Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 1 of 29 UNITED STA

TES ENVIRONMENTA L PROTECTION AGENCY WASHINGTON, D.C. 20460 OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVENTION MEMORA NDUM Date : 25 - AUG - 2010 . SUBJECT: Acequinocyl . P etition for U se on F ruiting V egetables, Hops, Okra , and Edible Podded B eans . Summary of Analytical Chemistry and Residue Data . PC Code: 0063 2 9 DP Barcode: D 369100 Decision No.: 417967 Registration No. : 66330 - 38 Petition No.: 9E7598 Regulatory Action: Section 3 Risk Assessment Type: NA Case No.: 7621 T XR No.: NA CAS No.: 57960 - 19 - 7 MRID No s .: 478194 - 01 thru - 04 40 CFR: § 180 .599 FROM: Sarah J. L evy , Chemist

Risk A ssessment Branch 1 (RAB1) Health Effects Division (HED) ( 7509P ) THROUGH: George F. Kramer, Ph.D., Senior Chemist

RAB1 /HED ( 7509P ) TO: Barbara Madden, RM Team 05

Registration Division (RD; 7505 P ) This document wa s originally prepared under contract by Dynamac Corporation (1901 Research Boulevard, Suite 220; Rockville, MD 20850). Executive Summary Acequinocyl is a qu inoline ty pe miticide registered for use in the U.S. on pome fruits, citrus fruits, grapes, tree nuts , pistachios, and strawberries for the control of various phy tophagous mite species. Acequinocyl i s currently registered to Ary sta L ifesci ence North Ameri ca Corporation as a 15% suspension - concentrate (SC) formulation . Under PP# 9E7598 , the Interregional Research Project No.4 (IR - 4) , on behalf of the Agricultural Experiment Station of AZ, CA, CO, FL , ID, NC, NJ, NY, OK, OR, TN, TX, VA, and WA, is requesting for the establishment of tolerances for the combined residues of the insecticide acequinocyl, 2 - (acetyloxy ) - 3 - dodecyl - 1,4 - naphthalenedione, and its metabolite, 2 - dodecyl - 3 - hydroxy- 1,4 - naphthoquinone, expressed as acequinocyl equivalents in/on the followin gAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 2 of 29 commodities : Vegetable, f

ruiting, group 8 ................................ ............................. 0.70 ppm Okra ................................ ................................ ................................ .. 0.70 ppm Bean, edible podded ................................ ................................ ......... 0.25 ppm Hop, dried cones ................................ ................................ .............. 3.5 ppm The end - use product proposed for use on f ruiting vegetables, hops, okra and snap beans is KanemiteTM 15 SC Miticide, a 1.25 lb/gal SC formulation. Up to two foliar applications are proposed for a maximum seasonal rate of 0.6 lb ai/A, with a 7 - day preharvest interval (PHI ) , except for okra for which a 1 - day PHIis proposed . T olerances are currently established under 4 0 CFR §180.5 99 (a) f or the combined residues of acequinocyl and its metabolite, 2 - dodecyl - 3 - hydroxy- 1,4 - naphth oquinone, expressed as acequinocyl equivalents , in/on a number of p lant and livestock commodities. Tolerances for plant commodities range from 0.02 ppm (tree nuts an d pistachios ) to 30 ppm (citrus oil), and tolerances for livestock commodities are established at 0.02 ppm in the fat and liver of cattle, goat, horse, and sheep . The nature of acequinocyl residues in apples, oranges, and eggplants is understood based on the previously

submitted and reviewed metabolism studies. In these crops , the metabolism of acequinocyl involves the loss of the acetyloxy moiety to form acequinocyl - OH, the opening of the quinone ring to form AKM - 18, and the subsequent degradation of the quinone ring to yield polar metabolites that degrade to phthalic acid. For purposes of risk assessment and the tolerance expression, HED has determined that the residues of concern in these commodities include parent and acequinocyl - OH (Memo, S. L evy , 07 - JAN - 2004; DP# 297872). There are no livestock feedstuffs associated with the proposed crop uses addressed herein . Therefore, no livestock metabolism data, enforcement methods, storage stability data, or feeding studies are required to support this petit ion. There are adequate residue analy tical methods for enforcing tolerances for acequinocy l residues of concern in/on the proposed/registered plant commodities. These methods include two high performance liquid chromatography methods with tandem mass - spe ctroscopy detection ( HP LC /MS/MS ) for determining residues in/on fruit and nut commodities (Morse Methods Meth - 133 and Meth - 135 ) . For each of these methods, residues are extracted with hexane or acetonitrile (ACN)/water and cleaned up by solvent partitioning, gel - permeation chromatography (GPC) and/or silica - gel solid - phase extraction (SPE). Residue data from the current field trial and processing studies were obtained using the approved enforcement methods, Meth - 13 5 (tomato, pepper and hops) and Meth - 13 3 (snap beans) with minor modifications . The methods are adequate for data collection based on acceptable method validation and concurrent method recovery data for tomato and its processed matrices , pepper , and snap beans . H owever, th e data - co llection method yi elded consistently low recoveries (~53%) for acequinocyl - OH in dried hop cones; therefore, residues of the metabolite from the hop field trials were corrected for low recoveries. The validated limit of quantitation (L OQ) was 0.0 1 0 ppm for acequinocyl and 0.025 ppm for acequinocyl - OH in/on tomato and pepper; 0.020Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 3 of 29 ppm each for acequinocyl and acequinocyl - OH in/on edible - podded beans ; and 0.10 ppm for acequinocyl in/on hop dried cones . The data requirements for multiresidue (MRM ) methods are fulfilled. Certain MRM protocols resulted in acceptable recoveries. The MRM testing data have been forwarded to the U.S. Food and Drug Administration ( FDA ) for further evaluation ( Memo, S. L evy , 18 - FEB - 2004; DP#: 298917 ). The submitted con current storage stability data for tomato, snap bean , and hops is adequate to support the storage intervals and conditions incurred by the field trial studies. In addition, the concurrent storage stability data for the parent acequinocyl is adequate to su pport the sample storage intervals and conditions for the pepper field trials and tomato processing studies. It is noted that zero - day

data were not provided. IR - 4 is reminded that storage stability studies should alway s include a zero - day sampling inter

val to establish the residue levels present at the time samples are placed into storage [see OPPTS 860.1380(d)(6)(i)]. The concurrent storage stability data indicate problems with the stability of acequinocyl - OH in peppers and processed tomato paste and puree. Because zero - day samples were not analy

zed, determination of residue levels present at the time samples were placed in frozen storage could not be made. In addition, an insufficient number of time points were analy zed in order to establish how mu ch of the residue (acequinocyl - OH) was lost at various time points. However, because residues of acequinocyl - OH in the pepper field trial were <10% of the parent value or were <LOQ , correction for 51% decline would not affect the results. Furthermore, in the tomato processing study , b ecause there were quantifiable residues of the parent in the raw agricultural commodity

( RAC ) and residues of acequinocyl - OH in the RAC were nonquantifiable, HED believes that any concentration of acequinocyl - OH residues wo uld not significantly

increase the total residue level. Therefore, HED is not requesting additional storage stability data at this time. T he submitted magnitude of the residue data for tomato es , pepper s , edible - podded beans , and hop s are adequate . The field trials r eflect the proposed use patterns and an adequate number of field trials were conducted in major crop growing regions . The submitted field trial data reflect a pplications made without the us e of a spray adjuvant . A revised Section B should be submitted incorporating an adjuvant– use re striction. The Agency ’s tolerance spreadsheet as specified by

the Guidance for Setting Tolerances Based on Field Trial Data SOP (August 2009 version) was used to determine the appropriate tolerance levels. The field trial data will support tolerances of: 0.70 ppm for fruiting vegetables; 0.70 ppm for okra; 0.25 ppm for edible - podded beans; and 4.0 ppm for dried hop cones . Itis noted that the proposed PHI for fruiting vegetables is 7 day s whereas the field trials reflect a 1 - day PHI . Residue decline trials for tomato and pepper demonstrate that residues generally decline with later sampling intervals ; therefore, the proposed /recommended tolerance will likely overestimate anticipated residues of acequinocyl an d acequinocyl - OH in/on fruiting vegetables. The available data support the proposed tolerances for fruiting vegetable s , okra, and edible podded beans; however, the proposed tolerance for hop dried cones is too low.Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 4 of 29 T he tomato processing study is adequate . The results indicate that residues of acequinocyl and acequinocyl - OH d id not concentrate in paste and puree processed from tomato fruit s bearing quantifiable residues of acequinocyl. N o tolerances are required for tomato processed matr ices . An adequ ate c onfined rotational crop study was previously submitted. These data reflect the maximum proposed use pattern for rotated crops (fruiting vegetables and edible - podded beans); the results indicate that residues of acequinocyl do not accumulate in rotate d crops. These data support a 30 - day plantback interval ( PBI ) for all non - labeled crops. Regulatory Recommendations and Residue Chemistry Deficiencies Pending submission of revised Sections B (see requirements under Directions for Use) and F ( see requirements under Proposed Tolerances ), and submission of analy tical reference standards to the EPA National Pesticide Standards Repository (see requirements under Residue Analy tical Methods) , there are no residue chemistry issues that wou ld preclude granting a permanent registration for the requested uses of acequinocyl or establishment of tolerances for residues of acequinocyl and acequinocyl - OH as follows: Vegetable, fruiting, group 8 ................................ ............................. 0.70 ppm Okra ................................ ................................ ................................ .. 0.70 ppm Bean, edible podded ................................ ................................ ......... 0.25 ppm Hop, dried cones ................................ ................................ .............. 4 . 0 ppm Note to PM: According to HED’s Interim Guidance on Tolerance Expressions (5/27/09, S. Knizner), the tolerance expression for acequinocyl should be revised to state: “Tolerances are established for residues of acequinocyl , includ ing i t s metabolites and degradates, in or on the commodities in the table below. Compliance with the tolerance levels specified below is to be determined by measuring only the sum of acequinocyl [ 2 - (acetyloxy) - 3 - dodecyl - 1,4 - naphthalenedione] and its metab olite, 2 - dodecyl - 3 - hydroxy - 1,4 - naphthoquinone , calculated as the stoichiometric equivalent of acequinocyl, in or on the commodity . A human health risk assessment is forthcoming. 860.1200 Directions for Use

 The proposed label (Section B) for the 1.25 lb/ gal SC should be revised to specify a 30 - day PBI restriction for all non - labeled crops.  The submitted field trial data reflect a pplications made without the us e of a spray adjuvant . A revised Section B should be submitted incorporating an adjuvant

– use res triction .  The data for fruiting vegetables supports a 1 - day PHIfor all fruiting vegetables. The petitioner may

amend the label for the 1.25 lb/gal SC to reduce the proposed PHI for fruiting vegetables from 7 day s to 1 day , based on field trial data .Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 5 of 29 860.1340 Residue Analy

tical Methods

 Submission of analy

tical reference standards to the EPA National Pesticide Standards Repository . 860.1550 Proposed Tolerances

 A revised Section F is required to amend the tolerances as specified in Table 7. Backgro und The chemical structure and nomenclature of acequinocyl and its regulated metabolite are presented in Table 1, and the phy sicochemical properties of acequinocyl are presented in Table 2. T able 1. Nom enclature of Test Com pound and Metabolites .

Comp ound O

O C H 2 ( C H 2 ) 1 0 C H 3 O C O C H 3 Common name Acequinocyl Company experimental names TM - 41301 or AKD - 2023 IUPAC name 3 - dodecyl - 1,4 - dihydro - 1,4 - dioxo - 2 - naphthyl acetate CAS name 2 - (acetyloxy) - 3 - dodecyl - 1,4 - naphthalenedione CAS # 57960 - 19 - 7 End - use products/EP KanemiteTM 15 SC (1.25 lb ai/gal; EPA Reg. No. 66330 - 38) Compound O

O C H 2 ( C H 2 ) 1 0 C H 3 O H Common name Acequinocyl - OH Company experimental names R1 IUPAC name 2 - dodecyl - 3 - hydroxy - 1,4 - napthoquinone CAS name 2 - dodecyl - 3 - hydroxy - 1,4 - naphthalenedione CAS # 57960 - 31 - 3 T able 2. Physicochem ical Properties . Parameter Value Reference (MRID) Melting point 59.6 C 45434906 pH 6.94 45434904 Density 1.13 g/cm3 45434904 Water solubility ( 20°C) 6.69 μg/L 45434906Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 6 of 29 T able 2. Physicochem ical Properties . Parameter Value Reference (MRID) Solvent so lubility (mg/L at 20°C) 1,2 - dichloroethane: >250 acetone: >250 ethyl acetate: >250 xylene: >250 methanol: 6.1 n - heptane: 36 n - octanol: 29.2 45434904

Vapor pressure at 25°C 1.69 x 10 - 9 pascals 45434905 Dissociation constant (pK a ) no measurable pK a 4543490 5 Octanol/water partition coefficient Log(K OW ) > 6.2 45434906 UV/visible absorption spectrum (  max, nm) neutral pH: 242, 248, 262, 270, 335 acid pH: 242, 248, 265, 270, 330 basic pH: 232, 245, 255, 275, 362 45434905 860.1200 Directions for Use The peti tioner provided a draft label for Kanemite TM 15 SC Miticide ( EPA Reg. No. 66330 - 38) , a 1.25 lb/gal SC formulation of acequinocyl. The acequinocyl formulation , which is currently registered for use on several fruit and nut crops , is proposed for use on fruiting vegetables, okra, edible - podded beans and hops . The proposed uses are summarized below in Table 3. Table 3 . Summary of Directions for Use of Acequinocyl . Applic. Timing, Ty pe, and Equip. Formulation

[EPA Reg. No.] Applic.

Rate (lb ai/A) Max. No.

Applic. per Season Max. Seasonal

Applic. R ate (lb ai/A) PHI

(days) Use Directions and

Limitations 1 Fruiting Vegetables (except cucurbits) (field grow n and greenhouse grown) [eggplant, groundcherry (Physalis spp. ), pepino, pepper (includes bell pepper, chili pepper, cooking pepper, pimento, sweet pepper), tomatillo, and tomato] Postemergence, foliar G round only 1.25 lb/gal

SC [66330 - 38] 0.3 2 0.6 7 Minimum spray volume of 100 gal/A ; minimum RTI of 21 day s. Okra Postemergence, foliar Ground only 1.25 lb/gal

SC [66330 - 38] 0.3 2 0.6 1 Minimum spray volume of 100 gal/A; minimum RTI of 21 days. Edible - podded Beans Postemergence, foliar Ground only 1.25 lb/gal

SC [66330 - 38] 0.3 2 0.6 7 Minimum spray volume of 100 gal/A; minimum RTI of 21 days . Hops Postemergence, foliar Ground only 1.25 lb/gal

SC [66330 - 38] 0.3 2 0.6 7 Minimum spray volume of 100 gal/A; minimum RTI of 21 days . 1 RTI = retreatment interval.Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 7 of 29 General label restrictions include: (i) do not apply through any

ty pe of irrigation sy stem; (ii) do not apply by air; (iii) do not apply

within 75 feet of aquatic areas; and (iv) not for indoor residential use. The product may be combined with most commonly used pesticides with the exception of strongly

alkaline material, which can reduce activity ; combination with Phos - ethyl (fosetyl) is pro hibited. Broad - spectrum insect control may be obtained by

tank - mixing the SC acequinocyl product with other miticide/insecticide products; a spray mix compatability

and phy totoxicity trial under local conditions should first be conducted. A 12 - hour restricted entry interval (REI ) is specified. No rotational crop restrictions are specified on the label. Conclusions : The proposed use directions are adequate to allow for evaluation of the submitted residue data relative to the proposed uses. T he proposed uses are generally supported by

the submitted field trial data; however, the data for fruiting vegetables supports a 1 - day PHIfor all fruiting vegetables . The petitioner may reduce the proposed PHI for fruiting vegetables from 7 day s to 1 day , based on field trial data. The submitted fruiting vegetable data do support the 1 - day PHIproposed for okra. Furthermore, the submitted field trial data reflect a pplications made without the us e of a spray adjuvant . A revised Section B should be submitted inco rporating an adjuvant– use re striction. An adequate confined rotational crop study was previously

submitted , reflecting the maximum proposed use pattern for rotated crops (fruiting veget ables and edible - podded beans). These data support a 30 - day

PBIfor a ll non - labeled crop s. A revised Section B should be submitted incorporating the r otational crop restriction . 860.1300 Nature of the Residue - Plants The qualitative nature of acequinocyl residues in fruit and nut crops is understood based on the availab le apple, orange, and eggplant metabolism studies ( Memo, S. L evy , 10 - MAR - 2004; DP# 284757). The data indicate that the metabolism of acequinocyl in these crops involves the loss of the acetyloxy

moiety to form acequinocyl - OH, opening of the quinone ring t o form AKM - 18, and subsequent degradation of the quinone ring to yield polar metabolites that degrade to phthalic acid. Based on the structural similarity of acequinocyl - OH to parent and the presence of acequinocyl OH at quantifiab le levels in crops, the HED Metabolism Assessment Review Committee (MARC) concluded that parent and acequinocyl - OH are the residues of concern for risk assessment and tolerance e xpression in apples, oranges, and eggplant commodities (Memo, S. Levy , 07 - JAN - 2004; DP# 297872) . For purposes of this petition, HED is willing to translate these results to hops and edible - podded beans as these two crop s are low - consumption food items. However, if in the future the petitioner requests new uses where apple, orange, and eggplant metabolism data cannot be translated, HED may ask for additional plant metabolism data.Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 8 of 29 860.1300 Nature of the Residue - Livestock There are no livestock feedstuff s assoc iated with the proposed uses . Therefore, data requirements for livest ock metabolism are not relevant to this tolerance petition . 860.1340 Residue Analytical Methods Enforcement methods: Adequate analy tical methods are available for enforcing acequinocyl tolerances in/on the proposed/registered plant commodities ( Memo, D. Soderberg 23 - MAY 20 06 ; DP# 321753 ; Memo, S. L evy , 25 - JUN - 2008; DP#s 351336 & 353313) . These methods include two L C/MS/MS methods for determining acequinocyl and acequinocyl - OH residues in fruit crops (Morse Method #Meth - 133, revision #3) and nut crops (Morse Method #Meth - 135). The three methods were forwarded by HED to the BEAD, ACB laboratory for a PMV. In lieu of a PMV, ACB completed a desk audit (Memo, P. Golden, 04 - APR - 2006; ACB#: B04 - 13) in which ACB recommended that the petit ioner revise methods # Meth - 133, Revision #3 (including the modification for orange oil), # Meth - 135, and # Meth - 139 Revision #2 to address deficiencies. The petitioner adequately addressed the modifications requested by ACB ( Memo, P. Golden, 04 - APR - 2006; ACB#: B04 - 13 ). Method s #Meth - 135, Revision #3 , #Meth - 133, Revision #4, and #Meth - 139, Revision #3 are suitable enforcement methods for the subject crop and livestock matrices and no additional data concerning th ese method s are necessary (Memo, S. Levy , 2 5 - AUG - 2010; DP#380302) . Data -gathering method

s : Samples of crop commodities that were collected from the magnitude of the residue studies were analy zed for residues of acequinocyl and acequinocyl - OH using modifications of the enforcement methods. S ample s from the tomato, pepper and hop field trials and tomato processing study were analy zed using Method Meth - 135 , and s amples from the edible - podded bean field trials were analy zed using Method Meth - 133 . Using the modified Meth - 135 method, residues in/on tomato and pepper samples were extracted with hexane in the presence of anhydrous sodium sulfate, centrifuged, filtered, and concentrated. The extract was cleaned up by silica - gel SPE using a Bond Elute - Si column, and residues were eluted with hexane:ethyl acetate (24:1, v:v for acequinocyl and 9:1, v:v for acequinocyl - OH). The eluates were concentrated to dry ness, and redissolved in ACN:acetone:0.4% formic acid (2:2:1, v:v:v) for HP LC /MS/MS analy sis . For hops, residues in/on samples were extracted with ACN:water (60:40, v:v) and filtered. The extract was brought to volume with additional ACN/water for cleanup by C18 SPE, and residues were eluted with ACN. The eluate was then partitioned with hexane; the hexane fraction was mixed with 1% decanol in ace tone (keeper solution), concentrated, and diluted with hexane for silica SPE cleanup. Residues were eluted with 5% ethyl ether in hexane, concentrated, and redissolved in ACN:acetone:0.4% formic acid (2:2:1, v:v:v) for HP LC /MS/MS analy sis. Using the mod ified Meth - 133 method , residues in/on snap bean samples were extracted with ACN:water (10:3, v:v). Salt (NaCl) was added to force separation of the water and ACN phases and centrifuged. The resulting ACN fraction was filtered through sodium sulfate. Residues were then partitioned into hexane. The hexane fraction was mixed with 1% decanol in acetone (keeper solution), concentrated, and diluted with hexane for silica gel SPE; residues were eluted withAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 9 of 29 hexane:ethyl acetate (9:1, v:v). The eluate was evaporated to dry ness and redissolved in acetone:ACN:0.4% aqueous formic acid (2:2:1, v/v/v) for HP LC /MS/MS analy sis . The methods were adequate for data collection based on acceptable method validation and concurrent method recovery data ; however recoveries for acequinocyl - OH from dried hop cones were consistently

low (~50%) at all fortification levels (0.10 - 3.0 ppm). The validated L OQ s w ere 0.01 0 ppm for acequinocyl and 0.025 ppm for acequinocyl - OH for tomato fruit, paste and puree, and peppers ; 0.02 0 ppm each for acequinocyl and acequinocyl - OH in edible - podded beans ; and 0.10 ppm for acequinocyl in hop dried cones (acceptable recoveries were not obtained for acequinocyl - OH from dried hop cones at the target LOQ of 0.10 ppm) . An interfe ring peak in the HPLC/MS/MS chromatograms was problematic for quantitation of acequinocyl - OH residues near the LLMV ; therefore gas chromatography (GC)/mass - selective detector (MSD) , analy sis was used to confirm that the OH metabolite was present at <0.10 p pm in untreated hop samples. Treated samples were also re - extracted for GC/MSD analy sis. GC/MSD analy ses using 2 or 4 confirmatory ions were inconclusive because ion ratios found in treated samples did not match those of standards. But significant peaks were observed for each ion monitored at the corresponding retention time for acequinocyl - OH, suggesting acequinocyl OH may be present along with smaller co - eluting matrix interferences with similar ions, thus affecting ion ratios. Therefore, the HPLC/MS/MS results for acequinocyl - OH were considered likely to be valid. Conclusions : Method s #Meth - 135, Revision #3 , #Meth - 133, Revision #4, and #Meth - 139, Revision #3 are suitable enforcement methods for the subject crop and livestock matrices (Memo, S. L evy , 25 - AUG - 2010; DP#380302) . Samples of crop commodities that were collected from the magnitude of the residue studies were analy zed for residues of acequinocyl and acequinocyl - OH using the LC/MS/MS enforcement methods, with minor modifications. The methods were generally

adequate for data - collection based on acceptable method validation and concurrent method recoveries from fortified tomato fruit, paste and puree, peppers, snap beans and hops ; however, the validation data indicate that the data collection/ e nforcement method may not be suitable for quantitation of acequinocyl - OH residues from dried hop cones . 860.1360 Multiresidue Methods Acceptable MRM method testing data were submitted for acequinocyl and acequinocyl - OH, and these data were forwarded to the U.S. FDA for further evaluation ( Memo, S. L evy , 18 - FEB 2004; DP# : 298917 ). Acequinocyl was adequately recovered from fortified apples using Method 302, E1 + C1 with GC/ electron - capture detector ( ECD ) , but was not recovered using Method 303 or 304 due t o poor recoveries from the Florisil cleanup. Acequinocyl - OH was completely recovered from fortified apples using Method 402, E1 or E2 + C1 with GC/ECD, but was not recovered using Methods 302, 303, or 304. 860.1380 Storage Stability Samples from the fie ld trial and processing studies were stored frozen from harvest to analysis. To support the sample storage conditions and durations , concurrent storage stability was conducted in conjunction with the analy sis of the field trial and processing samples. UntreatedAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 10 of 29 samples of tomato fruit, puree, and paste, peppers, snap beans , and dried hop cone s were fortified with acequinocyl or acequinocyl - OH at 0.10 ppm and stored frozen. Residues of acequinocyl and acequinocyl - OH were relatively stable in/on t omato f ruits stored frozen for up to 337 day s , snap beans stored frozen for up to 453 day s , and hop dried cones stored frozen for up to 411 day s. Although the storage intervals of the fortified samples did not encompass the longest hop and snap bean sample stora ge duration, only samples from one trial for each of the crops were stored past the demonstrated storage interval. Residues of acequinocyl were relatively stable in tomato paste and puree stored frozen for up to 85 and 146 day s, respectively , and in bell pepper stored frozen for up to 407 day s. However, for these crops residues of acequinocyl - OH appear not to be stable. Acequinocyl - OH residues in puree and paste declined to 29% and 34% following frozen storage for 119 and 146 day s, respectively , and resi dues in bell pepper declined to a 51% recovery following frozen storage for up to 408 day s . Because no 0 - day data were provided with the concurrent storage stability stud ies , the rate of decline of acequinocyl - OH residues in pepper, and tomato puree and p aste can not be determined. The storage duration s and conditions of samples from the crop field trial and processing studie s submitted to support this petition are presented in Table 4 . Table 4 . Summary of Storage Conditions and Duration s of Sam ples f rom C rop F ield T rial and P rocessing Studies. Matrix Storage

Tem perature (°C) Actual Storage

Duration Interval of Demonstrated Storage Stability Tom ato < - 20 84 - 285 days ( ≤9.4 months) Acequinocyl and acequinocyl - OH are relatively stable in/on

fortified tomato stored frozen for up to 11 months. Tom ato, puree 90 days (3.0 months) Acequinocyl is relatively stable in/on fortified puree stored

frozen for up to 3 months; acequinocyl - OH w as not stable in

puree stored frozen for up to 4 months. Tom ato, paste 156 - 157 days (5.2 months) Acequinocyl is relatively stable in/on fortified paste stored

frozen for up to 5 months; acequinocyl - OH w as not stable in

paste stored frozen for up to 5 months. Pepper 329 - 402 days ( ≤13.2 months) Acequinocyl is relatively stable in/on fortified pepper stored

frozen for up to 13 months; acequinocyl - OH w as not stable in pepper stored frozen for up to 13 months. Bean, snap 326 - 480 days ( ≤15.8 months) Acequinocyl and acequinocyl - OH ar e relatively stable in/on

fortified snap bean stored frozen for up to ~15 months. Hop, dried cones 440 - 449 days ( ≤14.8 months) Acequinocyl and acequinocyl - OH are relatively stable in/on

fortified dried hop cones stored frozen for up to ~14 months. Conc lusions : The submitted concurrent storage stability data for tomato, snap bean , and hops is adequate to support the storage intervals and conditions incurred by the field trial studies. In addition, the concurrent storage stability data for the parent ac equinocyl is adequate to support the sample storage intervals and conditions for the pepper field trials and tomato processing studies. Itis noted that zero - day data were not provided . IR - 4 is reminded that storage stability studies should alway s includ e a zero - day sampling interval to establish the residue levels present at the time samples are placed into storage [see OPPTS 860.1380(d)(6)(i)].Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 11 of 29 T he concurrent storage stability data indicate problems with the stability of acequinocyl - OH in peppers and processed tomato paste and puree. Because zero - day samples were not analy zed, determination of residue level s present at the time samples were placed in frozen storage could not be made. In addition, an insufficient number of time points were analy zed i n order to establish how much of the residue (acequinocyl - OH) was lost at various time points. However, because residues of acequinocyl - OH in the pepper field trial were <10% of the parent value or were <LOQ , correction for 51% decline would not affect the results. Furthermore, in the tomato processing study , b ecause there were quantifiable residues of the parent in the RAC and residues of acequinocyl - OH in the RAC were nonquantifiable, HED believes that any concentration of acequinocyl - OH residues woul d not significantly increase the total residue level . T herefore, HED is not requesting additional storage stability data at this time . 860.1500 Crop Field Trials DER References: 47819401.de1 (tomato)

47819402.der (pepper) 47819403.der ( snap bean) 47819404.der (hop ) IR - 4 submitted field trial data in support of the proposed uses on fruiting vegetables, hops, and edible - podded beans. The results of the field trials are summarized in Table 5. The submitted data are discussed below. Table 5 . Sum ma ry of Residue Data fromCrop Field Trials with Acequinocyl . Crop matrix Total Applic.

Rate (lb ai/A) PHI

(days) Total Acequinocyl and Acequinocyl - OH Residues (ppm)

n Min. Max. HAFT 1 Median Mean Std. Dev. F RUITING V EGETABLES (proposed use = 0.6 lb ai/A total application rate , 7 - day PHI) Tom ato 0.600 - 0.642 1 30 <0.05 <0.16 0.16 0.075 0.085 0.03 Tom ato (greenhouse) 0.622 - 0.630 1 6 <0.10 <0.20 0.19 0.13 0.14 0.04 Pepper, non bell 0.602 - 0.635 1 10 <0.035 0.338 0.307 0.108 0.160 0.117 Pepper, bell 0. 601 - 0.636 1 16 <0.035 0.607 0.515 0.074 0.125 0.158 Pepper, bell (greenhouse) 0.606 - 0.617 1 4 <0.131 0.292 0.214 0.161 0.186 0.075

EDIBLE - PODDED BEANS (proposed use = 0.6 lb ai/A total application rate, 7 - day PHI) Snap bean, pod with seeds 0.574 - 0.646 6 - 8 20 <0.04 0.16 0.12 0.06 0.07 0.03

HOPS (proposed use = 0.6 lb ai/A total application rate, 7 - day PHI) Hop, dried cones 2 0.588 - 0.641 7 6 1.32 2.83 2.74 2.09 2.11 0.577 1 HAFT = h ighest - average field trial result. 2 Determined using acequin o cyl - OH re sidues corrected for low recoveries.Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 12 of 29 Fruiting Vegetable, Group 8 Tomato Fifteen tomato field trials were conducted in North American Free Trade Agreement (NAFTA) Growing Zones 1 (NY, 1 trial), 2 (GA; 1 trial), 3 (FL; 2 trials), 5 (WI ; 1 trial) and 10 ( CA, NM; 10 trials), and three greenhouse trials were conducted in NAFTA Growing Zones 2 (NJ; 1 trial), 6 (TX; 1 trial) and 9 (CO; 1 trial) during the 2003 growing season. Each trial consisted of one untreated and one treated plot. At each site, a 1.25 lb /gal SC formulation of acequinocyl was applied to tomatoes as two broadcast or directed foliar applications during fruit development at rates of 0.291 - 0.321 lb ai/A/application, with a 19 - to 24 - day RTI , for a total seasonal rate of 0.600 - 0.642 lb ai/A (~1 x the maximum proposed seasonal rate) . Applications were made using ground equipment in volumes of 25 - 78 gal/A, without a spray adjuvant. Single control and duplicate treated samples of mature tomatoes were harvested from each site one at a 1 - day PHI . A dditional samples were taken from one field trial location and one greenhouse location at 0 - , 3 - , and 7 - day PHI s to assess residue decline . Residues of acequinocyl - OH were nonquantifiable (<0.025 ppm) in/on all tomatoes (field and greenhouse samples ) harv ested one day after foliar treatments with the SC formulation for a total rate of 0.600 - 0.642 lb ai/A. Residues of parent acequinocyl were 0.02 - 0.13 ppm in/on tomatoes grown in the field, and 0.07 - 0.17 ppm in/on tomatoes grown in greenhouses; residues of acequinocyl were slightly higher in greenhouse - grown tomatoes than in those grown in the field. Total residues of acequinocyl and acequinocyl - OH were <0.05 - <0.20 ppm in/on all tomatoes. Inthe residue decline studies, residues of acequinocy l declined s teadily

from the 0 - day

to the 7 - day sampling interval in/on tomatoes grown in the field . Residues of acequinocyl in tomatoes grown in a greenhouse increased initially , and then decreased steadily from the 1 - day

to 7 - day sampling interval. Pepper Eight bell pepper field trials were conducted in NAFTA Growing Zones 2 (GA, MD; 2 trials), 3 (FL; 2 trial s ), 5 (WI ; 1 trial), 6 (TX; 1 trial), and 10 (CA, NM; 2 trials); five non - bell pepper field trials were conducted in NAFTA Growing Zones (NJ; 1 trial), 3 (FL ; 1 trial), 5 (MI ; 1 trial), 6 (TX; 1 trial) , and 10 (NM; 1 trial); and two bell pepper greenhouse trials were conducted in NAFTA Growing Zones 6 (TX) and 9 (CO) during the 2003 growing season. Each trial consisted of one untreated and one treated plot. At each site, a 1.25 lb/gal SC formulation of acequinocyl was applied as two broadcast or directed foliar applications during fruit development at 0.297 - 0.327 lb ai/A/application, with a 15 - to 22 - day RTI , for a total rate of 0.60 1 - 0.636 lb ai/A (~1x the m aximum proposed seasonal rate) . Applications were made using ground equipment in spray

volumes of 21 - 56 gal/A, without a spray adjuvant. Single control and duplicate treated samples of mature peppers were harvested from each site one day after the last a pplication. Additional samples were taken from one non - bell and one bell field trial at 0 - , 3 - , and 7 - day PHI s to assess residue decline. Residues of acequinocyl were nonquantifiable (<0.010 ppm) to 0.564 ppm in bell peppers and <0.010 - 0.295 ppm in non - b ell peppers harvested one day after foliar treatments with the SCAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 13 of 29 formulation for a total rate of 0.60 1 - 0. 636 lb ai/A; average residues of acequinocyl were slightly higher in greenhouse - grown peppers than in those grown in the field . Residues of acequinoc yl OH were nonquantifiable (<0.025 ppm) to 0.043 ppm in/on bell peppers and <0.025 - 0.043 ppm in/on non - bell peppers. Total residues of acequinocyl and acequinocyl - OH were <0.035 - 0.607 ppm in/on bell peppers and <0.035 - 0.338 ppm in/on non - bell peppers . In the residue decline studies, residues of acequinocyl in bell and non - bell peppers grown in the field declined steadily

from the 0 - day

to the 7 - day

sampling interval. Conclusions : The submitted residue data for tomato and peppers are adequate with resp ect to the number and locations of field trials for the representative crops of the fruiting vegetable group 8. The data reflect the proposed single and maximum application rate s , but the proposed PHIis 7 day s for fruiting vegetables and the field trials reflect a 1 - day PHI . Residue decline trials for tomato and pepper demonstrate that residues generally decline with later sampling intervals ; therefore , residues at the later 7 - day PHIwould likely

be lower than those observed in the field trials. T he pe titioner may reduce the proposed PHI from 7 day s to 1 day

for fruiting vegetables, based on the field trial data. The submitted tomato and pepper field trial data reflect a pplications made without the us e of a spray adjuvant . A revised Section B should b e submitted incorporating an adjuvant– use re striction. B ecause residues of acequinocyl - OH in the pepper field trial were generally <10% of the parent value and quantifiable residues of acequinocyl - OH were not found in most pepper samples, correction for d ecline would not affect the results. Furthermore, in the tomato processing study , because there were quantifiable residues of the parent in the RAC and residues of acequinocyl OH in the RAC were nonquantifiable, HED believes that any concentration of aceq

uinocyl - OH residues would be covered by the parent. Therefore, HED is not requesting additional storage stability data at this time. The available residue data for total acequinocyl and acequinocyl - OH residues in/on tomato (field - and greenhouse - grown) , bell peppers (field - and greenhouse - grown), and non - bell peppers were separately

entered into the Agency ’s tolerance spreadsheet as specified by the Guidance for Setting Tolerances Based on Field Trial Data SOP (August 2009 version) to determine the appr opriate tolerance levels; see Appendix I . Based on the spreadsheet, the recommended tolerances are 0.25 ppm for tomato, 0.60 ppm for bell pepper, and 0.70 ppm for non - bell pepper. Because the minimum and maximum recommended tolerances differ by less than 5x, a crop group tolerance is appropriate for the vegetable, fruiting, crop group 8. The recommended value is 0.70 ppm, the maximum of the recommended individual tolerances. The tomato and pepper field trial data reflect the proposed use on okra (0.6 lb ai/A maximum application rate with a 1 - day PHI ), and may

be translated to okra. Okra has been recommended to be added as a member of the fruiting vegetable group 8; however, until okra has been officially added to the crop group, a separate tolerance is required for okra at the same tolerance level (0.70 ppm) as for fruiting vegetables. Bean, Edible P odded Ten snap bean field trials were conducted in NAFTA Growing Zones 1 (NY; 1 trial), 2 (GA, NJ;Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 14 of 29 2 trials), 3 (FL ; 1 trial), 5 (OH, WI ; 4 trials), 10 (C A; 1 trial) , and 11 (ID; 1 trial) during the 2004 growing season. Each trial consisted of one untreated and one treated plot. At each site, a 1.25 lb/gal SC formulation of acequinocyl was applied to snap beans as two broadcast or directed foliar applicat ions during vegetative development at rates of 0.263 - 0.332 lb ai/A/application, with a 13 - to 17 - day RTI , for a total rate of 0.574 - 0.646 ai/A (~1x the maximum proposed seasonal rate) . Applications were made using ground equipment in spray volumes of 29 - 5 1 gal/A, without a spray

adjuvant. Single control and duplicate treated samples of mature snap beans were harvested from each site at 6 - to 8 - day PHI s. Additional samples were collected at two trials 3 - or 4 - , and 10 - or 11 - day PHI s to assess residue dec line. Residues of acequinocyl were nonquantifiable (<0.02 ppm) to 0.14 ppm, and residues of acequinocyl - OH were at or below the LOQ ( ≤0.02 ppm) in/on snap beans harvested 6 - 8 day s after foliar treatments with the SC formulation for a total rate of 0.574 - 0 .646 lb ai/A. Total residues of acequinocyl and acequinocyl - OH were <0.04 - 0.16 ppm in/on snap beans. Inone residue decline study , residues of acequinocyl declined steadily from the 4 - day

to the 11 - day sampling interval. In the other decline study resid ues increased slightly , but decreased at the 10 - day sampling interval. Conclusions : The submitted residue data for snap beans are adequate with respect to the number and locations of field trials for edible - podded beans. The data reflect the proposed si ngle and maximum application rates, and minimum PHI . The submitted snap bean field trial data reflect a pplications made without the us e of a spray adjuvant . A revised Section B should be submitted incorporating an adjuvant– use re striction. The residue d ata for total acequinocyl and acequinocyl - OH residues in/on snap beans were entered into the Agency ’s tolerance spreadsheet as specified by the Guidance for Setting Tolerances Based on Field Trial Data SOP (August 2009 version) to determine the appropriate tolerance level; see Appendix I . Based on the spreadsheet, the recommended tolerance is 0.25 ppm for edible - podded beans. Hops Three hop field trials were conducted in NAFTA Growing Zone 11 (ID, OR, WA) dur ing the 2005 growing season. Each trial consi sted of one untreated and one treated plot. At each site, a 1.25 lb/gal SC formulation of acequinocyl was applied to hops as two directed foliar applications during cone development at rates of 0.288 - 0.330 lb ai/A/application, with a 19 - to 28 day RTI , fo r a total rate of 0.588 - 0.641 lb ai/A (~1x the maximum proposed seasonal rate) . Applications were made using ground equipment in spray volumes of 86 - 196 gal/A, without a spray adjuvant. Single control and duplicate treated samples of mature hops were har vested from each site at a 7 - day PHI . Because method validation and concurrent recoveries were consistently low (overall average recovery of 52.5%) for acequinocyl - OH from dried hop cones, residues of acequinocyl - OH were corrected. Residues of acequinocyl and acequinocyl - OH (corrected) were 1.09 - 2.53 and 0.229 - 1.08 ppm, respectively , in/on hop dried cones harvested 7 day s following foliar applications of the SC formulation for a total rate of 0.588 - 0.641 lb ai/A. Total residues of acequinocyl andAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 15 of 29 acequin ocyl - OH (corrected) were 1.32 - 2.83 ppm in/on dried hop cones. A residue decline study

was not conducted, and is not required as hops are con sidered a minor crop ( ≤3 trials required). Conclusions : The submitted residue data for hops are adequate with respect to the number and locations of field trials. The data reflect the proposed single and maximum application rates, and minimum PHI . The submitted hop field trial data reflect a pplications made without the us e of a spray adjuvant . A revised Section B should be submitted incorporating an adjuvant– use re striction. The residue data for total acequinocyl and corrected acequinocyl - OH residues in/on dried hop cones were entered into the Agency ’s tolerance spreadsheet as specified by the Guidance for Setting Tolerances Based on Field Trial Data SOP (August 2009 version) to determine the appropriate tolerance level; see Appendix I . Based on the s preadsheet, the recommended tolerance is 4.0 ppm for hop, dried cones. 860.1520 Processed Food and Feed DER Reference: 47819401.de2 (tomato) Tomato Ina field trial conducted in NAFTA Growing Zone 10 (CA) during the 2003 growing season, a 1.25 lb/gal S C formulation of acequinocyl was applied to maturing tomatoes as two broadcast foliar applications at 0.606 - 0.621 lb ai/A/application, with a 21 - day RTI , for a total rate of 1.227 lb ai/A (~2x the maximum proposed seasonal rate for tomato) . Applications w ere made using ground equipment in spray volumes of 25 - 26 gal/A, without a spray adjuvant. Mature tomatoes were harvested at a 1 - day PHI and processed into puree and paste using simulated commercial procedures. Samples were analy

zed for residues of acequ inocyl and its metabolite acequinocyl - OH using HP LC /MS/MS, Morse Meth - 135 with minor modifications. Meth - 135 is an approved enforcement method for crop commodities. The method was adequate for data collection based on acceptable method validation and con current method recovery data; however, it is noted that low method verification recoveries were obtained for the OH metabolite in tomato paste and puree at higher fortification levels (i.e., 1.0 ppm). The validated L OQ was 0.01 ppm for acequinocyl and 0.0 25 ppm for acequinocyl - OH for all tomato matrices. Sample storage conditions and durations are reported in Table 4. The storage conditions and durations are supported by concurrent storage stability data conducted in conjunction with the analy sis of the processing study samples. Based on the results of the concurrent storage stability study , residues of acequinocyl - OH in puree and paste declined to 29% and 34% after 119 and 146 day s, respectively , of frozen storage; however, because no 0 - day data were provided with the concurrent storage stability study , the rate of decline in puree and paste can not be determined. Residues of parent acequinocyl were 0.20 ppm (field sample) or 0.14 ppm (sample forAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 16 of 29 processing) in/on tomato (RAC) harvested 1 day follow ing foliar applications of the SC formulation at a total rate of 1.227 lb ai/A. Following processing, acequinocy l residues were 0.04 ppm in/on tomato puree and 0.05 ppm in/on tomato paste. Based on the study results, residues of acequinocyl do not appear to concentrate in puree (0.3x), and paste (0.4x). Residues of acequinocyl - OH were nonquantifiable (<0.025 ppm) in both the respective RAC and processed samples, therefore, processing factors can not be calculated. A summary

of the processing factors f or tomato matrices is presented in Table 6. The observed processing factors are below the maximum theoretical concentration factors, based on loss of water, of 1.4x for puree and 5.5x for paste (OPPTS 860.1520, Table 2). Table 6 . S ummary of Processing Factors for Acequinocyl .

RAC Processed Commodity Processing Factor Tom ato Fruit Puree 0. 3 x Paste 0.4 x Conclusions : The tomato processing study is adequate to support the proposed use pattern. Residues of acequinocyl - OH were fo und to degrade significantly during storage. However, b ecause there were quantifiable residues of the parent in the RAC and residues of acequinocyl OH in the RAC were nonquantifiable, HED believes that any concentration of acequinocyl - OH residues would be covered by the parent. The available data indicate that residues of acequinocy l and acequinocyl - OH are not likely to concentrate with processing of tomato fruit to paste and puree ; therefore, t olerances are not required for these commodities. 860.1650 Submittal of Analytical Reference Standards The available analy

tical standards for acequinocyl and acequinocyl - OH at the EPA National Pesticide Standards Repository (personal communication with Dallas Wright, ACB, 30 - APR 20 10 ) expir ed on 19 - APR - 2010 and 20 - APR - 2010 , respectively . This is a deficiency. T he petitioner should either recertify the lot in the repository

and send in an updated certificate of analy sis (COA), or submit new standards (different lot #) if the previous lots w ill not be recertified. I f new COAs are being submitted, they should be faxed to the repository at 410 - 305 - 2999. If new standards are being submitted, they should be sent to the Analy tical Chemistry

L ab, which is located at Fort Meade, to the attention o f Theresa Cole at the following address ( n ote that the mail will be returned if the extended zip code is not used) : USEPA National Pesticide Standards Repository /Analy tical Chemistry

Branch/OPP 701 Mapes Road Fort George G. Meade, MD 20755 - 5350 860.1850/1900 Confined and Field Accumulation in Rotational Crops The proposed uses under this petition includ e fruiting vegetables and edible - podded beans which are ty pically rotated crops. An acceptable confined rotational crop study was previously submitted ( Memo, S. L evy , 25 - JUN - 2008; DP#s 351336 & 353313) in support of uses on strawberries . The study

results (47332501.der) showed the extent and nature of the residueAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 17 of 29 uptake by crops (lettuce, turnip and wheat) planted 30 - , 120 - an d 365 - day s post - application in soil treated with 14 C - acequinocyl at 0.60 lb ai/A (1x maximum registered/proposed seasonal application rate to rotated crops ) . Residues in a majority of the rotational crop samples were either low or non - quantifiable (<0.01 ppm 14 C - acequinocyl equivalents). The only significant levels of TRR occurred at the 30 - day PBIin immature lettuce and turnip tops. Parent chemical along with its hydroxylated metabolite plus a variety of low but detectable metabolites, including metabo lite M1, could be found only in immature crops from the 30 - day PBI . Plant residues from other maturity

stages and replant intervals were largely non - extractable with organic solvent. A majority of the non - extractable residues could be released by enzy me, acid and base hydroly sis. A vast array

of products were detected by chromatographic assay

in hydroly

zed samples, though the nature of these residues could not be further delineated due to their low level coupled with lack of chromatographic resolution fo llowing analy sis. The available data support a 30 - day PBIfor all non - labeled crops. A revised Section B should be submitted incorporating the rotational crop restriction. 860.1550 Proposed Tolerances HED has determined that the residues of concern in both plant and ruminant commodities includes acequinocyl and acequinocyl - OH, and tolerances are currently established for the combined residues of acequinocyl and acequinocyl - OH, expressed as parent, in/on plant and livestock commodities [40 CFR §180.599(a)]. T he t olerance expression proposed by IR - 4 is appropriate . There are currently

no established Codex or Mexican maximum residue limits ( MRL s ) for acequinocyl ; Canadian MRL s include the parent and metabolite, but none are established for the crops propo sed for use under this petition. T he field trial data for tomato and pepper are considered adequate to support a crop group tolerance. The tomato, bell pepper and non - bell pepper datasets were separately entered into the tolerance spreadsheet (rev. Augus t 2009) in the Agency’s Guidance for Setting Pesticide Tolerances Based on Field Trial Data ; s ee Appendix I . The proposed tolerance (0.70 ppm) for the fruiting vegetable group 8 is appropriate. No tolerances are required for tomato paste or puree. Okra has been recommended to be added as a member of the fruiting vegetable group 8; however, until okra has been officially added to the crop group, a separate tolerance is required. The tomato and pepper field trial data will support the proposed tolerance ( 0.70 ppm) for okra. The snap bean and hop dried cone data are adequate, and were entered into the tolerance spreadsheet to determine the appropriate tolerances; see Appendix I . The proposed tolerance (0.25 ppm) for edible - podded beans is appropriate; ho wever, the tolerance proposed for hop dried cones is too low and should be increased to 0.40 ppm. The proposed and recommended tolerances are listed in Table 7.Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 18 of 29 Table 7 . Tolerance Sum ma ry for Acequinocyl . Commodity Proposed Tolerance (ppm) HED - Recommen ded

Tolerance (ppm) Comments ;

C orrect Commodity D efinition Vegetable, fruiting, group 8 0.70 0.70 Okra 0.70 0.70 Bean, edible podded 0.25 0.25 Hop, dried cones 3.5 4.0 References DP#: 297872 Subject: Acequinocyl . Report of the Metabolism Asse ssment Review Committee

(MARC). Meeting Date: 17 - DEC - 2003. From: S. L evy

/P. Terse To: Y. Donovan Dated: 07 - JAN - 2004 MRID: None DP#: 298917 From: S. L evy To: M. Wirtz Dated: 18 - FEB - 2004 MRID : 45651603 DP#s: 284757, 290204, 286425 Subject: Acequinocyl. Registration for Use on Pome Fruits, Citrus, Almonds, Pistachios,

and Strawberry . Summary of Analy tical Chemistry

and Residue Data. From: S. L evy To: D. Kenny

/M. L aws Dated: 10 - MAR - 20 04 MRID(s): 46602001 - 46602003 DP#: 321753 Subject: Acequi nocyl. Response to Submission of MRID#s 46602001, 46602002 and

46602003 by

Morse L aboratories Addressing a Need for Confirmation of Acequinocyl in Fruits, Almonds and L ivestock Tissues. From: D. Soderberg and S. Levy To: T. White Dated: 23 - MAY - 20 06 MRID(s): 46602001 - 46602003 DP# s : 330439, 337218, 337472 Subject: Acequinocyl. Petitions for Uses on Tree Nuts and Grapes . Summary of Analy tical Chemistry

and Residue Data. From: S. L evy To: M. Mautz Dated: 05 - SEP - 20 07Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 19 of 29 MRID(s): 46 776602, 47032402, & 469 52301 DP#s: 351336 & 353313 Subject: Acequinocyl; Review of Petitioner’s Amendment Dated 28 - JUN - 2008 Submitted

in Response to the Health Effects Division (HED) Memoranda, DP# 284757 (dated 10 - MAR - 2004). From: S. L evy To: J . Stone/J. Miller Dated: 25 - J UN - 20 08 MRID: 47332501 DP#s: 380302 Subject: Acequinocyl ; Response to the Health Effects Division (HED) Review of 25 - JUN 2008 (M emoranda, DP# s D 351336 & D353313 ) . From: S. L evy To: J. Hebert Dated: 25 - AUG - 2010 MRID(s): 48016603 - 48016605 Attachments: International Residue L imit Status (IRLS) sheet . Appendix I - Tolerance Assessment Calculations . RDI: G. Kramer ( 02 - MAY - 2010); RAB1 Chemists ( 02 - MAY - 2010) S. Levy:S - 10953:PY1:(703)305 - 0783:7509P Template Version September 2005Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 20 of 29 

## INTERNATIONAL RESIDUE LIMIT STATUS Chemical Name: 2 - (acetyloxy) - 3 - dodecyl - 1,4 - naphthalenedione Common Name: Acequinocyl X Proposed tolerance Reevaluated tolerance Other Date: 0 1 - MAR - 2010 

### Codex Status (Maximum Residue L imits) 

### U. S. Tolerances X N o Codex proposal step 6 or above No Codex proposal step 6 or above for the crops requested Petition Number: 9E7598 DP Number : 369100 Other Identifier: Decision Number: 417967 Residue definition (step 8/CXL): N/A Reviewer/Branch: S. Levy/RAB1 Resi due definition: Combined residues of a cequinocyl and a cequinocyl - OH, expressed as parent Crop (s) MRL (mg/kg) Crop(s) Tolerance (ppm) Vegetable, fruiting, Group 8 0.70 Okra 0.70 Bean, edible podded 0.25 Hop, dried cones 3.5 

### Limits for Canad a Limits for Mexico 1 ⁭No Limits √ No Limits for the crops requested √ No Limits ⁭ No Limits for the crops requested Residue definition: 2 - (acetyloxy) - 3 - dodecyl - 1,4 - naphthalenedione, including the metabolite 2 - dodecyl 3 - hydroxy - 1,4 - naphthalenedione. Residue definition: N/A Crop(s) MRL (mg/kg) Crop(s) MRL (mg/kg) Notes/Special Instructions: 1 Mexico adopts Codex MRLs or US tolerances for its export purposes. S. Funk, 01 - MAR - 2010Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 21 of 29 Appendix I . Tolerance Assessment Calculations. For each of the crops listed below, the Guidance for Setting Pesticide Tolerances Based on Field Trial Data ( SOP ) , along with the tolerance spreadsheet (August 2009 version) , was used for calculating recommended tolerances. As specified in the SOP, the minimum of the 95% upper confidence l imit (UCL ) on the 95 th percentile and the point estimate of the 99 th percentile was selected as the tolerance value in cases when the dataset was large (greater than 15 samples) and reasonably

lognormal. For datasets that were small ( ≤15 samples) and reas onably lognormal, the upper bound estimate of the 95th percentile based on the median residue value was compared to the minimum of the 95% UCL on the 95th percentile and the point estimate of the 99th percentile, and the minimum value was selected as the t olerance value. For datasets that were not lognormal, the upper bound on the 89 th percentile was selected as the tolerance value (distribution - free method). The rounding procedures specified in the SOP were also used. Fruiting Vegetables The dataset us ed to establish a tolerance for acequinocyl on the f ruiting v egetable, crop group 8 consisted of field trial data for tomato (field and greenhouse) , bell pepper (field and greenhouse) and non - bell pepper (the representative crops of the c rop group ), repres enting total application rates of 0.6 00 - 0.642 lb ai/A ( 2 applications at ~ 0.3 lb ai/A/application) , with a 1 - day PHI . The fi eld trial application rates are within 25% of the maximum label application rate . The minimum label PHI is 7 day s for fruiting veg etables; however, a full set of field trial samples were collected for tomatoes, bell peppers and non - bell peppers at a 1 - day PHI . The residue values that were entered into the tolerance spread sheet are provided in Table I - 1 . All field trial sample resul ts were above the combined LOQ for acequinocyl and acequinocyl - OH ( LOQ = 0.0 35 ppm ). The non - bell pepper dataset was small ( 10 samples). The tomato and bell pepper datasets were not small ( 3 6 and 20 samples, respectively ). For tomato , bell pepper, and n on - bell pepper , v isual inspection of the lognormal probability plot s (Figure s I - 1 , I - 3, and I - 5 ) and the results from the approximate Shapiro - Francia test statistic (Figure s I - 2 , I - 4, and I - 6 ) indicate d that the datasets were reason ably lognormal . Using the tolerance spreadsheet, the recommended tolerances are 0.2 5 ppm for tomato , 0.60 ppm for bell pepper , and 0.70 ppm for non - bell pepper . Because the minimum and maximum recommended tolerances differ by less than 5x, a crop group tolerance is appropriat e for the vegetable, fruiting, group 8 . The recommended value is 0.70 ppm, the maximum of the recommended individual tolerances.Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 22 of 29 Table I - 1. Residue D ata U sed to C alculate T olerance for Acequinocyl Residues on Fruiting Vegetables . Regulator: EPA EPA EPA Chemical: Acequinocyl Acequinocyl Acequinocyl Crop: Tomato Bell Pepper Non - Bell Pepper PHI: 1 day 1 day 1 day App. Rate: 0.600 - 0.642 lb ai/A 0.60 1 - 0.63 6 lb ai/A 0.60 2 - 0.63 5 lb ai/A Submitter: IR - 4 IR - 4 IR - 4 MRID Citation: MRID 47819401 MRID 47819402 MRID 47819402 Com bined Residues of Acequinocyl and Acequin o cyl - OH (ppm) 0.075 0.055 0.035 0.105 0.089 0.039 0.065 0.036 0.068 0.135 0.035 0.079 0.045 0.09 0.102 0.075 0.121 0.114 0.115 0.074 0.259 0.115 0.075 0.275 0.125 0.073 0.292 0.095 0.071 0.338 0.135 0.607 0.145 0.422 0.075 0.047 0.065 0.043 0.155 0.109 0.155 0.058 0.065 0.292 0.065 0.136 0.055 0.186 0.045 0.131 0.075 0.055 0.085 0.065 0.095 0.085 0.075 0.065 0.055 0.105 0.185 0.195 0.125 0.125 0.095 0.105Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 23 of 29 Figure I - 1. Lognorm al probability plot of Acequinocyl field trial data for Tom ato. Lognormal Probability Plot

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

0.5000

0.2500

0.1250

0.0625

0.0313 y = 0.3937x - 2.4044 R 2 = 0.9784

PercentilesConcentrations EPA Acequinocyl Tomato 1 day 0.600-0.642 lb ai/A IR-4

Figure I - 2. Tolerance spreadsheet sum ma ry of Acequinocyl field trial data for Tom ato . Regulator: EPA Chemical: Acequinocyl Crop: Tomato PHI: 1 day App. Rate: 0.600-0.642 lb ai/A Submitter: IR-4

n: 36 min: 0.05 max: 0.20 median: 0.09 average: 0.10 95th Percentile 99th Percentile 99.9th Percentile 0.20 0.20 0.25 (0.20) (0.25) (--) 0.20 0.25 0.35 (0.25) (0.30) (--) 0.25 0.25 0.45 0.9784 p-value > 0.05 : Do not reject lognormality assumption Approximate Shapiro-Francia Normality Test EU Method I Normal

UCLMedian95th 95/99 Rule EU Method II Distribution-Free Mean+3SDAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 24 of 29 Figur e I - 3 . Lognorm al probability plot of Acequinocyl field trial data for Bell Pepper Lognormal Probability Plot

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

0.5000

0.2500

0.1250

0.0625

0.0313 y = 0.7812x - 2.3271 R 2 = 0.9315

PercentilesConcentrations EPA Acequinocyl Bell Pepper 1 day 0.601-0.636 lb ai/A IR-4

Figure I - 4. Tolerance spreadsheet sum ma ry of Acequinocyl field trial data for Bell Pepper . Regulator: EPA Chemical: Acequinocyl Crop: Bell Pepper PHI: 1 day App. Rate: 0.601-0.636 lb ai/A Submitter: IR-4

n: 20 min: 0.04 max: 0.61 median: 0.08 average: 0.14 95th Percentile 99th Percentile 99.9th Percentile 0.40 0.50 0.60 (0.50) (0.70) (--) 0.40 0.60 1.1 (0.70) (1.3) (--) 0.30 0.60 0.45 0.9315 p-value > 0.05 : Do not reject lognormality assumption Approximate Shapiro-Francia Normality Test EU Method I Normal

UCLMedian95th 95/99 Rule EU Method II Distribution-Free Mean+3SDAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 25 of 29 Figure I - 5 . Lognorm al probability plot of Acequinocyl field trial data f or Non - Bell Pepper Lognormal Probability Plot

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

0.5000

0.2500

0.1250

0.0625

0.0313 y = 0.8667x - 2.1235 R 2 = 0.9267

PercentilesConcentrations EPA Acequinocyl Non-Bell Pepper 1 day 0.602-0.635 lb ai/A IR-4

Figure I - 6. Tolerance spreadsheet sum ma ry of Acequinocyl field trial data for Non - Bell Pepper . Regulator: EPA Chemical: Acequinocyl Crop: Non-Bell Pepper PHI: 1 day App. Rate: 0.602-0.635 lb ai/A Submitter: IR-4

n: 10 min: 0.04 max: 0.34 median: 0.11 average: 0.16 95th Percentile 99th Percentile 99.9th Percentile 0.40 0.45 0.60 (0.60) (0.70) (--) 0.50 0.90 1.7 (1.5) (3.5) (--) 0.60 0.60 0.70 0.9267 p-value > 0.05 : Do not reject lognormality assumption Approximate Shapiro-Francia Normality Test EU Method I Normal

UCLMedian95th 95/99 Rule EU Method II Distribution-Free Mean+3SDAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 26 of 29 Edible - Podded Beans The dataset used to establish a tolerance for acequinocy l on edible - podded beans consisted of field trial data rep resenting total application rates of 0. 574 - 0. 6 06 lb ai/A (2 applications at ~ 0.3 lb ai/A/application) , with a 7 - day PHI . The field trial application rates and PHI s are within 25% of the maximum label application rate and minimum label PHI , respectively . The residue values that were entered into the tolerance spreadsheet are provided in Table I - 2. Because 6 of 20 field trial sample results were below the combined LOQ for acequinocyl and acequinocyl - OH ( LOQ = 0.0 4 ppm ) , maximum - likelihood estimation (ML E) procedures were needed to impute censored values. T he dataset was not small ( 20 samples). Visual inspection of the lognormal probability plot (Figure I - 7 ) and the results from the approximate Shapiro - Francia test statistic (Figure I - 8 ) indicate d that the dataset was reason ably lognormal . Using the tolerance spreadsheet, the recommended tolerance is 0.2 5 ppm for edible - podded beans . Table I - 2. Residue D ata U sed to C alculate T olerance for Acequinocyl Residues on Edible - podded B eans. Regulator: EPA Ch emical: Acequinocyl Crop: Edible - podded beans (MLE) PHI: 6 - 8 days App. Rate: 0.574 - 0.606 lb ai/A Submitter: IR - 4 MRID Citation: MRID 47819403 Combined Residues of Acequinocyl and Acequin o cyl - OH (ppm) 0.040 0.023 1 0.050 0.050 0.110 0.110 0.090 0.110 0.026 1 0.029 1 0.031 1 0.033 1 0.080 0.160 0.060 0.070 0.040 0.038 1 0.070 0.070 1 MLE value calculated for residues below the LOQ (<0.04 ppm)Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 27 of 29 Figure I - 7 . Lognorm al probability plot of Acequinocyl field trial data fo r Edible - podded B eans Lognormal Probability Plot

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

0.5000

0.2500

0.1250

0.0625

0.0313

0.0156 y = 0.5689x - 2.8873 R 2 = 0.9754

PercentilesConcentrations EPA Acequinocyl Edible podded beans (MLE) 6-8 days 0.574-0.606 lb ai/A IR-4

Figure I - 8. Tolerance spreadsheet sum ma ry of Acequinocyl field trial data for Edible - podded B eans . Regulator: EPA Chemical: Acequinocyl Crop: Edible podded beans (MLE) PHI: 6-8 days App. Rate: 0.574-0.606 lb ai/A Submitter: IR-4

n: 20 min: 0.02 max: 0.16 median: 0.06 average: 0.06 95th Percentile 99th Percentile 99.9th Percentile 0.15 0.15 0.20 (0.20) (0.20) (--) 0.15 0.25 0.35 (0.25) (0.35) (--) 0.20 0.20 0.30 0.9754 p-value > 0.05 : Do not reject lognormality assumption Approximate Shapiro-Francia Normality Test EU Method I Normal

UCLMedian95th 95/99 Rule EU Method II Distribution-Free Mean+3SDAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 28 of 29 Hops The dataset used to establish a tolerance for the combined residues of acequinocyl and acequinocyl - OH on dried hop cones c onsisted of field trial data representing application rates of 0. 588 - 0. 6 41 lb ai/A ( 2 applications at ~ 0.3 lb ai/A/application) , with a 7 - day PHI . The field trial application rates and PHI s are within 25% of the maximum label application rate and minimum label PHI , respectively . The residue values that were entered into the tolerance spreadsheet are provided in Table I - 3 . All field trial sample results were above the combined LOQ for acequinocyl and acequinocyl - OH ( LOQ = 0. 2 0 ppm ). The dataset was small ( 6 samples). Visual inspection of the lognormal probability

plot (Figure I - 9 ) and the results from the approximate Shapiro - Francia test statistic (Figure I - 10 ) indicate d that the dried hop cone dataset was reasonably lognormal. Using the tolerance spr eadsheet, the recommended tolerance is 4.0 ppm for dried hop cones . Table I - 3 . Residue data used to calculate tolerance for Acequinocyl Residues on Hops. Regulator: EPA Chemical: Acequinocyl Crop: Hops PHI: 7 days App. Rate: 0.588 - 0.641 lb ai/A Sub mi tter: IR - 4 MRID Citation: MRID 47819404

Combined Residues of Acequinocyl and Corrected Acequin o cyl - OH (ppm) 2.825 2.656 1.658 1.319 2.204 1.980 Figure I - 9 . Lognorm al probability plot of Acequinocyl field trial data for HopsAcequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 29 of 29 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 y = 0.3102x + 0.7119 R 2 = 0.9708

PercentilesConcentrations EPA Acequinocyl Hops 7 days 0.588-0.641 lb ai/A IR-4

Figure I - 10. Tolerance spreadsheet sum ma ry of Acequinocyl field trial data for Hops . Regulator: EPA Chemical: Acequinocyl Crop: Hops PHI: 7 days App. Rate: 0.588-0.641 lb ai/A Submitter: IR-4

n: 6 min: 1.32 max: 2.83 median: 2.09 average: 2.11 95th Percentile 99th Percentile 99.9th Percentile 3.5 3.5 4.0 (4.5) (6.0) (--) 3.5 4.0 5.0 (6.0) (9.0) (--) 6.0 4.0 17 0.9708 p-value > 0.05 : Do not reject lognormality assumption Approximate Shapiro-Francia Normality Test EU Method I Normal

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