sugar conjugation of metolachlor directly

to the corresponding oxo - compounds. Residues of concern in plants include metolachlor and its metabolites, determined as the derivatives CGA - 37913 and C GA - 49751. The Agency

previously

concluded that the residues of concern for S - metolachlor are the same as for metolachlor (DP# 226780, 11/15/96, L . Kutney ). The Agency

has also reviewed plant metabolism data on S - metolachlor from field tests on soy beans and corn, in vitro tests on corn seedlings, and greenhouse tests on seedlings of corn, sorghum, soy

beans and peanuts (DP#s 278742 and 279110, 8/15/03, S. Kinard). These data support Sy

ngenta’s assertion that the metabolism of S - metolachlor in plants is sim ilar to that for the racemic mixture. The data did not address whether there is any conversion of the S - isomers of metolachlor or its metabolites to the R - isomer forms; however, HED previously concluded that such conversion of isomers in plants is not lik ely to be significant.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 20 of 52 860.1300 Nature of the Residue - Livestock Adequate studies are available depicting the metabolism of metolachlor in ruminants and poultry . Metolachlor is rapidly

metabolized and almost totally eliminated in the urine and feces of ruminants (goats), non - ruminants (rats), and poultry . Metolachlor per se was not detected in any of the excreta or tissues. As in plants, metolachlor residues of concern in livestock commodities include metolachlor and its metabolites, determined as the derivatives CGA - 37913 and CGA 49751. The residues of concern for S - metolachlor in livestock are the same as those for metolachlor. The Agency

has also reviewed livestock metabolism data on S - metolachlor (DP#s 278742, 8/15/03, S. Kinard). Data from a go at metabolism study indicated that S - metolachlor was readily absorbed and extensively metabolized by

goats via glutathione conjugation and/or oxidation reactions. Oxidized metabolites were also conjugated with glucuronic acid. Data from a poultry metabol ism study

indicated that S - metolachlor was also extensively metabolized via O demethylation and subsequent glucuronic acid conjugation or oxidation to dihydroxy or carboxylic acid metabolites that may also be conjugated with glucuronic acid. 860.1340 Resi due Analytical Methods Enforcement methods: Adequate methodology is available for enforcing the established and recommended tolerances. PAM Vol. II, Pesticide Regulation Section 180.368, lists a GC/NPD method (Method I) for determining residues in/on crop commodities and a GC/MSD method (Method I I) for determining residues in livestock commodities. These methods determine residues of metolachlor and its metabolites as either CGA - 37913 or CGA - 49751 following acid hydrolysis. IR - 4 and Sy

ngenta have pro posed an L C/MS/MS enantiomer - specific method for the enforcement of the proposed tolerances, Method 1848 - 01. This method has been previously reviewed by

HED (DP# 296904, 4/17/06, R. L oranger). The method as written uses a chiral HPL C column to separate o ut the S - enantiomers (SYN506357 and SYN508500) of the hydrolysis products CGA - 37913 and CGA - 49751. Data -gathering methods: Samples of crop commodities from the submitted field trial and processing studies were analy zed for residues of metolachlor and i ts metabolites convertible to the derivatives CGA - 49751 and CGA - 37913 using GC/MS, GC/NPD, or L C/MS/MS methods. All methods involved acid hydrolysis in 6 N HCl at reflux for 16 hours to convert residues of metolachlor and its metabolites to either CGA - 497 51 or CGA - 37913. Samples of blueberry

were analy

zed for metolachlor residues of concern using a GC method with either NP or MS detection, developed from Method I in the PAM Vol. I I. Briefly , samples were subjected to acid hydrolysis in 6 N HCl at reflux for 16 hours and the hydrolysate was isolated by filtration and diluted to volume with 6 N HCl. For determination of CGA - 49751, an aliquot was partitioned with dichloromethane (DCM). The DCM phase was subjected to solid - phase extraction (SPE) cleanup pri or to derivatization with 10% boron trifluoride 2 - chloroethanol. TheS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 21 of 52 derivatized product was diluted with 7% aqueous Na2 SO 4, partitioned into hexane, and the hexane phase cleaned up using an alumina column for analysis by GC/MSD. For determination of CGA - 37913, a second aliquot was basified with 50% NaOH and partitioned into hexane for analysis by

GC/NPD. The lower limit of method validation (LLM V) was 0.05 ppm for CGA 49751 and 0.03 ppm for CGA - 37913 in blueberry . Caneberry

samples were analy

zed for me tolachlor residues of concern using a GC/NPD method developed from Method I in PAM Vol. I I. Briefly , samples were subjected to acid hydrolysis in 6 N HCl at reflux for 16 hours and the hydrolysate was isolated by filtration and diluted to volume with wate r. For determination of CGA - 49751, an aliquot was partitioned with DCM and the DCM phase was evaporated to dry ness and then derivatized with 10% boron trifluoride 2 - chloroethanol. The derivatized product was diluted with aqueous 7% Na2 SO 4 and partitioned into hexane for analysis. For determination of CGA - 37913, a separate aliquot was basified with 50% NaOH and partitioned into hexane for analysis. Residues of each analy te were quantitated by GC/NPD analy sis. The LLM V was 0.05 ppm for CGA - 49751 and 0.03 ppm for CGA - 37913 in caneberry . Samples of cantaloupe and sesame commodities (seed, meal, and oil) were analy zed for metolachlor residues of concern using an LC/MS/MS method developed from Method I in PAM Vol. I I. Briefly , samples were subjected to acid hydrolysis in 6 N HCl at reflux for 16 hours and the hydrolysate was isolated by filtration and diluted to volume with water; oil hydrolysates were first partitioned with hexane. For determination of CGA - 49751, an aliquot was partitioned with DCM. The D CM phase was filtered and subjected to SPE cleanup (sesame seed and cantaloupe only ) prior to L C/MS/MS analy sis. For determination of CGA - 37913, another aliquot was basified with 50% NaOH and partitioned with hexane (or DCM for oil). The organic phase wa s filtered and dried over anhydrous sodium sulfate, evaporated to near dry ness, and reconstituted in methanol or mobile phase for L C/MS/MS analy sis. The LLM V was 0.05 ppm for CGA - 49751 and 0.03 ppm for CGA - 37913 in cantaloupe, and 0.05 ppm for each analy t e in sesame commodities. Samples of carrot, cucumber, mustard greens, and sweet sorghum stalk and sy rup were analy

zed for residues of S - metolachlor and its metabolites convertible to CGA - 37913 and CGA 49751 using a modified version of L C/MS/MS Method No. 1848 - 01. This method has been previously reviewed by

HED (DP# 296904, 4/17/06, R. L oranger). The method as written uses a chiral HPL C column to separate out the S - enantiomers (SYN506357 and SYN508500) of the hydrolysis products CGA - 37913 and CGA - 49751. However, the analy tical laboratory

did not use a chiral HPL C column in the analyses; therefore, the working method determined residues of both the R - and S - enantiomers of the hydrolysis products CGA - 37913 and CGA 49751. Ingeneral, samples were subjecte d to acid hydrolysis in 6 N HCl at reflux for 16 hours; the hydrolysate was isolated by filtration and an aliquot was diluted to volume with water and then made basic using 25% NaOH and Na2 CO 3 . The hydrolysate was partitioned with DCM and the DCM phase wa s concentrated, and brought to volume with methanol or 5% isopropanol in methanol for analysis by

L C/MS/MS. The LLM V was 0.05 ppm for each analy te in each commodity

based on fortifications with SYN508500 and SYN506357.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 22 of 52 The methods were adequately validat ed prior to and concurrent with the analysis of field trial and/or processing study

samples. Inthe sesame, cantaloupe, and caneberry submissions, the petitioner stated that combined residues were reported in parent equivalents; however, the study revie wer could not verify this statement. In the blueberry , carrot, cucumber, mustard greens, and sorghum submissions, no information was provided indicating whether derivative and/or total residues were reported in terms of the analy

te or in terms of parent m etolachlor. The Agency requested corrected calculations, which were provided in an MRID addendum to MRIDs 47829401 through 47829408 . This MRID addendum was assigned MRID 48020601. All calculations now are in terms of total parent metolachlor equivalent s. Conclusions . Adequate enforcement methods are available for determining residues in crop and livestock commodities. The petitioner has proposed the enantiomer - specific LC/MS/MS method, Method No. 1848 - 01, for enforcement purposes. HED concludes that the method is not appropriate for enforcement purposes because it does not determine residues of the R - isomers which are included in the tolerance expression. The S:R ratio in the active ingredient is 88:12; therefore, there is potential for residues of the R - isomers of metolachlor and its metabolites in crop commodities. The method could be adapted for enforcement by changing the method to measur e both the S - and the R - enantiomers. 860.1360 Multiresidue Methods Adequate data are available on the re covery of metolachlor through Multiresidue Method Testing Protocols. The FDA PESTDATA database indicates that metolachlor is completely recovered through Method 302, PAM Vol. I (3 rd ed., revised 10/97). 860.1380 Storage Stability Adequate storage stabil ity data are available for crop commodities . Previously submitted data (DP# 292881, 8/15/03, S. Kinard) indicate that: CGA - 37913 is stable at ≤ - 10 °C for at least 2 ye ars in corn (grain and forage), peanut, potato (tubers, wet peel and flakes), soy bean (hulls and meal) and tomatoes, for at least 29 months in cottonseed oil, and for at least 37 months in cottonseed and corn oil; and CGA - 49751 is stable at ≤ - 10°C for at least 2 years in corn (grain, forage, and oil), peanuts, potatoes (tubers, wet peel and flakes), soy beans (hulls and meal) and tomatoes, and for at least 37 months in cotton seed and cottonseed oil. In addition, storage stability studies conducted concurrently with previously

submitted asparagus, carrot, and green onion field trials indicate that both analy tes are stable at - 20 oC for at least 14.1 months in asparagus, 24.3 months in carrots, and 21.7 months in green onions. Concurrent storage stability studies were conducted with the caneberry , cantaloupe, carrot, cucumber, mustard greens, sesame, and sorghum field trial and processing studies submitted with this petition. These data indicate that the metolachlor derivatives CGA - 49751 and CGA - 37913 are stable during frozen storage for up to 48.8 months in/on fortified caneberry ; for up to 26.2S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 23 of 52 months in/on fortified cantaloupe; for up to 30.2 months in/on fortified sesame seed; and for up to 28.2 months in fortified sesame meal and oil. In addition, S - metolachlor derivatives SYN506357 and SYN508500 were found to be relatively stable during frozen storage for up to 25.2 months in/on fortified carrots; for up to 18.0 months in/on fortified cucumber; for up to 24.7 months in/on fortified mustard greens; for up to 17.4 months in/on fortified sorghum stalks; and for up to 10.6 months in fortifie d sorghum sy rup. It is noted that zero - day data were not provided with any of the concurrent storage stability studies; IR - 4 is reminded that storage stability studies should always include a zero - day sampling interval to establish the residue levels pres ent at the time samples are placed into storage [see OPPTS 860.1380(d)(6)(i)]. The durations and conditions of samples from the current crop field trials and processing studies are presented in Table 4. Table 4. Summary of Storage Conditions and Duration s of Samples fromCrop Field Trial and

Processing Studies. Matrix Storage Temperature (°C) Actual Storage

Duration Interval of Demonstrated Storage Stability Blueberry < - 3 364 - 462 days (12.0 - 15.2 months) CGA - 49751 and CGA - 37913 are stable for up

to 2 years in/on various frozen crop commodities, including tomato. Caneberry ≤ - 16 1447 - 1491 days (47.5 - 49.0 months) CGA - 49751 and CGA - 37913 are stable for up

to 48.8 months in/on frozen caneberry. Cantaloupe ≤ - 1 437 - 718 days (14.4 - 23.6 months) CGA - 49751 an d CGA - 37913 are stable for up

to 26.2 months in/on frozen cantaloupe. Carrot root ≤ - 3 488 - 756 days (16.1 - 24.9 months) SYN508500 and SYN506357 are relatively

stable for up to 25.2 months in/on frozen carrot root. Cucumber ≤ - 4 392 - 444 days (12.9 - 14.6 month s) SYN508500 and SYN506357 are stable for up

to 18.0 months in/on frozen cucumber. Mustard greens ≤ - 2 421 - 748 days (13.8 - 24.6 months) SYN508500 and SYN506357 are stable for up

to 24.7 months in/on frozen mustard greens. Sesame seed ≤ - 1 856 - 893 days (28.2 - 29.4 months) CGA - 49751 and CGA - 37913 are stable for up

to 30.2 months in/on frozen sesame seed and 28.2 months in/on frozen meal and oil. Sesame meal 774 - 807 days (25.5 - 26.5 months) Sesame oil 824 days (27.1 months) Sweet sorghum, stalks ≤ - 20 46 9 - 522 days (15.4 - 17.1 months) SYN508500 and SYN506357 are stable for up

to 17.4 months in/on frozen sorghum stalks and up to 10.6 months in frozen sorghum syrup. Sorghum syrup 314 - 324 days (10.3 - 10.7 months) Conclusions . Adequate storage stability data are available to support the storage durations and conditions for samples from the submitted field trial and processing studies. No corrections for potential decline during storage are needed.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 24 of 52 860.1400 Water, Fish, and Irrigated Crops There are no proposed uses that are relevant to this guideline topic. 860.1460 Food Handling There are no proposed uses that are relevant to this guideline topic. 860.1480 Meat, Milk, Poultry, and Eggs The reregistration requirements for magnitude of the residue in m eat, milk, poultry , and eggs are fulfilled (DP# 292881, 8/15/03, S. Kinard). Adequate ruminant and poultry feeding studies are available for metolachlor, and these data will also support the use of S - metolachlor. The proposed uses of S - metolachlor in thi s petition include one livestock feedstuff, carrot culls. The dietary

burdens for livestock to S - metolachlor residues were recently recalculated in conjunction with a request to amend use directions for sorghum and soy bean (DP#s 332846, etc., 10/21/08, D. McNeilly

). At that time, the dietary burdens were calculated to be 26.2 ppm for cattle, 0.51 ppm for poultry , and 0.44 ppm for swine. It was concluded that the established tolerances for livestock commodities were adequate to support existing metolachlo r uses. HED has recalculated the reasonable dietary burdens (RDBs) to livestock using the most recent guidance (June 2008) and the existing and proposed tolerances for residues of metolachlor in/on livestock feedstuffs; see Table 5. The RDBs are 3.11 ppm for beef cattle, 20.2 ppm for dairy cattle, 0.48 ppm for poultry , and 0.40 ppm for swine. Because these RDBs are less than the dietary burdens that were calculated previously , no changes to the established tolerances for livestock commodities are needed to support the proposed uses. Table 5. Calculation of Dietary Burdens of S - Metolachlor Residues to Livestock. Feedstuff Ty pe 1 % Dry Matter2 % Diet2 Tolerance (ppm) Dietary Contribution (ppm) 3 Beef Cattle Corn, field, forage R 40 15 6.0 2.25 Beet, sugar, molasses CC 75 10 2.0 0.27 Potato, processed waste CC 15 30 0.20 0.40 Sorghum, grain CC 86 40 0.30 0.14 Sunflower, meal PC 92 5 1.0 0.054 TOTAL BURDEN -- -- 100 -- 3.11 Dairy Cattle Grass forage R 25 45 10 18.0 Corn, sweet, cannery waste CC 30 10 6.0 2.0 Sorghum, grain CC 86 35 0.30 0.12 Sunflower, meal PC 92 10 1.0 0.11 TOTAL BURDEN -- -- 100 -- 20.2S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 25 of 52 Table 5. Calculation of Dietary Burdens of S - Metolachlor Residues to Livestock. Feedstuff Ty pe 1 % Dry Matter2 % Diet2 Tolerance (ppm) Dietary Contribution (ppm) 3 Poultry Sorghum, grain CC 2 NA 75 0.30 0.23 Sunflower, meal PC NA 25 1.0 0.25 TOTAL BURDEN -- -- 100 -- 0.48 Swi ne Corn, field, grain CC NA 5 0.10 0.005 Sorghum, grain CC 3 NA 80 0.30 0.24 Sunflower, meal PC NA 15 1.0 0.15 TOTAL BURDEN -- -- 100 -- 0.40 1 R: Roughage; CC: Carbohydrate concentrate; PC: Protein concentrate. 2 OPPTS 860.1000 Table 1 Feedstuffs (June 2008). 3 Contribution = ([tolerance /% DM] X % diet) for beef and dairy cattle; contribution = ([tolerance] X % diet) for poultry and swine. Conclusions . The proposed uses for S - metolachlor will have no significant i mpact on the dietary burden of metolachlor to livestock. As a result, no changes are required in the current tolerances for metolachlor residues in livestock commodities. 860.1500 Crop Field Trials DER References: 47829401.de1.doc (Sesame)

47829402.de r.doc (Cantaloupe) 47829403.der.doc (Caneberry) 47829404.der.doc (Blueberry) 47829405.de1.doc (Sweet sorghum) 47829406.der.doc (Mustard greens) 47829407.der.doc (Cucumber) 47829408.der.doc (Carrot) The petitioner submitted field trial data i n support of the proposed uses on bushberry , caneberry , carrot, cucumber, leafy

Brassica greens, melon, sesame, and sweet sorghum. The results of the field trials are summarized in Table 6. The petitioner is rely ing on existing data to support the propos ed uses on bulb and green onion, and okra. The submitted and available data for each crop are discussed below. Table 6. Summary of Residue Data fromCrop Field Trials with S - Metolachlor. Crop matrix Total Applic.

Rate (lb ai/A) [kg ai/ha] PHI

(days) Co mb ined Residues of Metolachlor Derivatives (ppm) in Metolachlor Equivalents n Min. Max. HAFT 1 Median Mean Std. Dev. BUSHBERRY SUBGROUP 13 - 07B (proposed use = 1.27 lb ai/A total application rate, 28 - day PHI) Blueberry, highbush 1.25 - 1.38

[1.41 - 1.54] 2 7 - 33 20 <0.10 <0.10 0.10 0.10 0.10 -- 2.42 - 2.76 [2.71 - 3.09] 27 - 33 20 <0.10 0.17 0.14 0.10 0.11 0.014S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 26 of 52 Table 6. Summary of Residue Data fromCrop Field Trials with S - Metolachlor. Crop matrix Total Applic.

Rate (lb ai/A) [kg ai/ha] PHI

(days) Co mb ined Residues of Metolachlor Derivatives (ppm) in Metolachlor Equivalents n Min. Max. HAFT 1 Median Mean Std. Dev. Blueberry, low bush 1.22

[1.36] 29 2 0.90 1.0 0.96 0.96 0.96 -- 2.54 [2.84] 29 2 1.6 1.6 1.6 1.6 1.6 -- CANEBERRY SUBGROUP 13 - 07A (proposed use = 3.8 lb ai/A total application rate, 28 - day PHI) Caneberry 2.60 - 2.72

[2.92 - 3.04] 28 - 30 10 <0.10 <0.10 0.10 0.10 0.10 -- 3.85 - 4.05 [4.31 - 4.54] 28 - 30 10 <0.10 <0.10 0.10 0.10 0.10 -- CARROT (proposed use = 1.27 lb ai/A total application rate for mineral soils and 1.9 lb ai/A total application rate for m uck soils, 64 - day PHI) Carrot root 0.61 - 0.71

[0.68 - 0.79] 26 - 121 28 <0.13 0.17 0.16 0.13 0.13 0.01 1.23 - 1.36 [1.38 - 1.52] 26 - 121 28 <0.13 0.38 0.37 0.13 0.15 0.06 CUCUMBER (proposed use = 1.27 lb ai/A total ap plication rate, 30 - day PHI) Cucumber 0.89 - 1.00

[1.00 - 1.12] Postemergence 32 - 52 22 <0.13 <0.13 0.13 0.13 0.13 -- 1.22 - 1.31 [1.36 - 1.47] Postemergence 32 - 52 20 <0.13 <0.13 0.13 0.13 0.13 -- 0.92 - 1.00 [1.03 - 1.12] Preemergence 45 - 76 21 <0.13 <0.13 0.13 0.1 3 0.13 -- 1.22 - 1.36 [1.36 - 1.51] Preemergence 45 - 76 20 <0.13 <0.13 0.13 0.13 0.13 --

LEAFY BRASSICA GREENS SUBGROUP 5B (proposed use = 1.27 lb ai/A total application rate, 30 - day PHI) Mustard greens 0.61 - 0.68

[0.69 - 0.76] Postemergence 20 - 40 24 <0.13 <0. 25 0.24 0.16 0.18 0.05 1.24 - 1.35 [1.39 - 1.51] Postemergence 20 - 40 24 <0.13 0.94 0.89 0.32 0.39 0.23 0.63 - 0.66 [0.71 - 0.74] Preemergence 33 - 62 24 <0.13 0.23 0.21 0.13 0.15 0.03 1.21 - 1.38 [1.35 - 1.54] Preemergence 33 - 62 24 <0.13 0.57 0.55 0.17 0.24 0.14S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 27 of 52 Table 6. Summary of Residue Data fromCrop Field Trials with S - Metolachlor. Crop matrix Total Applic.

Rate (lb ai/A) [kg ai/ha] PHI

(days) Co mb ined Residues of Metolachlor Derivatives (ppm) in Metolachlor Equivalents n Min. Max. HAFT 1 Median Mean Std. Dev. ME LON SUBGROUP 9A (proposed use = 1.21 lb ai/A total application rate, 60 - day PHI) Cantaloupe 1.23 - 1.46

[1.38 - 1.64] Banded 61 - 112 22 <0.1 0 <0.10 0.1 0 0.10 0.10 -- 1.26 - 1.38 [1.42 - 1.55] Broadcast 61 - 112 22 <0.10 <0.10 0.10 0.10 0.1 0 -- SESAME (proposed use = 1.9 lb ai/A total application rate, 100 - day PHI) Sesame, seed 1.99 - 2.02

[2.23 - 2.26] 101 -

128 8 <0.13 <0.13 0.13 0.13 0.13 -- SWEET SORGHUM (proposed use = 1.59 lb ai/A total application rate for preem ergence application and

1.27 lb ai/A total applic ation rate for postem ergence application, 90 - day PHI) Sweet sorghum, stalks 0.64 - 0.65

[0.72] Postemergence 87 - 92 6 <0.13 <0.13 0.13 0.13 0.13 -- 1.27 - 1.29 [1.42 - 1.45] Postemergence 87 - 92 6 <0.13 <0.13 0.13 0.13 0.13 -- 1.00 - 1.02 [1.12 - 1.15] Preemergen ce 92 - 108 6 <0.13 <0.13 0.13 0.13 0.13 -- 1.68 - 1.72 [1.88 - 1.93] Preemergence 92 - 108 6 <0.13 <0.13 0.13 0.13 0.13 --

1 HAFT = Highest average field trial result. Bushberry , subgroup 13 - 07B 47829404.der.doc IR - 4 has submitted field trial data for S - met olachlor on blueberry as the representative crop of bushberry subgroup 13 - 07B. Eleven blueberry trials were conducted in the U.S. and Canada in Zones 1 (ME; 1 trial), 2 (NJ, NC; 3 trials), 5 (MI ; 2 trials), 5B (QC; 1 trial), 10 (CA; 1 trial), and 12 (BC, OR; 3 trials) during the 2004 growing season. The ME trial used a lowbush blueberry variety ; the other trials used highbush blueberry varieties. Each trial site consisted of one untreated plot and two treated plots. At each highbush blueberry trial loc ation, a single banded application of a 7.64 lb/gal EC formulation of S - metolachlor was made to the soil surface on both sides of the plant row at 1.25 - 1.38 lb ai/A (1.41 - 1.54 kg ai/ha) at one of the treated plots or at 2.42 - 2.76 lb ai/A (2.71 - 3.09 kg ai/h a) to the other treated plot. At the one lowbush blueberry trial location, a single foliar broadcast application of the 7.64 lb/gal EC formulation was made to fruiting plants at 1.22 lb ai/A (1.36 kg ai/ha) at one of the treated plots or at 2.54 lb ai/A ( 2.84 kg ai/ha) to the other treated plot. The application rates represent ~1x and 2x the proposed maximum seasonal rate to bushberries. All applications were madeS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 28 of 52 using ground equipment, in 17 - 37 gal/A (155 - 346 L/ha) spray volumes, without an adjuvant. Commercially

mature berries were collected 27 - 33 days after application. Samples of blueberry

were analy

zed for residues of metolachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate GC/MS method (CGA - 49751) or GC/NPD method (CGA - 37913). The LLM V was 0.05 ppm for CGA - 49751 and 0.03 ppm for CGA 37913. The combined LLM V was 0.10 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the blueberry field trials. The results of the blueberry field trials are summarized in Table 6. Following a single soil banded application of the 7.64 lb/gal EC formulation to highbush blueberries at 1.25 - 1.38 lb ai/A (1.41 - 1.54 kg ai/ha), residues of CGA - 49751 and CGA - 37913 were each below the LLMV (<0.05 ppm for CGA - 49751 and <0.03 ppm for CGA - 37913) in/on all samples of highbush blueberry harvested 27 - 33 days following application; total metolachlor residues were below the combined LLM Vs (<0.10 ppm in metolachlor equivalents). Residues of CGA - 49751 were nondetectable (<0.023 ppm) in/on all highbush blueberry samples from this treatment rate; residues of CGA - 37913 residues were nondetectable (<0.009 ppm) in 1 4 of 20 samples. Following treatment at the higher rate of 2.42 - 2.76 lb ai/A (2.71 - 3.09 kg ai/ha), residues of CGA 49751 and CGA - 37913 were <0.05 - 0.080 and <0.03 - 0.047 ppm, respectively , in/on highbush blueberry ; total metolachlor residues were <0.13 - 0.21 ppm, expressed as metolachlor equivalents. In these samples, residues of CGA - 49751 were nondetectable in 15 of 20 samples and residues of CGA - 37913 were nondetectable in 11 of 20 samples. Inthe single trial using a lowbush blueberry variety , reflecting a single foliar broadcast application of the 7.64 lb/gal EC formulation at a rate of 1.22 lb ai/A (1.36 kg ai/ha), residues of CGA - 49751 were 0.295 and 0.321 ppm, and residues of CGA - 37913 were 0.394 and 0.463 ppm in/on lowbush blueberry

harvested at a 29 - day

PHI ; total metolachlor residues were 0.90 and 1.0 ppm. Following treatment at the higher rate of 2.54 lb ai/A (2.84 kg ai/ha), residues of CGA 47951 were 0.541 and 0.553 ppm, and residues of CGA - 37913 were 0.626 and 0.595 ppm in/on lowbush blueberry ; total metolachlor residues were 1.6 and 1.4 ppm. No decline trials were conducted. Conclusions . The submitted field trial data are not adequate to support the proposed uses on the bushberry subgroup because only

one field trial reflecting broadcast fol iar application on lowbush blueberry was conducted. The number and locations of field trials are in accordance with OPPTS Guideline 860.1500 for blueberry , but are not in accordance with PMRA Directive 98 - 02, Section 9 for blueberry ; three additional trials would be needed in Zone 1A. No decline trials will be required to support use on highbush blueberry

because residues were below the LOQ in/on all samples treated at 1x. The submitted broadcast foliar data for blueberries are not adequate to support the requested tolerances for lowbush blueberry . In addition, the proposed use patterns differ significantly . The submitted banded, soil directed application data for highbush blueberry would support aS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 29 of 52 tolerance for bushberry , subgroup 13 - 07B (with use on lowbush blueberry and other low bush varieties of berries prohibited on the label), at 0.20 ppm, expressed as total metolachlor equivalents. If the petitioner wishes to support broadcast foliar use on lowbush blueberry, two additional crop field trials must be submitted before a tolerance may be established

– one additional trial in Region 1, one additional trial in Region 5 . A lternatively , with the additional field trial data reflecting broadcast foliar use, the petitioner may wish to submit data and propose a tolerance for the low growing berry , except strawberry , subgroup 13 - 07H. . Four additional field trials, conducted on lowbush blueberry or cranberry

would be required. T he tolerance for S - metolachlor residues on the bushberry subgroup can be e stablished, provided the use is limited to banded application directed at the soil, and use on low - bush blueberries is deleted from the label . Caneberry , subgroup 13 - 07A 47829403.der.doc IR - 4 has submitted field trial data for S - metolachlor on blackberry and raspberry , the representative crops of the caneberry subgroup 13 - 07A. Five caneberry trials were conducted in the U.S. in Zones 1 (PA; 1 trial), 5 (MI ; 1 trial), and 12 (OR; 3 trials) during the 1998 growing season. One trial used a blackberry varie ty ; the other trials used raspberry varieties. Each trial site consisted of one untreated plot and two treated plots. A single banded application of a 7.62 lb/gal EC formulation of S - metolachlor was made to the soil surface on both sides of the cane at 2.60 - 2.72 lb ai/A (2.92 - 3.04 kg ai/ha) at one of the treated plots or at 3.85 - 4.05 lb ai/A (4.31 - 4.54 kg ai/ha) at the other treated plot. The application rates represent ~0.8x and 1x the proposed maximum seasonal rate to caneberry . Applications were ma de using ground equipment, in 21 - 42 gal/A (194 - 395 L/ha) spray volumes, without an adjuvant. Commercially mature berries were collected 28 - 30 days after application. Samples of caneberry

were analy

zed for residues of metolachlor and its metabolites as de rivatives CGA - 49751 and CGA - 37913 using an adequate GC/NPD method. The LLM V was 0.05 ppm for CGA - 49751 and 0.03 ppm for CGA - 37913. The combined LLM V was 0.10 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the caneberry field trials. The results of the caneberry field trials are summarized in Table 6. Residues of the metolachlor derivatives CGA - 49751 and CGA - 37913 were each below the respective LLMV (<0.05 or <0.03 ppm) in/on all samples of caneberry harvested 28 - 30 days following a single banded application of the 7.62 lb/gal EC formulation at 2.60 - 2.72 lb ai/A (2.92 - 3.04 kg ai/ha) or 3.85 - 4.05 lb ai/A (4.31 - 4.54 kg ai/ha). R esidues , expressed as total metolachlor equivalents, were below the combined LLM Vs (<0.10 ppm) in/on all treated caneberry samples. No decline trials were conducted; however, decline trials are not required given that all residues wer e nonquantifiable.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 30 of 52 Conclusions . The submitted field trial data are tentatively adequate to support the proposed uses on the caneberry

subgroup. The number and locations of field trials are in accordance with OPPTS Guideline 860.1500 for caneberry subgro up 13 - 07A but not in accordance with PMRA Directive 98 - 02, Section 9 for raspberry ; one additional trial would be needed in Zone 5B. The submitted data support a single postemergence banded (to the soil) application of S - metolachlor to caneberry at up to 3.8 lb ai/A with a 28 - day

PHI . The submitted data will support a tolerance for S - metolachlor residues in/on the caneberry

subgroup 13 - 07A of 0.10 ppm. Carrot 47829408.der.doc IR - 4 has submitted field trial data for S - metolachlor on carrot. Fourteen tri als were conducted in the U.S. and Canada in Zones 1A (PE; 1 trial), 2 (GA; 1 trial), 3 (FL ; 1 trial), 5 (ON, WI ; 3 trials), 5B (QC; 2 trials), 6 (TX; 1 trial), 10 (CA; 4 trials), and 11 (WA; 1 trial) during the 2004 growing season. Each trial site cons isted of one untreated plot and two treated plots. A single foliar broadcast application of a 7.64 lb/gal EC formulation of S - metolachlor was made to carrot plants, at approximately

the 3 - to 5 - leaf stage, at either 0.61 - 0.71 lb ai/A (0.68 - 0.79 kg ai/ha) or 1.23 - 1.36 lb ai/A (1.38 - 1.52 kg ai/ha). The application rates represent ~0.5x and 1x the proposed maximum seasonal rate to carrot. Applications were made using ground equipment in ~25 - 39 gal/A (238 - 363 L/ha) spray volumes, without an adjuvant. Mature carrot root was harvested 26 - 121 days following application. Samples of carrot were analy zed for residues of metolachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS method, modified Method No. 1848 - 01. The LLM V was 0.05 ppm for each analy te based on fortifications with SYN508500 and SYN506357. The combined LLM V was 0.13 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequat e storage stability data are available to support the carrot field trials. The results of the carrot field trials are summarized in Table 6. Residues of CGA - 49751 were below the LLM V (<0.05 ppm) and residues of CGA - 37913 were <0.05 - 0.078 ppm in/on carrot roots harvested 26 - 121 days following a single foliar broadcast application of the 7.64 lb/gal EC formulation at 0.61 - 0.71 lb ai/A (0.68 - 0.79 kg ai/ha); total metolachlor residues were <0.13 - 0.17 ppm, expressed as metolachlor equivalents. Following a s ingle foliar broadcast application of the 7.64 lb/gal EC formulation at the higher rate of 1.23 - 1.36 lb ai/A (1.38 - 1.52 kg ai/ha), residues of CGA - 49751 were <0.05 - 0.132 ppm and residues of CGA - 37913 were <0.05 - 0.169 ppm in/on carrot roots harvested 26 - 121 day s following treatment; total metolachlor residues were <0.13 - 0. 3 8 ppm, expressed as metolachlor equivalents.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 31 of 52 No decline trials were conducted; however, because applications are made early in the growth stage, no decline trials are required. Conclusio ns . The submitted field trial data are tentatively adequate to support the proposed uses on carrot. The number and locations of field trials are in accordance with OPPTS Guideline 860.1500 and PMRA Directive 98 - 02, Section 9 for carrot. Crop field trial data for carrot have been submitted previously . Under PP#7E04916 (DP# 292881, 8/15/03, S. Kinard), adequate carrot data were submitted reflecting a single preemergence application of metolachlor (racemic mixture) to carrots grown in muck soils at 2.0 - 8.0 lb ai/A, equivalent to 1.25 - 3.0 lb ai/A S - metolachlor (requested application rate was 2.5 lb ai/A S - metolachlor). Combined residues, expressed as parent equivalents, were <0.04 - 0.115 ppm in/on carrots harvested 64 - 91 days following treatment. HED conclu ded that the data were adequate to support a 0.2 - ppm tolerance provided application was limited to carrots grown in muck soils. Under PP#3E6787 (DP# 296904, 4/17/06, R. L oranger) , adequate field trial data for carrot and radish were submitted reflecting a single broadcast preplant incorporated or preemergence application of S - metolachlor at 1.3 lb ai/A. Samples were analy zed for combined S - metolachlor residues SYN506357 and SYN508500 using the L C/MS/MS method, Method No. 1848 - 01, which separated the S - enantiomers of the derivatives from the R - enantiomers. Combined residues, expressed as S - metolachlor equivalents, were <0.08 ppm in/on radish root and <0.08 - 0.27 ppm in/on carrot root harvested 71 - 171 days following treatment. HED concluded that the data we re adequate to support a 0.3 ppm tolerance for the root vegetable, except sugar beet, subgroup 1B . The submitted data support a single postemergence foliar application of S - metolachlor to carrot at up to 1.3 lb ai/A, provided that application is only made to carrots up to the 5 - leaf growth stage. The available data for carrot support the proposed preemergence applications at up to 1.3 lb ai/A for carrots grown in mineral soils and up to 1.9 lb ai/A for carrots grown in muck soils, but do not support poste mergence applications to carrots grown in muck soils at rates >1.3 lb ai/A. The submitted data will support a tolerance for S - metolachlor residues in/on carrot of 0.4 ppm, expressed as metolachlor. The existing tolerance for crop subgroup 1B will need t o be revised to exclude carrot. Although the previously

requested uses were not added to the Section 3 labels for EPA Reg. Nos. 100 - 816 or 100 - 818, 24(c) labels with these uses were issued (based on an OPPI N search). The same situation applies to onions (discussed below). Cucumber 47829407.der.doc IR - 4 has submitted field trial data for S - metolachlor on cucumber. Twelve trials were conducted in the U.S. and Canada in Zones 2 (GA, MD, NC; 3 trials), 3 (FL ; 1 trial), 4 (TN; 1 trial), 5 (ON;S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 32 of 52 2 trials), 5B (QC; 2 trials), 6 (TX; 1 trial), 10 (NM; 1 trial), and 12 (BC; 1 trial) during the 2005 growing season. Each trial site consisted of one untreated plot and four treated plots. A single application of a 7.64 lb/gal EC formulation of S - metolachlor was m ade to each plot. At two plots, a preemergence broadcast application was made to the soil surface 0 - 4 days after planting at 0.92 - 1.00 lb ai/A (1.03 - 1.12 kg ai/ha) or 1.22 - 1.36 lb ai/A (1.36 - 1.51 kg ai/ha). At the other two treatment plots, foliar broadc ast applications were made early post - emergence (1 - 2 leaf stage) at 0.89 - 1.00 lb ai/A (1.00 - 1.12 kg ai/ha) or 1.22 - 1.31 lb ai/A (1.36 - 1.47 kg ai/ha). The application rates represent ~0.8x and 1x the proposed maximum seasonal rate to cucumber. Application s were made using ground equipment in ~16 - 34 gal/A (145 - 317 L/ha) spray volumes, without an adjuvant. Mature cucumbers were harvested 32 - 52 days after postemergence treatment, and 45 - 76 days after preemergence treatment. Low crop y ields (due to phy

totoxi city ) prevented collection of samples from a total of 6 plots (one treated preemergence at the low rate, two treated preemergence at the high rate, one treated postemergence at the low rate, and two treated postemergence at the high rate); in addition, at one plot (treated preemergence at the low rate), only one sample could be collected. Samples of cucumber were analy zed for residues of metolachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS method, modified Method No. 1848 - 01. The LLM V was 0.05 ppm for each analy te based on fortifications with SYN508500 and SYN506357. The combined LLM V was 0.13 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the cucumber field trials. The results of the cucumber field trials are summarized in Table 6. Residues of CGA - 49751 and CGA - 37913 were each below the LLMV (<0.05 ppm) in/on all cucumber samples harvested 32 - 76 days following a single preemergence soil broadcast application or early postemergence foliar broadcast application of the 7.64 lb/gal EC formulation at 0.89 - 1.00 lb ai/A (1.00 - 1.12 kg ai/ha) or at the higher rate of 1.22 - 1.36 lb ai/A (1.36 - 1.51 kg ai/ha). Total metolachlor residues, in metolachlor equivalents, were below the combined LLM Vs (<0.13 ppm) in/on all treated cucumber samples. No decline trials were conducted; however, no decline trials are required given tha t all residues were nonquantifiable and applications were made at an early growth stage. Conclusions . The submitted field trial data are adequate to support the proposed uses on cucumber. The number and locations of field trials are in accordance with O PPTS Guideline 860.1500 and PMRA Directive 98 - 02, Section 9 for cucumber. The submitted data support a single postemergence foliar application of S - metolachlor to cucumber at up to 1.3 lb ai/A, provided that application is only made to cucumber up to th e 2 - leaf growth stage. The submitted data will support a tolerance for S - metolachlor residues in/on cucumber of 0.13 ppm, expressed as metolachlor equivalents.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 33 of 52 Leafy Brassica greens, subgroup 5B 47829406.der.doc IR - 4 has submitted field trial data for S - metolachlor on mustard greens as the representative crop of the Brassica leafy

greens, subgroup 5B. Twelve trials were conducted on mustard greens in the U.S. and Canada in Zones 2 (NJ, NC; 3 trials), 3 (FL ; 1 trial), 4 (TN; 1 trial), 5 (MI , ON; 3 trials ), 6 (TX; 1 trial), 10 (CA; 2 trials), and 12 (BC; 1 trial) during the 2004 growing season. Each trial site consisted of one untreated plot and four treated plots. A single application of a 7.64 lb/gal EC formulation of S - metolachlor was made to each pl ot. At two plots, a preemergence broadcast application was made to the soil surface 0 - 5 days after planting at 0.63 - 0.66 lb ai/A (0.71 - 0.74 kg ai/ha) or 1.21 - 1.38 lb ai/A (1.35 - 1.54 kg ai/ha). At the other two treatment plots, foliar broadcast applicatio ns were made early postemergence (1 - 2 leaf stage) at 0.61 - 0.68 lb ai/A (0.69 - 0.76 kg ai/ha) or 1.24 - 1.35 lb ai/A (1.39 - 1.51 kg ai/ha). The application rates represent ~0.5x and 1x the proposed maximum seasonal rate to leafy greens. Applications were made using ground equipment in ~19 - 42 gal/A (178 - 389 L/ha) spray volumes, without an adjuvant. Mature mustard greens were harvested 20 - 40 days following postemergence application or 33 - 62 days following preemergence application. Samples of mustard greens wer e analy zed for residues of metolachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS method, modified Method No. 1848 - 01. The LLM V was 0.05 ppm for each analy te based on fortifications with SYN508500 and SYN506357. The combined LLM V was 0.13 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the mustard greens field trials. The results of the mustard greens field trials are summarized in Table 6. Residues of CGA 49751 and CGA - 37913 were <0.05 - 0.065 and <0.05 - 0.107 ppm, respectively , in/on mustard greens harvested 33 - 62 days following a single preemergence soil broadcast appl ication of the 7.64 lb/gal EC formulation at 0.63 - 0.66 lb ai/A (0.71 - 0.74 kg ai/ha); total metolachlor residues were <0.13 - 0.23 ppm, expressed as metolachlor equivalents. Following a preemergence soil application at the higher rate of 1.21 - 1.38 lb ai/A (1 .35 - 1.54 kg ai/ha), residues of CGA - 49751 and CGA - 37913 were <0.05 - 0.188 and <0.05 - 0.244 ppm, respectively , in/on mustard greens harvested 33 - 62 days after treatment; total metolachlor residues were <0.13 - 0.57 ppm, expressed as metolachlor equivalents. Re sidues of CGA - 49751 and CGA - 37913 were <0.05 - 0.056 and <0.05 - 0.134 ppm, respectively , in/on mustard greens harvested 20 - 40 days following a single early postemergence foliar broadcast application of the 7.64 lb/gal EC formulation at 0.61 - 0.68 lb ai/A (0.69 - 0.76 kg ai/ha); total metolachlor residues were <0.13 - <0.25 ppm, expressed as metolachlor equivalents. Following an early

postemergence foliar application at the higher rate of 1.24 - 1.35 lb ai/A (1.39 - 1.51 kg ai/ha), residues of CGA - 49751 and CGA - 37913 w ere <0.05 - 0.172 and <0.05 - 0.552 ppm, respectively , in/on mustard greens harvested 20 - 40 days after treatment; total metolachlor residues were <0.13 - 0.94 ppm, expressed as metolachlor equivalents. Residues were generally

higher in samples treated early pos temergence (foliar application), than in those treated preemergence (soil application).S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 34 of 52 No decline trials were conducted however, no decline trials are required because applications were made at an early

growth stage. In addition, previously submitted re sidue decline data for sorghum forage indicated that combined residues decreased with increasing sampling intervals (DP#s 332846, etc., 10/21/08, D. McNeilly ). Conclusions . The submitted field trial data are tentatively adequate to support the proposed u ses on leafy Brassica greens. The number and locations of field trials are in accordance with OPPTS Guideline 860.1500 for mustard greens as a representative crop of subgroup 5B; PMRA does not specify any field trial requirements for mustard greens. Th e submitted data support a single postemergence foliar application of S - metolachlor to leafy Brassica greens at up to 1.3 lb ai/A, provided that application is only

made to crops up to the 2 - leaf growth stage. The submitted data will support a tolerance f

or S - metolachlor residues in/on leafy Brassica greens at 1. 8 ppm. HED now considers turnip greens to be a member of the leafy Brassica greens subgroup. Pending revision of 40 CFR §180.41, a separate tolerance must be established for turnip greens, at th e same level as the tolerance for leafy Brassica greens. Melon, subgroup 9A 47829402.der.doc IR - 4 has submitted field trial data for S - metolachlor on cantaloupe as the representative crop of the melon subgroup 9A. Eleven cantaloupe trials were conduct ed in the U.S. and Canada in Zones 2 (NJ, NC; 2 trials), 5 (MI , ON; 2 trials), 5B (QC; 1 trial), 6 (TX; 2 trials), and 10 (CA, NM; 4 trials) during the 2003 growing season. Each trial site consisted of one untreated plot and two treated plots. At one o f the treated plots, a single banded application of a 7.64 lb/gal EC formulation of S - metolachlor was made to the row middles 1 - 4 days after planting (preemergence) or 0 - 14 days prior to transplanting of cantaloupes (cantaloupes were planted at 5 sites and transplanted at 6 sites). At the other treated plot, a single broadcast application of the 7.64 lb/gal EC formulation was made to the soil after planting or prior to transplanting of cantaloupes. At five trial sites, cantaloupes were grown in plastic mu lch; at these sites, broadcast applications were made before and banded applications were made after the laying of the plastic mulch. Application rates ranged 1.23 - 1.46 lb ai/A (1.38 - 1.64 kg ai/ha; ~1x the proposed maximum seasonal rate to melons), and we re made using ground equipment in 20 - 40 gal/A (186 - 378 L/ha) spray volumes, without an adjuvant. Commercially mature cantaloupes were collected 61 - 112 days after application. Samples of cantaloupe were analy zed for residues of metolachlor and its metabol ites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS method. The LLM V was 0.05 ppm for CGA - 49751 and 0.03 ppm for CGA - 37913 in cantaloupe. The combined LLM V was 0.10 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the cantaloupe field trials.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 35 of 52 The results of the cantaloupe field trials are summarized in Table 6. Residues of CGA - 49751 and CGA - 3 7913 were each below the LLMV (<0.05 ppm for CGA - 49751 and <0.03 ppm for CGA - 37913) in/on all cantaloupe samples harvested 61 - 112 days following a single preemergence or pre - transplant, banded or soil broadcast application of the 7.64 lb/gal EC formulation at 1.23 - 1.46 lb ai/A (1.38 - 1.64 kg ai/ha). Total metolachlor residues were below the combined LLM Vs (<0.10 ppm, expressed as metolachlor equivalents) in/on all treated cantaloupe samples. No decline trials were conducted; however, decline trials are n ot required given that all residues were nonquantifiable and applications were made early in the growth stage. Conclusions . The submitted field trial data are adequate to support the proposed uses on melon subgroup 9A. The number and locations of field trials are in accordance with OPPTS Guideline 860.1500 for cantaloupe as a representative crop of subgroup 9A, and for PMRA Directive 98 - 02, Section 9 for melon. The submitted data support a single preemergence or pre - transplant broadcast or banded (to th e soil) application of S - metolachlor to melon at up to 1.2 lb ai/A. The submitted data will support a tolerance for S - metolachlor residues in/on melon subgroup 9A at 0.10 ppm in metolachlor equivalents. Okra D296904.mem.doc, PP#3E6787, 4/17/06, R. Lorang er No field trial data were submitted to support the requested use on okra. The petitioner is relying on previously

submitted residue data for fruiting vegetables to support the proposed use on okra. Residue data for S - metolachlor on fruiting vegetables were submitted under PP#3E6787 (DP# 296904, 4/17/06, R. L oranger). In a total of 50 tests conducted at 21 field locations in 2002, a 7.6 lb/gal EC formulation of S - metolachlor was applied as single application at 1.62 - 1.79 lb ai/A to bell peppers (15 tes ts), hot peppers (8 tests), and tomatoes (27 tests). Three different treatment regimes were used with 2 or 3 different ty pes of applications used in side - by- side tests at each trial site on each crop. The different applications included either a preplant incorporated (PPI) application prior to transplanting, or a broadcast postemergence application at the 8 - to 10 - leaf stage (early

) or prior to fruit set (late). Duplicate samples of mature tomato, bell pepper, and hot pepper samples were collected 73 - 130 day s and 89 - 149 days following the PPIapplication, 39 - 89 days and 54 - 103 days following the early postemergence application, and 40 - 64 days and 69 - 80 days following the later postemergence application. Samples were analy zed for combined S - metolachlor re sidues SYN506357 and SYN508500 using the L C/MS/MS method, Method No. 1848 - 01, which separated the S - enantiomers of the derivatives from the R - enantiomers. The combined residues of SYN506357 and SYN508500, expressed as parent equivalents, were <0.08 ppm (< LOQ) in/on all bell pepper (n=60), hot pepper (n=32), and tomato (n=106) samples from all tests. The established tolerance for S - metolachlor residues in/on the fruiting vegetable group, except tabasco pepper, is 0.10 ppm [180.368(a)(2)]; a separate tolerance for tabasco pepper has been established because the use pattern on tabasco peppers is substantially different from that for the other members of the fruiting vegetable crop group.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 36 of 52 The proposed use on okra is similar to the supported use on the fruitin g vegetables crop group (except tabasco pepper): a single postemergence application at the maximum rate of 1.9 lb ai/A with a 60 - day

PHI . HED has approved adding okra to the fruiting vegetable crop group (see minutes of the ChemSAC meeting of 10/18/06). Until 40 CFR §180.41 is updated, a separate tolerance must be established for okra. The available field trial data for fruiting vegetables may be translated to okra; these data would support a tolerance of 0.10 ppm for okra. Onion, bulb, subgroup 3 - 07 A and onion, green, subgroup 3 - 07B D296904.mem.doc, PP#3E6787, 4/17/06, R. Loranger No field trial data were submitted to support the requested uses on onion subgroups 3 - 07A and 3 - 07B. The petitioner is relying on previously submitted residue data for bu lb onion, the representative commodity of subgroup 3 - 07A, and green onion, the representative commodity of subgroup 3 - 07B, to support the proposed uses. Residue data for S - metolachlor on onions were submitted under PP#3E6787 (DP# 296904, 4/17/06, R. L or anger). A total of 11 field trials were conducted on green and dry bulb onions during the 2002/2003 growing season. In the 5 green onion tests, a 7.6 lb/gal EC formulation of S - metolachlor was applied as a single postemergence application at the 2 - to 6 - leaf stage at 1.29 - 1.33 lb ai/A (1x the maximum proposed rate for subgroup 3 - 07B), in a volume of 2 - 26 gal/A. In the 6 dry bulb onion tests, a 7.6 lb/gal EC formulation of S - metolachlor was applied as two postemergence applications at 1.27 - 1.34 lb ai/A/ application at retreatment intervals of 21 - 53 day s, for a total of 2.58 - 2.68 lb ai/A/season (~1x the maximum proposed rate for subgroup 3 - 07A), in a volume of 15 - 29 gal/A. The initial application to bulb onions was made at the 2 - to 6 - leaf stage. Duplicate treated samples of green onions were harvested 21 - 22 days following treatment from four tests and 50 days following treatment from one test, and duplicate treated samples of dry

bulb onions were harvested at 54 - 62 days following treatment. Samples were analy zed for combined S - metolachlor residues SYN506357 and SYN508500 using the LC /MS/MS method, Method No. 1848 - 01, which separated the S - enantiomers of the derivatives from the R - enantiomers. Residues were reported in S - metolachlor equivalents. Followi ng a single postemergence application at 1.3 lb ai/A, the combined S - metolachlor residues were 0.16 - 1.76 ppm in/on 8 samples of green onions collected 21 - 22 days posttreatment (proposed PHI) from four of the five tests. In the other green onion test, comb ined residues were 0.10 and 0.32 ppm in/on two samples collected 50 days posttreatment. Following the last of two postemergence applications totaling ~2.6 lb ai/A, combined S - metolachlor residues were <0.08 - <0.09 ppm in/on 12 samples of bulb onion samples collected at 54 - 62 days posttreatment. Based on these data, tolerances were established for S - metolachlor residues in/on garlic bulb, bulb onion, and shallot bulb at 0.10 ppm, and in/on green onion at 2.0 ppm. The proposed use on bulb onion subgroup 3 - 0 7A is identical to the supported use on bulb onion and the proposed use on the green onion subgroup 3 - 07B is identical to the supported use on green onion. The available data for bulb onion are adequate to support use on the bulb onion subgroup 3 - 07A and the available data for green onion are adequate to support use on the green onion subgroup 3 - 07B. The proposed tolerances of 0.10 ppm for subgroup 3 - 07A and 2.0 ppm for subgroup 3 - 07B are appropriate. When these tolerances are established, the existingS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 37 of 52 t olerances under 180.368(a)(2) for the following commodities should be removed: garlic, bulb; onion, bulb; onion, green; and shallot, bulb. Sesame 47829401.der.doc IR - 4 has submitted field trial data for S - metolachlor on sesame. Four sesame field trials were conducted in the U.S. in Zone 6 (TX) during the 2000 growing season. All four trials were conducted in the same county ; two of the trials were conducted on the same tract of land, and the other two trials were conducted nearby , on plots in close pro ximity to each other. Each trial site consisted of one untreated plot and one treated plot. A single broadcast application of a 7.62 lb/gal EC formulation of S - metolachlor was made to the soil surface 3 - 4 day s after planting (preemergence) at 1.99 - 2.02 lb ai/A (2.23 - 2.26 kg ai/ha), 1x the proposed maximum seasonal rate to sesame. Applications were made using ground equipment, in 20 - 22 gal/A (188 - 208 L/ha) spray volumes, without an adjuvant. Mature sesame seed was harvested 101 - 128 days after applicati on. Samples of sesame seed were analy zed for residues of metolachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS method. The LLM V was 0.05 ppm for each analy te. The combined LLM V was 0.13 ppm total metolachlor r esidues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the sesame field trials. The results of the sesame field trials are summarized in Ta ble 6. Residues of CGA - 49751 and CGA - 37913 were each below the LLMV (<0.05 ppm) in/on sesame seed harvested 101 - 128 days following a single preemergence soil broadcast application of the 7.62 lb/gal EC formulation at 1.99 - 2.02 lb ai/A (2.23 - 2.26 kg ai/ha) . Total metolachlor residues were below the combined LLM Vs (<0.13 ppm, expressed as metolachlor equivalents) in/on all treated sesame seed samples. Conclusions . The submitted field trial data are tentatively adequate to support the proposed uses on sesame. HED concludes that the submitted field trials reflect only two field trial sites; the two trials conducted on the same tract of land reflect one site and the other two trials, which were conducted in close proximity , reflect a second site. According to “Food and Feed Crops of the United States” (G.M. Markle, J.J. Baron, and B.A. Schneider. Second Edition, Meister Publishing Co. 1998), sesame is grown in Zones 6, 8, and 10. The petitioner has stated that the request for S - metolachlor use on sesame was made on behalf of the Agricultural Experiment Stations of OK and TX. The two field trials are adequate to reflect use on sesame. The submitted data support a single preemergence application of S - metolachlor to sesame at up to 1.9 lb ai/A. The submitte d data will support a tolerance for S - metolachlor residues in/on sesame seed at 0.13 ppm.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 38 of 52 Sorghum, sweet 47829405.der.doc D332846.mem.doc, 10/21/08, D. McNeilly IR - 4 has submitted field trial data for S - metolachlor on sweet sorghum. Three trials were co nducted in the U.S. in Zones 4 (TN; 2 trials) and 6 (TX; 1 trial) during the 2005 growing season. The two TN trials were conducted in very close proximity , with the same study director and personnel; applications were made one day later in the second TN trial but all TN samples were harvested on the same day ; therefore, HED concludes that the two TN trials only represent one field site. Each trial site consisted of one untreated plot and four treated plots. A single application of a 7.64 lb/gal EC formu lation of S - metolachlor was made to each plot. At two plots, a preemergence broadcast application was made to the soil surface 0 - 2 days after planting at 1.00 - 1.02 lb ai/A (1.12 - 1.15 kg ai/ha) or 1.68 - 1.72 lb ai/A (1.88 - 1.93 kg ai/ha); the application rat es represent ~0.6x and 1x the proposed maximum single preemergence application rate to sweet sorghum. At the other two treatment plots, a single foliar broadcast application was made early postemergence (seedling stage) at 0.64 - 0.65 lb ai/A (0.72 kg ai/ha) or 1.27 - 1.29 lb ai/A (1.42 - 1.44 kg ai/ha); the application rates represent ~0.5x and 1x the proposed maximum single postemergence application rate. Applications were made using ground equipment in ~16 - 20 gal/A (152 - 191 L/ha) spray volumes, without an ad

juvant. It is noted that sorghum seed was treated with Concep II Herbicide Antidote (safener) prior to planting to protect the seed from the effects of S - metolachlor. Mature sorghum stalks were harvested 87 - 92 days following postemergence application, or 92 - 108 days following preemergence application. Samples of sorghum stalk were analy zed for residues of metolachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS method. The LLM V was 0.05 ppm for each analy te based on fortifications with SYN508500 and SYN506357. The combined LLM V was 0.13 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are availa ble to support the sweet sorghum field trials. The results of the sweet sorghum field trials are summarized in Table 6. Residues of CGA 49751 and CGA - 37913 were each below the LLMV (<0.05 ppm) in/on all sorghum stalk samples harvested 87 - 108 days followi ng a single preemergence soil broadcast application of the 7.64 lb/gal EC formulation at 1.00 - 1.02 lb ai/A (1.12 - 1.15 kg ai/ha) or 1.68 - 1.72 lb ai/A (1.88 - 1.93 kg ai/ha), or an early

postemergence foliar broadcast application of the 7.64 lb/gal EC formulation at 0.64 - 0.65 lb ai/A (0.72 kg ai/ha) or 1.27 - 1.29 lb ai/A (1.42 - 1.44 kg ai/ha). Total metolachlor residues were below the combined LLMVs (<0.13 ppm, expressed as metolachlor equivalents) in/on all treated sweet sorghum stalk samples. Conclusions . The submitted field trial data are adequate to satisfy data requirements . The number of field trials and geographic representation is adequate. HED has previously

concluded that residues on sweet sorghum commodities will be covered by sorghum grain and stover tolerances (see Table 1 of OPPTS 860.1000). A tolerance for S metolachlor residues in/on sorghum grain has been established at 0.3 ppm ; and a toler ance for S -S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 39 of 52 metolachlor residues in/on sorghum stover at 4.0 ppm . Field trial data for sorghum were recently submitted in support of a request to add postemergence use to the label for the 7.62 lb/gal EC formulation (EPA Reg. No. 100 - 816); see DP#s 332846, etc., 10/21/08, D. McNeilly ). In 12 field trials conducted in Zones 2, 4, 5, 6, 7 and 8 during 200 2, S - metolachlor (7.64 lb/gal EC) was applied to sorghum using three different application regimes, each at a target rate of 1.7 lb ai/A. S - Metolachlor was applied as either a PPI application at planting at 1.63 - 1.69 lb ai/A (Trt #2), a broadcast soil sur face application at planting at 1.64 - 2.28 lb ai/A (Trt #3), or a postemergence foliar application when plants were ~5 - inches in height at 1.64 - 1.71 lb ai/A (Trt #4). The postemergence application was tested at all 12 field sites, and the two soil applicat ions were each tested at 8 of the 12 field sites. Forage, grain, and stover samples were collected at all sites; only

the data for grain are summarized below. Residues of S - metolachlor in/on sorghum commodities were determined as SYN506357 and SYN508500 using an adequate LC/MS/MS method (Method No. 1848 - 01); residues were expressed in parent equivalents. Following a PPIapplication at 1.63 - 1.69 lb ai/A (Trt #2), combined residues were <0.08 - 0.11 ppm in/on grain harvested 120 - 149 days after treatment (DAT ). Following a soil surface application at 1.64 - 2.28 lb ai/A (Trt #3), combined residues were <0.08 - 0.11 ppm in/on grain harvested 120 - 149 DAT. Following a post - emergence application at 1.64 - 1.71 lb ai/A (Trt #4), combined residues were <0.08 - 0.09 ppm in/on grain harvested 95 - 133 DAT. The available data for sorghum grain may be translated to support the proposed use on sweet sorghum: a single preemergence application at up to 1.67 lb ai/A or a single postemergence application at up to 1.3 lb ai/A. The proposed use should be amended to specify that postemergence application may be made to crops up to 5 inches in height. A tolerance for sweet sorghum grain is not needed. The tolerance for sorghum, grain, stover will be translated to sorghum, sweet, stal k, and set at 4.0 ppm. 860.1520 Processed Food and Feed DER References: 47829401.de2.doc (Sesame)

47829405.de2.doc (Sweet sorghum) The petitioner submitted processing studies with sesame and sweet sorghum. The results of the processing studies are summarized in Table 7. Sesame IR - 4 submitted a processing study for S - metolachlor with sesame seed. In a sesame crop field trial conducted in TX during the 2000 growing season, a single broadcast application of a 7.62 lb/gal EC formulation of S - metolach lor was made to the soil surface 4 days after planting (preemergence) at 2.02 lb ai/A (2.26 kg ai/ha), ~1x the proposed maximum rate. The study was conducted in conjunction with the sesame field trials. Mature sesame seed was harvested 128 day s after app lication, and processed into meal and oil using procedures simulating commercial practices. Samples of sesame commodities were analy zed for residues of metolachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS metho d. The LLM VS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 40 of 52 was 0.05 ppm for each analy te in each commodity . The combined LLM V was 0.13 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the sesame processing study . Residues of CGA - 49751 and CGA - 37913 were each below the LLMV (<0.05 ppm) in/on sesame seed harvested 128 days following a single preemergence soil broadcast application of the 7.62 lb/gal EC formu lation at 2.02 lb ai/A (2.26 kg ai/ha); total metolachlor residues were below the combined LLM Vs (<0.13 ppm). Residues of CGA - 49751 and CGA - 37913 were also below the LLM V in processed sesame meal and oil; therefore, processing factors could not be calculated. No theoretical processing factors are presented for sesame in 860.1520. Sweet sorghum IR - 4 submitted a processing study for S - metolachlor with sweet sorghum. In a sorghum crop field trial conducted in TX during the 2005 growing season, a single broadcast application of a 7.64 lb/gal EC formulation of S - metolachlor, was made to the soil surface 2 days after planting (preemergence) at 1.72 lb ai/A (1.93 kg ai/ha), ~1x the proposed maximum rate for preemergence application. The study was conducted in conjunction with the sorghum field trials. Mature sorghum stalks were harvested 92 days following treatment, and processed into sy rup using procedures simulating commercial practices. Samples of sorghum stalk and sy rup were analy

zed for residues of meto lachlor and its metabolites as derivatives CGA - 49751 and CGA - 37913 using an adequate LC/MS/MS method. The LLMV was 0.05 ppm for each analy te based on fortifications with SYN508500 and SYN506357. The combined LLM V was 0.13 ppm total metolachlor residues, expressed as metolachlor equivalents. Sample storage conditions and durations are reported in Table 4. Adequate storage stability data are available to support the sweet sorghum processing study . Residues of CGA - 49751 and CGA - 37913 were each below the LLM V (<0.05 ppm) in/on sorghum stalks harvested 92 days following a single preemergence soil broadcast application of the 7.64 lb/gal EC formulation at 1.72 lb ai/A (1.93 kg ai/ha); total metolachlor residues were below the combined LLM Vs (<0.13 ppm, expr essed as metolachlor equivalents). Average residues of CGA - 49751 and CGA - 37913 were 0.088 and 0.059 ppm, respectively , in sy rup processed from sorghum stalks with nonquantifiable metolachlor residues; total metolachlor residues averaged 0.191 ppm in proce ssed sorghum sy rup. Based on the results of the sweet sorghum processing study , metolachlor residues appear to concentrate in sorghum sy rup (>1.5x processing factor). No theoretical processing factors are presented for sweet sorghum in 860.1520.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 41 of 52 Table 7 . Summary of Processing Factors for S - Metolachlor.

RAC Processed Commodity Combined Residues (ppm) Processing Factor Sesame Seed (RAC) <0.13 Not applicable Meal <0.13 Not calculated Oil <0.13 Not calculated Sweet sorghum Stalk (RAC) <0.13 Not applic able Syrup 0.191 >1.5x Conclusions . The submitted processing data are tentatively adequate to support the proposed uses on sesame and sorghum. Although the sesame processing study was conducted at only

1x with nonquantifiable residues in the RAC, i t is unlikely

that a study

conducted at an exaggerated rate will result in quantifiable residues in the RAC because applications are made preemergence. The submitted data indicate that no tolerances will be needed for sesame processed commodities. Combin ed metolachlor residues were found to concentrate in sweet sorghum sy rup. However, HED concludes that no tolerance will be required because the observed residues in sy rup (0.191 ppm, expressed as metolachlor equivalents) processed from sorghum treated at 1x are less than the established tolerance for S - metolachlor residues in/on sorghum stover ( 4. 0 ppm). 4 860.1650 Submittal of Analytical Reference Standards Analy tical standards for the following compounds related to metolachl or are currently available in the EPA National Pesticide Standards Repository (personal communication with Dallas Wright, ACB, 1/20/10; expiration data in parentheses): metolachlor (11/10/2010); S - metolachlor (8/1/2012); metolachlor derivative CGA - 37913 ( 4/30/2010); metolachlor derivative CGA - 49751 (4/30/2011); metolachlor, ethane sulfonic acid sodium salt (CGA - 354743, 4/1/2011); and metolachlor, oxanilic acid (CGA - 51202, 4/1/2011). 860.1850 Confined Accumulation in Rotational Crops D207842, 10/12/94, S. Hummel D292881, 8/15/03, S Kinard The data requirements for confined accumulation in rotational crops are not fulfilled. A confined rotational crop study

with [ 14 C]metolachlor was reevaluated by HED (DP# 207842, 10/12/94, S. Hummel) after review of rotat ional crop data was transferred to HED. It was concluded that the available study

was inadequate but potentially upgradable. Additional data were required characterizing the 14 C - residues in plants, along with information on the percentage of the 14 C resi dues measured by

the current enforcement method; sample storage conditions and intervals and supporting storage stability data were also required. These data requirements, which were reiterated in the Metolachlor TRED (DP# 292881, 8/15/03, S. Kinard), rem ain outstanding. A confined rotational crop study using S - metolachlor has also been submitted. The study was reviewed by

HED (DP# 283235, 8/15/03, S. Kinard) and found to be scientifically adequate. Although 14 C - residue in the representative rotational crops were adequately identified andS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 42 of 52 characterized, the [ 14 C] - S - metolachlor was applied at only 1.45 lb ai/A, which is ~0.4x the maximum seasonal use rate for corn. Based on the available data, HED concluded that the metabolism of [ 14 C]S - metolachlor in ro tational crops is similar to the metabolism observed in the primary crops. Metabolism in rotational crops primarily involves two pathways: (i) conjugation of the parent molecule with glutathione by substitution of the chlorine, followed by the degradation of the glutathione moiety to form a variety

of sulfur containing metabolites; and (ii) direct oxidation of parent or secondary metabolites, primarily

on the chloroacetyl side chain. Complete degradation of secondary metabolites either in the soil and/or plants also resulted in the incorporation of molecule fragments into natural plant constituents. The residues of concern for both metolachlor and S - metolachlor in rotational crops are the same as for primary crops, metolachlor and its metabolites, determi ned as the derivatives CGA - 37913 and CGA - 49751. 860.1900 Field Accumulation in Rotational Crops D292881, 8/15/03, S Kinard D332846, 10/21/08, D. McNeilly D296904, 4/17/06, R. Loranger Field rotational crop data have been submitted previously which are adequate to support the existing rotational crop restrictions on the labels for the 7.62 and 7.64 lb/gal EC formulations (EPA Reg. Nos. 100 - 816 and 100 - 818), provided that the restrictions on the label for EPA Reg. No. 100 - 816 are amended as specified unde r 860.1200 Directions for Use. In the TRED it was concluded that adequate residue data are available to support a PBI of 4 months for non - grass animal feeds and the current 1.0 - ppm tolerance for rotated non - grass animal feed (DP# 292881, 8/15/03, S. Kinard); additional data were required to support cereal grain rotational crop restrictions. Inresponse, field rotational crop data for oats and wheat were submitted which have been reviewed by

HED (DP#s 332846, etc., 10/21/08, D. McNeilly ). Fourteen field trials were conducted with wheat and fifteen trials were conducted with oats. I n each test, the 7.64 lb/gal EC formulation of S - metolachlor was applied to a primary crop of field corn as a PPIapplication at planting at 2.36 - 2.49 lb ai/A, followed by a se cond directed application at lay- by at 1.25 - 1.4 lb ai/A, for a total of 3.61 - 3.83 lb ai/A/season (1x the maximum use rate on corn). Wheat was planted ~60 days and oats were planted ~7 months following the last application. These field trials were consid ered sufficient for assessing rotational crop tolerances for small grains rotated with corn, which has the highest labeled use rate. Following a final lay- by application to corn, the wheat field trials reflect a ty pical plant - back interval (2 months) for small grains that can be planted in the fall (barley , oats, rye and wheat), and the oat field trials reflect the ty pical plant - back interval (7 months) for small grains that can be planted the following spring (barley , oats, rice, rye and wheat). Itwas c oncluded that the wheat and oat data support tolerances of 0.5 ppm for rotated barley hay and straw, oat forage, hay and straw, rye forage and straw, and wheat forage, grain and straw, and tolerances of 0.1 ppm for the grain of rotated barley , oats, rye an d wheat. For rice and buckwheat, which would only be rotated to the following spring (7 - month PBI), the oat field trial data support tolerances of 0.1 ppm for rotated buckwheat grain and rice grain.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 43 of 52 Itwas also concluded that 60 - day PBI s for root veget ables (subgroup 1B), tuberous and corm vegetables (subgroup 1C), bulb vegetables (group 3), leaf petiole vegetables (subgroup 4B), head and stem Brassica vegetables (subgroup 5A), fruiting vegetables (group 8), and winter squash are acceptable based on the available field trial data supporting the tolerances and uses of S - metolachlor on these crops (DP# 296904, 4/17/06, R. L oranger) provided that (i) the application to the previous crop was less than or equal to the maximum approved rates for the respective crops and crop groups, and (ii) the label directions are amended to prohibit application of S - metolachlor to the replanted crops. Although the first condition is met on the current label for EPA Reg. No. 100 - 816, the label directions have not yet been am ended to prohibit application of S - metolachlor to crops planted at a 60 - day PBI . 860.1550 Proposed Tolerances The residues of concern in plant and animal commodities include S - metolachlor, its R enantiomer, and its metabolites, determined as the derivatives CGA - 37913 and CGA - 49751. Tolerances for S - metolachlor are currently established [40 CFR §180.368(a)(2) and (d)(2)] for the combined residues (free and bound) of S - metolachlor, its R - enantiomer, and its metabolites, determined as the derivatives, CGA - 37913 and CGA - 47951, each expressed as parent compound. The tolerances proposed by IR - 4 are listed in Table 8. The tolerance expression proposed by IR 4 does not include the R - enantiomer. The tolerance expression in Section F of the submitted petitio n should be revised to include the R - enantiomer of metolachlor and to conform to current HED guidance (HED’s Interim Guidance on Tolerance Expressions, 5/27/09, S. Knizner): Tolerances are established for residues of S - metolachlor, including its metaboli tes and degradates, in or on the commodities in the table below. Compliance with the tolerance levels specified below is to be determined by measuring only

the sum of free and bound S metolachlor, S - 2 - chloro - N - (2 - ethyl - 6 - methylphenyl) - N - (2 - methoxy- 1 - methylethyl)acetamide, its R - enantiomer, and its metabolites, determined as the derivatives, 2 - (2 - ethyl - 6 - methylphenyl)amino - 1 - propanol and 4 - (2 - ethyl - 6 - methylphenyl) - 2 - hydroxy- 5 - methyl - 3 - morpholinone, calculated as the stoichiometric equivalent of S metolachlo r, in or on the commodity . No maximum residue limits (MRL s) for S - metolachlor have been established or proposed by Codex. MRL s for S - metolachlor have been established in Canada and MRL s for metolachlor have been established in Mexico; however, no MRL s have been established in either country for the requested crops. HED notes that a tolerance currently exists for residues of S - metolachlor in/on the root vegetable, except sugar beet, subgroup, 1B. When the requested tolerance for carrot is established, the existing tolerance for subgroup 1B must be revised to “vegetable, root, except carrot and sugar beet, subgroup 1B.” The submitted broadcast foliar data for blueberries are not adequate to support the requested tolerances for lowbush blueberry . In addi tion, the proposed use patterns for the different berries differ significantly . The submitted banded, soil directed application data for highbush blueberryS - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 44 of 52 would support a tolerance for bushberry , subgroup 13 - 07B (with broadcast foliar use deleted and use on lowbush blueberry and other low bush varieties of berries prohibited on the label), at 0.20 ppm, expressed as total metolachlor equivalents. Additional crop field trial data must be submitted before a tolerance may be established to cover broadcast fo liar use on lowbush blueberry

– one additional trial in Region 1, one additional trial in Region 5; alternatively, with the additional field trial data reflecting broadcast foliar use, the petitioner may wish to submit data and propose a tolerance for the low growing berry , except strawberry , subgroup 13 - 07H. The available field trial data for fruiting vegetables may be translated to support the requested tolerance for okra; these data support the proposed 0.10 ppm tolerance. Adequate data have been sub mitted previously to support the requested tolerances for the bulb onion and green onion subgroups; the proposed tolerance levels of 0.10 ppm and 2.0 ppm are appropriate. Concomitant with the establishment of tolerances for bulb onion subgroup 3 - 07A and green onion subgroup 3 - 07B, the established tolerances for S - metolachlor and its metabolites in/on bulb garlic (0.10 ppm), bulb onion (0.10 ppm), bulb shallot (0.10 ppm), and green onion (2.0 ppm) under 180.368(a)(2) should be removed. The requested tolerance for sweet sorghum will be based on data for grain sorghum ; the existing tolerance for S - metolachlor residues in/on sweet sorghum stover of 4.0 ppm is adequate to cover residues in/on sweet sorghum commodities. T he submitted processing data indicate th at no tolerances are needed for S - metolachlor residues in the processed commodities of sesame or sweet sorghum. HED’s tolerance calculations are different from those done by IR - 4 for carrot and mustard greens because HED used the full value of the LLM V wh en calculating combined residues (IR - 4 used 1/2 LLM V for residues <LLMV when calculating combined residues for carrot and mustard greens). Table 8. Tolerance Sum ma ry for Metolachlor. Commodity Established/ Proposed Tolerance (ppm) Recommended

Toleranc e (ppm) Comments;

Correct Commodity Definition Proposed tolerances under §180.368(a)(2) Blueberry, low

bush 1.4 Remove Additional data needed before tolerance may be established. Bushberry subgroup 13 - 07B 0.15 0.15 Use must be prohibited on lowbush vari eties, since inadequate data were submitted for lowbush blueberries. Caneberry, Subgroup 13 - 07A 0.08 0.10 Caneberry subgroup 13 - 07A Carrot 0.3 0.40 Cucumber 0.1 0.13 Le afy Brassica Greens, Subgroup 5 B 1.2 1.8 Brassica, leafy greens, subgroup 5B Melo n subgroup 9A 0.08 0.10 Okra 0.1 0.10S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 45 of 52 Table 8. Tolerance Sum ma ry for Metolachlor. Commodity Established/ Proposed Tolerance (ppm) Recommended

Toleranc e (ppm) Comments;

Correct Commodity Definition Onion, Bulb, Subgroup 3 - 07A 0.1 0.10 Onion, bulb, subgroup 3 - 07A Onion, Green, Subgroup 3 - 07B 2.0 2.0 Onion, green, subgroup 3 - 07B Sesame, seed 0.1 0.13 Sorghum, sweet 0.1 4.0 Sorghum, sweet, stalk The existing tolerance for S - metolachlor residues in/on sorghum grain of 0.3 ppm and sorghum stover of 4.0 ppm is sufficient to cover residues in/on sweet sorghum commodities. The sorghum stover tolerance will be translated to sweet sorghum stalk. Turnip greens 1.2 1.7 Turnip, greens Established tolerances under §180.368(a)(2) Garlic, bulb 0.10 Remove Garlic will be covered by the tolerance for Onion, bulb, subgroup 3 - 07A Onion, bulb 0.10 Remove Bulb onion will be covered by the tolerance for Onion, bulb, subgrou

p 3 - 07A Onion, green 2.0 Remove Green onion will be covered by the tolerance for Onion, green, subgroup 3 - 07B Shallot, bulb 0.10 Remove Shallot will be covered by the tolerance for Onion, bulb, subgroup 3 - 07A Vegetable, root, except sugarbeet, subgroup 1B 0.30 0.30 Revise to Vegetable, root, except carrot and sugarbeet, subgroup 1B , since a separate, higher tolerance is being established on carrot. References DP#: 207842 Subject: Metolachlor (108801) Addendum to RED, Reregistration Case No. 0001.

Co nfined Rotational Crop Data (GL N 165 - 1). CB No. 14435 From: S. Hummel To: J. Mitchell/W. Waldrop Dated: 10/12/94 MRID: 41470601S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 46 of 52 DP#: 226780 Subject: Replacement of Metolachlor Technical (Racemic Metolachlor) with Alpha Metolachlor (formerly

called Chiral Metolachlor) Technical; Review of Bridging Data. From: L. Kutney To: R. Griffin Dated: 11/15/96 MRIDs: 43928901 - 43928903, 43928939 - 43928942 DP#s: 278742 and 279110 Subject: S - Metolachlor. Information Supporting the Assertion That the Metabolism of

S - Meto lachlor I s Essentially the Same as for the Racemic Mixture. From: S. Kinard To: S. Kinard Dated: 8/15/03 MRIDs: 45499603, 45499604, 45499605, 45533103 DP#: 283235 Subject: Sandmeier, P. (2001) Outdoor Confined Accumulation Study on Rotational Crops after Bare ground Application of [Phenyl - U - 14C] CGA77102: L ab Project Number: 99PSA53; 1287 - 99. Unpublished study prepared by

Sy ngenta Crop Protection, Inc. 252 p. From: S. Kinard To: N/A (DER) Dated: 8/15/03 MRID: 45672302 DP#: 292881 Subject: PP#s: 7F04897 , 9E06055, 7E04916, 2E06374, 4E04420, 8E05029, and 8E05030.

Revised Metolachlor and S - metolachlor Residue Chemistry Chapter for the Tolerance Reassessment Eligibility Decision (TRED) and Registration for Use on Asparagus, Carrots, Cotton, Horseradish, Gree n Onions, Peppers, Rhubarb, Sugar Beet, Sunflower, and Swiss Chard. From: S. Kinard To: H. Jamerson Dated: 8/15/03 MRIDs: 44378401, 44908701, 45544701 DP#: 296904 Subject: PP# 3E6787. S - Metolachlor. Petition for Tolerances on Various Crops, Crop

Groups, and Livestock Commodities. Summary of Analy tical Chemistry

and Residue Data. From: R. L oranger To: B. Madden/S. Jackson Dated: 4/17/06 MRIDs: 45499609, 45499610, 46046501 - 46046506S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 47 of 52 DP#s: 332846, 332847, 332848, 332849, 350604, 350942, 351174, 351226 Subj ect: S - Metolachlor. Amended Use Directions for Sorghum and Soy beans; Revisions to Rotational Crop Restrictions; Registrant’s Responses to Deficiencies Noted in the Revised S - Metolachlor TRED. Summary of Analy tical Chemistry

and Residue Data. From: D. McN eilly To: E. Wilson/J. Miller and R. L ouie/N. Anderson Dated: 10/21/08 MRIDs: 46829501 - 46829504, 47121701, 47121702, 47304701, 47304702 RDI : RAB4 Chemists (x/x/10) SHummel: S10827:PY - S:(703)305 - 7689:7509P:RAB4 Attachments: International Residue L imit Status sheet Tolerance/MRL Spreadsheet Template Version September 2005S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 48 of 52 

## INTERNATIONAL RESIDUE LIMIT STATUS Chemical Name: 2 - chloro N - (2 - ethyl - 6 - methylphenyl) -N - [(1S)2 - methoxy - 1 - methylethyl] - acetamide Common Name: S - Metolachlor X Proposed tolerance □ Reevaluated tolerance □ Other Date: 1/20/10

Codex Status (Maximum Residue Limits) U. S. Tolerances X No Codex proposal step 6 or above □ No Codex proposal step 6 or above for the crops requested Petition Number: PP#9E7607 DP#: D369005 Other Identifi er: Decision No. 418569 Residue definition (step 8/CXL): N/A Reviewer/Branch: HED/RAB4 S. Hummel Residue definition: Combined residues (free and bound) of S - metolachlor, its R - enantiomer, and its metabolites, determined as the derivatives CGA - 37913 and CGA 49751, calculated as parent equivalents Crop (s) MRL (mg/kg) Crop(s) Tolerance (ppm) Bushberry subgroup 13 - 07B 0.15 Caneberry, Subgroup 13 - 07A 0.10 Carrot 0.4 Cucumber 0.13 Leafy Brassica Greens, Subgroup 5 - B 1.8 Melon subgroup 9A 0.10 Okra 0.13 Onion, Bulb, Subgroup 3 - 07A 0.10 Onion, Green, Subgroup 3 - 07B 2.0 Sesame, seed 0.13 Sorghum, sweet, stover 4.0 Turnip greens 1.8 Limits for Canada Limits for Mexico □ No Limits X No Limits for the crops requested □ No Limits X No Limits for the crops requested Residue definition: 2 - chloro -N - (2 - ethyl - 6 - methylphenyl) -N - [(1S ) - 2 - methoxy - 1 - methylethyl)acetamide and 2 - chloro -N - (2 - ethyl - 6 - methylphenyl) -N - [(1R) - 2 - methoxy - 1 - methylethyl)acetamide, including the metabolites 2 - [ (2 - ethyl - 6 - methylphenyl)amino] - 1 - propanol and 4 - (2 - ethyl 6 - methylphenyl) - 2 - hydroxy - 5 - methyl - 3 - mo rpholinone Residue definition: Only metolachlor is listed (2004), and none of the requested crops.

Crop(s) MRL (mg/kg) Crop(s) MRL (mg/kg) Notes/S pecial Instructions: S. Funk, 01/25/2010.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 49 of 52 Appendix II. Tolerance Assessment Calculations. For each of the crops listed below, the Guidance for Setting Pesticide Tolerances Based on Field Trial Data (SOP), along with the tolerance spreadsheet (January 2008 version), was used for calculating recommended tolerances. As specified in the SOP, the minimum of the 95% upper confidence limit (UCL) on the 95 th percentile and the point estimate of the 99 th percentile was selected as the tolerance value in cases when the dataset was large (greater than 15 samples) and reasonably

lognormal. For datasets that were small ( ≤15 samples) and reasonably lognormal, the upper bound estimate of the 95th percentile based on the median residue value was compared to the minimum of the 95% UCLon the 95th percentile and the point estimate of the 99th percentile, and the minimum value was selected as the tolerance value. For datasets that were not lognormal, the upper bound on the 89 th percentile was selected as the tolerance v alue (distribution - free method). The rounding procedures specified in the SOP were also used. Mustard Greens The datasets used to establish a tolerance for S - Metolachlor on mustard greens consisted of field trial data with application rates of 1.27

– 1. 28 lb ai/A (applied early post - emergence) with a 33 to 62 - day PHI . The field trial application rates and PHI s reflect the maximum label application rate and the minimum label PHI , respectively . The residues that were entered into the tolerance spreadshee t are provided in Table II - 1. All except 4 field trial sample results (results for 2 field trials) for total S - metolachlor in/on mustard greens were above the LLMV (LLMV = 0.05 ppm for each analy te ; 0.13 ppm total metolachlor equivalents ). The field tria l sample results for the 4 of 24 field trial sample results for garden beet roots which were below LLMV, were entered as 1⁄2 the LLMV. V isual inspection of the lognormal probability plot (Figure II - 1) and the results from the approximate Shapiro - Francia te st statistic (Figure II - 2) indicated that the dataset was reasonably lognormal. Using the tolerance spreadsheet, the recommended tolerance for residues of total metolachlor is 1.8 ppm for mustard greens.S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 50 of 52 Table I I - A1. Field Trial Data Set

Regulator: EPA Chemical: S-Metolachlor Crop: Mustard Greens PHI: early post-E App. Rate: 1.27-1.28 lb ai/A Submitter: IR-4

Residues LN(Residues) Z-scores 0.20 -1.61 -0.37 0.19 -1.66 -0.48 0.33 -1.11 0.26 0.40 -0.92 0.37 0.27 -1.31 -0.05 0.17 -1.77 -0.73 0.43 -0.84 0.60 0.52 -0.65 0.88 0.51 -0.67 0.73 0.41 -0.89 0.48 0.83 -0.19 1.50 0.94 -0.06 1.95 0.31 -1.17 0.16 0.30 -1.20 0.05 0.07 -2.73 -1.95 0.07 -2.73 -1.50 0.17 -1.77 -0.60 0.16 -1.83 -0.88 0.78 -0.25 1.24 0.75 -0.29 1.04 0.22 -1.51 -0.16 0.20 -1.61 -0.26 0.07 -2.73 -1.24 0.07 -2.73 -1.04S - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 51 of 52 Lognormal Probability Plot

99.9 99 98 95 90 80 70 50 30 20 10 5 2 1 0.1 1.0000

0.5000

0.2500

0.1250 y = 0.5726x - 1.3739 R 2 = 0.9355

PercentilesConcentrations EPA S-Metolachlor Mustard Greens early post-ES - Metolachlor Summary of Analytical Chemistry and Residue Data DP#: 369005

Page 52 of 52 / Regulator: EPA Chemical: S-Metolachlor Crop: Mustard Greens PHI: early post-E App. Rate: 1.27-1.28 lb ai/A Submitter: IR-4

n: 24 min: 0.07 max: 0.94 median: 0.29 average: 0.35 95th Percentile 99th Percentile 99.9th Percentile 0.80 1.0 1.2 (1.0) (1.2) (--) 95/99 Rule 1.1 1.8 3.5 (1.8) (4.0) (--) 1.0 Mean+3SD 1.2 UCLMedian95th 1.6 0.9492 p-value > 0.05 : Do not reject lognormality assumption Would you like the above values rounded? (Y or N)==> Y EU Method I Normal EU Method II Distribution-Free Approximate Shapiro-Francia Normality Test Statistic