Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WA SHINGTON, D.C. 20460 OFFICE OF C HEMI CAL SAFETY AND POLLU TION PREVENTION 

### MEMORANDUM Date: 28 - July- 2010 Subject: **Spirodiclofen** in/on the Bushberry Subgroup 13 - 07B . **Summary of Analytical Chemistry and**  **Residue Data. PC Code:**  124871 **DP Barcode:** D 3 71643 **Decision No.:** 4 21907 **Registration No. :**  264 - 83 1 **Petition No.:** 9E7632 **Regulatory Action:** Section 3 **Risk Assessment Type:** not applicable **Case No.:** 7443 **T XR No.:**  not applicable **CAS No.:** 148477 - 71 - 8 **MRID Nos:** 47 886201 **40 CFR:** 180.608 

### From: Tom Bloem, Chemist

R isk Assessment Branch I , Health Effects Division (RAB I/HED; 7509C) Through: George F. Kramer, Ph.D., Senior Chemist

HED/RABI(7509P) To: Barbara Madden/Laura Nolle n (RM 0 5 )

Regi stration Division (RD; 7505P) Interregional Research Project Number 4 (IR - 4; Princeton, NJ ) proposed a Section 3 registration for application of spirodiclofen (3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4.5]dec - 3 - en - 4 - yl 2,2 - dimethylbutanoate; see attachment 1 for structure) to the bushberry subgroup 13 - 07B for the control of blueberry

budmite. In conjunction with the request, the petitioner proposed the establishment of a 4.0 ppm tolerance for residues of spirodiclofen per se in/on the bushberry subgroup 1 3 - 07B.Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### Executive Summary **Background:** Spirodiclofen is a tetronic acid with acaricidal action (group 23) . It acts by interfering with mite development and controls such pests as Panonychus spp., Phyllocoptruta spp., Brevipalpus spp., and Aculus and Tetranychus species. The petitioner stated that spirodiclofen is active by

contact to mite eggs, all ny mphal stages, and adult females (adult males are not effected). Spirodiclofen is currently registered for application to citrus fruit, grape, pome frui t, stone fruit, tree nuts, avocado, black sapote, canistel, mamey sapote, mango, papaya, sapodilla, star apple, and hops with tolerances for residues of spirodiclofen per se of 0.10 - 30 ppm; milk and ruminant meat, meat by products, and fat tolerance for the combined resi dues of spirodiclofen and BAJ 2510 are a lso established (0.02 - 0.1 ppm). **Proposed Application Scenarios:** The petitioner provided proposed use directions for application of Envidor® 2 SC Miticide (suspension - concentrate; 2 lbs ai/gallon ; E PA Reg. No. 264 - 831 ) to the bushberry subgroup 13 - 07B for the control of blueberry budmite (see Table 1 for summary ). Application through irrigation equipment and in enclosed structures is prohibited. Although the label does not indicate that adjuvants ( e . g. ; crop - oil concentrate, nonionic surfactant, methylated seed oil) should be added to the spray solution, it does not prohibit the inclusion of adjuvants. Since the field trial data submitted in support of the proposed action did not include adjuvant s , HED requests a revised Section B prohibiting the addition of adjuvants to the spray solution. **Table 1 :**  **Summary of Proposed Application Scenarios .**  Applic. Type Max. Single Applic.

Rate (lb ai/acre) Max. No. Applic.

per Season PHI 1

(days) Comments **bu shberry subgroup 13**  **- 07B**  (aronia berry, highbush blueberry, lowbush b lueberry, B uffalo currant, Chilean guava, black currant, red c urrant, elderberry, European barberry, gooseberry, highbush cranberry, honeysuckle, huckleberry, jostaberry, juneberry, lingo nberry, native Currant, salal, and sea buckthorn) foliar spray 0.25 - 0. 28 1 7 ● M inimum spray volume of 3 0 gallons per acre . ● M aximum seasonal application rate - 0. 28 lb ai/acre . 1 PHI = preharvest interval . 

### Nature of the Residue **- P**  **rimary Crops :**  Based on the results of previously submitted apple and grape processing studies and citrus, grape, and apple metabolism studies (D285249, T. Bloem, 18 - Apr - 2005; D341847, T. Bloem, 25 - Oct - 2007; D359773, T. Bloem, 24 - Jun - 2009), HED concluded the following: **(1)** citrus fruit, pome fruit, stone fruit, and tree nut - the residue of concern for risk assessment and tolerance enforcement is spirodiclofen per se and **(2)** grape - the residue of concern for tolerance enforcement is spirodiclofen per se and residues of concern for risk assessment are spirodiclofen and BAJ 2510. Since the grape process ing study demonstrated degradation of spirodiclofen to BAJ 2510, HED is requesting that the petitioner submit an orange processing study

monitoring for residues of spirodiclofen, BAJ 2510, 3 - OH - enol, and 4 - OH - enol (apple processing study

did not demonstrat e this degradation). Pending the submission of the orange processing data, human - health risk assessments should assume default processing factors for all processed commodities excluding the processed commodities for apple and grape. HED is willing to translate these conclusions to the proposed crops. The refore, the residue of concern in the requested crops is spirodiclofen per se . The following is a summary of the currently- available plant metabolism data.Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### The apple, citrus, and grape metabolism st udies indicate that the metabolism of spirodiclofen in fruit crops involves the following steps: cleavage of the ester linkage to form BAJ 2510 ; hydroxylation of BAJ 2510 on the cyclohexyl rin g to form 3 - OH - enol and 4 - OH - enol metabolites; and cleavage of the enol ring structure to form 2,4 - dichloro - mandelic acid cyclohexylester , which undergoes hydroxylation/conjugation and further degradation to yi eld 2,4 - dichloro - mandelic acid (free and conjugated). The grape processing study indicates that residues of spirodiclofen degrade to BAJ 2510 during processing of grapes to juice, juice concentrate, jelly , and raisin (apple processing study did not demonstrate this). The majority

of the residues in/on fruit were surface residues or were associated with the pe el with nearly

all these being comprised of parent compound. Overall , spirodiclofen accounted for 34 - 99% of the total radioactive residues (TRR). Minor amounts of the following compounds were also identified: BAJ 2510 ( ≤2% TRR), 3 - OH - enol ( ≤3% TRR), 4 - O H - enol (<1% TRR), 2,4 - dichloro - mandelic acid - cyclohexylester compounds (free and conjugated; ≤9% TRR), and 2,4 - dichloro - mandelic acid (free and conjugate; ≤12% TRR). **Magnitude of the Residue -**  **P rimary Crops**  **:** Insupport of the proposed registration, six l owbush (North American Free Trade Agreement (NAFTA) growing zones 1 (n=4) and 5 (n=2)) and six highbush (n=6; NAFTA growing zones 2 (n=3), 5 (n=1), and 12 (n=2)) blueberry field trials were submitted. Provided a revised Section B is submitted, the application scenario employed in the field trials supports the proposed application scenario and resulted in spirodiclofen per se residues in/on highbush and lowbush blueberry of 0.362 - 1.069 ppm and 0.100 - 2.333 ppm, respectively . Based on these data, the Agency's tolerance calculator recommended for highbush and lowbush blueberry tolerances for residues of spirodiclofen per se of 1.4 ppm and 3.5 ppm, respectively . The representative commodity for the bushberry

subgroup 13 - 07B is highbush blueberry with lowbus h blueberry

included in the subgroup. HED notes that additional trials in zones 1 (n=1) and 5 (n=2) are needed to fulfill the geographical distribution specified in OPPTS 860.1500 for highbush blueberry . Since the petitioner submitted six lowbush blueber ry field trials and the data for these trials indicates that residues are higher in/on lowbush blueberry as compared to highbush blueberry , HED concludes that additional data are unnecessary . Based on the submitted data, HED concludes that a tolerance of 3.5 ppm for residues of spirodiclofen per se in/on the bushberry

subgroup 13 - 07B is appropriate. A revised Section F is requested. **Analytical Enforcement Method:** HED determined that the Bayer analy tical method 109351 was appropriate for enforcement of the hop, c itrus, grape, pome fruit, stone fruit, and tree nut tolerances and forwarded this method to Food and Drug Administration (FDA) for inclusion in the Pesticide Analy

tical Manual (PAM; D368434, T. Bloem, 23 - Sep - 2009). Based on the similarities of the tolerance enforcement and the adequately validated data collection methods , HED concludes that the current enforcement method is appropriate for enforcement of the tolerances recommended as part of the current petition. **FDA Multiresidue Methods**  **:** Sp irodiclofen and BAJ 2510 were screened through the FDA MRM protocols. Since both spirodiclofen and BAJ 2510 are not N - methylcarbamates, naturally fluorescent, acids, phenols, or substituted ureas, testing through protocols A, B, and G is unnecessary . Pro tocol C modules DG1 and DG10 gave acceptable results for BAJ 2510 and spirodiclofen, respectively (both are GC/ECD sy stems). Using fortified orange samples,Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### acceptable recoveries of spirodiclofen were attained through Protocols D (80 - 103%) and E (54 - 77%). Using fortified ground beef samples, unacceptable recoveries of spirodiclofen were attained through protocol F (16 - 30%). BAJ 2510 was not recovered through the florisil clean - up column, and therefore, gave unacceptable recoveries for Protocol D (fortifi ed orange samples) and F (fortified ground beef samples). Since BAJ 2510 was not recovered through Protocol D, Protocol E was not tested. These data have been forwarded to FDA (D308565, T. Bloem, 29 - Sep - 2004). **Nature /Magnitude**  **of the Residue -**  **Livestock :**  Based on the revised Table 1 feeds tuffs (OPPTS 860.1000), none of the proposed crops have feed commodities; therefore a discussion concerning the nature/magnitude of the residue in livestock is unnecessary . **Nature/Magnitude of the Residue -**  **Rotationa l Crops:**  Since all of the requested crops are perennials, a discussion concerning the nature/magnitude of the residue in rotational crops is unnecessary . **Recommendations:** Provided revised Sections B and F are submitted, HED concludes that the residue chemistry

database supports an un conditional registration for application of spirodiclofen to the bushberry

subgroup 13 - 07B and establishment of the following permanent tolerance for residues of only

spirodiclofen (180.608(a)(1)): Bushberry subgroup 13 - 0 7B - 3.5 ppm. A human - health risk assessment will be prepared as a separate document. Inaccordance with the most recent guidance concerning tolerance expressions, HED recommends that the tolerance expression for 180.608(a)(1) and 180.6(a)(2) be change d as indicated below. HED notes that this alteration in the tolerance expression does not necessitate a change in the currently

established or recommended tolerance levels. A revised Section F specifying the new tolerance expression , the currently establ ished commodity

/tolerance levels, and the HED - recommended bushberry subgroup 13 - 07B tolerance should be submitted. 180.608(a)(1): Tolerances are established for residues of spirodiclofen , including its metabolites and degradates, in or on the commoditi es listed below. Compliance with the following tolerance levels is to be determined by

measuring only spirodiclofen (3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4.5]dec - 3 - en - 4 - yl2,2 - dimethylbutanoate . 180.608(a) ( 2): Tolerances are established for residues of spirodiclofen, including its metabolites and degradates, in or on the commodities listed below. Compliance with the following tolerance levels is to be determined by

measuring only spirodiclofen (3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4.5]dec - 3 - en - 4 - yl 2,2 - dimethylbutanoate ) and its metabolite 3 - (2,4 - dichlorophenyl) - 4 - hydroxy- 1 - oxaspiro[4,5] dec - 3 - en - 2 - one . 

### Summary of Residue Chemistry Deficiencies:

 Revised Section B  Revised Section FSpirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### Detailed Considerations **Background** Spirodiclofen is a tetroni c acid with acaricidal action (group 23) . It acts by interfering with mite development, and controls such pests as Panonychus spp., Phyllocoptruta spp., Brevipalpus spp., and Aculus and Tetranychus species. The petitioner stated that spirodiclofen is act ive by contact to mite eggs, all ny

mphal stages, and adult females (adult males are not effected). Tables 2 and 3 are summaries of spirodiclofen nomenclature and physical chemical properties, respectively . **Table 2:**  **Nom enclature.**  Spirodiclofen O O Cl Cl

O O C H 3 C H 3 C H 3

Common name Spirodiclofen Company experimental name BAJ2740 IUPAC name 3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4,5]dec - 3 - en - 4 - yl 2,2 - dimethylbutyrate CAS name 3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4,5]dec - 3 - en - 4 - yl 2,2 - dimethylbutanoate CAS registry number 148477 - 71 - 8 End - use product (EP) 2 lb/gal FlC (ENVIDOR ® 2 SC Miticide; EPA Reg. No. 264 - 831) **Table 3:**  **P hysicochem** **ical Properties of Spirodiclofen**  **.** Melting point 94.8oC

D315459, S . Mathur , 20 - Apr - 2005 pH 4.2 Density (20oC) 1.29 g/cm3 Water solub ility (20oC at pH 4) 50μg/L

Solvent solubility (g/L at 20°C) n - heptane xylene dichloromethane 2 - propanol 1 - octanol polyethylene glycol acetone ethyl acetate acetonitrile dimethylsulfoxide 20

>250 >250 47 44 24 >250 >250 >250 75 Vapor pressure (20oC) 3 x 10 - 7 Pa Diss ociation constant, pKa Not determinable due to the instability in aqueous solutions at >pH 4 Log(KOW) at pH 4 and 20oC 5.83 UV/visible absorption spectrum λmax = 201 nm: Not expected to absorb UV at λ >350 nmSpirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### 860.1200 Directions for Use The peti tioner provided proposed use directions for application of Envidor® 2 SC Miticide (suspension - concentrate; 2 lbs ai/gallon; EPA Reg. No. 264 - 831) to the bushberry subgroup 13 - 07B for the control of blueberry budmite (see Table 1 for summary ). Application through irrigation equipment and in enclosed structures is prohibited. Although the label does not indicate that adjuvants (e. g.; crop - oil concentrate, nonionic surfactant, methylated seed oil) should be added to the spray solution, it does not prohibit the inclusion of adjuvants. Since the field trial data submitted in support of the proposed action did not include adjuvants, HED requests a revised Section B prohibiting the addition of adjuvants to the spray solution. **860.1300 Nature of the Residue -**  **Plants** Based on the results of previously submitted apple and grape processing studies and citrus, grape, and apple metabolism studies (D285249, T. Bloem, 18 - Apr - 2005; D341847, T. Bloem, 25 - Oct 2007; D359773, T. Bloem, 24 - Jun - 2009), HED concluded the res idue of concern in the proposed crops is spirodiclofen per se (see Executive Summary for more information). **860.1300 Nature of the Residue -**  **Livestock** Based on the revised Table 1 feedstuffs (OPPTS 860.1000), none of the proposed crops have feed commod ities; therefore a discussion concerning the nature of the residue in livestock is unnecessary . **860.1340 Residue Analytical Methods Tolerance Enforcement:**  HED forwarded Bayer analy tical method 1 09351 t o FDA for inclusion in the PAM ( D368434, T. Bloem, 23 - Sep - 2009 ). Briefly , fruit samples are extracted with acetonitrile:water (2:1; v:v) containing a small amount of aqueous 20% cysteine hydrochloride , filtered, and acidified with HCl . The extract is subjected to clean up on an ENVI - carb cartridge preco nditioned with DCM, methanol , and water with residues eluted with DCM under vacuum. The resulting eluent is concentrated to dry ness and reconstituted in ACN and water for analy sis by L C/MS/MS. The L OQ was reported to be 0.01 ppm (LOD ranged from 0.001 - 0. 006 ppm). Based on the similarities of the tolerance enforcement and the adequately validated data collection methods , HED concludes that the current enforcement method is appropriate for enforcement of the tolerances recommended as part of the current pe tition. **Data Collection:** The blueberry field trial samples were analy zed for residues of spirodiclofen per se using an adequately validated liquid chromatograph/mass spectrometer/mass spectrometer (LC/MS/MS) method. Briefly , homogenized samples were e xtracted by blending with acetonitrile:water (2:1; v:v) and 20% cy steine hydrochloride. Samples were filtered, acidified with 1.2N HCl, and partitioned with dichloromethane (DCM) prior to analysis by L C/MS/MS. The submitted method validation and concurre nt recovery data were adequate. Based on the LLM V, the L OQ was 0.0102 ppm. The study indicated that the statistically determined L OQ and LOD were 0.1644 ppm and 0.0548 ppm, respectively (standard deviation at LLM V multiplied by the one - tailed 99% t - stat) . However, HED found an error in the calculation and recalculated the LOQ and LOD as 0.0 08 ppm and 0.0 03 ppm respectively (calculation used a value of 0.102 ppm rather than 0.0102 ppm).Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### 860.1360 Multiresidue Methods Spirodiclofen and BAJ 2510 were scree ned through the FDA MRM protocols. S ince both spirodiclofen and BAJ 2510 are not N - methylcarbamates, naturally fluorescent, acids, phenols, or substituted ureas, testing through p rotocols A, B, and G is unnecessary . Protocol C modules DG1 and DG10 gave a cceptable results for BAJ 2510 and spirodiclofen, respectively (both are GC/ECD sy stems). Using fortified orange samples, acceptable recoveries of spirodiclofen were attained through Protocols D (80 - 103%) and E (54 - 77%). Using fortified ground beef sampl es, unacceptable recoveries of spirodiclofen were attained through protocol F (16 - 30%). BAJ 2510 was not recovered through the florisil clean - up column, and therefore, gave unacceptable recoveries for Protocol D (fortified orange samples) and F (fortified ground beef samples). Since BAJ 2510 was not recovered through Protocol D, Protocol E was not tested. These data have been forwarded to FDA (D308565, T. Bloem, 29 - Sep - 2004). **860.1380 Storage Stability** The blueberry

s amples from the field trials were s tored frozen for up to 3 2 7 day s prior to analy sis. As part of the current study , the petitioner submitted storage stability which indicate that residues of spirodiclofen per se are stable in/on blueberry when stored frozen for 352 day s. HED notes that the se data did not include a zero day analy sis as requested in the OPPTS 860.1380 guidelines. The petitioner previous ly submitted storage stability data which indicated that residues of spirodiclofen per se are stable when stored frozen for the following crop /intervals (D285249, T. Bloem, 18 - Apr - 2005): 391 day s (grape), 231 day s (raisin), 226 day s (grape juice concentrate), 231 day s (apple juice concentrate), 231 day s (dried apple), 391 day s (peaches), 306 day s (prunes), 410 day s (almond nutmeat), and 305 day s (almond hulls). The almond hull data indicated a 26% reduction in residues for samples stored 410 days. These data support the storage intervals and conditions for the blueberry samples collected as part of the current study . **860.1480 Meat, Milk, Poul try, and Eggs**  Based on the revised Table 1 feedstuffs (OPPTS 860.1000), none of the proposed crops have feed commodities; therefore a discussion concerning the magnitude of the residue in livestock is unnecessary . **860.1500 Crop Field Trials** 47 886201 .de r.doc 

### Insupport of the proposed registration, six lowbush (NAFTA growing zones 1 (n=4) and 5 (n=2)) and six highbush (n=6; NAFTA growing zones 2 (n=3), 5 (n=1), and 12 (n=2)) blueberry field trials were submitted. Provided a revised Section B is submitt ed, the application scenario employed in the field trials supports the proposed application scenario and resulted in spirodiclofen per se residues in/on highbush and lowbush blueberry of 0.362 - 1.069 ppm and 0.100 - 2.333 ppm, respectively (see below for summary ) . Based on these data, the Agency's tolerance calculator recommended for highbush and lowbush blueberry tolerances for residues of spirodiclofen per se of 1.4 ppm and 3.5 ppm, respectively (see attachment 3 ) . The representative commodity for the b ushberry

subgroup 13 - 07B is highbush blueberry with lowbush blueberry included in the subgroup. HED notes that additional trials in zones 1 (n=1) and 5 (n=2) are needed to fulfill the geographical distribution specified in OPPTS 860.1500 forSpirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### highbush blue berry . Since the petitioner submitted six lowbush blueberry field trials and the data for these trials indicates that residues are higher in/on lowbush blueberry as compared to highbush blueberry , HED concludes that additional data are unnecessary . Based on the submitted data, HED concludes that a tolerance of 3.5 ppm for residues of spirodiclofen per se in/on the bushberry

subgroup 13 - 07B is appropriate . A revised Section F is requested. Blueberry (4 7886201 .der.wpd): IR - 4 submitted six lowbush blueb erry (NAFTA growing zones 1 (n=4) and 5 (n=2)) and six highbush blueberry (NAFTA growing zones 2 (n=3), 5 (n=1), and 12 (n=2)) field trials conducted during 2006. Each trial consisted of one untreated plot and one treated plot with the treated plots recei ving a single foliar - directed (highbush blueberry ) or foliar broadcast (lowbush blueberry ) application of spirodiclofen (SC; 2 lb ai/gal) at 0.271 - 0.307 lb ai/acre (19 - 66 GPA; no adjuvant). Single control and duplicate treated blueberry samples were harve sted 6 - 8 day s after application . Additional samples were collected at one of the highbush blueberry and lowbush blueberry

field trials at 1, 3, 10, and 14 days after application. The harvested samples were analy zed for residues of spirodiclofen per se using an adequately validated LC /MS/MS method (storage interval has also been validated). Residues of spirodiclofen per se in/on highbush blueberry harvested 6 - 8 day s after a single foliar - directed application of spirodiclofen (SC) at 0.278 - 0.288 lb ai/ac re were 0.362 - 1.069 ppm (see Table 4) . Residues of spirodiclofen per se in/on lowbush blueberry harvested 6 - 7 day s after a single broadcast - foliar application of spirodiclofen (SC) at 0.271 - 0.307 lb ai/acre were 0.100 - 2.333 ppm (see Table 4) . The highbus h blueberry and lowbush blueberry

residue decline data indicate that residue of spirodiclofen per se declined as the PHI increased from 1 to 14 day s. **Table 4. Sum**  **ma ry of Residue Data from** **Crop Field Trials with Spirodiclofen.** Commodity Total App. Rate (lb ai/acre) PHI

(days) Residue Levels (ppm) 1

n Min. Max. HAFT 2 Median Mean Std. Dev. Highbush blueberry 0.278 - 0.288 6 - 8 12 0.362 1.069 1.054 0.551 0.621 0.237 Lowbush blueberry 0.271 - 0.307 6 - 7 12 0.100 2.333 2.296 1.282 1.305 0.624 1 Based on the LLMV, the LOQ = 0.01 ppm. 2 HAFT = highest - average field trial. 

### 860.1520 Processed Food and Feed Based on Table 1 of OPPTS 860.1000, there are not processed commodities associated with the proposed crops. **860.1850/860.1900 Confined and Field Accum ulation in Rotational Crops**  Since all of the requested crops are perennials, a discussion concerning the nature/magnitude of the residue in rotational crops is unnecessary .Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### 860.1550 Proposed/Recommended Tolerances Table 5 is a summary

of the propose d and recommended tolerance for residues of spirodiclofen per se . There are no Canadian maximum residue limits (MRL s) in/on the requested crops. Codex does have a MRLfor residues of spirodiclofen per se in/on black/red currant at 1 ppm; since the Codex tolerance is lower than the maximum residues form the submitted field trials, harmonization is not possible. Inaccordance with the most recent guidance concerning tolerance expressions, HED recommends that the tolerance expression for 180.608(a)(1) an d 180.6(a)(2) be changed as indicated below. HED notes that this alteration in the tolerance expression does not necessitate a change in the currently

established or recommended tolerance levels. A revised Section F specifying the new tolerance expressio n , the currently established commodity

/tolerance levels, and the HED - recommended bushberry subgroup 13 - 07B tolerance should be submitted. 180.608(a)(1): Tolerances are established for residues of spirodiclofen, including its metabolites and degradates, in or on the commodities listed below. Compliance with the following tolerance levels is to be determined by

measuring only spirodiclofen (3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4.5]dec - 3 - en - 4 - yl2,2 - dimethylbutanoate . 180.608(a) ( 2): Tolerances are es tablished for residues of spirodiclofen, including its metabolites and degradates, in or on the commodities listed below. Compliance with the following tolerance levels is to be determined by

measuring only spirodiclofen (3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - ox aspiro[4.5]dec - 3 - en - 4 - yl2,2 - dimethylbutanoate ) and its metabolite 3 - (2,4 - dichlorophenyl) - 4 - hydroxy- 1 - oxaspiro[4,5] dec - 3 - en - 2 - one . **Table 5**  **: Tolerance Sum**  **ma ry**  **.** Commodity Proposed

Tolerance (ppm) HED - Recommended

Tolerance (ppm) Comments Bushberry subgr oup 13 - 07B 4.0 3.5 A revised Section F , specifying the correct tolerance value and tolerance expression is requested .



### Attachment 1: Chemical Structures Attachment 2: Codex Attachment 3: Tolerance Calculation RDI : RAB1 Chemis ts ( 16 - June - 20 10 ) T. Bloem:S10945:Potomac Yard 1:703 - 605 - 0217:7509P:RABISpirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### Attachment 1: Chemical Structures

**Chem ical Nam**  **e Structure**  Spirodiclofen; BAJ2740 3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4,5]dec - 3 - en - 4 - yl 2,2 - dimethylbutanoate O O Cl Cl

O O C H 3 C H 3 C H 3

BAJ 2510 3 - (2,4 - dichlorophenyl) - 4 - hydroxy - 1 - oxaspiro[4.5]dec - 3 - en - 2 - one O Cl Cl

O O H

3 - OH - enol 3 - OH - enol spirodiclofen O Cl Cl

O O H O H

4 - OH - enol 4 - OH - enol spirodiclofen O Cl Cl

O O H

O HSpirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### Attachment 2: International residue L imit Statu s 

# INTERNATIONAL RESIDUE LIMIT STATUS **Chem ical Nam**  **e** : 3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4,5]dec - 3 - en - 4 - yl 2,2 - dimethylbutanoate **Com mo**  **n Nam e:**  spirodiclofen X Proposed tolerance

Reevaluated tolerance Other - HED recommended tolerances Date: 4 - May - 2010 Codex Status (Maximum Residue Limits) U. S. Tolerances No Codex proposal step 6 or above No Codex proposal step 6 or above for the crops requested Petition Number: 9E7632 DP Number: 371469 Other Identifier: Residue definition: spirodiclofen Rev iewer/Branch: Tom Bloem/RAB1 Residue definition: spirodiclofen Crop (s) MRL (mg/kg) Crop(s) Tolerance (ppm) Currants, black, red, w

hite 1 bushberry subgroup 13 - 07B 4.0 Limits for Canada Limits for Mexico No Limits √ No Limits for the crops requested No Limits (no information after 2004) No Limits for the crops requested Residue definition: 3 - (2,4 - dichlorophenyl) - 2 - oxo - 1 - oxaspiro[4.5]dec - 3 - en - 4 - yl2,2 - dimethylbutanoate . Residue definition: Mexico adopts Co dex and/or US MRLs/tolerances for its export purposes. Crop(s) MRL (mg/kg) Crop(s) MRL (mg/kg) Notes/Special Instructions: S.Funk , M. Negussie/05/06/2010Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

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### Attachment 3: Tolerance Calculation

**Lognormal Probability Plot**

99.9 99 98 95 90 80 70 50 30 20 10 5 2 1 0.1 2.0000

1.0000

0.5000

0.2500 y = 0.3534x - 0.5352 R 2 = 0.914

**Percentiles C** **o n** **c e** **n t** **r a** **t i** **o n** **s EPA spirodiclofen highbush blueberry 6-8 days 1 x 0.278-0.288 IR-4** 

**Reg ulat**  **or:** EP A **Ch emic**  **al:** sp irod iclof en **Cr op:**  hi ghbu sh bl uebe rry **PH I:**  6- 8 da ys **App . Ra**  **te:** 1 x 0. 278-0 .288 **Sub mitt**  **er:** IR -4

**n:** 12 **mi n:**  0.3 6 **ma x:**  1.0 7 **medi an:**  0.5 5 **av era**  **ge:** 0.6 2 **95th Per**  **centi le**  **99 th P**  **erce ntile**  **99.9 th Pe**  **rcen tile**  1. 1 1.2 1. 4 (1. 3) (1 .6) (--) 1. 1 **1.4** 1. 8 **(1. 6)**  (2 .5) (--) 1.6 **1.4 3.5**  0.91 40 p- valu e > 0.05 : Do not reje ct l ogno rmali ty a ssump tion **Appr oxima**  **te Sh**  **apir o-Fra**  **ncia Norm**  **alit y Tes**  **t EU M**  **ethod I**  **Norm al** 

**UC LMe**  **dian9 5th**  **95 /99**  **Rule EU**  **Meth od II**  **Dis trib**  **ution -Fre**  **e Me**  **an+ 3SD** Spirodiclofen Summary of Analy tical Chemistry and Residue Data D371643

page 13 of 13 **Lognormal Probability Plot**

99.9 99 98 95 90 80 70 50 30 20 10 5 2 1 0.1 3.0000

1.5000

0.7500

0.3750

0.1875

0.0938 y = 0.7349x + 0.0697 R 2 = 0.7097

**Percentiles C** **o n** **c e** **n t** **r a** **t i** **o n** **s EPA spirodiclofen lowbush blueberry 6-7 days 1 x 0.271-0.307 IR-4** 

**Regulator:** EPA **Chemical:** spirodiclofen **Crop:** lowbush blueberry **PHI:** 6-7 days **App. Rate:** 1 x 0.271-0.307 **Submitter:** IR-4

**n:** 12 **min:** 0.10 **max:** 2.33 **median:** 1.28 **average:** 1.30 **95th Percentile 99th Percentile**  **99.9th Percentile** 2.5 3.0 3.5 (3.5) (4.0) (--) 4.5 **8.0** 14 **(11)** (25) (--) 3.5 **3.5 8.0**  0.7097 p-value <= 0.01: Reject lognormality assumption **Approximate Shapiro-Francia**  **Normality Test EU Method I**  **Normal**

**UCLMedian95th 95/99 Rule**  **EU Method II Distribution-Free**  **Mean+3SD**