Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 1 of 17 **UNITED STA TES ENVIRONMENTA**  **L PROTECTION A GENCY** 

**WA SHINGTON, D.C. 20460**  **OFFICE OF CHEMICAL SAFETY**  **AND POLLUTION PREVENTION**  **MEMORANDUM Date**  **:** 2 6 Nov ember 2012 **SUBJECT:** Halosulfuron - methyl . Section 3 Registration on Artichoke , and Caneberry

Subgroup 13 - 07A . Summary of Anal yt ical Chemistry

and Residue Data . **PC Code:** 128721 **DP Barcode:** D405659 **Decision No.:** 465913 **Re gistration**  **No. :**  81880 - 18, 81880 - 2 **Petition No .**  **:** 2E8050 **Regulatory Action:** Section 3 Registration **Risk A**  **ss essment Type**  **:** NA **Case No.:**  NA **T XR No.**  **:** NA **CAS No.:** 100784 - 20 - 1 **MRID No .**  **:** See MRID Summary T able **40 CFR:** 180.479 **FROM:** Leung Cheng , Chemist

Risk Assessment Branch III (RAB3) Health Effects Division (7509P) **THROUGH:** Jeff Dawson, Acting Branch Chief

RAB3/HED (7509P) **TO:** Barbara Madden/S ydne y Jackson (RM Team 03 )

Risk Integration M inor U se, and E mergency R esponse Branch Registration Division (7505 P )

**MRID Summary Table MRID No.**  **Study Type Comments**  4 88567 01 860.1500 Artichoke New DER 48856701 .der 48856702 860.1500 Caneberry New DER 48856702.derHalosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 2 of 17 **Executive Summary** Halosulfuron - methyl is a selective herbicide belonging to the sulfonylurea group of herbicides, which inhibits the action of acetolacetate sy nthase, a specific plant enzy me. Halosulfuron methyl is used for the pre - and postemergence control of annual broadleaf weeds and nut s ed ges in select ed crops, as well as residential turf grass and ornamentals, and is formulated as a dry flowable/water - dispersible granule formulation. The Interregional Research Project No. 4 (IR - 4) , State Agricultural Experiment Station, Rutgers, The S tate University of New Jersey, Princeton, New Jersey, on behalf of the IR - 4 Project and the Agricultural Experimental Stations of California (for artichoke) and California, Georgia, Oregon, Kentucky, and North Carolina (for caneberry) submitted this petiti on (PP#2E8050) and requested the submission be reviewed under the Pesticide Registration Improvement Act . IR - 4 also requested that the establishment of a tolerance for residues of the herbicide halosulfuron - methyl , methyl 3 - chloro - 5 - [[[[(4,6 - dimethoxy- 2 - py rimidinyl)amino]carbonyl]amino]sulfonyl] - 1 - methyl 1 H - py razole - 4 - carbox yl ate , in/on the following raw agricultural commodit ies : Artichoke ................................ ............................ 0.05 ppm C aneberry subgroup 13 - 07A ............................... 0.05 ppm The petitioner proposed to amend SANDEA herbicide (EPA Reg. No. 81880 - 18) and GWN 3061 h erbicide ( EPA Reg. No. 81880 - 2) to add uses on artichoke and caneberry . F oliar application s are proposed at a maximum application rate of 0.094 lb active ingredient ( ai ) /A. A 5 - day or 14 - day

preharvest interval is proposed for artic hoke and caneberry subgroup 13 - 07A , respectivel y . Permanent tolerances are established under §180.479(a)(1) for residues of halosulfuron - methyl , m ethyl 3 - chloro - 5 - [[[[(4,6 - dimethoxy- 2 - py rimidinyl)amino]carbonyl]amino]sulfonyl] - 1 - methyl 1 H - py razole - 4 - carb ox yl ate , including its metabolites and degradates, in or on the meat by products of cattle, goat, hog, horse, and sheep at 0.1 ppm . Compliance with the tolerance levels specified is to be determined by measuring only

those halosulfuron - methyl residues containing the 3 - chlorosulf o namide (3 - CSA) moiety , expressed as the s toichiometric equ ivalent of halosulfuron - methyl. Tolerances are established under §180.479(a)(2) for residues of halosulfuron - methyl , including its metabolites and degradates, in/on a variety of field, fruit, and vegetable crop commodities , at levels ranging from 0.05 to 2.0 ppm. Compliance with the tolerance levels specified is to be determined b y measuring only halosulfuron - methyl. The nature of the residue in plants has been adequately delineated based on acceptable metabolism studies with corn, sugarcane, and soy bean treated both pre - and postemergence . HED has concluded that the residue of concern i n plants is halosulfuron - methyl . The nature of the residue in livestock has been adequatel y delineated based on metabolism studies with goats and hens . HED has concluded that the residue of concern in r uminants is halosulfuron - methyl . HED previousl y concluded that tolerances for halo sulfuron - methyl residues in poultry

commodities were not required due to low use rates, low residues of halosulfuron - methyl in poultry feed stuff s, and the low transfer rate of residues to poultry tissues.Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 3 of 17 Adequate anal yt ical methods (gas chromatograph y) are available for the enforcement of tolerances for residues of halosulfuron - methyl in plants (Method RES - 109 - 97 - 4) , and for residues of halosulfuron - methyl and its 3 - CSA metabolites in livestock commodities (Method RES - 046 - 93). The plant method determine s halosulfuron - methyl as its rearrangement ester (RRE), and the livestock method converts residues of halosulfuron - methyl and metabolites containing the 3 - CSA moiety to 3 - CSA for determination. Samples from the submitted artichoke and caneberry studies we re anal yz ed for residues of halosulfuron - methyl using a modified version of the plant enforcement method . A B iological and Economic Analy sis Division (B EAD/EPA ) method validation for Method RES - 109 - 97 - 4 (MRID 44495801) in rice straw, sugar cane, milo grai n, field corn grain, cotton gin by products, and almond nutmeats indicated a quantitation limit of 0.05 ppm (DP#250584, G. Jeff re y Herndon, 10/28/98). Residues of halosulfuron - methyl and 3 - CSA are not adequatel y recovered by FDA Multiresidue M ethod protoc ol s . Adequate concurrent storage stability data are available for halosulfuron - methyl t o support the storage conditions and intervals of artichoke and caneberry samples collected from the field trial s. The re are no livestock feedstuffs associated with the proposed use on artichoke and caneberry , and the livestock dietary

burden i s not altered . T herefore, no changes to the existing livestock commodity

tolerances are ne ed ed . Adequate confined and limited field rotat ional crop data are available. HED previously concluded that rotational crop tolerances and restrictions are not required for halosulfuron methyl. There are no Codex or Canadian maximum residue limits ( MRL s ) established for residues of halosulfuron - methyl in/on artichoke and caneberry . **Regulatory Recommendations and Residue Chemistry Deficiencies** HED has examined the residue chemistry database for halosulfuron - methyl. Pending submission of a reference standard for the RRE of halosulfuron - methyl (see requirements under Submittal of Analy tical Reference Standards) , there are no residue chemistry issues that would preclude granting a Section 3 registration for the requested uses on artichoke and caneberry , or the establishment of a tolerance for residues of the halosulfuron - methyl , methyl 3 - chloro - 5 - [[[[(4,6 - dimethoxy- 2 - p yrimidin yl )amino]carbon yl ] - amino]sulfonyl] - 1 - methyl - 1 H - py razole - 4 - carbox yl ate , including its metabolites and degradates, in/on the commodities below. Compliance w ith the tolerance levels specified is to be determined by mea suring onl y halosulfuron - methyl . Artichoke ................................ ............................ 0.05 ppm C aneberry

subgroup 13 - 07A ............................... 0.05 ppm A human health risk assessment is forthcoming. Note to RD

– the tolerance expression under 40 CFR § 180.479 (a) (2) should be revised to the following: “ residues of the herbicide halosulfuron - methyl, methyl 3 - chloro - 5 - [[[[(4,6 -Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 4 of 17 dimethoxy- 2 - py

rimidinyl)amino]carbonyl]amino]sulfonyl] - 1 - methyl - 1 H - pyrazole - 4 - carbox yl ate , including its metabolites and degradates, in or on the commodities i n the following table.” 860.1650 Submittal of Analy tical Reference Standards

 An an al yt ical reference standard for the rearrangement ester (RRE) of halosulfuron methyl must be submitted to the EP A National Pesticide Standards Repository . **Background** The chemical structure and nomenclature of halosulfuron - methyl and the 3 - CSA moiety are presented in Table 1. The phy sicochemical properties of the technical grade of halosulfuron methyl are presented in Table 2. **Table 1. Test Compound**  **Nomenclature** . Chemical structure

Common name H alosulfuron - methyl Com pany experimental name MON 12000, NC - 319 IUPAC name M ethyl 3 - chloro - 5 - (4,6 - dimethoxy pyrimidin - 2 - ylcarb amoyl sulf amoyl) - 1 - methylpyrazole - 4 - carboxylate CAS name M ethyl 3 - chloro - 5 - [[[[(4,6 - dimethoxy- 2 - pyrimidinyl)amino]carbonyl]amino]sulfonyl] - 1 - methyl - 1 H

- py razole - 4 - carboxylate CAS registry number 100784 - 20 - 1 End - use product (EP) 75% dry flowable SANDEA Herbicide ; EPA Reg. No. 81880 - 18 ) and 75% WG ( GWN - 3061 Herbicide ; EPA Reg. No. 81880 - 2) Chemical structure of 3 - chlorosulfonamide moiety ( 3 - CSA)

3 - C hloro - 1 - methyl - 5 - sulfamoyl - 1 H - py razole - 4 - carboxylic acid N N C H 3 Cl

N N N H N H O S O O

O C H 3 O C H 3 O O C H 3

N N C H 3 Cl NH 2

S O O O H OHalosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 5 of 17 **Table 2. Physicochemical Properties of**  **Halosulfuron -**  **me thyl**  **.** Parameter Value Reference Melting point/range 175.5 - 177.2 oC MRID 42139403; DP#s 173627 & 180565, 7/30/92, G.J. Herndon pH 4.11 at 25 oC (1% w /v slurry) Density 1. 6 18 g/mL at 25 oC Water solubility at 20 oC pH 5 0.0015 g/100 mL pH 7 0.165 g/100 mL pH 9 0.747 g/100 mL Solvent solubility at 20 oC methanol 0.1616 g/100 mL n - hexane 0.001278 g/100 mL Vapor pressure <1 x 10 - 7 mm Hg at 25 oC Dissociation constant, Ka 3.61 x 10 - 4 at 22.4 oC Octanol/water partition coefficient, Log(KOW ) at 23 oC 1.67 at pH 5

- 0.0186 at pH 7

- 0.542 at pH 9 UV/visible absorption spectrum Not available **860.1200 Directions for Use** Copies of undated labels were provided for a 75% formulation of halosulfuron - methyl ( SANDEA herbicide, EPA Reg. No. 81880 - 18; GWN - 3061 h erbicide , EPA Reg. No. 81880 - 2) with uses on artichoke and caneberry . Subsequently , RD transmitted amended Section B (dated November 12, 2012) for caneberry subgroup 13 - 07A and a revised SANDEA label. The proposed use directions from the SANDEA and GWN - 3061 label are summarized in Table 3. According to the SANDEA label, it is a dry flowable formulation; no specification is available on the GWN label. However, the two p roposed label use rates on artichoke and caneberry are identical.Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 6 of 17 **Table 3**  **. Summary of Directions for Use of**  **Halosulfuron -**  **Methyl .**  Applic. Timing, Ty pe, and Equip. Applic.

Rate (lb ai/A) Max. No.

Applic. per Season Max. Seasonal

Applic. Rate (lb ai/A) PHI (day) Use Directions and Limitations Caneberry subgroup 13 - 07A including: blackberry, loganberry, raspberry, black and red, wild raspberry, cultivars, varieties, and/or hybrids of these

Application to either side of crop row , Ground 0. 5 - 1 oz

(East of the Rockies) 0.75 - 2 oz (West of the Rockies) SANDEA or GWN 3061 (0.024 - 0.094) 2 2 oz (0.094) 1 5 Apply a single or sequential application with an interval of 45 days (0.024 - 0.094 lb ai/A) uniformly with ground equipment in a minimum of 15 gals of water per acre to the ground on either side of the row . Do not apply less than 15 days before harvest. Do not apply if excessive weed growth prevents herbicide contact with ground. Use a non - ionic surfactant with post emergence applications. Artichoke Application to either side of crop row , Ground only 1 - 2 oz

SANDEA or GWN 3061 (0.047 - 0.094) Not

specified 2 oz

(0.094) 5 Apply at 0.0 47 - 0.094 lb ai/A uniformly with ground equipment in a minimum of 15 gals of water per acre to the ground on either side of the row and avoiding crop foliage . Do not apply less than 5 days before harvest. Do not apply by air . Use a non - ionic surfactant with post - emergence applications. Conclusions . The proposed use directions for the 75% WG formulation s are adequate. **8 60.1300 Nature of the Residue**  **- Plants**  Residue Chemistry Memo DP# 251007, 12/10/98, M. Doherty (PP#8F4937) Residue Chemistry Memo , No DP#, 5/21/96, G.J. Herndon (Metabolism Committee decision) Residue Chemistry Memo DP# 198361, 7/21/94, G. Otakie (PP#4G4279) Residue Chemistry Memo DP#s 173627 & 180565, 7/30/92, G.J. Herndon (PP#2G4073) The nature of the residue in plants is adequatel y understood based on acceptable metabolism studies with corn, sugarcane , and so yb ean; all studies investigated pre - and postemergence uses. The metabolism of halosulfuron - methyl was si milar in the three tested crops but dependent on the mode of application (pre - or postemergence) . When halosulfuron - methyl was applied preemergence, initial breakdown of the herbicide in the soil and preferential uptake of the py razole moieties resulted i n the primary residue being 3 - CSA, which has been determined to be less toxic than the parent. With a postemergence application, the major residue was the parent compound with minimal translocation of the herbicide in the plant, except in grain where the major residue was 3 - CSA. Based on the very

low toxicity

of the metabolite 3 - CSA, relatively low toxicity

of the parent compound, and low residue levels of both parent compound and the 3 - CSA metabolite, HEDHalosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 7 of 17 previously concluded that the residue of concern in plants is the parent compound , halosulfuron methyl . **860.1300 Nature of the Residue -**  **Livestock** Residue Chemistry Memo DP# 223801, 11/17/98, M. Doherty (PP#6F4661) Residue Chemistry Memo , No DP#, 5/21/96, G.J. Herndon ( Metabolism Committee decision) Residue Chemistry Memo DP# 204062, 6/2 2 /94, G.J. Herndon (PP# 3F4193 ) Residue Chemistry Memo DP# 184435, 1/15/93, G.J. Herndon (PP#2G4073) Residue Chemistry Memo DP# 181023, 11/12/92, G.J. Herndon Residue Chemistry Memo DP#s 173627 & 180565, 7/30/92, G.J. Herndon (PP#2G4073) Acceptable livestock metabolism studies conducted on goats and hens were previously submitted in conjunction with petitions for uses on corn and sorghum. In goat milk and tissues, the major extractable residue was the parent; acid hydrol ys is released bound or conjugated residues of aminopy rimidine and 3 - CSA. As HED previousl y concluded , the residue of concern in ruminants is halosulfuron - methyl . H owever, because the approved enforcement method for livest ock commodities quantifies the parent compound and metabolites containing the 3 - CSA moiety by converting residues to 3 - CSA, tolerances for residues of parent and its metabolites in livestock commodities are d etermined as 3 - CSA, expressed in halosulfuron - me thyl equivalents. HED previousl y concluded (PP#2G4073) that tolerances for halosulfuron - methyl residues in poultry commodities were not required d ue to low use rates, low residues of halosulfuron - methyl in poultry feed items, and the low transfer rate o f residues to poultry tissues. **860.1340 Residue Analytical Methods** Residue Chemistry Memo DP# 250584, 10/28/98, G.J. Herndon (PP#s 6F4620 & 8F4937) Residue Chemistry Memo DP# 214890, 5/3/95, G.J. Herndon (PP#3F4193) Residue Chemistry Memo DP# 202131, 10/4/94, G.J. Herndon (PP#3F4193) Plants Enforcement method: An adequate anal yt ical method is available for enforcement of tolerances for halosulfuron - methyl residues in plants. The gas chromatograph y ( GC ) method quantifies halosulfuron - methyl as its RRE ( 1 -H - py razole - 4 - carbox yl ic acid, 3 - chloro - 5 - [(4,6 - dimethoxy- 2 - py rimidinyl)amino] - 1 - methyl, methyl ester) using thermionic - specific detection (TSD, nitrogen specific). Monsanto Analy tical Method RES - 109 - 97 - 4 (MRID 44495801) has been validated as an enfo rcement method by the Anal yt ical Chemistry Branch (ACB)/BEAD . The limit of quantitation o n rice straw, sugarcane, milo grain, field corn grain, cotton gin by products, and almond nutmeats was estimated to be 0.05 ppm (DP#250584, G. Jeff re y Herndon, 10/28/ 9 8). For confirmation, the RRE can be determined b y GC/MS with monitoring at m/z 327.Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 8 of 17 Rearrangement ester (RRE) of halosulfuron - methyl Data collection method: Samples from the artichoke and caneberry studies associated with the subject petition were analy zed for residues of halosulfuron - methyl using the available tolerance enforcement method , Method RES - 109 - 97 - 4, with modifications. Briefl y, samples were extracted with acetonitrile (ACN)/water, filtered, and partitioned with dichloromethane (DCM). The DCM extract was evaporated to dry ness and redissolved in 15% methanol/DCM for clean up through a Florisil solid phase extraction (SPE) cartridge. The eluate was mixed with 0.5 M potassium carbonate to convert halosulfuron - methyl residues to the RRE. The reaction mixture was then extracted with DCM, and the DCM extract was evaporated to dryness; residues were reconstituted in eth ylacetate for further clean - up through a silica SPE column. The eluate wa s evaporated to dry

ness and redissolved in 50% ethyl acetate/isooctane for analy sis by gas chromatograph y with nitrogen specific detection (GC/N PD) . R esidues were expressed in terms o f halosulfuron - methyl. The GC/N PD method was adequate for data collecti on based on acceptable method validation and concurrent method recoveries. Conclusions . The residue anal yt ical methods data are adequate to satisfy data requirements for the subject action. Acceptable enforcement methodology is available for tolerance enforcement purposes for residues in/on crop commodities, and residues of halosulfuron - methyl in/on artichoke and caneberry commodities from the crop field trial were determined using an acceptable data collection method. Livestock There are no livestock feed stuffs associated with the proposed uses. Therefore, this topic is not relevant. **860.1360 Multiresidue Methods** Residue Chemistry Memo DP# 189198, 3/8/94, G.J. Herndon (PP#3F4193) Adequate multiresidue method data for halosulfuron - methyl and 3 - CSA w ere submitted previously

in conjunction with PP# 3F4193 . Residues of halosulfuron - methyl and 3 - CSA are not recoverable b y the FDA Multiresidue Protocols A through E. The results have been forwarded to FDA. **860.1380 Storage Stability** Residue Chemistry Memo DP# 189198, 3/8/94, G.J. Herndon (PP#3F4193) Adequate storage stability data were previously submitted (DP#243050, M. Doherty, 1/5/99) indicating that halosulfuron - methyl is stable in c orn grain stored frozen for up to 823 day s ( 27 N N O C H 3

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

C H 3Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 9 of 17 months ) and in so ybeans, wheat, lettuce, and sugar beets stored frozen for up to 996 day s (33 months) . Samples from the artichoke and caneberry field trial s were stored frozen (~ - 20 oC) from harvest/processing to analy sis for up to 70 0 day s for artichoke and 627 days for caneberry . Concurrent storage stability data were provided to support the new studies. Conclusions . The concurrent storage stability data are adequate to support the new studies. **860.1400 Water, Fish, and Irrigated Crops** There are no propose d 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** There are no livestock feed stuffs associated with the proposed uses. Therefore, this topic is not relevant. **860.1500 Crop Field Trials** Artichoke DER Reference : 48856701.der .doc The petitioner ha s submitted field trial data on artichoke . Three field trials were conducted in the United States during the 2009 growing season in the North American Free Trade Agreement (NAFTA) Growing Zone 10 (CA; 3 trials). Each trial consisted of one untreated plot and one treated plot. At each trial location, the treated plots received a single banded application to the ground of a 75% ai formulation ( Sandea Herbicide ) at 0.093 lb ai/A. All applications were made using a backpack in spray volumes of 30 gal/A. An additive (NI S Exit at a concentration of 0.21% v/v) was added to the spray mixture for each of the applications for all trials . Samples of artichoke head (bud) were harvested at 5 day s after application , i.e., at a preharvest interval (PHI) of 5 day s. Samples were anal yz ed for residues of halosulfuron - methyl using the method “Anal yt ical Method for the Determination of MON 12000 in Raw Agricultural Commodities and Processed Fractions” , RES - 109 - 97 - 4, December 1997. The method was validated at 0.05 and 0.5 ppm and , therefore , the LOQ ( determined as the lowest level of method validation, LLMV) is 0.05 ppm. The calculated limit of detection is 0.013 ppm. Samples were placed in frozen storage at the field sites within 45 minutes of collection. All samples were shipped within 60 day s of collection by Agricultural Chemicals Development Services, Inc. (ACDS) freezer truck to the USDA - ARS Research Station, Salinas, CA for frozen storage. Samples were maintained frozen ( - 20 °C) for about 22 months prior to extraction andHalosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 10 of 17 anal ys is at USDA - ARS - SAA, Tifton, GA. The results of the artichoke field trials are summarized in Table 4. Following a single foliar broadcast application of the herbicide Sandea at 0.093 - 0.094 lb ai /A, residues (and per trial averages) of halosulfuron - methyl in/on artichoke heads harvested at 5 - day PHI s were all <0.05 ppm. **TABLE 4**  **. Summary of Residue Data from**  **Crop Field Trials with**  **Halosulfuron -**  **me thyl**  **.** Commodity Total

Rate lb ai/A PHI

(days) Residue Levels (ppm) 1

n Sample Min. Sample

Max. LAFT 2 HAFT 2 Median Mean Std . Dev. Heads 0.093 - 0.094 5 3 0.05 0.05 0.05 0.05 0.05 0.05 NA 1 Except for sample min/max, values reflect per trial averages; n = no . of field trials . For calculation of median, mean, and standard deviation, the LOQ (0.0 5 ppm) was used for any results reported as <LOQ in Table C.3 . N/A = Not applicable. 2 LAFT = lowest average field trial; HAFT = highest average field trial. Conclusions . The number and locations of the field trials are in accordance with OCSPP 860.1500 for artichoke. The submitted field trial data reflect a singl e postemergence application directed to the ground at 0.0 9 3 - 0.0 94 lb ai/A, with artichoke heads harvested at PHI s of 5 day s. An acceptable me thod was used for the quantitation of residues of halosulfuron - methyl, and the study is supported b y adequate storage stability data. Caneberry DER Reference : 48856702.der.doc The petitioner has submitted field trial data on caneberry . Four raspberry field trials were conducted in the United States and Canada during the 2008 growing season in the North American Free Trade Agreement (NAFTA) Growing Zones 1 (Williamson, NY), 12 (OR; 2 trials), and 5A (Frelighsburg, QC). Also, four blackberry field tria ls were conducted in Zones 2 (Jackson Springs, NC), 5 (Lansing, MI), 10 (Kingsbury , CA), and 12 (Aurora, OR). Each trial consisted of one untreated plot and one treated plot. At each trial location, the treated plots received a single banded application to the ground on either side of the caneberry row of a 75% ai formulation ( Sandea Herbicide ) at 0.094 lb ai/A (range of 0.093 - 0.098 lb ai/A). All applications were made using a backpack sprayer in spray volumes of 21 - 36 gal/A. An additive (NI S Induce at a concentration of 0.25% v/v) was added to the spray mixture for onl y the NC trial . Samples of blackberry

and raspberry were harvested at 13 - 15 day s after application , i.e., at a PHI of 13 - 15 day s. Samples were anal yz ed for residues of halosulfuron - methyl using the method “Anal yt ical Method for the Determination of MON 12000 in Raw Agricultural Commodities and Processed Fractions” , RES - 109 - 97 - 4, December 1997. The method was validated at 0.05 and 0.5 ppm and , therefore , the LOQ ( determined as the lowest level of method validation, LLMV) is 0.05 ppm. The calculated limit of detection is 0.016 ppm. Samples were placed in frozen storage at the field sites within 3 hours of collection. All samples were shipped within 60 day s of collection by Agric ultural Chemicals Development Services, Inc. (ACDS) freezer truck to the USDA - ARS Research Station, Salinas, CA for frozen storage. Samples were maintained frozen ( - 20 °C) for about 21 months prior to extraction and anal ys isHalosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 11 of 17 (within 7 day s of extraction) at USDA - ARS - SAA, Tifton, GA. The results of the caneberry field trials are summarized in Table 5. Following a single foliar broadcast application of the herbicide Sandea at 0.093 - 0.094 lb ai/A, residues (and per trial averages) of halosulfuron - methyl in/ on caneberry harvested at 13 - 15 day

PHI s were all <0.05 ppm. **TABLE 5.**  **Summary of Residue Data from Crop**  **Field Trials with Halosulfuron**  **- me**  **thyl .**  Commodity Total

Rate lb ai/A PHI

(days) Residue Levels (ppm) 1

n Sample Min. Sample

Max. LAFT 2 HAFT 2 Median Mean Std . Dev. Berries 0.093 - 0.098 13 - 15 3 0.05 0.05 0.05 0.05 0.05 0.05 NA 1 Except for sample min/max, values reflect per trial averages; n = no . of field trials . For calculation of median, mean, and standard deviation, the LOQ (0.0 5 ppm) was used for any results reported as <LOQ in Table C.3 . N/A = Not applicable. 2 LAFT = lowest average field trial; HAFT = highest average field trial. Conclusions . The number and locations of the field trials are in accordance with OCSPP 860.1500 for caneberry . The submitted field trial data reflect a single postemergence application directed to the ground at 0.093 - 0.098 lb ai/A, with caneberry harvested at PHI s of 13 - 15 day s. An acceptable method was used for the quantitation of residues of halosulfuron - methyl, and the study is supported b y adequate storage stability data. **860.1520 Processed Food and Feed** There are no processed commodities associated with the proposed uses. Therefore, this topic is not relevant. **860.1650 Submittal of Analytical Reference Standards** An an al yt ical standard is currentl y available in the EPA National Pesticide Standards Repository for halosulfuron - methyl (expiration 6/14/13) . HED note s that a standard for the rearrangement ester (RRE ) of halosulfuron - methyl is also required in support of the tolerance enforcement method for plant commodities. An aly tical reference standard s of the 3 - CSA metabolite and the RRE must be supplied and supplies replenished as requested b y the Repository. T he reference standard s should be sent to the Analy tical Chemistry

L ab, which is located at Fort Meade, to the attention of Theresa Cole at the following address: USEPA National Pesticide Standards Repository /Anal yt ical Chemistry

Branch/OPP 701 Mapes Ro ad Fort George G. Meade, MD 20755 - 5350 (Note that the mail will be returned if the extended zip code is not used.) **860.1850 and 860.1900**  **Confined /Field**  **Accumulation in Rotational Crops** Residue Chemistry Memo DP# 225273 , 10 /29 /9 8 , G.J. Herndon Residue Chemistry Memo No DP#, 5/21/96, G.J. Herndon (M etabolism Committee decision) Residue Chemistry Memo DP# 192510, 8/30/93, G. Kramer Residue Chemistry Memo DP# s 188144 and 188814 , 3/11/93, G.J. Herndon ((PP#2G4073)Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 12 of 17 A cceptable confined rotational and limited field rotational crop studies were previousl y submitted. The results of both studies indicate that metabolites containing the py razole moiety may accumulate in harvested crops planted at intervals greater than one year. The confined rotational crop study , conducted at 0.19 lb ai/A, indicate d that no measurable residues of halosulfuron - methyl were detected in an y rotational crop commodities of wheat, soy bean, radish and lettuce at an y plantback interval (30, 120 , and 360 day s after treatment) . The limited field rotational crop study, conducted at 0.22 lb ai/A in a split (preplant + postemergence) application with rotated crops of winter wheat, spring wheat, soy bean, sugar beet , and leaf lettuce indicate d that no measurable residues of halosulfuron - methyl were detected in any field rotational crop samples, except in one spring wheat forage sample at 0.090 ppm (364 - day plantback interval ) . HED previousl y concluded that the residue of concern in rotational crops is halosulfuron - methyl. Based on the absence of the parent compound in the confined studies and in the limited field rotational crop studies , with the exception of one forage sample, HED previously concluded that rotational crop tolerances and restrictions are not required for halosulfuron - methyl . **860.1550 Proposed Tolerances** The petitioner proposed the following tolerance expression on artichoke and caneberry subgroup 13 - 07A: residues of halosu lfuron - methyl, methyl 3 - chloro - 5 - [[[[(4,6 - dimethox y- 2 - py rimidinyl)amino]carbonyl]amino]sulfonyl] - 1 - methyl - 1 H - py razole - 4 - carboxylate . RD should revise 40 CFR § 180.479 (a) (2) to include the following tolerance expression: “residues of the herbicide halos ulfuron - methyl, methyl 3 - chloro - 5 - [[[[(4,6 - dimethoxy- 2 - py rimidinyl)amino]carbonyl]amino]sulfonyl] - 1 - methyl - 1 H - py razole - 4 - carboxylate , including its metabolites and degradates, in or on the commodities in the following table.” The compliance statement is co rrect. Because all residue values for artichoke and caneberry are below the LOQ, the Agency ’s Guidance for Setting Pesticide Tolerances Based on Field Trial Data i s not utilized for determining an appropriate tolerance level. There are no Codex or Canadian MRLs established for residues of halosulfuron - methyl in/on artichoke and caneberry . **Table 5**  **. Tolerance Summary for**  **Halosulfuron -**  **methyl** Commodity Proposed Tolerance (ppm) Recommended

Tolerance (ppm) Comments ; C orrect Commodity D efinition Artichoke 0.05 0.0 5 Caneberry subgroup 13 - 07A 0.05 0.05Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 13 of 17 **References** DP#s: 173627 & 180565 Subject: PP#2G4073. Temporary Tolerance Petition and Experimental Use Permit for Use

of MON 12000 (Permit ® ) on Corn; 000524 - EUP - TO. Evaluation of Anal ytical Method and Residue Data. From: G.J. Herndon To: J. Miller/D. Kenn y and A. Kocialski Dated: 7/30/ 9 2 MRIDs: 42139400 - 08 DP#s: 181023 Subject: 000524 - EUP - TA. Experimental Use Permit for Use of MON 12000 and MON

13900 Together as MON 12041 (Battalion®) on Corn; Evaluation of Analy tical Method and Residue Data. CBTS#: 10295. From: G.J. Herndon To: J. Miller/D. Kenn y and A. Kocialski Dated: 11/12/92 MRIDs: 42396202 and 42396203 DP#s: 184435 Sub ject: PP#2G4073. Temporary Tolerance Petition and Experimental Use Permit for Use

of MON 12000 (Permit ® ) on Corn; 000524 - EUP - TO. Amendment of 7/30/92 Addressing Anal yt ical Method and Residue Data Deficiencies. CBTS#: 10948. From: G.J. Herndon To: J. Miller/D. Kenn y and A. Kocialski Dated: 1/15/93 MRIDs: 42538400 - 42538404 DP# s : 188144 & 188814 Subject: PP#2G4073 . Temporary Tolerance Petition and Experimental Use Permit for Use

of MON 12000 (Permit®) on Corn; 000524 - EUP - TO . Amendment of 2/10/93 Addressing Anal yt ical Method and Proposed Label Deficiencies . Impact of the Confined Rotational Crop Study Results (EFGWB) on this EUP Request . CBTS#: 11374 and 11451. From: G .J. Herndon To: J. Miller

/D. Ke nny and A. Kocialski Dated: 3/11/ 9 3 MRIDs: NoneHalosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 14 of 17 DP#: 192510 Subject: ID # 000524 - UAT . Review of limited field rotational study of MON 12000 [3 - chloro - 5 - [[[[(4,6 - dimethoxy- 2 - py rimidinyl)amino]carbonyl]amino] - sulfonyl] - 1 - methyl - 1H - py

razole - 4 - carbox yl ic acid, methyl ester]. Case 023936 . CBTS# 12079. From: G. Kramer To: J. Miller Dated: 8/30/ 9 3 MRIDs: 42812104 DP#s: 1 89198, 198051, 189189, 189178, 189183 & 189195 Subject: PP#3F04193. Permanent Tolerance Request for Use of MON 12000

(Halosulfuron) on Field Corn and Grain Sorghum (Milo). Evaluation of Analy tical Method and Residue Data. From: G.J. Herndon To: J. Mi ller/D. Kenn y and A. Kocialski Dated: 3/8/ 9 4 MRIDs: 42661401 - 07, 43042601 - 02 DP#: 204062 Subject: PP#3F04193. Section 3 Registration and Permanent Tolerance Request for Use

of MON 12000 (Halosulfuron) on Field Corn and Grain Sorghum (Milo). Submission Received 2/24/93 Addressing Deficiencies in the Nature of the Residue in Plants and Animals. CBTS# 13817, 13861. From: G.J. Herndon To: J. Miller/D. Kenn y and A. Kocialski Dated: 6/22/94 MRIDs: 42678001 - 03 DP#: 198361 Subject: PP#4G04279 and 524 - EUP - 74 - EUP and Temporary Tolerance Request for the New Chemical MON 12000 on Sugarcane and Sorghum . CBTS No. 13092. From: G. Otakie To: J. Miller

/D. Kenn y and A. Kocialski Dated: 7/21/ 9 4 MRIDs: 4299 1201 - 02 DP#: 202131 Subject: PP#3F04193. Section 3 Registration and Permanent Tolerance Request for Use

of MON 12000 (Halosulfuron) on Field Corn and Grain Sorghum (Milo). Submission Received 3/29/94 Addressing Deficiencies in the Regulatory Enforcement Method for Animal Products and the Proposed Section F. CBTS# 13568 From: G.J. Herndon To: J. Miller/D. Kenn y and A. Kocialski Dated: 10/4/94 MRIDs: 43195001 and 43177501 DP#: 214890Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 15 of 17 Subject: PP#3F04193 . Halosulfuron (MON 12000) on Animal Commodities. Results of

the Petition Method Validation Request. CBTS# 15480. From: G.J. Herndon To: J. Miller

/D. Kenn y and J. Smith Dated: 5/3/ 9 5 MRIDs: 43195001 DP#: None Subject: Halosulfuron (MON 12000) . The HED Metabolism Committee Meeting Held on

May 20, 1996. From: G.J. Herndon To: HED Metabolism Committee Dated: 5/21/ 9 6 MRIDs: None DP#: 250584 Subject: PP#6F462 0 and 8F4937. Halosulfuron - methyl on Various Commodities. Results

of the Petition Method Validation Request for the Proposed Enforcement Method. From: G.J. Herndon To: V. Walters/ J. Tompkins Dated: 10/28/ 9 8 MRIDs: 44495801 and 44555901 DP#: 22527 3 Subject: Halosulfuron. Revised Section F Proposing Deletion of Existing Rotational Crop

Tolerances. From: G.J. Herndon To: V. Walters/ J. Tompkins Dated: 10/29/ 9 8 MRIDs: None DP#: 223801 Subject: PP6F4661. Section 3 Registration and Request for Permanent Tolerances for

Halosulfuron - methyl on Sweet Corn and Popcorn. Evaluation of Anal yt ical Methods and Residue Data. From: M. Dohert y To: J. Tompkins/V. Walters Dated: 11/17/98 MRIDs: 43918501Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 16 of 17 DP#: 251007 Subject: PP8F4937. Request for Permanent Tolerances for Halosulfuron - methyl on

Cotton, Rice, Pistachio Nuts, and Tree Nut Crop Group (Crop Group 14 as listed in 40 CFR 180.41). Evaluation of Metabolism of Halosulfuron - methyl in Soy bean. From: M. Dohert y To: J. Tompkins/V. Walters Dated: 12/10/ 9 8 MRIDs: 44689501 Attachment: Appendix 1: International Residue L imit Status sheet Template Version September 2005Halosulfuron - methyl Summary of Analytical Chemistry and Residue Data DP#: 405659

Page 17 of 17 **Appendix 1**  **. International Residue Limits**



### Halosulfuron - me thyl (PC Code 128721); 10 / 3 1/2012 Table A. 1 Summary

of US and International Tolerances and Maximum Residue L imits Residue Definition : US Canada Mexico 2 Codex 3 40 CFR 180. 479 (a) (2) : Tolerances are established for residues of the herbicide halosulfuron - methyl , methyl 3 - chloro - 5 - [[[[(4,6 - dimethoxy - 2 - pyrimidinyl)amino]carbonyl]amino]sulfon yl] - 1 - methyl - 1 H

-pyrazole - 4 - carboxylate , including its metabolites and degradates, in the table below . Compliance with the tolerance levels specified in the following table is to be dete rmined by measuring only halosulfuron - methyl . None None

Commodity 1 Tolerance (ppm) /Maximum Residue Limit (mg/kg) US Canada Mexico 2 Codex 3 Artichoke 0.05 Caneberry sub group 13 - 07A 0.05

Completed: L. Cheng ; 11/2 1 /2012 1 Includes only commodities of interest for this action. Tolerance values should be the HED recommendations and not those proposed by the applicant. 2 Mexico adopts US tolerances and/or Codex MRLs for its export purposes. 3 * = absent at the limit of quantitation; Po = postharvest treatment, such as treatment of stored grains. PoP = processed postharvest treated commodity, such as processing of treated stored wheat. (fat) = to be measured on the fat portion of the sample. MRLs indicated as p roposed have not been finalized by the CCPR and the CAC.