Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

1 of 22 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. 20460

OFFICE OF CHEMICAL SAFETY AND

POLLUTION PREVENTIO N

MEMORANDUM

Date: 31 October 2012

Subject: Thiacloprid: Request for Food Uses on Stone Fruits and Peppers. Amended Summary of Analytical Chemistr y and Residue Data.

PC Code: 014019 DP Barcode: D406397 Petition Nos.: PP#0F7706, PP#0E7704 Registration No.: 264-806, 264-807 Assessment Type: Single Chemical Regulatory Action: Section 3 Registration TXR No.: N/A Registration Case No.: N/A

Decision No.: 430158 CAS No.: 111988-49-9 MRID No.: 47947701, 45829901, 45829902, 45829903, 46677901, 46677902 40 CFR 180.594

From: Michael A. Doherty, Ph.D., Senior Chemist

Risk Assessment Branch II Health Effects Division (7509P)

Through: Elizabeth Holman, Chemist

Risk Assessment Branch II Health Effects Division (7509P)

To: Andrew Ertman/Barbara Madden (Team 05) Risk Integration, Minor Use, and Emergency Response Branch Registration Division (7505P)

Marianne Lewis/Venus Eagle (Team 01)

Insecticide-Rodenticide Branch Registration Division (7505P)

This document updates the previous residue chemis try summary to (1) include the review of the soybean and wheat rotational crop studies and (2) provide the results of Organisation for Economic Cooperation and Development (OECD) harmonized MRL calculation procedures.

Executive Summary

Thiacloprid, 3-[(6-chloro-3-pyr idinyl)methyl]-2-thiazolidinyliden e cyanamide, is a neonicotinoid insecticide that Bayer CropScience and Interregi onal Research Project Number 4 (IR-4) have proposed for use on pepper (bell and non-bell) and the stone fruit crop group. Thiacloprid would be applied foliarly to peppers and stone fruits as an aerial or airblast spray made from a 40%Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

2 of 22 active ingredient (a.i.) flowable formulation (Calypso 4 Flowable). Applications would be made to stone fruits at a maximum single applicati on rate of 0.25 lb ai/A, with a minimum 7-day retreatment interval (RTI). The total applica tion rate would not exceed 0.38 lb ai/A/season and the preharvest interval (PHI) would be 14 days . For peppers, the proposed label specifies a maximum single application rate of 0.094 lb ai/A , a 7-day RTI, and a 7-day PHI. The total application rate for peppers would not exceed 0.28 lb ai/A/season.

Concurrently, Bayer CropScience and IR-4 ha ve submitted petitions (PP#s 0F7706 and 0E7704, respectively) to establish tolerances for thiaclop rid and its thiazolidine co ntaining metabolites in or on the following commodities: pepper (bell an d non-bell) at 1.1 ppm and fruit, stone, group 12, at 0.5 ppm. This Summary Document addresse s the adequacy of the residue chemistry data submitted to support those petitions.

The nature of the residue has been adequately de fined for purposes of this petition. The residue

definition for tolerance enforcement is thiacl oprid only. For risk assessment, the residue definition is thiacloprid plus meta bolites with an intact thiazoli dine ring. A prev iously approved analytical method, using HPLC-MS/MS, is available for tolerance enforcement.

Residue data from bell peppers, non-bell peppers, cherries, peaches, plums (fresh and dried) are supported by adequate storage stability studies. The residue trial data are acceptable and show residues ranging from <0.01 to 0.18 ppm in/on be ll peppers, <0.01 to 0.22 ppm in/on non-bell peppers, <0.02 to 0.26 ppm in/on sweet cherry, 0.03 to 0.42 in/on peaches, and <0.02 to 0.03 ppm in/on plums. Residues increased by 2.6X fo ld during drying of plums into prunes. The

NAFTA Harmonized Tolerance/MRL Calculator suggests tolerances of 0.60 ppm for peppers and 0.70 ppm for stone fruit, except plum. The calc ulated tolerance level for plum is 0.05 ppm. The recommended tolerances (see below) for resi dues in peppers and stone fruit (except plum)

have been revised from the calculated va lues in order to harmonize with Codex.

Residue Chemistry Deficiencies

Prior to Registration – Section F. A revised Section F should be submitted to address the following issues with the proposed tolerances and tolerance definition: Pepper (bell and non-bell) : The submitted residue data for bell peppers and non-bell peppers are adequate to support a Code x-harmonized tolerance of 1.0 ppm pending

submission of a revised Section F in order to : (i) propose a lower to lerance level, from 1.1 ppm; and (ii) reflect the preferred Agen cy food and feed commodity vocabulary: from “pepper (bell and non-bell)” to “pepper”.

Stone Fruits (Crop Group 12) : The submitted residue data for cherries, peaches, and plums, the representative commodities of st one fruits, are adequate to support a Codexharmonized crop group tolerance of 0.50 ppm (except plum) pending submission of a revised Section F in order to (i) reflect th e preferred Agency food and feed commodity vocabulary: from “stone fruit” to “fruit, stone, group 12”, and (ii) to provide for a separate tolerance of 0.05 ppm for residues in/on plum.

The tolerance definition should be revised to be in terms of the parent compound onlyThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

3 of 22 (i.e., Compliance with the tolerance levels is to be determined by measuring only thiacloprid, ( Z )-[3-[(6-chloro-3-pyridinyl)methyl]- 2-thiazolidinylidene]cyanamide.

Prior to Registration – Label Issues. Section B of the petition indica tes that registration is being requested for both Calypso® 4 Flowable and Ca lypso® 70 WG. It is HED’s understanding that the 70 WG product is not actually part of the pe tition. A revised Section B should be submitted in which only the Calypso® 4 Flowable product is listed.

Based on the results of the field rotational crop studies with soybean and wheat, soybean and cereal grains may be added to th e list of crops that may be ro tated after a 30-day plant-back

interval.

Conditional Data – Field Accumulation in Rotational Crop Data . Limited field accumulation studies in wheat and soybeans were required per previous HED review (11 June 2003, D279818, D. Soderberg) and have been submitted to the Agency (MRIDs 46677901 and 46677902). A

review of these studie s is included herein.

Note: The current tolerance expression is not consistent with the recommendation made by HED in its 2003 assessments or with current guidanc e regarding tolerance la nguage. The current

tolerance definition is:

“Tolerances for combined residues of the insecticide thiacloprid ([3-[(6-chloro-3- pyridinyl)methyl]-2-thiazolidinylidene] cyanamide) and metabolites retaining the thiazolidine ring intact, measured and expressed in terms of thiacloprid, per se, in or on the following commodities:”

HED recommends that the CFR be revised to specify the following tolerance expression:

“Tolerances are established for residues of thiacloprid, including its metabolites and degradates, in or on the commodities in the ta ble below. Compliance with the tolerance levels specified below is to be determined by measuring only thiacl oprid ([3-[(6-chloro3-pyridinyl)methyl]-2-thiazoli dinylidene] cyanamide).”

Residue Chemistry Conclusions

For the requested uses on bell and non-bell pe ppers (PP#0E7704) and stone fruit (PP# 0F7706), there are no major residue chemistry issues that would preclude granting permanent tolerances and Section 3 registrations for th e requested uses. Prior to gran ting any registrations, the issues detailed above should be considered. The pr oposed uses and the submitted data support the following tolerances for residues of thiacloprid in/on:

Pepper ..............................................................................................1.0 ppm Fruit, stone, group 12, except plum .................................................0.50 ppm Plum .................................................................................................0.05 ppm

Except for plums, the recommended tolerance leve ls are harmonized with existing Codex MRLs. The significantly different residue levels in the trials with plums as compared to the otherThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

4 of 22 representative commodities in th e stone fruit crop group make it necessary to set a separate regulatory level for residues in plums.

A human health risk assessment is forthcoming.

Background

Thiacloprid {3-[((6-chloro-3- pyridinyl)methyl]-2-thiazoli dinylidene cyanamide} is a

neonicotinoid insecticide that is effective for th e control of various in sects including aphids, leafhoppers, plant bugs, whiteflies, leafminers, mire d bugs, codling moths, plum curculio, scales and maggots. The active ingredient is formulated as 40% a.i. flowable formulation (Calypso 4 Flowable) or a 70% a.i. in a wettable granule formulation (Calypso 70 WG). Foliar applications

are applied aerially or by ground sprayer.

The first food/feed uses of thiacloprid were approved on co tton and pome fruits (Crop Group 11). The residue chemistry data supporting thes e crop uses are summarized by HED in a June 11, 2003 memo (DP#s 279818, D. Soderberg). Tole rances are currently established [40 CFR §180.594] for the combined residues of the in secticide thiacloprid ([3-[(6-chloro-3- pyridinyl)methyl]-2-thiazolidinylidene] cyanamide) and metabolites retaining the thiazolidine ring intact, measured and expresse d in terms of thiacloprid, per se , in/on pome fruit, group 11 at 0.30 ppm; wet apple pomace at 0.60 ppm, cotto n, undelinted seed at 0.02 ppm; cotton gin byproducts at 11.0 ppm; and animal commodities at 0.02-0.15 ppm.

The chemical structure and nomenclature of thiacloprid are presented in Table 1. The physiochemical properties of the technical gr ade of thiacloprid are presented in Table 2.

TABLE 1 Test Compound Nomenclature.

Compound Chemical Structure:

Common name Thiacloprid Company experimental name YRC 2894, IUPAC name [3-[(6-Chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]cyanamide CAS name (Z)-[3-[(6-chloro-3-pyridinyl) methyl]-2-thiazolidinylidene]cyanamide

CAS # 111988-49-9 End-use product/EP Calypso® 4 Flowable Insecticide; EPA Reg. No. 264-806Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

5 of 22

TABLE 1 Test Compound Nomenclature.

Compound (primary metabolite) Chemical Structure:

Common name Thiacloprid amide metabolite Company experimental name YRC 2894 amide IUPAC name (Z)-[3-[(6-Chloro-3-pyridinyl)methyl]-2-thiazolidinyldene)urea

CAS name unknown

CAS # 676228-91-4 End-use product/EP Not applicable

Compound (primary metabolite) Chemical Structure:

Common name Thiacloprid hyrdoxy amide metabolite Company experimental name 4-hydroxy YRC 2894 amide , IUPAC name Urea, N-[(2Z)-3-[(6-chloro-3-pyridinyl)methyl]-4-hydroxy-2-thiazolidinylidene]

CAS name unknown

CAS # unknown End-use product/EP Not applicable

Table 2 Physicochemical Properties of the Technical Grade Test Compound

Parameter Value

Melting point/range 136° C

pH 7.40 at 20° C

Density 1.46 g/mL at 20° C

Water solubility ( 20  ̊ C) 185 mg/L

Solvent solubility (g/L) n-Heptane: < 0.1 Xylene: 0.30

1-Octanol:1.4 2-Propanol: 3.0 Ethyl acetate: 9.4 Polyethylene glycol (PEG): 42

Acetonitrile: 52

Acetone: 64 Dimethylsulfoxide (DMSO): 150

Dichloromethane: 160.

Vapor pressure at 20 & 25° C 23 x 10 (-10) Pa at 20° C 8 x 10(-10) Pa at 25° C

Dissociation constant (pK

a ) AI has no basic or acidic properties in aqueous solutionsThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

6 of 22

Table 2 Physicochemical Properties of the Technical Grade Test Compound

Parameter Value

Octanol/water partition coefficient Log(K OW )

K OW 1.26 at 20° C

18

UV/visible absorption spectrum λ max Extinction coefficient

295-300 nm 49.1828

301-305 nm 39.3463

860.1200 Directions for Use

The petitioners (Bayer CropScience and IR-4) su bmitted draft labels dated 2/26/10 for the 4 lb ai/gal SC formulation (Calypso® 4 Flowable ; EPA Reg. No. 264-806). Both labels were identical, except the label submitted by Bayer CropS cience also included use on peppers. In Section B of both petitions, the petitioners stat e that two formulated products consist of a

flowable concentrate at 40.4% a.i. and a wettable granular (WG) at 70% a.i. A specimen label was not provided for the 70% WG formulation. It is HED’s understand ing that the 70% WG formulation is not actually part of the petition. A summary of the proposed use patterns for the 40.4% a.i. product is detailed in Table 3.

Table 3. Summary of Directions for Use of Thiacloprid.

Applic. Timing, Type, and Equip. Formulation Applic.

Rate (lb ai/A) Max. No. Applic. per

Season Max.

Seasonal Applic. Rate

(lb ai/A) PHI (days) Use Directions and

Limitations

Stone Fruit Group 12

Foliar application Calypso 4

Flowable 0.25 Not Specified 0.38 14 Near lakes, rivers,

permanent streams,
marshes or natural ponds, estuaries, and

commercial fish farm ponds: no aerial application within 100 feet; do not allow airblast spray to go beyond cultivated area.

Pepper

Foliar application Calypso 4

Flowable 0.094 Not Specified 0.281 7 Near lakes, rivers,

permanent streams,
marshes or natural ponds, estuaries, and

commercial fish farm ponds: no aerial application within 100 feet; do not allow airblast spray to go beyond cultivated area.Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

7 of 22 The following rotational crop restrict ions are specified for the 4 lb/gal SC formulation: Roots, tubers and bulb vegetables whose tops are not us ed for feed may be rotated with cotton after a plan back interval of 30 days. Leafy vegetabl es may be rotated after a 6 month plant back interval. Do not plant any other crop in the treated area for at l east one year afte r application.

Conclusions . The submitted labels for the 4 lb ai/g al SC formulation (Calypso® 4 Flowable; EPA Reg. No. 264-806) appropriately reflect the conditions used in the thiacloprid field trials and are adequate to allow evalua tions of the residue data relativ e to the proposed uses. Although

the flowable formulation was not tested in ei ther the pepper or stone fruit trials, 480 SC (suspension concentrate) formulation was test ed. Since a flowable formulation can be considered equivalent to a suspension con centrate formulation from a residue chemistry perspective, the field trials are adequate to cover use of the 40.4% a.i. flowable formulation as

well as the 70 WG% formulation.

Based on the results of the field rotational crop studies with soybean and wheat, soybean and cereal grains may be added to th e list of crops that may be ro tated after a 30-day plant-back

interval.

860.1300 Nature of the Residue – Plants

Residue Chemistry Memo DP# 279818, 6/11/2003, D. Soderberg (PP#9F06060) Residue Chemistry Memo DP# 288833, 4/7/2003, D. Soderberg (HED MARC Decision Document)

The nature of the residue has been adequately defined for cotton, rice, tomatoes, apples and the rotational crops: wheat, turnips and lettuce. By fa r the most predominant residue is thiacloprid,

per se , in plants. In general, where metabolism occu rs, the thiazolidine ring is less stable than the pyridinyl ring and the bridge methylene grou p generally tends to cl eave on the thiazolidine side. Plants do not appear to metabolize thiaclop rid at all; but metabolism does occur in soil, and plants can translocate such metabolized residue s of thiacloprid from the soil and sometimes subsequently form further conjugates of them. In plants and animals, the residue of concern is parent only for the purposes of tolerance assess ment and parent and metabolites with intact thiazolidine ring for risk a ssessment (DP# 288833, 4/7/2003, D. Soderberg; HED Metabolism Assessment Review Committee).

Conclusion: For the purposes of the current tolerance pe titions, the available apple and tomato

metabolism studies are considered sufficient to delineate the nature of the residues. The residues of concern remain thiacloprid, per se

.

860.1300 Nature of the Residue – Livestock

There are no livestock feedstuffs associated with the request to establis h tolerances on peppers and stone fruit. Therefore, data requirements for livestock metabolism are not relevant to the current tolerance petitions.

860.1340 Residue Analytical MethodsThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

8 of 22 Residue Chemistry Memo DP# 279818, 6/11/2003, D. Soderberg (PP#9F06060)

Enforcement methods

Previously, Bayer had submitted three potential enforcement methods for determining residues of thiacloprid in/on plants. They included the following: (1) HPLC/U V method for determining thiacloprid, per se , in/on plants; (2) GC/MS me thod for determining residues of thiacloprid as the common moiety 6-CNA in/on plants; and (3) HPLC-MS/MS method for determination of thiacloprid, thiacloprid amide and hydroxythiacl oprid amide in/on plants. The HPLC-MS/MS for plants is adequate for enforcement of thiacloprid in plants.

Data-collection methods

Samples of stone fruits (sweet cherry, peach, and plum) collected from the magnitude of the residue and processing studies we re analyzed for residues of thiacloprid, thiacloprid amide metabolite, and thiacloprid hydroxyl amide metabolit e using the University of California, Davis working method derived from Bayer Ag. Draft Method, “Modified Residu e Analytical Method for the Determination of YRC 2894, Y RC 2894-Amide and 4-Hydroxy-YRC 2894-Amide Residue in Pecan Matrices” (April 8, 2001) with modifications. The lim it of quantitation (LOQ),

defined as the lowest level of method validati on (LLMV) at which accep table recovery can be achieved for this HPLC-MS/MS method, was 0.02 ppm for each analyte in all matrices. The method is acceptable based on concurrent recoveries.

Samples of peppers (bell and non-be ll) collected from the magnitude of the residue studies were analyzed for residues of thiacloprid and its metabolites, YRC 2894 amide and 4-hydroxy YRC 2894 amide, using a method titled “An analytic al method for the determination of YRC 2894, amide-YRC 2894, 4-hydroxy YRC 2894 amide, and YRC 2894 sodium sulfonate residues in various plant matrices by HPLC-MS/MS.” The LOQ, defined as the LLMV at which acceptable recovery can be achieved, was 0.01 ppm for each analyte. The method is acceptable based on

concurrent recoveries.

Conclusions . An adequate HPLC-MS/MS is available for determination of thiacloprid residues in plant matrices. This method can be suppor ted by existing radiovalidation and metabolism data. This method has adequate confirmatory ions available in the MS as described in the ILV. HED recommends that Bayer propose this meth od for tolerance enforcement in plant tissues.

Residues of thiacloprid, thiacloprid amide metabo lite, and thiacloprid hydroxyl amide metabolite in/on peppers (bell and non-bell) and stone frui t (sweet cherry, peach, plum) were determined using acceptable data collection methods.

860.1360 Multiresidue Methods

Residue Chemistry Memo DP# 279818, 6/11/2003, D. Soderberg (PP#9F06060)

Multiresidue method testing data were previously submitted for thiacloprid as part of the data package for PP#9F06060. This study has been forwarded to the Analytical Chemistry Laboratory; Biological and Economic Analysis Division of OPP for review. A brief examinationThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

9 of 22 of the submitted study (MRID 44927625) indicates that thiacloprid may be suitable for analysis

via Protocol D.

860.1380 Storage Stability

Residue Chemistry Memo DP# 279818, 6/11/2003, D. Soderberg (PP#9F06060)

The storage durations and conditi ons of samples from the residue field trials and processing studies which were submitted to support the current petitions are presented in Table 4.

Table 4. Summary of Storage Conditions and Durations of Samples from Crop Field Trial and Processing Studies.

Matrix [MRID] Storage Temperature ( °C) Actual Storage Duration Interval of Demonstrated Storage Stability

Peppers, fresh fruit [47947701] -22 to -24 60-220 days (2.0-7.2 months) 18 months 1

Sweet cherry, fresh fruit [45829903] <-20 78-138 days (2.6-4.6 months) 139 days 2

Peach, fresh fruit [45829902] <-20 13-109 days (0.4-3.6 months) 162 days 2

Plum, fresh fruit [45829901] <-20 83-176 days (2.7-5.8 months) 161 days 2

Dried Plum [45829901] <-20 119-133 days (3.9-4.4 months) 120 days 2

1 Storage stability data translated from DP# 279818, 6/11/2003, D. Soderberg.

2 Storage stability determined from concurrent field trial samples.

Conclusions . Adequate storage stability data for appl es, tomatoes, and melons were reviewed in

PP#9F06060. It was show n that thiacloprid per se is stable under frozen conditions in apples, tomatoes, and melons for up to 18 months. By translation, these storag e stability data support the pepper residue field trials for the current petition.

To support the current stone fruit field trial da ta, storage stability st udies were conducted in conjunction with the field trials. For each crop, control samples of the respective matrices were fortified with thiacloprid, thiacloprid amid e metabolite, and thiacloprid hydroxy amide metabolite at target level of 0.200 ppm and placed in storage under the same frozen conditions as the treated samples. No zero-day analyses were conducted on the fortified samples placed into storage. Rather, triplicate stor ed samples were analyzed along w ith a control sample and freshly fortified samples at an interval reflecting the ma ximum storage intervals from the field trials. Average corrected recoveries of thiacloprid following frozen storage were 95% from sweet cherry after 139 days, 100% from peach after 162 days, 98% from pl um after 161 days, and 104% for dried plum after 120 days. These storag e stability data support the stone fruit (sweet cherry, peach, and plum) field trial a nd processing (dried plum) studies.

There are no unresolved storage stability issues, and no corrections need to be applied to the various residue crop studies.Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

10 of 22 860.1400 Water, Fish, and Irrigated Crops

There are no proposed or registered uses th at are relevant to this guideline topic.

860.1460 Food Handling

There are no proposed or registered uses th at are relevant to this guideline topic.

860.1480 Meat, Milk, Poultry, and Eggs

There are no significant livestock feedstuffs a ssociated with the proposed use on peppers and stone fruit. Therefore, data requirements pertaining to meat , milk, poultry, and eggs are not relevant to the current tolerance petitions.

860.1500 Crop Field Trials

Pepper (bell and non-bell)

DER Reference List 47947701.der.doc

Bayer CropScience has submitted field trial data fo r thiacloprid in/on bell peppers and non-bell peppers. Nine field trials were conducted, six on bell peppers and three on non-bell peppers in the US. The bell pepper trials were in Zones 2 ( GA, 1 trial), 3 (FL, 1 trial), 5 (NE, 1 trial), 6 (TX, 1 trial), and 10 (CA, 2 trials). The non-bell pepper trials were in Zones 2 (GA, 1 trial), 3 (FL, 1 trial), and 10 (AZ, 1 trial). One trea ted plot and one untreated control plot were

established at each trial site. Fo r each trial, three foliar applica tions of the test substance YRC 2894 480 SC (a suspension concentrate formulation nom inally containing 4 lb ai/gal thiacloprid) were made at a target rate of 0.094 lb ai/A/application, with re-treat ment intervals (RTI) of 5 to 8 days. The total target app lication rate was 0.282 lb ai/A/season (~1x the proposed maximum seasonal rate of 0.281 lb ai/A). All applications were made using ground equipment at spray volumes of 10 to 34 gallons per acre (GPA). There were no adjuvants added to the spray mixture. Pepper (fresh fruit) samples were collec ted at pre-harvest interv als (PHIs) of 0, 2-3, and 6-7 days. At one trial site (Y4066-01D), sample s were collected at PHIs of 0, 3, 7, 10 and 14 days to assess residue decline.

Residues of thiacloprid and its metabolites , YRC 2894 amide and 4-hydroxy YRC 2894 amide, were determined using a met hod titled “An analytical method fo r the determination of YRC 2894, amide-YRC 2894, 4-hydroxy YRC 2894 amide, and YRC 2894 sodium sulfonate residues in various plant matrices by LC/MS-MS.” Th e limit of quantitation (LOQ), defined as the

lowest level of method validati on (LLMV) at which acceptable recovery can be achieved, was 0.01 ppm for each analyte. The limit of detec tion (LOD) was determined to be 0.001 ppm for thiacloprid and 4-hydroxy YRC 2894 amide and 0.002 for YRC 2894 amide. The method is acceptable based on concurrent recoveries.

The maximum storage duration from sampling to extraction was 220 days (7.2 months). All sample extracts were analyzed within 6 days of extraction. Available st orage stability indicate that residues of thiaclop rid, per se, are stable in tomatoes for up to 18 months when stored frozenThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

11 of 22 at < -18  C (DP# 279818, 6/11/2003, D. Soderberg). No st orage stability data are available for residues of thiacloprid amide and thiacloprid hydroxy amide in peppers or fruiting vegetables, however, these residues have been shown to be st able during freezer storage (<-20oC) for at least 161 days in plum (MRID 45829901), 139 days in cherries (MRID 45829903) and 162 days on peaches (MRID 458299 02). Based on translation, ade quate storage stability data are available to support the storage conditions an d durations for the pepper study.

Following three foliar broadcast applications of thiacloprid at a total target application rate of 0.282 lb ai/A, residues of thiacloprid range d from 0.040 to 0.209 ppm in/on bell peppers harvested at a 0-day PHI, from 0.014 to 0.224 ppm in/on bell peppers harvested at a PHI of 2-3 days and from <0.01 to 0.180 ppm in/on bell peppe rs harvested at a PHI of 6-7 days. For nonbell peppers, residues of thiacloprid ranged fr om 0.052 to 0.344 ppm at a 0-day PHI, from <0.01 to 0.333 ppm at a PHI of 2-3 days and from <0. 01 to 0.221 ppm at a PHI of 6-7 days. Residues of YRC 2894 amide and 4-hydroxy YRC 2894 amid were less than the LOQ in all samples. A summary of residue data from the pepper trials is presented in Table 5.

The residue decline stud y showed that residues of thiaclop rid in/on peppers declined between Day 0 and Day 14.

Table 5. Summary of Residue Data fr om Pepper Field Trials with Thiacloprid.
Commodity Total Applic.

Rate (lb ai/A) PHI (days) Residue Levels (ppm)

n Min. Max. HAFT Median (STMdR) Mean (STMR) Std. Dev.

Proposed use pattern: Foliar appl ications made at a single maxi mum of 0.094 lb ai/A/application, for a total of 0.281 lb ai/A/season; 7-day PHI Thiacloprid Bell Pepper 0.281 - 0.287 6-7 12 <0.0 1 0.180 0.132 0.030 0.053 0.051

Non-bell Pepper 0.281 - 0.287 7 6 <0.01 0.221 0.210 0.006 0.073 0.106

Amide Metabolite Bell Pepper 0.281 - 0.287 6-7 12 <0.01 <0.01 <0.01 <0.01 <0.01 NA

Non-bell Pepper 0.281 - 0.287 7 6 <0.01 <0.01 <0.01 <0.01 <0.01 NA

Hydroxy Amide Metabolite Bell Pepper 0.281 - 0.287 6-7 12 <0.01 <0.01 <0.01 <0.01 <0.01 NA

Non-bell Pepper 0.281 - 0.287 7 6 <0.01 <0.01 <0.01 <0.01 <0.01 NA

Conclusions . The submitted residue data for pepper (bell and non-bell) are adequate to fulfill data requirements. The number and location of crop field trials are in accordance with OPPTS Guideline 860.1500. The trials reflect the proposed use pattern.

Stone fruit (group 12)

DER Reference List 45829901.der.doc (plum) 45829902.der.doc (peach) 45829903.der.doc (sweet cherry)

Cherry, Sweet: The IR-4 Project at Rutgers, The State University of New Jersey has submitted field trial data for thiacloprid in /on sweet cherries. Seven field trials were conducted in the USThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

12 of 22 during the 2001 season in Zones 5 (M I, 2 trials), 10 (CA, 2 trials), and 11 (WA, 1 trial; ID, 1 trial; and OR, 1 trial). One treate d plot and one untreated control plot were establ ished at each trial site. For each trial, two foliar applica tions of the test substance, Calypso 480SC (a suspension concentrate formulation containing 4 lb /gal of the active ingredient, thiacloprid), were made at a target rate of 0.125 lb ai/A/application for the fi rst application a nd 0.250 lb ai/A for the second application, with re treatment intervals (RTIs) of 6 - 8 days. The total target application rate was 0.375 lb ai/A/season (~1x the proposed maximum seasonal rate of 0.38 lb ai/A). All applications were made using gr ound equipment in 62 to 364 GPA; no adjuvant was added to the spray mixtures. Samples of mature sweet cherries were harvested at PHIs of 13-14 days and 25-28 days. At one trial site (07812.01- WA25), an additional bulk sample of sweet

cherries were collected from the field site to determine the effect of washing, cooking, and drying the sweet cherries on thiacloprid residues.

Residues of thiacloprid, thiacloprid amide meta bolite, and thiacloprid hydroxy amide metabolite were determined using Univers ity of California, Davis worki ng method derived from Bayer Ag. Draft Method “Modified Residue Analytical Method for the Determination of YRC 2894, YRC 2894-Amide and 4-Hydroxy-YRC 2894-Amide Residue in Pecan Matrices” ( April 8, 2001) with modifications. The limit of quantitation (LOQ), defi ned as the lowest level of method validation (LLMV) at which acceptable recovery can be achieved, was 0.02 ppm for each analyte. The limit of detection (LOD) was determined to be 0.003 ppm for each analyte. The method is acceptable based on concurrent recoveries.

The maximum storage duration from sampling to extraction was 138 days (4.6 months). All sample extracts were analyzed on the day of extraction. To evaluate storage stability, a concurrent storage stability study was conducted using control sample s of cherries fortified with thiacloprid, thiacloprid amide metabolite, and thiacloprid hydroxy amide metabolite at target level of 0.200 ppm. These samples were stored frozen (<-20 oC) and then analyzed at 139 days with freshly fortified samples. The results show that residues of thi acloprid, thiacloprid amide metabolite, and thiacloprid hydroxy amide are stab le in cherry RAC for up to 139 days when stored frozen. These data support the residue data from the cherry field trial samples.

Residues of thiacloprid ranged from <0.020 ppm to 0.263 ppm on sweet cherries harvested at a PHI of 13-14 days following two fo liar applications of the Calypso 480SC at a total rate of 0.371-0.385 lb ai/A. Residues of the thiacloprid amide metabolite a nd thiacloprid hydroxy amide metabolite were all less than the LLMV ( 0.020 ppm). The residue data are summarized in

Table 6.

Peach: The IR-4 Project at Rutgers, The State Univer sity of New Jersey has submitted field trial data for thiacloprid on peaches. Eleven field tria ls were conducted in the US in Zones 1 (NY, 1 trial), 2 (NJ, 1 trial; NC, 2 trials), 3 (FL; 1 trial), 5 (MI; 1 trial), 6 (TX; 1 trial), 10 (CA; 3 trials), and 11 (ID; 1 trial). One treated pl ot and one untreated control plot were established at each trial site; at the North Carolina and Florida trials, two treated plots were established. For each trial, two foliar applications of the test substan ce, Calypso 480SC (a suspension concentrate formulation containing 4 lb/gal of the active ingredient, thiacloprid), were made at a target rate of 0.125 lb ai/A for the first ap plication and 0.250 lb ai/A for th e second application for a total seasonal rate of 0.375 lb ai/A (~1x the proposed maximum seasonal rate of 0.38 lb ai/A). TheThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

13 of 22 retreatment interval (RTI) was 6 - 8 days. At the NJ trial, the sec ond application was under applied by approximately 51%, for a total of appr oximately 0.245 lb ai/A. At the NY trial, a third application was made at approximately 0.250 lb ai/A, for a total of approximately 0.625 lb ai/A, to allow the peaches to mature; the third application wa s made at a 13-day RTI. All applications were made using ground equipment in 50 to 300 GPA; no adjuvant was added to the spray mixtures. Samples of peaches were harveste d from the untreated and treated plots at 12 to 15 days and at 21 to 29 days following the final application. At the No rth Carolina and Florida trials, samples were collected from one treated plot at a PHI of 14 days and from the second treated plot at a 28-day PHI. At one trial site (01-NC11), an additional bulk sample of peaches

was collected from the field site to determ ine the effect of washing, cooking, and drying on thiacloprid residues.

Residues of thiacloprid, thiacloprid amide meta bolite, and thiacloprid hydroxy amide metabolite were determined using Univers ity of California, Davis worki ng method derived from Bayer Ag. Draft Method “Modified Residue Analytical Method for the Determination of YRC 2894, YRC 2894-Amide and 4-Hydroxy-YRC 2894-Amide Residue in Pecan Matrices” (April 8, 2001), with modifications. The limit of quantitation (LOQ), defi ned as the lowest level of method validation (LLMV) at which acceptable recovery can be achieved, was 0.02 ppm for each analyte in all matrices. The method is acceptable ba sed on concurrent recoveries.

The maximum storage duration from sampling to extraction was 109 days (3.6 months). All sample extracts were analyzed on the day of extraction. To support the residue trials, a concurrent storage stability st udy was conducted using control samp les of peach fortified with thiacloprid, thiacloprid amide metabolite, and thiacloprid hydroxy amide metabolite at target level of 0.200 ppm. These samples were stored frozen (<-20oC) and then analyzed at 162 days with freshly fortified samples. The results show that residues of thi acloprid, thiacloprid amide metabolite, and thiacloprid hydroxy amide metabolite are stable in peach RAC for up to 162 days

when stored frozen.

Residues of thiacloprid ranged from 0.0305 ppm to 0.423 ppm on peach es harvested at a PHI of 12-15 days and from <0.02 ppm to 0.359 ppm on peaches harvested at a PHI of 21-29 days following two foliar applications of Calypso 480SC at a total rate of 0.371-0.382 lb ai/A. The residue decline study showed that residues of thiacloprid on peaches declined over time.

Plum: The IR-4 Project at Rutgers, The State Univer sity of New Jersey has submitted field trial data for thiacloprid in/on plums. Six field trials were conducted in the US during the 2001 growing season in Zones 5 (MI, 1 trial), 10 (CA, 4 trials) and 12 (OR, 1 tria l). One treated plot and one untreated control plot were established at each trial site. For each trial, two foliar applications of the test subs tance, Calypso 480SC (a suspension concentrate formulation containing 4 lb/gal of the active ingredient, thiacloprid), were ma de at a target rate of 0.125 lb ai/A for the first application and 0.250 lb ai/A for the second application, with retreatment intervals (RTIs) of 7-8 days. The total target application rate was 0.375 lb ai/A/season (~1x the proposed maximum seasonal rate of 0.38 lb ai/A). All applications were made using ground equipment at 44-263 GPA; no adjuvants were adde d to the spray mixtures. Samples of plums were harvested at PHIs of 14-15 days and 26-29 in a ll trials. At one trial site (01-MI19), samples were collected immediately after the application (0-day) and at PHIs of 7, 14, 28 and 33 days toThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

14 of 22 assess residue decline. At trial site 01-CA57, add itional samples of plums were collected at PHIs of 15 and 29 days to determine the effect of drying the plums on thiacloprid residues.

Residues of thiacloprid, thiacloprid amide metabo lite, and thiacloprid hydroxyl amide metabolite were determined using the University of Calif ornia, Davis working method derived from Bayer Ag. Draft Method, “Modified Residue Analyti cal Method for the Determination of YRC 2894, YRC 2894-Amide and 4-Hydroxy-YRC 2894-Amide Resi due in Pecan Matrices” (April 8, 2001)

with modifications. The lowest level of me thod validation (LLMV) for both plum RAC and dried plum was determined to be 0.020 ppm for each analyte. The limit of detection (LOD) was determined to be 0.004 ppm for thiacloprid and the amide metabolite in plum RAC samples, 0.009 ppm for the hydroxy amide metabolite in pl um RAC, 0.003 ppm for th iacloprid in dried plums, 0.005 ppm for the amide metabolite in dried plums and 0.01 ppm for the hydroxy amide metabolite in dried plums. The method is accep table based on concurrent recoveries.

The maximum storage duration from sampling to extraction was 176 days (5.8 months) for plum RAC and 133 days (4.4 months) for dried plums. All sample extracts were analyzed on the day of extraction. To support the residue data, a concurrent storage stab ility study was conducted using control samples of plums fortified with thiacloprid, thiacloprid amide metabolite, and thiacloprid hydroxy amide metabolite at target level of 0.20 ppm. These samples were stored frozen (<-20oC) and then anal yzed at 161 days (plum RAC) a nd 120 days (dried plum) with freshly fortified samples. The results show that residues of thiacl oprid, thiacloprid amide metabolite, and thiacloprid hydroxy amide metabolit e are stable in plum RAC and dried plums for up to 161 and 120 days, respectively, when stored frozen.

Residues of thiacloprid ranged from <0.020 ppm to 0.032 ppm in/on plum RAC harvested at PHIs of 14-15 days and 26-29 days following two folia r directed applications of thiacloprid at a

total rate of 0.376-0.383 lb ai/A. Residues of the thiacloprid am ide metabolite a nd thiacloprid hydroxy amide metabolite were all less than the LLMV (0.020 ppm). The residue decline study showed that residues of thiaclopri d on plums declined over time.

A summary of residue data from the represen tative commodities of Cr op Group 12 is presented

in Table 6.

Table 6. Summary of Residue Data from Stone Fruit Crop Group 12 Field Trials with Thiacloprid.
Commodity Total Applic. Rate (lb ai/A) PHI (days) Residue Levels (ppm)

n Min. Max. HAFT Median (STMdR) Mean (STMR) Std. Dev.

Proposed use pattern: Foliar appl ications made at a single maxi mum of 0.25 lb ai/A/application, for a total of 0.38 lb ai/A/season; 14-day PHI Thiacloprid Sweet Cherry, fresh fruit 0.371-0.385 13-14 14 <0.02 0.263 0.239 0.176 0.163 0.072
Peach, fresh fruit 0.371-0.382 12-15 18 0. 031 0.423 0.369 0.126 0.167 0.121
Plum, fresh fruit 0.375 14-15 12 <0.0 2 0.032 0.031 0.020 0.023 0.004

Amide Metabolite Sweet Cherry, fresh fruit 0.371-0.385 13-14 14 <0.02 <0.02 <0.02 <0.02 <0.02 0.000
Peach, fresh fruit 0.371-0.382 12-15 18 <0.02 <0.02 <0.02 <0.02 <0.02 0.000
Plum, fresh fruit 0.375 14-15 12 <0.02 <0.02 <0.02 <0.02 <0.02 0.000 Hydroxy Amide Metabolite Sweet Cherry, fresh fruit 0.371-0.385 13-14 14 <0.02 <0.02 <0.02 <0.02 <0.02 0.000Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

15 of 22

Table 6. Summary of Residue Data from Stone Fruit Crop Group 12 Field Trials with Thiacloprid.
Commodity Total Applic. Rate (lb ai/A) PHI (days) Residue Levels (ppm)

n Min. Max. HAFT Median (STMdR) Mean (STMR) Std. Dev.

Peach, fresh fruit 0.371-0.382 12-15 18 <0.02 <0.02 <0.02 <0.02 <0.02 0.000
Plum, fresh fruit 0.375 14-15 12 <0.02 <0.02 <0.02 <0.02 <0.02 0.000

Conclusions for stone fruits . The submitted residue data for sweet cherry, peach, and plum, as representative crops of the stone fruit group (Crop Group 12), are adequate to fulfill data requirements. The number and location of cherry and plum crop field trials are in accordance with OPPTS Guideline 860.1500. For peaches, the loca tions of trials conducted according to the

label are not in strict accordance with O PPTS Guideline 860.1500 due to issues with the application rates. Additional tria ls are not being requested. The to tal number of field trials is in accordance with the guideline.

860.1520 Processed Food and Feed

Data depicting residues of thi acloprid in processed cherry, p each, and plum commodities were

included in the residue field trial reports for each of these crops. Details of these studies can be found in Section 860.1500, above. Residues in processed commodities and the associated processing factors are summarized in Table 7.

TABLE 7. Residue Data from the Processing Study with Thiacloprid.

Commodity Total Rate (lb ai/A) PHI (days) Residues (ppm, all as thiacloprid) Processing

Factor 1 Thiacloprid Amide Hydroxy Amide
Cherry RAC

0.397 14 0.1525 <0.020 <0.020 NA Cherry (Washed) 0.1383 <0.020 <0.020 0.91x Cherry (Cooked) 0.1210 <0.020 <0.020 0.79x

Cherry (Dried) 0.5483 <0.020 <0.020 3.6x

Peach RAC

0.3768 27 0.0500 <0.020 <0.020 NA Peach (Washed) 0.0 230 <0.020 <0 .020 0.46x Peach (Cooked) <0.0 2 <0.020 <0 .020 <0.40x

Peach (Dried) 0.1 793 <0.020 <0.020 3.6x

Plum RAC 0.375 15 0.0228 <0.020 <0.020 NA Plum (Dried) 0.0465 <0.020 <0.020 2.0x

Plum RAC 0.375 29 <0.02 <0.020 <0.020 NA Plum (Dried) 0.0618 <0.020 <0.020 3.1x
LLMV = 0.020 ppm

1 Processing factors are calculated (by the reviewer) in terms of thiacloprid only by dividing the thiacloprid residues in each

processed fraction by the thiacloprid residues in the RAC. Reported residues are average values.

Conclusions . The processing data satisfy requirements. The data indicate that residue levels are reduced in these fruits by washing and/or c ooking, and that residues concentrate during the production of dried fruit. Based on the dried fruit con centration factor, the highest average field trial residues and the recommended tolerance levels, separate tolerances for dried commodities are not likely to be necessary.

860.1850 Confined Accumulation in Rotational Crops

Residue Chemistry Memo DP# 279818, 6/11/2003, D. Soderberg (PP#9F06060)Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

16 of 22 A confined rotational crop study was submitted and reviewed in PP#9F06060. The study was deemed adequate to satisfy data requirements provided the application ra te use in the study is confirmed to approximate 1x. To date, the re quested information has not been submitted.

Based on the results of the confined accumulatio n study, limited field accumulation in rotational crop studies were required for wheat and for s oybeans. Cotton may be planted at any time. Roots, tubers and bulb vegetables whose tops ar e not used for feed may be rotated with cotton after a PBI of 30 days. Leafy vegetables may be rotated after a 6-month PBI. Wheat, other grains, and vegetables other than those descri bed above may not be planted in rotation until limited field accumulation in rotational crop studies are received for those crops. Studies were required for wheat and soybeans as st ated above regardless of the PBI.

The tolerance expression and/or the residues for risk assessment for rotational crops will be determined when field rotational crop studies be come available. Based on information in the confined rotational crop studies, parent th iacloprid, YRC 2894 amide, and 4-OH-YRC 2894 amide need to be measured in the edible portions of the rotated crops. The residues in various rotational crops consis t of significant proportions of YRC 2894 amide, 4-OH-YRC 2894 amide, thiacloprid sulfonic acid and 6-picolinyl alcoho l (6-CPA). The MARC had concluded that 6- CPA and thiacloprid sulfonic acid can be neglecte d, but believes that actual field measurements of thiacloprid, YRC 2894 amide and 4-OH YRC 2894 amide are needed to establish the correct

residues for risk assessment a nd any tolerance expressions th at may be needed (D 288833, D. Soderberg, 7 April 2003).

860.1900 Field Accumulation in Rotational Crops

MRID Numbers 46677901 and 46677902

Limited field accumulation studies in wheat a nd soybeans were required per previous HED review (11 June 2003, D279818, D. Soderberg) and have been submitted to the Agency (MRIDs 46677901 and 46677902). An abbreviated review of these studies follows:

Rotational crop field trials were conducte d with soybean (MRID 46677901) and wheat (MRID 46677902). Twenty trials were conducted for each crop and at each trial three broadcast spray applications were made to bare soil at a nominal rate of 0.095 lb a.i./A/application. Approximately 30 days after the la st application, the soil was tilled and the soybean or wheat was planted. At maturity, crops were harveste d for grain, forage, hay, and straw (wheat only).

Samples were analyzed for residues of thiaclop rid, thiacloprid amide, thiacloprid hydroxyamide, and thiacloprid sodium sulfonate. The sodium su lfonate does not contain an intact thiazolidine moiety,is not, therefore, a residu e of concern, and is not discusse d further in this review. The analytical method used solvent extraction (MeOH:H 2 O, 3:1, v:v), solid-phase clean up, and LCMS/MS separation and detection/ quantitation. The method incor porated deuterated internal standards to aid in method performance. The LOQ of the method, defined as the lower limit of method validation, was 0.01 ppm for all analytes in all matric es. Method performance was satisfactory based on method valida tion and concurrent recovery results, and apparent residues were < LOQ in all control samples.Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

17 of 22 Residues of all analytes were < 0.01 ppm in all soybean matrices and wheat grain. Quantifiable residues of thiacloprid amide occurred in a fe w samples of wheat forage, hay, and straw. Residues of the hydroxyamide metabolite were < 0.01 ppm in all samples, except for three samples of wheat hay. Residue s are summarized in Table 8.

Table 8. Summary of Residue Data from Soybean and Wheat Rotational Crop Trials with Thiacloprid. Commodity Total Applic.

Rate (lb ai/A) PBI (days) Residue Levels (ppm)

n Min. Max. HAFT Median (STMdR) Mean (STMR) Std.

Dev. Thiacloprid Soybean, seed 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Soybean, forage 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Soybean, hay 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, grain 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, forage 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, hay 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 --
Wheat, straw 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 --

Amide Metabolite Soybean, seed 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Soybean, forage 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Soybean, hay 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, grain 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, forage 0.285 30 20 <0.01 0.030 0.030 0.01 0.011 0.004 Wheat, hay 0.285 30 20 <0.01 0.035 0.032 0.010 0.014 0.007
Wheat, straw 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Hydroxy Amide Metabolite Soybean, seed 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Soybean, forage 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Soybean, hay 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, grain 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, forage 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 -- Wheat, hay 0.285 30 20 <0.01 0.019 0.017 0.01 0.010 0.001
Wheat, straw 0.285 30 20 <0.01 <0.01 <0.01 <0.01 <0.01 --

Conclusions : Results indicate that tolerances for re sidues of thiacloprid are not needed for rotational crops. Similarly, resi dues in rotational crops are not a matter of concern for risk assessment. Residues were below the LOQ in all samples of huma n foods and should not significantly increase the total toxic residue wh en estimating the livestock dietary burden. The higher polarity of the metabol ites relative to the parent compound indicates that these compounds are likely to be more readily excret ed and further reduces the concern for human exposure via secondary residues in livestock commodities.

860.1550 Proposed Tolerances

For purposes of tolerance expression, HED has de termined that the residue of concern is the parent compound thiacloprid for all plant and animal commoditi es. Permanent tolerances are currently established for the combined residues of the insecticide thiacloprid and metabolites retaining the thiazolidine ring intact, measur ed and expressed in terms of thiacloprid, per se in/onThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

18 of 22 various plant and animal commodities rangi ng from 0.02 ppm to 11 ppm [40 CFR §180.594]. The tolerance expression proposed by Baye r CropScience (PP#0E7706) for pepper (bell and non-bell) and IR-4 (PP#0F7704) for stone fruits ar e for the combined resi dues of the insecticide thiacloprid and metabolites retaining the thiazoli dine ring intact, measured and expressed in terms of thiacloprid, per se. A revised Section F should be submitted, revising the tolerance definition to be in terms of only thiacl oprid ([3-[(6-chloro-3-pyridinyl)methyl]-2- thiazolidinylidene] cyanamide). The tolerance levels should also be revised to those listed in

Table 8.

Using the Agency’s Guidance for Setting Pesticide Tole rances Based on Field Trial Data , the recommended tolerance levels are 0.40 ppm fo r peppers, and 0.8 ppm for stone fruit, except plum and 0.04 ppm for plum (see Appendix I). There are currently no established Canadian, or Mexican maximum residue limits (MRLs) for thiacloprid in/on the proposed commodities.

Codex MRLs have been established for residues of thiacloprid in/on sw eet peppers (including pimento or pimiento) at 1 ppm and stone fruit, crop 12 at 0.5 ppm. C odex MRLs are expressed in terms of thiacloprid per se . Since the Codex MRLs are expre ssed on the same analytical basis

as the recommended tolerance definition and the calculated tolerances are reasonably similar to the Codex MRLs (except plum), the U.S. toleran ces, if established, should be harmonized with the Codex MRLs (see Table 9). A separate tole rance listing for plum will be necessary due to the significantly different residues in/on that fruit. An Internati onal Residue Limit (IRL) form is appended to this Summary Document and follows this section.

Table 9. Tolerance Su mmary for Thiacloprid

Commodity Proposed Tolerance (ppm) Recommended Tolerance (ppm) Comments; Correct Commodity Definition

Pepper (bell and non-bell) 1.1 1.0 Pepper , recommended tolerance is

harmonized with the Codex MRL.

Stone Fruit, except plum 0.5 0.5 Fruit, stone, group 12

, recommended tolerance is

harmonized with the Codex MRL.

Plum -- 0.05 PlumThiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

19 of 22 International Residue Limits

Thiacloprid (PC Code 014019; 9/16/2010)

Summary of US and International Tolerances and Maximum Residue Limits Residue Definition :

US Canada Mexico 2 Codex 3

40 CFR 180.594: Plant/Livestock: thiacloprid ([3-[(6- chloro-3-pyridinyl)methyl]-2- thiazolidinylidene] cyanamide) and metabolites retaining the thiazolidine ring intact, measured and expressed in terms of thiacloprid, per se (Z )-[3-[6-chloro-3- pyridinyl)methyl]-2- thiazolidinylidene]cyana mide, including metabolites retaining the thiazolidine ring intact Thiacloprid

Commodity 1 Tolerance (ppm) /Maximum Residue Limit (mg/kg)

US Canada Mexico 2 Codex Pepper (bell and non-bell)

1.0 Peppers,

Sweet (including pimento or pimiento) 1 Fruit, stone, group 12, except plum 0.70 0.5

Plum 0.05

Completed: M. Negussie; 09/17/2010

1 Includes only commodities of interest for this action. Tolerance values should be the HED recommendations and not those proposed by the applicant.

2 Mexico adopts US tolerances and/or Codex MRLs for its export purposes.

3 * = absent at the limit of quantitation; Po = postharvest treatment, such as treatment of stored grains. PoP = processed postharvest treated co mmodity, such as processing of treated stored wheat. (fat) = to be measured on the fat portion of the sample. MRLs indicated as proposed have not been finalized by the CCPR and the CAC.Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

20 of 22 Appendix 1 - Tolerance Assessment Calculations

For each of the crops listed below, the OECD harmonized MRL Calculation Procedures were used to obtain a recommended tolerance. As per the policy for using the procedure, the average

residue level from each field trial was used as input to obtain the recommended tolerance.

PP#0E7706

Pepper (Bell and Non-Bell)

The dataset used to obtain a tolerance recomm endation for thiaclopridon pepper (bell and nonbell) consisted of field trial data represen ting application rates of 0.281-0.287 lb ai/A (3 applications at ~0.094 lb ai/A/app lication) with PHIs of 6-7 days. As specified by the SOP, the trial application rates and PHIs are within 25% of the maximum label application rate and minimum label PHI, respectively. The residue valu es used to calculate the tolerance for bell and non-bell pepper are provide d in the table below.

All field trial sample results except for one sa mple of bell pepper were above the LOQ (LOQ = 0.01 ppm); 4 of 6 field trial sample results fo r non-bell pepper were below LOQ (LOQ = 0.01 ppm).

Using the OECD harmonized MRL calculation pr ocedures, the calculated tolerances are 0.30 ppm for bell pepper and 0.6 ppm for non-bell pepper. Both values were flagged as having high uncertainty due to small data set. In addition, the non-bell pepper tolerance was flagged as being highly censored. The calculati on-procedure-recommended toleran ce for pepper is 0.60 ppm, the

maximum of the recommended individual toleran ces. The Codex MRL for peppers is 1.0 ppm. HED is recommending that the tolerance, if estab lished, be set at 1.0 ppm in order to harmonize

with Codex.

PP#0E7704

Stone Fruits, Crop Group 12

The dataset used to obtain a tole rance recommendation for thiaclopr id on stone fruit consisted of field trial data for sweet cherry, peach, and plum (as representatives of crop group 12). The trials conducted reflect application ra tes of 0.371-0.385 lb ai/A (two applications at ~0.125 lb ai/A/application) with PHIs of 12-15 days. As specified by the SOP, the trial application rates

and PHIs are within 25% of the maximum labe l application rate and minimum label PHI, respectively. The residue values that were ente red into the tolerance sp readsheet are provided in

the table below.

All field trial sample results except for two sa mples of sweet cherry were above the LOQ (LOQ = 0.02 ppm). All field peach trial sample resu lts were above the LOQ (LOQ = 0.02 ppm). 8 of 12 field trial sample results for plum were below LOQ (67%).Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D406397

21 of 22 Using the OECD MRL harmonization procedures , the recommended tolera nces are 0.50 ppm for cherry, 0.70 ppm for peach, and 0.05 ppm for plum . The disparity of approximately 10X between plum and the other representative commod ities indicates that a separate tolerance for residues in/on plum is appropriate. The calcu lation-procedure-recommended tolerance for Crop Group 12, except plums is 0.70 ppm. This toleran ce level recommendation is slightly higher than the level (0.5 ppm) proposed by the pe titioner for Crop Group 12. The calculationprocedure-recommended tolerance for residues in /on plum is 0.05 ppm. The Codex MRL for stone fruit is 0.5 ppm. In order to harmonize with the Codex MRL, HED is recommending that the tolerance, if estab lished, be set at 0.5 ppm for residues in/on fruit, stone, group 12, except plum. HED’s recommended tolerance leve l for residues in/on plum is 0.05 ppm.Thiacloprid Summary of Analytical Chemistry and Residue Data DP#: D40639722 of 22Summary of the OECD MRL CalculationProcedure Inputs and Outputs for Thiacloprid in/on Peppers and Stone Fruit.**Compound Thiacloprid** **Thiacloprid Thiacloprid** **Thiacloprid Thiacloprid** **Crop Bell Pepper** **Non-Bell Pepper Sweet Cherry** **Peach Plum** **Total number of data (n)**6 3 7 9 6**Percentage of censored data**17% 67% 14% 0% 83%**Number of non-censored data**5 1 6 9 1**Lowest residue**0.010 0.010 0.010 0.042 0.010**Highest residue**0.132 0.210 0.239 0.369 0.031**Median residue**0.040 0.010 0.176 0.125 0.014**Mean**0.053 0.077 0.162 0.167 0.016**Standard deviation (SD)**0.048 0.115 0.078 0.121 0.008**Correction factor for censoring (CF)**0.889 0.556 0.905 1.000 0.444**Proposed MRL estimate - Highest residue** 0.132 0.210 0.239 0.369 0.031**- Mean + 4 SD**0.247 0.537 0.473 0.650 0.049**- CF x 3 Mean**0.142 0.128 0.440 0.500 0.021**Unrounded MRL**0.2470.5370.4730.6500.049**Rounded MRL 0.3** **0.6 0.5** **0.7 0.05** Highuncertaintyof MRLestimatedue tosmalldataset.High uncertainty ofMRL estimate due tosmall dataset andhigh level ofcensoring.Highuncertainty ofMRL estimatedue to smalldataset.Highuncertaintyof MRLestimate dueto smalldataset andhigh level ofcensoring.**Residues (mg/kg)** **Residues (mg/kg)** **Residues (mg/kg)** **Residues (mg/kg)** **Residues (mg/kg)** 0.0866 0.0100 * 0.2391 0.0418 0.0177 *0.0252 0.0100 * 0.1244 0.1231 0.0178 *0.0115 0.2096 0.0100 * 0.0649 0.0100 *0.0104 * 0.1649 0.1257 0.0100 *0.1324 0.2316 0.1881 0.0100 *0.0545 0.1878 0.3694 0.03090.1762 0.12470.09740.3650