Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 1 of 14 **UNITED STA TES ENVIRONMENTA**  **L PROTECTION A GENCY**  WA SHINGTON, D.C. 20460 **OFFICE OF CHEMICAL SAFETY AND**  **POLLUTION PREVENTION MEMORANDUM**  **Date:** 6 / 6 /201 2 **Subject:** Cl opy

rali d . Petition for the Section 3 Registration and the Establishment of Tolerances on Apples, Brassica Leafy Greens (Subgroup 5 - B), Teff, and Rapeseed (Subgroup 20 - A) Except Gold of Pleasure . Summary of Analy tical Chemistry

and Residue Data **PC Code:** 117403 (acid)

117401 (alkanolamine salts) **DP Barcode:** D391 747 **Decision No.:** 45 0262 **Registration No s**  **. :**  62719 - 73, 62719 - 80, 62719 - 81, and 62719 - 84 **Petition:** 1E7882 **Regulatory Action:** Section 3 Registration **Risk Assessment Type:** NA **Case No.:**  7053 **T XR No.:**  NA **CAS No.:** 1702 - 17 - 6 (acid) 57754 - 85 - 5 (monoethanolamine salt) **MRID No.:** 48504801 **40 CFR:** 180.431 **From:** Douglas A. Dotson , Ph.D., Chemist

RABII Health Effects Division ( 7509P ) **Through:** Michael Doherty , Ph.D., Senior Chem ist

RABII Health Effects Division (7509P) **To:** Laura Nollen/Barbara Madden , RM Team 5

RIMUERB Registration Division ( 7505P )Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 2 of 14 **Executive Summary** Clopy ralid ( 3,6 - dichloro - 2 - py

ridinecarboxylic acid) is a py ridine herbicide registered for use on a variety of food and feed crops in the U.S. for the postemergen ce control of broadleaf weed s , particularl y thistles and clover. T olerances are established for residues of clopy ralid in/on a wide variety of plant commodities at levels ranging from 0.5 ppm in/on stone fruits and bushberries (Crop subgroup 13 - 07B) to 500 ppm in/on grass forage and hay ( 40 CFR §180.431(a) ) . To lerances are also established for residues of clo py ralid in livestock commodities at levels ranging from 0.1 ppm in eggs to 36 ppm in meat byproducts, except liver, of cattle, goats, horses and sheep . Currently

there are no tolerances for inadvertent or indirect residues of clopy ralid. The Interregional Research Project Number 4 (IR - 4) submitted a tolerance petition proposing the use of clop yralid on apples. As part of the same tolerance petition, IR - 4 proposed to amend the Stinger ® Herbicide label (EPA Reg. No. 62719 - 73) to expand the mustard greens u se to the entire Brassica leafy

greens subgroup (5 - B), and to expand the use on canola, crambe, and rapeseed to the entire Rapeseed s ubgroup (20 - A), except gold of pleasure. In addition, IR - 4 submitted a separate tolerance petition for the use of clopyral id on teff . The only study that IR - 4 submitted in support of the current petition was a combined field trial/processing study

for apples. For the other commodities, IR - 4 is proposing that currentl y established tolerances be extended to the proposed commo dities. A tolerance of 5.0 ppm is established for mustard greens. IR - 4 is proposing that this tolerance be extended to the Brassica leafy greens subgroup. A tolerance of 3.0 ppm is established for canola seed. IR - 4 is proposing that this tolerance be e xtended to rapeseed (Subgroup 20 - A) e xcept g old of p leasure. The following tolerances are established for wheat and barley commodities: 3.0 ppm for grain, 9.0 ppm for straw, 9.0 ppm for forage (wheat onl y), and 9.0 ppm for hay (barley onl y). IR - 4 is proposing that these tolerances be extended to teff commoditie s. The end - use product that IR - 4 proposed for use on these commodities is Stinger® Herbicide , which is a 3 lb acid equivalent (ae)/gal emulsifiable concentrate (EC) formulation of the monoethanolamine salt of clopy ralid . Based on the available cabbage, grass, wheat , and barley metabolism studies, the nature of clopy ralid residues in plants is adequatel y understood for purposes of this petition. The residue of concern in plants for both risk assessment and tolerance enforcement is parent clop yr alid . A lthough teff commodities and wet apple pomace are animal feedstuffs, the maximum reasonabl y balanced diet (MRBD) previously determined by

HED will not increase as a result of the addition of these commodities to the currently permitted uses for clop yr alid. Clopy ralid is already registered for use on cereal grain commodities, grass forage and hay (both with tolerances of 500 ppm) , as well as other more esoteric feedstuffs (such as sugar beet molasses at 10 ppm). As a result, issues pertaining to residues i n livestock commodities do not need to be addressed in the current petition.Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 3 of 14 An a dequate gas chromatograph/electron - capture detection (GC/ECD) method ( Method ACR 75.6 ) is available for enforcing tolerances for clopy ralid in/ on plant commodities . In the submitted apple field trials, residues of clop yr alid in apple fruit, juice, and wet pomace were determined using a slightly modified version of the current enforcement method. Th e method was adequatel y validated in conjunction with the analysis of field trial samples . T he lowest level of method validation (LLMV) was 0.05 ppm for apple fruit, juice, and wet pomace . The submitted apple field trial data are adequate and support the proposed use. IR - 4 performed an adequate number of trials and they were performed in the recommended EPA growing zones. The application rate was 1x the maximum proposed rate, and the samples were collected at the proposed PHI. Residues of clopy ralid in/on each commodity were determined using an adequate GC/ECD method , and the duration and conditions of sample storage are supported b y the available storage stability data. The available field trial data support an LOQ tolerance of 0.05 ppm for apple fruit. For the other commodities in this tolerance petition, th e tolerances are being translated from other commodities with established tolerances . In the apple processing study , no detectable residues were found in the samples of apple fruit, apple juice, or wet apple pomace. Because of ph ytotoxicity concerns, IR - 4 did not perform an exaggerated rate study. No residues were found in the processed commodities ; which indicates that if concentration did occur, it was not to a considerable extent. T he existing confined rotational crop study adequately supports the ro tational crop restrictions specified on the current label. MRLHarmonization There are no Codex or Mexican maximum residue limits (MRL s) for residues of clopy ralid in/on the proposed commodities (Attachment I). However, there is a Canadian MRLfor resid ues of clopy ralid in or on flax at 0.2 ppm. This MRLdoes not harmonize with the existing U.S. tolerance of 3.0 ppm for flax seed (or the proposed tolerance of 3.0 ppm for the rapeseed subgroup). Based on the differing use patterns and the available resi due data, the recommended tolerance for the flaxseed subgroup cannot be harmonized with the Canadian MRLon flax. **Regulatory Recommendations and Residue Chemistry Deficiencies** T here are no residue chemistry data deficiencies that would preclude granting the requested registrations and establishing tolerances for residues of clop yralid on the proposed commodities. The proposed tolerances, the recommended tolerances , and the correct commodity definitions are given in Table 7 . **Background** Clopy ralid is a selective, postemergence py ridine herbicide that is used for the control of broadleaf weed s , particularly thistles and clover , in a variety of crops .Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 4 of 14 I R - 4 submitted a tolerance petition proposing the use of clop yralid on app les. As part of the same tolerance petition, IR - 4 proposed to amend the Stinger ® Herbicide label (EPA Reg. No. 62719 - 73) to expand the mustard greens use to the entire Brassica leafy greens subgroup (5 - B), and to expand the use on canola, crambe, and rape seed to the entire Rapeseed s ubgroup (20 - A), except gold of pleasure. In addition, IR - 4 submitted a separate tolerance petition for the use of clopy ralid on teff

. The only study that IR - 4 submitted in support of the petition was a combined field trial/processing study

for apples. For the other commodities, IR - 4 is proposing that currentl y established tolerances be extended to the proposed commodities. A tolerance of 5.0 ppm is established for mustard greens. IR - 4 is proposing that this tolerance be extended to the Brassica leafy greens subgroup. A tolerance of 3.0 ppm is established for canola seed. IR - 4 is proposing that this tolerance be extended to rapeseed ( Subgroup 20 - A) except gold of pleasure. The following tolerances are established for wheat and barley commodities: 3.0 ppm for grain, 9.0 ppm for straw, 9.0 ppm for forage (wheat onl y), and 9.0 ppm for hay (barley onl y). IR - 4 is proposing that these to lerances be extended to teff commodities. The chemical structure and nomenclature of the monoethanolamine salt of clopy ralid is summarized in Table 1, and the phy sicochemical properties of clopy ralid are summarized in Table 2. **Table 1.**  **Clopyralid Nomenclature**  Compound

Common name Clopyralid, monoethanolamine salt Company experimental name Dowco 290 IUPAC name 3,6 - dichloropyridine - 2 - carboxylic acid, monoethanolamine salt CAS name 3,6 - dichloro - 2 -pyridinecarboxylic acid, monoethanolamine salt CAS registry number 1702 - 17 - 6 (acid) 57754 - 85 - 5 (monoethanolamine salt) End -use product s (EUP) Stinger ® H erbicide ( EPA Reg. No. 62719 - 73) Lontrel ® 35A H erbicidal Concentrate ( EPA Reg. No. 62719 - 84 ) **Table 2. Physicochemical Properties of the Technical**  **Grade Clopyralid** Parameter Value References Physical State Solid A world Compendium, The Pesticide Manual, 14 th Edition. C.D. S Tomlin (Editor) , 2006. Color Colorless Melting P oint/Range 151 - 152°C Dissociation Constant (pKa) 2 N Cl Cl O O O H N H 3 +Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 5 of 14 **Table 2. Physicochemical Properties of the Technical**  **Grade Clopyralid** Parameter Value References Density at 20°C 1.57 g/cm3 Vapor P ressure at 25°C 1.0 x 10 - 5 mm Hg ( 1.33 mPa) Water S olubility at 20°C 7.85 g/L Solvent solubility (g/L) at 20°C Acetone : 250 Ethyl acetate : 102 Xylene : 4.6 Hexane : 6.0 Octanol/water partition coefficient, Log (K OW ) - 1.81 (pH 5)

- 2.63 (pH 7)

- 2.55 (pH 9) **860.1200 Directions for Use** Stinger ® Herbicide is currently registered to Dow AgroSciences for use on a wide variety of crops for the postemergence control of weeds . The label includes use directions for the following crops: (1) mustard greens, (2) canola (rapeseed) and crambe, and (3) barley , oats, and wheat. IR - 4 submitted supplemental labels for the Brassica leafy greens subgroup and the rapeseed subgroup. The us e directions on those supplemental labels are consistent with the use directions for the commodities from which the tolerances are being extended. IR - 4 also submitted a supplemental label for apples. The use directions for teff are the same as those on the Stinger ® label for barley , oats, and wheat . The proposed use directions are summarized below in Table 3. **Table 3. Summary of Directions for Use of Clopyralid**  Applic. Timing, Type, and Equip. 1 Formulation [EPA Reg. No.] Applic.

Rate (lb ae/A) Max. No.

Applic. per Season Max.

Seasonal Applic. Rate (lb ae/A) PHI Use Directions and Limitations 2 **Apple** Apply to non -bearing (well established, 1 year or older) and bearing trees. Apply to actively growing weeds. Apply with ground equipment only. Stinger, 3.0 lb ae/gal EC [62719 - 73] 0.094 -

0. 25 1 0. 25 30 days Apply in a minimum of 10 gal/A . Do not use in Florida or in Nassau or Suffolk Counties, New York. Do not apply by aircraft. **Leafy Brassica Greens Subgroup, 5 -**  **B 3**  Apply to actively growing weeds. Apply with ground equipment only. Stinger, 3.0 lb ae/gal EC [62719 - 73] 0.06 - 0.25 2 0.5 30 days Apply in a minimum of 10 gal/A, with a minimum RTI of 14 days. Do not apply by aircraft.Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 6 of 14 **Table 3. Summary of Directions for Use of Clopyralid**  Applic. Timing, Type, and Equip. 1 Formulation [EPA Reg. No.] Applic.

Rate (lb ae/A) Max. No.

Applic. per Season Max.

Seasonal Applic. Rate (lb ae/A) PHI Use Directions and Limitations 2 **Rapeseed Subgroup 20 -**  **A, Except Gold of Pleasure** Apply in the 2 - to 6 - leaf stage of crop growth. Apply to actively growing weeds. Apply with ground and aerial equipment only. Stinger, 3.0 lb ae/gal EC [62719 - 73] 0.113 -

0.25 1 0.25 7 days Use in the State of Oregon only. Apply in a minimum of 20 gal/A. Do not use with a surfactant. Apply with ground and aerial equipment only. **Teff (Use Directions for Barley, Oats, and Wheat)**  Apply when crop is from 3 - leaf stage up to early boot stage of growth. Stinger, 3.0 lb ae/gal EC [62719 - 73] 0.094 -

0.1 25 1 0.125 Not Speci fied Do not harvest hay from treated grain fields 4

. 1 Do not apply through any type of irrigation system. 2 The label for the 3 lb ae/gal EC contains the following rotational crop restrictions: barley, canola, cole crops, flax, gard en beets, grasses, corn (field, pop and sweet), oats, spinach, sugar beets, turnips and wheat may be planted at anytime followin g a treated crop. Depending on the amount of soil organic matter, rainfall and location (state), the plant -back intervals for all other crops range from 10.5 to 18 months. 3 For use and distribution only in the states of AZ, AR, CA, CO, DE, FL, GA, MD, MI, M O, NJ, NM, NY, NC, OH, OK, PA, SC, TX, VA and WI. Not for sale or distribution in Nassau and Suffolk Counties in New York State. 4 Do not permit lactating dairy animals or meat animals being finished for slaughter to forage or graze treated grain fields within one week after treatment . Conclusions . The supplemental label for apples i s adequate to allow evaluation of the residue data relative to the proposed use. The available field trial data support the proposed use directions. The supplemental labe l s for Brassica leafy greens and rapeseed as well as the SLN label for teff are adequate . The use directions and restrictions are adequate to ensure that over tolerance residues will not result in any plant or animal commodities. **860.1300 Nature of the Residue**  **- Plants**  DP # 270507 , 8/ 6/2002 , D. Dotson The nature of the residue in plants is adequatel y understood for purposes of this petition based on the acceptable cabbage, grass, barley , and wheat metabolism studies . Ineach of these studies, the majo r 14 C - residue was determined to be onl y parent compound. Although data are available for only two dissimilar crops (leafy vegetable s and cereal grain s ), HED has concluded that the residue of concern in plants for purposes of this petition is clopy ralid. However, the Agency reserves the right to require additional metabolism studies in the future should the petitioner request the establishment of clopy r alid tolerances for additional crops. **860.1300 Nature of the Residue -**  **Livestock** Goat and poultry

metabolism studies were previously reviewed. The nature of the residue in livestock commodities is understood. The onl y major residue is parent clopy rali d. Although teffClopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 7 of 14 commodities and wet apple pomace are animal feedstuffs, the maximum reasonably balanced diet (MRBD) previously

determined by

HED will not increase as a result of the addition of these commodities to the currently permitted uses for clopy

r alid. Clopy

ralid is already registered for use on cereal grain commodities, grass forage and hay (both with tolerances of 500 ppm), as well as other more esoteric feedstuffs (such as sugar beet molasses at 10 ppm). As a result, issues pertaining to resid

ues in livestock commodities do not need to be addressed in the current petition. **860.1340 Residue Analytical Methods Enforcement method**  . The Pesticide Anal yt ical Manual (PAM) Vol. II lists a GC/ECD method for determining clop yr alid residues in/on plant commodities (Method Ior Method ACR 75.6). For this method, residues are extracted with dilute NaOH (0.25% or 0.1%) and filtered. The extract is then acidified and salinized, and residues are partitioned into ethyl ether. Residues are then methylated u sing diazomethane and cleaned up on an activated alumina column. Residues are then determined b y GC/ECD using external standards. The reported LOQs are 0.5 ppm for grains and 2.0 ppm for green forage. **Data C**  **ollection M**  **ethod** . Inthe submitted field trials, residues of clop yr alid in/on samples of apples and apple processed commodities were determined using a slightl y modified version of the current tolerance enforcement method. The method that was used was the Cornell Analy tical Laboratory

Method titled : “Residue Anal ys is of 3, 6 - Dichloropicolinic Acid (Clopy ralid) Residues by

GC/Electron Capture Detector , Version #19 . ” Ten grams of sample are extracted with 0.5% NaOH. A portion i s then extracted with ether and meth ylated with freshly prepared diazomethane. After evaporation of the ether, the residue i s re - dissolved in toluene and cleaned up on an activated alumina A column and eluted with toluene. The sample i s the n anal yz ed for clopy ralid methyl ester by

GC/ECD. The residue anal yt ical method for clop yr alid residues in/on apple and apple processing samples was adequatel y validated in conjunction with field sample anal ys es and is acceptable as a data gathering method. The calculated limits of quantitation (L OQ) wer e 0.05 ppm for apple fruit, 0.04 ppm for apple juice, and 0.07 ppm for apple pomace. The lowest level of method validation (LLMV) was 0.0 5 ppm in/on all three matrices (fruit, juice, and pomace). The calculated limit s of detection (LOD) were 0.02 ppm for apple fruit, 0.01 ppm for apple juice, and 0.02 ppm for apple pomace. Conclusions . An adequate GC/ECD method (Method ACR 75.6) is available for enforcing the proposed tolerances on apples, Brassica leafy vegetables, rapeseed, and teff . The data collect ion method used for analy sis of apples and processed apple commodities is also adequate. **860.1360 Multiresidue Methods** The FDA Pestrak D atabase (PAM Vol. I, Appendix dated 11/6/90) indicates that the existing FDA multiresidue methods are not likel y to recover clop yr alid. C lopy ralid does appear to be adequatel y recovered b y the “QuEChERS” multiresidue method (http://www.quechers.com).Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 8 of 14 **860. 1380 Storage Stability**  DP # 270507 , 8/ 6/2002 , D. Dotson Under frozen storage conditions, clopy ralid has been shown to be stable in plant commodities for the following durations: 50 months in safflower seeds, so ybeans, sugar beet roots and tops, and oat fo rage, grain and straw; 30 months in strawberries; 26 months in dried hops cones; 16 months in cherries and plums; 15 months in canola meal; 10 months in canola seed and oil; 9 months in cabbage and spinach; 5 months in mustard greens; and 3 months in peach es. Samples collected from the submitted field trials were stored frozen within 3 hours of harvest, shipped frozen to the analy tical laboratory

2 - 40 day s later, and stored at - 21°C at the anal yt ical laboratory

until anal ys is. The maximum frozen storage intervals, from harvest to analy sis of samples, are listed in Table 4. **Table 4 .**  **Summary o f Storage Conditions**  **Matrix (RAC or**  **Extract) Analyte**  **Storage Temperature**  **(**  **C) Recoveries** 

**(%) Actual Storage** 

**Duration (days)**  **Interval of**

**Demonstrated Storage Stability**  **(days)** Apple Fruit Clopyralid
- 21 ± 7  C 108 - 120 76 - 279 267 Apple Juice Clopyralid
- 21 ± 7  C 106 - 108 104 175 Apple Pomace Clopyralid
- 21 ± 7  C 92

– 96* 113 179 *After subtracting apparent residues of 0.058 ppm observed in the untreated control apple pomace sample Conclusions . Adequate storage stability data are available to support the sample storage conditions and durations in the submitted apple field trials and processing studies . **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** Although teff commodities and wet apple pomace are animal feedstuffs, the maximum reasonabl y balan ced diet (MRBD) previously determined by

HED will not increase as a result of the addition of these commodities to the currently permitted uses for clop yr alid. Clopy ralid is already registered for use on cereal grain commodities, grass forage and hay (both with tolerances of 500 ppm), as well as other more esoteric feedstuffs (such as sugar beet molasses at 10 ppm). As a result, issues pertaining to residues in livestock commodities are not being addressed in the current petition.Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 9 of 14 **860.1500 Crop Field Trials**  The only study that IR - 4 submitted in support of the current tolerance petition was a combined field trial/processing study for apples. For the other commodities, IR - 4 is proposing that currentl y established tolerances be extended to the proposed commodities. As a result, no new field trial data were submitted for the Brassica leafy greens subgroup, the rapeseed subgroup, or for teff. 4 8504801 .der ( Apples ) As stated above, IR - 4 submitted a field trial study to support the proposed uses of clo py ralid (3 lb ae/gal EC) on apples . Apples have two associated regulated processed commodities, apple juice and wet apple pomace. The study that IR - 4 submitted was a combined field trial/processing study . The results of the field trial s tudy are discussed below , and the residue data are summarized in Table 5. **Table 5. Summary of Residue Data from Crop Field Trials with Clopyralid**  **C rop Matrix**  **Total Applic.**

**Rate 1**  **(lb ae/A** **) PHI** 

**(days) Residue Levels (ppm)** 

**n Mean**  **Std.**

**Dev. HAFT**  **2 M**  **i n**  **M ax**  Apple Fruit 0.244

–0.275 28 - 30 2 4 <0.05 NA 3 < 0.05 < 0.05 < 0.05 1 One foliar application of Stinger Herbicide at approximately 0.25 lb ae/A wa s made 2 HAFT = Highest Average Field Trial. 3 NA = Not applicable **Apples** . IR - 4 conducted twelve field trials in the 2007 and 2008 growing seasons . T hree trials were conducted in New York (EPA Growing Region 1), one in North Carolina (Region 2), two in Michigan (Region 5), one in Colorado (Region 9), one in California (Region 10) and four in Washingt on State (Region 11). The total number of field trials was in accordance with OPPTS Guideline 860.1500. At each trial, treatment was via a single broadcast application to the orchard floor at the approximate rate of 0.25 lb acid equivalent per acre ( a e/A ) . S pray adjuvant s w ere not used in any of the field trials. Samples were harvested 28 to 30 day s after the application and placed into frozen storage shortl y after harvest. At the NY27 trial, an additional apple sample was taken from each plot for processing into apple juice and apple pomace. The maximum storage duration w as 279 day s for field - treated fresh apple samples . Th is duration is supported by

appropriate storage stability data. In all 24 samples of apple fruit, residues were below the LOQ of 0.05 ppm. Although no quantifiable residues were found in the samples of apple fruit, the registrant did not perform an exaggerated rate study.Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 10 of 14 Conclusions . The magnitude of the residue study of clopy ralid on apple is acceptable . The number and lo cation of the field trials satisfy OPPTS Guideline 860.1500. The residue data are adequate to support the establishment of a tolerance of 0.05 ppm for apple fruit. **860.1520 Processed Food and Feed** Apples At one of the apple field trial sites ( the NY27 trial ) , an apple sample was taken from each plot for processing into apple juice and apple pomace. The trial was performed at a 1x application rate (0.246 lb ae/A ) and samples were taken at a PHI of 30 day s. Because of phy totoxicity concerns, IR - 4 did no t perform an exaggerated rate study . The samples were processed at the processing facility on the day

of harvest. A grab sample was taken from each of the processing apple samples prior to processing into juice and wet pomace. The processed and grab samples were stored frozen until being shipped. A ty pical commercial process was used for processing . Small lots of fresh apples (1 - 2 bushels) were ground in a Hammer - mill. Wet mash was collected in a container and loaded into one or more cloth stacks (cheeses) on the h ydraulic press. When the stack was complete (up to 5 cloths depending on sample size), the hydraulic pump was activated and the sample was pressed to 2200 - 3000 psi for a minimum of 5 minutes to achieve efficient juice yield. The juice w as collected in 1⁄2 to 1 gallon plastic bottles for storage. After the pressing cycle, the cloths were opened up and the wet pomace cake was broken up to obtain the wet pomace sample. The maximum storage duration w as 279 day s for field - treated fresh apple samples , 104 day s for apple juice, and 113 day s for pomace. These durations are supported by appropriate storage stability data. Clopy ralid residues were below the LOQ of 0.05 ppm in the apple fruit samples (both treated and untreated). No quantifiable residues were found in apple juice. A residue of 0.056 ppm was found in the treated apple pomace sample; however, the corresponding untreated control sample had an apparent residue of 0.042 ppm. After subtraction of the residue detected in the control from the residue in the treated pomace sample, the resulting residue would be 0.014 ppm, which is consid erabl y below the reported LOQ. **T able**  **6 .**  **Residue Data from Apple Processing Study with Fluazinam** Location (City, State; Year) Total Rate

(lb ae/A) PHI

(days) Commodity Fluazinam Residues (ppm) Fluazinam

Processing Factor North Rose , NY; 1993 0.246 30 Fruit (RAC) <0.05 , <0.05 NA Juice <0.05 NA Wet Pomace <0.05 1 NA 1 After subtracting apparent residue (0.042 ppm) detected in the untreated control sample from the residue in the wet pomace sample (0.056), the residue level was < 0.05 ppm.Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 11 of 14 Conclusions . The apple processing study is acceptable . Itcan be concluded that if concentration occurred in juice and pomace, it was to a very limited extent. **860.1650 Submittal of Analytical Reference Standards** An anal yt ical reference standard for clopy ralid monoethanolamine salt is currentl y available in the EPA National Pesticide Standards Repository . The e xpiration d ate is 2 - 26 - 2015 ( electronic communication , Theresa Cole, ACB, 2 /2 7 /20 12 ). **860.1850 /1900**  **Confined and Field**  **Accumulation in Rotational Crops** DP # 193219, 8/4/93, G. Kramer An acceptable confined rotational crop study is available for clopy

ralid. In this study , the total radioactive residues in/on representative rotational crop commodities (lettuce, turnips, green beans, and wheat) were below 0.01 ppm at plant back intervals of 49 - 98 day s following application of [ 14 C]clopy

ralid to the soil at 0.29 lb ae/A (1.17x the maximum seasonal rate for crops which can be rotated). The current label for the 3 lb ae/gal EC of clop yr alid allows for the replanting of the following crops at an y time: barley, canola, cole crops, flax, garden beets, grasses, corn (field, pop and sweet), oats, spinach, sugar beets, turnips , and wheat. The plant - back interval for all other crops is 10.5 to 18 months , d epending on the amount of soil organic matter, rainfall , and location . The established rotational crop restrictions are adequate. L imited field rotational crop studies are not required, and no tolerances are required for inadvertent or indirect residues in rotational crops. **860.1550 Proposed Tolerances** The submitted apple field trial and processing st udies are adequate to support the proposed tolerance of 0.05 ppm for apple, fruit. The trials were performed at a 1x application rate and samples were taken at the proposed PHI. Geographic representation of the field trials was adequate. Separate tolerances are not needed for apple juice or wet apple pomace. HED uses the OECD tolerance calculator to determine recommended tolerances. However, in cases where all field trial samples are below the LOQ of the anal ytical method, HED recommends that the tolerance be set at the LOQ. As a result, the recommended tolerance for apple is 0.05 ppm. For the other commodities in this tolerance petition, IR - 4 is proposing that currentl y- established tolerances be extended to the proposed commodities. A tolerance of 5 .0 ppm is established for mustard greens. IR - 4 is proposing that this tolerance be extended to the Brassica leafy greens subgroup. A tolerance of 3.0 ppm is established for canola seed. IR - 4 is proposing that this tolerance be extended to rapeseed (Subgroup 20 - A) except gold of pleasure. The following tolerances are established for wheat and barley commodities: 3.0 ppm for grain, 9.0 ppm for straw, 9.0 ppm for forage (wheat onl y), and 9.0 ppm for hay (barley onl y). IR - 4 is proposing that these tolerances be extended to teff commodities. There are no residue chemistry issues that would preclude the extension of these tolerances.Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 12 of 14 There are no Codex or Mexican maximum residue limits (MRL s) for residues of clopy ralid in/on the propos ed commodities (Att achment I). However, there is a Canadian MRLfor residues of clopy ralid in or on flax at 0 . 2 ppm . Th is MRL does not harmonize with the existing U.S. tolerance of 3.0 ppm for flax seed (or the proposed tolerance of 3.0 ppm for the rapeseed subgroup) . Bas ed on the differing use patterns and the available residue data, the recommended tolerance for the flaxseed subgroup cannot be harmonized with the Canadian MRL on flax . Table 7 provides a summary of the recommended tolerances for the proposed commodities . **Table 7**  **. Tolerance Summary for Clopyralid** Commodity as Proposed by Registrant Proposed Tolerance (ppm) Recom mended Tolerance (ppm) Comments

(correct commodity definition) **40 CFR §180.431(a)** Apple 0.05 0.05 Adequate field trial data are available. Leafy Brassica greens subgroup 5B 5.0 5.0 The proposed and recommended tolerance is based on the existing tolerance for mustard greens, the representative commodity of the Leafy Brassica greens subgroup ( **Brassica, leafy greens, subgroup 5B** ) Rapeseed subgroup 20A, except Gold of pleasure, seed 3.0 3.0 The proposed and recommended tolerance is based on the existing tolerance of 3.0 ppm for rapeseed, canola, and flax seed ( **Rapeseed, subgroup 20A, except gold of pleasure**  ) Rapeseed subgroup 20A, except Gold of pleasure, meal 6.0 6.0 The proposed and recommended tolerance is based on the existing tolerance of 6.0 ppm for canola meal and flax meal ( **Rapeseed, meal** ) Rapeseed subgroup 20A, except Gold of pleasure, forage 3.0 Non e Tolerance is n ot needed because rapeseed forage is not a significant livestock feed item. Teff, forage 9.0 9.0 Based on wheat forage (9.0 ppm) Teff, grain 3.0 3.0 Based on wheat and barley grain (3.0 ppm) Teff, hay 9.0 9.0 Based on barley hay (9.0 ppm) Teff, straw 9.0 9.0 Based on wheat and barley straw (9.0 ppm)Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 13 of 14 **References** MRID No. 48504801 . J . Corley , (2010). Clopy ralid: Magnitude of the Residue on Apple. Project Number: 03623. Unpublished study prepared by

The Center for Minor Crop Pest Management Technology Center of New Jersey

Rutgers, The Stat e University of New Jersey D361787, M. Doherty, Clopy ralid

– Petition for Tolerances on Swiss chard, Bushberry Subgroup 13 - 07B, and Strawberry

(Regional Restriction). Summary of Anal yt ical Chemistry

and Residue Data , 10/27/2009 D361316, M. Doherty, et al ., Clopy ralid

– Human Health Risk Assessment to Evaluate New Uses on Swiss Chard, Bushberry Subgroup (13 - 07B), and Strawberry (Regional Restriction), 12/3/2009 D270507, D. Dotson , Clopy ralid. Review of Residue Chemistry Data in Support of Permanent or Time - Limited Tolerances Propo sed for Canola... Summary of Anal yt ical Chemistry

and Residue Data , 8/6/2002 D 193219, G. Kramer , ID # 062719 - 00073. Review of confined rotational study of clopy ralid, MRID# 428150 - 01 , 8/4/93Clopyralid Summary of Analytical Chemistry and Residue Data DP Number D 391747

Page 14 of 14 **A ttachment**  **I. International Residue Limit Status**  **S heet**  

### Clopyralid ( 117403 ; 2 - 22 - 2012 ) Summary of US and International Tolerances and Maximum Residue Limits Residue Definition : US Canada Mexico 2 Codex 3 40 CFR 180.431: Plant s /Livestock: clopyralid , 3,6 - dichloro 2 -pyridinecarboxylic acid 3,6 - dichloro - 2 - pyridinecarboxylic acid None

Commodity 1 Tolerance (ppm) /Maximum Residue Limit (mg/kg) US Canada Mexico 2 Codex 3 Apple 0.05 Leafy brassica greens, subgroup 5 - B 5.0 Teff, grain 3.0 Teff, hay 9.0 Teff, forage 9.0 Teff, straw 9.0 Rapeseed, subgroup 20 - A, except gold of pleasure, seed 3.0 0.2 flax Rapeseed, subgroup 20 - A, except gold of pleasure, meal 6.0 Rapeseed, subgroup 20 - A, except gold of pleasure, forage 3.0 Completed: M. Negussie; 02/24/2012 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 proposed have not been finalized by the CCPR and the CAC.