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                 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
                            WASHINGTON, D.C.  20460

                                                  OFFICE OF CHEMICAL SAFETY AND
                                                                                POLLUTION PREVENTION

MEMORANDUM

Date:	November 12, 2013

Subject:	Chlorantraniliprole.  Petition for the Establishment of Permanent Tolerances and Registration for Use on Peanuts and on Green Onion, Addition of Use on Greenhouse Tomato and Greenhouse Pepper  and Greenhouse Cucumber, Crop Group Conversions for Stone Fruit and Tree Nuts, and Label Amendment to Shorten the PHI for Passionfruit, Papaya, and Mayhaw.   Condition of Registration Data for Rice, Crayfish, Coffee, Strawberry, and Livetock Analytical Methods.  Summary of Analytical Chemistry and Residue Data.

PC Code: 090100
DP Barcode:  D407350; D416101
Decision No.: 476038; 477960; 477964; 477967;
477972; 477962 ; 477952; 477965; 477970;
477963;  477954; 477966; 477971; 417413
Registration No.: 352-728; 352-729; 352-730; 352-820; 352-841; 352-838; 352-844

Petition Nos.: 3E8170; 3F8158
Regulatory Action: Section 3 Registration
Risk Assessment Type:  NA
Case No.: N/A
TXR No.:  NA
CAS No.:  500008-45-7
MRID No.:  See Below
40 CFR§180.628

From:	Steve Funk, Senior Chemist
	Risk Assessment Branch III (RAB III)
	Health Effects Division (HED; 7509P)

Through:	Christine Olinger, Branch Chief
	Risk Assessment Branch III (RAB III)
         Health Effect Division (HED; 7509P)

To: 	Venus Eagle/Jennifer Urbanski, RM 01
	Registration Division (RD; Mail Stop 7505P)

         And

         Barbara Madden/Laura Nollen, MR 05
	Registration Division (RD; Mail Stop 7505P)

OCSPP 860 Series Guideline
MRID Number
Title

860.1340
48930702
Vogl, E.; Stry, J. (2012) Analytical Method for the Determination of Chlorantraniliprole and IN-ECD73 in Crayfish Using LC/MS/MS.  Project Number: DUPONT/31473/OCR, ABC/66393/M.  Unpublished study prepared by ABC Laboratories, Inc.
860.1340
48930705
Henze, R.; Wadsley, M.; Stry, J. (2011) Analytical Method for the Determination of Chlorantraniliprole and Metabolites in Poultry Tissues and Eggs Using LC/MS/MS.  Project Number: DUPONT/31085/OCR. Unpublished study prepared by DuPont Crop Protection.
860.1500
48930701
Rice, F. (2012) Magnitude of Chlorantraniliprole Residues in Rice and Crayfish Following Seed Treatment with Chlorantraniliprole (DPX-E2Y45) FS [50% (w/w)] - U.S., 2011 - 2012.  Project Number: DUPONT/30021/OCR, ABC/66393.  Unpublished study prepared by ABC Laboratories, Inc.
860.1500
48930707
Rice, F. (2012) Magnitude of Chlorantraniliprole Residues in Coffee Following Foliar Applications with Chlorantraniliprole (DPX-E2Y45) 35WG - U.S., 2011.  Project Number: DUPONT/30023/OCR, ABC/66392. Unpublished study prepared by ABC Laboratories, Inc.
860.1500
48930708
Rice, F. (2012)  Magnitude of Chlorantraniliprole Residues in Strawberries Following Foliar Applications with Chlorantraniliprole (DPX-E2Y45) 20SC [200 g/L (w/v);18.4% (w/w] - U.S. and Canada, 2011.  Project Number: DUPONT/30024/OCR, ABC/66391.  Unpublished study prepared by ABC Laboratories, Inc.
860.1500
49076103
Dorschner, K. (2012) Chlorantraniliprole: Magnitude of the Residue on Cherry, Papaya and Lychee.  Project Number: B10204/OCR, B10204/09/FLR18, B10204/09/FL69.  Unpublished study prepared by University of Hawaii.
860.1500
49076101
Dorschner, K. (2010) Chlorantraniliprole: Magnitude of the Residue on Greenhouse Cucumbers.  Project Number: 10004/OCR, 10004/08/FLR07, 08/MD21.  Unpublished study prepared by University of Maryland/LESREC, Colorado State University and Interregional Research Project No. 4.
860.1500
49076102
Dorschner, K. (2009) Chlorantraniliprol: Magnitude of the Residue on Greenhouse Tomato.  Project Number: 09477/OCR, 09477/07/FLR09, 09477/07/CO06.  Unpublished study prepared by Colorado State University.
860.1500
49076104
Dorschner, K. (2012) Chlorantraniliprole: Magnitude of the Residue on Green Onion (Fresh and Dried) and Dill Seed.  Project Number: A10204/OCR, A10204/09/FLR17, A10204/09/CA/99.  Unpublished study prepared by University of California.
860.1500
49071201
Rice, F. (2012) Magnitude of Chlorantraniliprole Residues in Peanuts Following Foliar Applications with Chlorantraniliprole (DPX-E2Y45) 20SC [200 g/L (w/v); 18.4% (w/w)] - U.S., 2011.  Project Identification Numbers: DuPont-31666, ABC 66664.  Unpublished study prepared by ABC Laboratories and E.I. du Pont de Nemours and Company

                               Table of Contents

1.0	Executive Summary	5
2.0	Regulatory Recommendations	5
2.1	Data Deficiencies/Data Needs	5
2.2	Tolerance Considerations	5
2.2.1	Enforcement Analytical Method	6
2.2.2	Recommended Tolerances	6
2.2.3	Revisions to Petitioned-For Tolerances	7
2.2.4	International Harmonization	7
3.0	Introduction	8
3.1	Chemical Identity	8
3.2	Physical/Chemical Characteristics	9
3.3	Pesticide Use Pattern/Directions for Use (860.1200)	10
4.0	Metabolite/Degradate Residue Profile	12
4.1	Nature of the Residue	12
4.1.1 	Summary of Plant Metabolism (860.1300)	13
4.1.3	Summary of Confined Rotational Crops (860.l850)	14
5.1	Residue Analytical Methods (860.1340)	14
5.1.1	Data Collection Methods	14
5.1.2	Multi-Residue Methods (860.1360)	17
5.1.3	Tolerance Enforcement Methods	17
5.1.4	Submittal of Analytical Reference Standards (860.1650)	18
5.2	Storage Stability (860.1380)	18
5.3.1	Crop Field Trials (860.1500)	19
49071201.der	20
5.3.2	Field Rotational Crops (860.1900)	29
5.3.3	Processed Food and Feed (860.1520)	30
5.3.4	Meat, Milk, Poultry and Eggs (860.1480)	31
<IP_ADDRESS>	Dietary Burden	31
<IP_ADDRESS>	Estimated Secondary Residues in Livestock	31
5.3.5.	Food Handling (860.1460)	31
5.3.6	Water, Fish, and Irrigated Crops (860.1400)	31
6.0	Tolerance Derivation	32
Appendix A.  International Residue Limits Table	34
Appendix B.  OECD MRL Calculation Procedure Inputs/Outputs	35

1.0	Executive Summary

Adequate field trial data were submitted to support use on greenhouse tomato, greenhouse pepper, and greenhouse cucumber. The existing tolerances from field use cover the expanded use pattern.

Condition of registration data submitted for field trials for rice, coffee, and strawberry confirm the existing tolerances.  A study submitted as confirmatory data for crayfish supports a lowering of the crayfish tolerance.

A condition of registration requirement for an analytical method for data collection for poultry commodities has been fulfilled.

Condition of registration data on field trial residue decline for cherry, papaya, and leechee support existing tolerances for certain tropical fruits and allow for lowering of the PHIs from 10 days to 1 day, with an increase in tolerance from 2 ppm to 4 ppm, for papaya and passionfruit.

Adequate field trial data were submitted to support new uses on peanuts and the green onion subgroup 3-07B.

Additional field trial data support an increase in the spice subgroup 19B tolerance.

Crop group conversions for the tree nut group, pome fruit group,  and stone fruit group are acceptable.  The tolerances for mayhaw and pistachio will be removed with their addition to the pomefruit and tree nut groups, respectively.

2.0	Regulatory Recommendations

There are no residue chemistry considerations that would preclude granting the requested registration and establishing the recommended tolerances for chlorantraniliprole on peanuts and the green onion subgroup 3-07B.   A modified Section F must be submitted to request a change in the crayfish tolerance to 0.01 ppm and a change in the spice subgroup 19B tolerance to 90 ppm.  Likewise, the requested crop group conversions are acceptable.  Condition of registration requirements for field trials on strawberry, coffee, and rice have been fulfilled.  A condition for registration requirement for crayfish trials has been fulfilled.  A condition of registration requirement for an analytical method for data collection for poultry commodities has been fulfilled.  The specific tolerance recommendations are discussed in 2.2, and label modifications are discussed in section 2.3

2.1	Data Deficiencies/Data Needs

There are no data deficiencies related to the present submission.

2.2	Tolerance Considerations

2.2.1	Enforcement Analytical Method

An adequate enforcement method (liquid chromatography/tandem mass spectrometry (LC/MS/MS), DuPont-11374) is available for the determination of chlorantraniliprole residues in/on plant commodities.   The purified extract is analyzed by LC/MS/MS operating in the positive ionization mode.  For the determination of chlorantraniliprole, the following ion transitions are monitored (m/z 484  453, 484  286, 284  112, 284  177).  The limit of quantitation (LOQ) is reported at 0.01 ppm for parent chlorantraniliprole.  The LC/MS/MS method was adequately validated on a variety of matrices:  corn fodder, raisins, grapes, soybean seed, cotton gin trash, white rice, brown rice, tomato, bell pepper, lettuce, and tea leaves and an acceptable Independent Laboratory Validation (ILV) study was conducted on apples, wheat grain, and almond nutmeat.  The method for the determination of chlorantraniliprole and its metabolites in processed commodities is a LC/MS/MS method, DuPont-14314, which is a slightly modified version of DuPont-11374.  These methods have been accepted by the Analytical Chemistry Branch (ACB)/Biological and Economical Analysis Division (BEAD; DP#340358, C. Stafford, 02/06/2008).

An adequate enforcement method (LC/MS/MS) is available for the determination of residues of chlorantraniliprole and its metabolites in/on animal commodities.  Atmospheric pressure chemical ionization (APCI) MS/MS detection operated in the positive ion mode is used.  The LOQ is reported at 0.010 ppm for the parent and each of the metabolites.  The method has been accepted by ACB/BEAD (DP#340358, C. Stafford, 02/06/2008).

2.2.2	Recommended Tolerances

The current tolerance definition is found at 40CFR§180.628.  Compliance with the tolerance is based on measuring only chlorantraniliprole for both plant and animal commodities.

Table 2.2.2.  Tolerance Summary for Chlorantraniliprole
Commodity
                     Established/Proposed Tolerance (ppm)
                        HED-Recommended Tolerance (ppm)
                                   Comments
                        (correct commodity definition)
Papaya
2.0
4.0

Passionfruit
2.0
4.0

Peanut, nutmeat
0.06
0.06

Peanut, hay
0.20  (exp 04/10/14)
90 proposed
90
Translation from alfalfa hay
Onion, green, subgroup 3-07B
3.0
3.0

Spice subgroup 19B
14[1] established/40 proposed
90

Nut, tree, group 14-12
0.04
0.02
Crop group conversion.
International harmonization.
Nut, tree, group 14
0.04
Remove
Replaced by crop group 14-12
Pistachio
0.04
Remove
Replaced by crop group 14-12
Fruit, pome, group 11-10
1.2
1.2
Crop group conversion
Fruit, pome, group 11, except mayhaw
1.2
Remove
Replaced by crop group 11-10
Mayhaw
0.6
Remove
Replaced by crop group 11-10
Fruit, stone group 12-12, except cherry, Chickasaw plum, and damson plum
4.0
4.0
Crop group conversion
Fruit, stone group 12, except cherry, Chickasaw plum, and damson plum
4.0
Remove
Replaced by crop group 12-12
Crayfish
8.0
0.01

Onion, green
0.20 (exp 04/10/14)
Remove
Replaced by Onion, green, subgroup 3-07B
Onion, welsh
0.20 (exp 04/10/14)
Remove
Replaced by Onion, green, subgroup 3-07B
Shallots, fresh leaves
0.20 (exp 04/10/14)
Remove
Replaced by Onion, green, subgroup 3-07B
Leek
0.20 (exp 04/10/14)
Remove
Replaced by Onion, green, subgroup 3-07B
[1] A tolerance of 14 ppm was recommended (D361791, D. Rate, 01/08/2010), but is not listed in 40CFR§180.628.  This was based on the translation of alfalfa seed data, with adjustments for adjuvant use (2x) and application rate (2x).

2.2.3	Revisions to Petitioned-For Tolerances

The petitioned tolerances are the same as the recommended tolerances, except for spice subgroup 19B and crayfish.  Residue data on dill seed was presented in support of a spice subgroup 19B tolerance.  HED had previously recommended for a spice subgroup 19B tolerance of 14 ppm.  The petitioner requested 40 ppm, but evaluation of the dill seed data indicates that 90 ppm is appropriate.  See Appendix B.

A crayfish tolerance of 8 ppm was previously established based on a fish bioconcentration study and the estimated residues in water, sediment, and rice straw. The present crayfish study showed no residues (<0.01 ppm) at various sampling intervals from the use of chlorantraniliprole as a seed treatment on rice.   This reflects the actual use pattern. A tolerance of 0.01 ppm is appropriate.  A modified Section F is required.

A crop group conversion for tree nut group 14 to tree nut group 14-2 was requested.  This is acceptable, but the tolerance will be changed from 0.4 ppm to 0.2 ppm to harmonize with Canada and Codex.

The registrant must submit a revised Section F requesting tolerances of 90 ppm and 0.01 ppm  for the spice subgroup 19B and crayfish, respectively.

2.2.4	International Harmonization

Residue definitions are harmonized among the US, Canada, and Codex, with the common definition chlorantraniliprole.   Relevant maximum residue limits (MRLs) are summarized in the International Residue Limits (IRL) table in Appendix A.

The existing US tolerance for the tree nut group is 0.04 ppm, whereas the tolerance in both Canada and Codex is 0.02 mg/kg.  The US tolerance is based upon the evaluation of field trial data for pecans and almonds with the use of the North American Free Trade Agreement (NAFTA) statistical spreadsheet (N. Tsaur, D357727, 03/03/2009).  The data were reevaluated using the current procedure, the OECD spreadsheet, as shown in Appendix B. The new tolerance estimate is 0.02 ppm.  Therefore, the tolerance for tree nuts, including pistachio, is lowered to 0.02 ppm, and harmonization with Canada and Codex is achieved.

The existing US tolerance for the pome fruit group is 1.2 ppm.  The Codex MRL for pome fruit is 0.4 ppm, and the Canada MRL for various pome fruits (apple, pear, mayhaw, quince) is 0.4 ppm.  The original US tolerance for pome fruits was 0.3 ppm, but it was adjusted upwards to 1.2 ppm to accommodate the use of adjuvants and a shortened PHI (D361791, D. Rate, 01/08/2010).  Therefore, the 1.2 ppm value cannot be lowered to harmonize with Codex and/or Canada.

The existing US tolerance for the stone fruit group (except cherry, chickasaw plum, and damson plum) is 4.0 ppm.  The Codex MRL for stone fruits is 1 mg/kg and the Canada MRL for various stone fruits (apricot, nectarine, peach, plum, plumcots, cherries) is 2.5 mg/kg.  The original US tolerance for stone fruits was 1.0 ppm, but it was adjusted upwards to 4.0 ppm to accommodate the use of adjuvants and a shortened PHI (D361791, D. Rate, 01/08/2010).  Therefore, the 4.0 ppm value cannot be lowered to harmonize with Codex and/or Canada.

Codex has not established MRLs for passionfruit, papaya, peanuts, green onions, herbs, or spices.  Therefore, there is no harmonization issue with Codex.  Canada does not have MRLs for these same commodities, with the exception of green onions and peanuts.  Canada and the US are conducting a joint review for green onions and peanuts and have agreed upon harmonized MRL values.

2.3	Label Recommendations

The proposed labels are acceptable.

3.0	Introduction

Chlorantraniliprole (DPX-E2Y45) is an anthranilic acid (or 2-aminobenzoic acid) diamide insecticide belonging to a class of compounds that acts on the ryanodine receptor.  Section 3 registrations of chlorantraniliprole for use in the United States have been approved  for the numerous  crop groups or crop subgroups and individual commodities. Chlorantraniliprole is registered to E.I. du Pont de Nemours and Company (DuPont).

3.1	Chemical Identity

Table 3.1.  Chlorantraniliprole Nomenclature.
Chemical structure

Common name
Chlorantraniliprole
Company experimental name
DPX-E2Y45
IUPAC name
3-bromo-4′-chloro-1-(3-chloro-2-pyridyl)-2′-methyl-6′-(methylcarbamoyl)pyrazole-5-carboxanilide
CAS name
3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-
pyridinyl)-1H-pyrazole-5-carboxamide
CAS registry number
500008-45-7
End-use product (EP)
DuPont(TM) Altacor[(R)] WG (35%; EPA Reg. No. 352-730)
DuPont(TM) Coragen(R) SC Insect Control (1.67 lb ai/gal; EPA Reg. No. 352-729)
DuPont(TM) Dermacor(R) X-100 Seed Treatment (FS, 5.21 lb ai/gal; EPA Reg No. 352-820)

3.2	Physical/Chemical Characteristics

The log octanol/water partition coefficient is <3 over a range of pHs, suggesting that chlorantraniliprole is not highly soluble in fat-type matrices and hydrocarbon solvents.  This is confirmed by the solubility data in water and various organic solvents.   The low vapor pressure means low volatility.

Table 3.2.	 Physicochemical Properties of Technical Grade of Chlorantraniliprole.
Parameter
Value
Reference
Melting point/range (°C)
200-202 (95.9%)/208  -  210 (99.2%)
46889033
pH
5.77 +- 0.087 at 20°C
46889031
Relative Density
1.5189 (95.9%)/1.507 (99.2%) at 20°C
46889033
Water solubility (20°C)

Deionized Water            1.023 mg/L
pH 4                                0.972 mg/L
pH 7                                0.880 mg/L
pH 9                                0.971 mg/L
46889026

Solvent solubility (20°C)
Acetone                          3.446 +- 0.172 g/L
Acetonitrile                     0.711 +- 0.072 g/L
Ethyl Acetate                  1.144 +- 0.046 g/L
Dichloromethane            2.476 +- 0.058 g/L
Dimethylformamide        124 +- 4 g/L
n-Octanol                        0.386 +- 0.01 g/L
Methanol                         1.714 +- 0.057 g/L
n-Hexane                         <0.0001 g/L
o-Xylene                          0.162 +- 0.01 g/L
46889030

Vapor pressure
6.3 x 10-12 Pa @ 20°C, 2.1 x 10-11 Pa @ 25°C
46889130
Dissociation constant, pKa
10.88 +- 0.71
46889034
Octanol/water partition coefficient, KOW (20°C)
Deionized Water              589
pH 4                                 588
pH 7                                 721  (log 2.8)
pH 9                                 654
46889032
UV/visible absorption (max)
pH <2 no absorption max >200 nm, at 290 ε = 3941
pH 7 no absorption max >200 nm, at 290 ε = 4185
pH >10 absorption max at ~320 nm which may be
due to decomposition of DPX-E2Y45, at 290 ε = 6082
46889027

3.3	Pesticide Use Pattern/Directions for Use (860.1200)

Table 3.3.  Summary of Proposed Directions for Use of Chlorantraniliprole
Applic. Timing, Type, and Equip.
                                  Formulation
                                [EPA Reg. No.]
                                 Applic. Rate
                                   (lb ai/A)
                          Max. No. Applic. per Season
                          Max. Seasonal Applic. Rate
                                   (lb ai/A)
                                      PHI
                                    (days)
                        Use Directions and Limitations
                                    Peanut
Foliar
(ground; aerial)

18.4% SC
1.67 lb ai/gal
Coragen
(352-729)
0.045  -  0.065
4
0.2 (from all chlorantranili-prole sources)
1
Minimum interval between treatments is 3 days.

Foliar
(ground; aerial)
5% SC
0.43 lb ai/gal
Prevathon
(352-844)
0.047-0.067
4
0.2 (from all chlorantranili-prole sources)
1
Minimum interval between treatments is 3 days.

               Bulb Vegetables (including green onion subgroup)
Foliar
(ground; aerial)
18.4% SC
1.67 lb ai/gal
Coragen
(352-729)
0.045  -  0.065
4
0.2 per crop
0.6 per year
(from all chloroantranili-prole sources)
1
Minimum interval between treatments is 4 days.

         Greenhouse Cucumbers, Greenhouse Peppers, Greenhouse Tomatoes
Foliar

18.4% SC
1.67 lb ai/gal
Coragen
(352-729)
0.031 tomato
0.045 pepper, cucumber
3 (per crop cycle)
0.134 per crop cycle
1
Minimum interval between treatments is 7 days.
Mix 1.6 fl oz per 100 gal spray volume (0.0209 lb ai/100 gal)
Maximum application is 150 gal spray solution per acre for tomato and 214 gal spray solution per acre for cucumber and pepper.

                                Tropical Fruits
Foliar
35.0% WDG
Altacor
(352-730)

0.066- 0.099
3
0.2 (from all chloroantranili-prole sources)
1[1]

10 (acerola, jaboticaba, and lychee)
Minimum interval between treatments is 7 days.
Do not apply dilute solutions of more than 200 gal water per acre.
Do not apply less than 30 gal water per acre

                      Low growing berry (subgroup 13-07G)
Foliar
35.0% WDG
Altacor
(352-730)

0.066-0.099
3
0.2 (from all chloroantranili-prole sources)
1
Minimum interval between treatments is 7 days.
Do not apply dilute solutions of more than 200 gal water per acre.
Do not apply less than 30 gal water per acre.
Do not apply to strawberry or cranberry.

Foliar
18.4% SC
1.67 lb ai/gal
Coragen
(352-729)
0.045-0.065
4
0.2 per crop (from all chloroantranili-prole sources)
0.4 per year  (from all chloroantranili-prole sources)
1
Minimum interval between treatments is 7 days.

                                     Rice
Seed treatment
50% FS
5.21 lb ai/gal
Dermacor X-100
0.084
1
N/S
N/S
Do not use DERMACOR(R) X-100 treated rice field
for the aquaculture of edible fish or Crustacea
(including crawfish) during the rice production cycle
(planting through harvest).
                                    Coffee
Foliar
35.0% WDG
Altacor
(352-730)

0.066-0.099
3
0.2 (from all chloroantranili-prole sources)
7
Minimum interval between treatments is 14days.
Do not apply dilute solutions of more than 200 gal water per acre.
Do not apply less than 30 gal water per acre.

                               Herb Subgroup 19A
Foliar
18.4% SC
1.67 lb ai/gal
Coragen
(352-729)
0.045  -  0.065
4
0.2 per crop (from all chloroantranili-prole sources)
0.8 per year (from all chloroantranili-prole sources)
1
Minimum interval between treatments is 3 days.

                              Spices Subgroup 19B
Foliar
18.4% SC
1.67 lb ai/gal
Coragen
(352-729)
0.045  -  0.065
4
0.2 per crop (from all chloroantranili-prole sources)
0.8 per year (from all chloroantranili-prole sources)
1
Minimum interval between treatments is 3 days.

[1]The PHI for papaya and passionfruit has been reduced from 10 days to 1 day.

Conclusions.

The label information is adequate to allow evaluation of the residue data relative to the proposed uses.   No label changes are needed for the uses presented in Table 3.3.

4.0	Metabolite/Degradate Residue Profile

4.1	Nature of the Residue

The nature of the residue in plants is adequately understood.  HED has determined that parent chlorantraniliprole is the residue of concern in plant commodities for tolerance expression and risk assessment (DP#343519, C. Olinger, 02/29/2008).

The HED's ROCKS (DP#343519, C. Olinger, 02/29/2008) previously determined that the residue of concern in ruminants is chlorantraniliprole for the purposes of the tolerance expression.  ROCKS also determined that the residue of concern in ruminants is chlorantraniliprole for the purposes of risk assessment, unless the level of the dietary burden significantly increased.  With an increase of dietary burden of ruminants, for risk assessment purposes, the following metabolites are now included: IN-HXH44 and IN-K9T00.  Upon consultation with members of ROCKS, the chlorantraniliprole risk assessment team previously determined that the residue of concern for the tolerance expression in poultry is chlorantraniliprole and that metabolites (IN-H2H20, IN-K7H29 and IN-GAZ70) would be included with chlorantraniliprole in the risk assessment for eggs. However, the poultry feeding study revealed concentrations of metabolites IN-H2H20, IN-F9N04, IN-K7H29, and IN-GAZ70 often equal to the concentration of chlorantraniliprole in liver, eggs, meat, and fat (with skin).  These metabolites are structurally similar to the parent (Appendix I).  Therefore, the residue definition for dietary risk assessment in poultry commodities was altered to be the sum of chlorantraniliprole and metabolites IN-H2H20, IN-F9N04, IN-K7H29, and IN-GAZ70, calculated as chlorantraniliprole (D404708, S. Funk, 09/10/2013).

4.1.1 	Summary of Plant Metabolism (860.1300)

Studies have been conducted depicting the metabolism of chlorantraniliprole in apple, cotton, lettuce, rice, and tomato (DP#336941, L. Cheng, 02/25/2008).  In the apple, cotton, lettuce and tomato studies, the plants were treated at 3 x 100 g ai/ha by foliar application (~ 0.5x proposed maximum application rate), and rice was treated at 1 x 150 g ai/ha by soil drench (0.68x, based on the proposed Section 18 use).  Total radioactive residues were measured in apples (0.092 and 0.138 ppm at 15- and 30-day PHIs, respectively), lettuce (0.301 and 0.372 ppm at 7- and 15-day PHIs, respectively), cottonseed (<0.01 ppm at 126-day PHI), tomato (0.056 and 0.013 ppm at 7- and 15-day PHIs, respectively), and rice (0.155 ppm at 132-day PHI).  For apple, lettuce and tomato, the majority of the residues were surface residues.  In all these crops, unchanged chlorantraniliprole was the major residue (57-92% of the total radioactive residue (TRR)).

Very little degradation of chlorantraniliprole was observed in apple, cotton, lettuce and tomato.  Many metabolites were found in rice commodities and the metabolism in rice generally involves:  (i) hydroxylation of the N-methyl group (to IN-H2H20) or hydroxylation of the tolyl methyl group (to IN-HXH44); (ii) cyclization with loss of water to a quinazolinone derivative (IN-EQW78); and similar condensation of IN-H2H20 with an additional loss of CH2O (to IN-GAZ70); and (iii) N-demethylation via IN-H2H20 to IN-F9N04.

4.1.2	Summary of Livestock Metabolism (860.1300)
DP#343519, C. Olinger, 2/29/2008 (Residues of Concern Knowledgebase Subcommittee)
DP#336941, L. Cheng, 2/25/2008 (PP#7F7181)
DP#361791, D. Rate, 01/08/2010 (PP#9F7513)

Adequate metabolism studies with chlorantraniliprole in hens and goats have been reviewed (DP#336941, L. Cheng, 02/25/2008).  The metabolic fate of chlorantraniliprole in livestock was investigated by the conduct of radiolabeled studies in laying hens and lactating goats.

Following oral administration to laying hens, chlorantraniliprole and its metabolites were eliminated in the excreta (>98% of the dose).  Eggs and edible tissues contained approximately 3% of the total administered dose.  The major components of the radioactivity in eggs were parent chlorantraniliprole (12-23% TRR in egg yolk; 26-32% TRR in egg white) and IN-GAZ70 (4-7% TRR in egg yolk; 33-40% TRR in egg white); and parent chlorantraniliprole was the major component in skin with fat (18% TRR).  Chlorantraniliprole was also detected in liver (4% TRR) and muscle (4% TRR). The poultry feeding study, reviewed below, revealed significant concentrations of several metabolites in poultry commodities.

When [14]C-chlorantraniliprole was orally administered to a lactating goat at 10 ppm in the feed, a large proportion of the dose was eliminated in the excreta (93.57% of the dose).  Milk, liver, and kidney combined contained approximately 1% of the administered total dose.  Parent chlorantraniliprole was the major component of the extracted radioactivity identified in kidney, muscle, and fat samples and was also identified in liver.  The radioactivity in fat was higher than in muscle, indicating that chlorantraniliprole and its residues are likely to be designated as "fat-soluble."

The entire radioactivity in milk was extracted.  Three metabolites were identified in addition to chlorantraniliprole in the extracts.  Unchanged parent compound accounted for 23.58% TRR (0.016 ppm, 0.19% dose).  The three metabolites were IN-K9T00 at 26.1% TRR (0.017 ppm, 0.21% dose), IN-HXH44 at 26.92% TRR (0.018 ppm, 0.21% dose), and IN-HXH40 at 5.87% TRR (0.004 ppm; 0.05% dose).

4.1.3	Summary of Confined Rotational Crops (860.l850)

DP#336941, L. Cheng, 2/25/2008 (PP#7F7181)

Acceptable confined rotational crop studies have been reviewed and deemed adequate to satisfy data requirements.  Unchanged parent was the major identified residue in all rotational crop commodities including lettuce (64-85% TRR), wheat grain (48% TRR from an exaggerated rate at 120 DAT), wheat forage (54-84% TRR), wheat hay (51-73% TRR), and wheat straw (37-69% TRR); TRR were <0.01 ppm in wheat grain, beet root, and beet foliage.  HED (DP#343519, C. Olinger, 2/29/2008) has determined that the parent compound is the residue of concern in rotational crops for the purposes of tolerance expression and risk assessment.

5.1	Residue Analytical Methods (860.1340)

5.1.1	Data Collection Methods
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LC/MS/MS method DuPont-13294, a modification of the enforcement method, was utilized for the analysis of chloranatranilirprole in plant commodities.  Briefly, samples were hydrated and then extracted twice with acetonitrile (ACN) and filtered.  An aliquot of the extract was evaporated to dryness under a stream of nitrogen, reconstituted in ACN:water (40:60, v:v), and filtered for analysis by LC/MS/MS. The LOQ (determined as the LLMV) was 0.01 ppm for chlorantraniliprole in/on cucumbers, tomato, green onion, strawberry, peanut, lychee, cherry, papaya, and rice grain .

In this submission, E.I. du Pont de Nemours and Company (DuPont) has provided validation data for analytical method  31085 for the determination of residues of chlorantraniliprole and metabolites IN-H2H20, IN-F9N04, IN-K7H29, IN-GAZ70, and IN-EQW78 in poultry tissues and eggs.  This is a data collection method.

Briefly, homogenized samples are extracted once with water, acetonitrile (ACN), and hexane and once with ACN and hexane using a Genogrinder.  After centrifugation, the ACN layers are combined and diluted to volume with ACN.  For egg commodities (whole egg, egg white, and egg yolk), an aliquot is evaporated to dryness and redissolved in ACN, methanol, and water for analysis by liquid chromatography/tandem mass spectrometry (LC/MS/MS).  For poultry tissues, an aliquot is cleaned up on an Oasis Hydrophobic-Lipophilic Balance (HLB) solid-phase extraction (SPE) cartridge using ACN followed by 0.5% formic acid in ethyl acetate to elute residues; the eluate is diluted to volume with ACN, and an aliquot is evaporated to dryness and redissolved in ACN, methanol, and water for analysis by LC/MS/MS.  LC/MS/MS analysis is conducted in the positive ion mode monitoring at least two ion transitions for each analyte; one ion transition is used for quantitation and the relative ratio of the fragment ions is used for confirmation of analyte presence.

The method included an alternate extraction procedure for egg commodities.  Homogenized egg samples are mixed with water and extracted with ACN and hexane using a homogenizing probe.  After centrifugation, the ACN layer is removed and the remaining hexane and solids are extracted with ACN using the homogenizing probe.  The mixture is centrifuged and the ACN layers are combined and diluted to volume with ACN.  An aliquot is mixed with concentrated formic acid and then evaporated to dryness and redissolved in ACN, methanol, and water for LC/MS/MS analysis.

The method using the Genogrinder extraction was validated with samples of whole eggs, poultry muscle, poultry liver, and poultry fat fortified with chlorantraniliprole and metabolites IN-H2H20, IN-F9N04, IN-K7H29, IN-GAZ70, and IN-EQW78 at 0.010 and 0.10 ppm each.  Reasonably acceptable method validation recoveries were obtained for all analytes in every matrix using this method.  Recoveries [and coefficients of variation (CVs)] of chlorantraniliprole, IN-H2H20, IN-F9N04, IN-K7H29, IN-GAZ70, and IN-EQW78 ranged from 80-120% (2.0-8.3%) in whole eggs; from 89-123% (1.6-13.9%) in muscle; from 85-116% (2.7-9.6%) in liver; and from 83-157% (1.2-9.2%) in fat.  With few exceptions, individual recoveries were within the acceptable range of 70-120%.  High recoveries were obtained for chlorantraniliprole from fat (all samples; 122-157%), for IN-H2H20 from muscle (121%), and for IN-F9N04 from muscle (123%).

The method using the homogenizing probe was validated with samples of whole eggs, egg whites, and egg yolks fortified with chlorantraniliprole and metabolites IN-H2H20, IN-F9N04, IN-K7H29, IN-GAZ70, and IN-EQW78 at 0.010 and 0.10 ppm each.  Reasonably acceptable method validation recoveries were obtained for all analytes using this method.  Recoveries (and CVs) of chlorantraniliprole, IN-H2H20, IN-F9N04, IN-K7H29, IN-GAZ70, and IN-EQW78 ranged from 81-128% (4.3-14.8%) in whole eggs; from 74-122% (2.2-17.2%) in egg whites; from 87-127% (1.9-10.7%) in egg yolks.  High recoveries were obtained for chlorantraniliprole from egg yolks (127%), for IN-GAZ70 from whole eggs (122, 128, and 128%), and for IN-F9N04 from egg whites (122%).

The limit of quantitation (LOQ), based on the lowest level of method validation (LLMV), is 0.010 ppm for each analyte in each matrix.

In this submission, DuPont provided a data collection method (DuPont 31473) for the determination of chloranatraniliprole and metabolite IN-ECD73 in crayfish.  The method is similar to the livestock commodity enforcement method.

Briefly, samples are extracted once with purified water, acetonitrile (ACN), and hexane by shaking.  After centrifugation, the lower ACN/water layer is extracted again using ACN, and any remaining hexane is removed from the combined ACN/water layers by nitrogen evaporation.  The extract is diluted to volume with ACN, and an aliquot is mixed with ACN:0.01 M aqueous formic acid (75:25, v:v).  The extract is filtered through a 0.45-um polytetrafluoroethylene syringe filter for analysis by liquid chromatography/tandem mass spectrometry (LC/MS/MS).  LC/MS/MS analysis is conducted in the positive ion mode, monitoring ion transitions amu 484.0 to 286.0 for chlorantraniliprole and 279.2 to 244.0 for IN-ECD73.

The method was validated with samples of crayfish fortified at 0.010 and 0.100 ppm for both chlorantraniliprole and IN-ECD73.  Acceptable method validation recoveries were obtained. Recoveries of chlorantraniliprole and IN-ECD73 ranged from 83-103% (average of 95% and standard deviation of 6%) and from 82-105% (average of 92% and standard deviation of 6%), respectively.  Individual recoveries at each fortification level were within the acceptable range of 70-120%, and coefficients of variation (CVs) ranged from 1.2-10%.

The limit of quantitation (LOQ), based on the lowest level of method validation (LLMV), is 0.010 ppm for each analyte.

The solvents used for the extraction of samples in this method are the same as those used in the crayfish toxicity study (DuPont Report No. 24137).  Therefore, radiovalidation data for this method are not required.

Conclusions.

For data collection, LC/MS/MS method DuPont-13294 was used for the analysis of chlorantraniliprole residues in samples from the field trial studies submitted in conjunction with the subject petitions.  The adequacy of data-collection methods was verified with method recoveries in the acceptable 70-120% range.

DuPont-31085 was utilized for the analysis of samples from a poultry feeding study.   The adequacy of data-collection methods was verified with method recoveries in the acceptable 70-120% range, except as noted above.

Method DuPont 31473 is acceptable as a data collection method for residues of chlorantraniliprole and IN-ECD73 in crayfish.  The limits of quantitation (LOQs), based on the lowest levels of method validation (LLMVs), were 0.010 ppm for chlorantraniliprole in crayfish and 0.010 ppm for IN-ECD73 in crayfish. The method was adequate for data collection based on acceptable concurrent recoveries, as well as method validation for both analytes in crayfish. The method may be used for enforcement of tolerance purposes, based on its similarity to the livestock enforcement method (DuPont 11376).  An ILV study is not required.

5.1.2	Multi-Residue Methods (860.1360)
DP#336941, L. Cheng, 2/25/08 (PP#7F7181)

Multiresidue data for chlorantraniliprole are available.  The study evaluated chlorantraniliprole using the appropriate FDA multiresidue methods as outlined in the FDA Pesticide Analytical Manual, Volume I, Third Edition (January 1994).  Testing of Protocol A was not conducted since chlorantraniliprole does not naturally fluoresce.  Protocol B was not tested since chlorantraniliprole does not contain a carboxylic acid or phenolic group.  When subjected to Protocol C testing, chlorantraniliprole yielded multiple peaks on different columns and detectors.  The recovery of chlorantraniliprole through Protocol D could not be quantified because of matrix interference.  No or low recoveries of chlorantraniliprole were observed through Protocol E and F.  Protocol G was not tested since chlorantraniliprole does not contain a substituted urea function.

Conclusions.  The requirements for multiresidue methods data are fulfilled.  Chlorantraniliprole is not recovered by the US FDA's multiresidue methods.

5.1.3	Tolerance Enforcement Methods

DP#345790, L. Cheng, 11/6/2007 (PP#7F7181; PMV Request)
DP#340358, C. Stafford, 2/6/2008 (ACB/BEAD)
DP#336941, L. Cheng, 2/25/2008 (PP#7F7181)
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An adequate enforcement method (LC/MS/MS, DuPont-11374) is available for the determination of chlorantraniliprole residues in/on plant commodities.  Briefly, samples are soaked in water before extraction with acetonitrile (ACN).  An aliquot of the extract is diluted with water, filtered through a strong anion exchange (SAX) solid phase extraction (SPE) cartridge connected in series with an Oasis hydrophilic-lipophilic balanced (HLB) cartridge.  After washing the cartridges with water/acetonitrile, the cartridges are air dried, and the Oasis cartridge is separated from the SAX cartridge.  Chlorantraniliprole is eluted from the Oasis cartridge with acetone.  The eluant is evaporated to dryness and the residue is reconstituted in ACN and diluted with water.  The extract is analyzed by LC/MS/MS operating in the positive ionization mode.  For the determination of chlorantraniliprole, the following ion transitions are monitored (m/z 484  453, 484  286, 284  112, 284  177).  The LOQ is reported at 0.01 ppm for parent chlorantraniliprole.  The LC/MS/MS method was adequately validated on a variety of matrices:  corn fodder, raisins, grapes, soybean seed, cotton gin trash, white rice, brown rice, tomato, bell pepper, lettuce, and tea leaves and an acceptable ILV study was conducted on apples, wheat grain, and almond nutmeat.  The method for the determination of chlorantraniliprole and its metabolites in processed commodities is an LC/MS/MS method, DuPont-14314, which is a slightly modified version of DuPont-11374.  These methods have been accepted by the Analytical Chemistry Branch (ACB)/Biological and Economical Analysis Division (BEAD; DP#340358, C. Stafford, 02/06/2008).

An adequate enforcement method (LC/MS/MS, Du[pont 11376)) is available for the determination of residues of chlorantraniliprole and its metabolites in/on animal commodities.  Atmospheric pressure chemical ionization (APCI) MS/MS detection operated in the positive ion mode is used.  The LOQ is reported at 0.010 ppm for the parent and each of the metabolites.  The method has been accepted by ACB/BEAD (DP#340358, C. Stafford, 02/06/2008).

Conclusions.

Adequate methods are available for the enforcement of tolerances for chlorantraniliprole residues in/on crops (LC/MS/MS Method DuPont-11374) and livestock (LC/MS/MS; MRID 46889003).  The LOQs are 0.01 ppm for chlorantraniliprole in crop and livestock matrices.

5.1.4	Submittal of Analytical Reference Standards (860.1650)

The analytical reference standard is available from the EPA National Pesticide Standards Repository.  It expires 04/24/2014.

5.2	Storage Stability (860.1380)

Adequate storage plant commodity stability studies were previously submitted in conjunction with PP#7F7181 (DP#336941, L. Cheng, 2/25/2008).  The study results demonstrate that residues of chlorantraniliprole are reasonably stable at approximately -20C for at least 24 months in diverse crops (apple, grape, tomato, leaf lettuce, cauliflower, potato, wheat grain, wheat straw, alfalfa hay, and cotton seed), including water-, oil-, protein-, and starch-containing commodities as represented by fruits, a fruiting vegetable, a root crop, a non-oily grain, and an oilseed.  Additional study results demonstrate that residues of chlorantraniliprole and its metabolites (IN-ECD73, IN-EQW78, and IN-F6L99) are stable for at least 12 months in processed crop fractions including predominantly water-, oil-, protein-containing, and dry fractions (raisins, ketchup, apple juice, cottonseed meal, and cottonseed oil) stored at approximately -20ºC.

Samples of plant commodities from the crop field trial studies associated with this petition were stored frozen from harvest to analysis.  The storage durations and conditions are presented under the respective field trials.

Adequate livestock commodity stability studies were previously submitted in conjunction with PP#7F7181 (DP#336941, L. Cheng, 2/25/2008; Monograph B.7) .Residues of chlorantraniliprole and its metabolites IN-HXH44, IN-K9T00, IN-GAZ70 and IN-EQW78 in fortified (each at 0.10 ppm) control samples of bovine liver, kidney, muscle, fat, and milk were shown to be stable during freezer storage for 12 months.  A concurrent storage stability study was conducted with the crayfish study (see 5.3.6).

Conclusions

The storage stability data are adequate to support the crop field trials considered herein.  All commodities were analyzed within the interval of demonstrated storage stability.

5.3	Residue Data

5.3.1	Crop Field Trials (860.1500)

Green  (Spring) Onion
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The Interregional Research Project Number 4 (IR-4) has submitted field trial data for chlorantraniliprole on green onion (fresh and dried).  Five green onion trials were conducted in the NAFTA Growing Zones 1 (QC; 1 trial), 2 (MD; 1 trial), 5A (ON; 1 trial), and 10 (CA; 2 trials.

Each trial consisted of one untreated plot and one treated plot.  At each trial location, the treated plot received two foliar broadcast applications of a 1.67 lb ai/gal suspension concentrate (SC) formulation of chlorantraniliprole (Coragen(R) 20SC) at 0.098-0.105 lb ai/A/application for a total seasonal rate of 0.199-0.203 lb ai/A.  Applications were made at a 3- to 4-day retreatment interval (RTI) using ground equipment in spray volumes of 22-45 gal/A with a nonionic surfactant (NIS) included in each spray mix.  Samples of mature green onion (fresh) were harvested at a preharvest interval (PHI) of 1 day.  Additional green onion samples from each site were dried for up to 10 days prior to collection.

Samples were analyzed for residues of chlorantraniliprole using a high performance liquid chromatography method with LC/MS/MS based on DuPont-13294.  The limit of quantitation (LOQ; determined as the lowest level of method validation, LLMV) was 0.01 ppm in/on green onion. The method was adequate for data collection based on acceptable method validation and concurrent recovery data.  The fortification levels used in method validation and concurrent method recovery were adequate to bracket expected residue levels.  Recoveries and residues in treated samples were not corrected for residues in controls.

Samples were stored frozen (-38 to -0.6 °C) from collection to analysis for 504-734 days (16.6-24.1 months) for green onion.  Samples were analyzed within 0-5 days of extraction.  To support the sample storage intervals, a concurrent storage stability study was conducted with the field trial study.  The data demonstrate that residues of chlorantraniliprole were stable in/on green onion stored frozen for up to 746 days (24.5 months).  No 0-day data were provided.  HED has concluded (see minutes of 6/19/13 Chemistry Science Advisory Council (ChemSAC) meeting) that recovery data from 0-day fortified samples are desirable for storage stability studies but are not mandatory

Following two foliar broadcast applications of the 1.67 lb ai/gal SC formulation of chlorantraniliprole at a total rate of 0.199-0.203 lb ai/A, residues of chlorantraniliprole (and per trial averages) in/on fresh green onion and dried green onion respectively, harvested at a 1-day PHI, were 0.371-1.50 (0.406-1.49) ppm and  0.900-11.1 (1.00-10.8) ppm.  The processing data indicate that residues of chlorantraniliprole concentrate in dried onions (processing factors of 2.1-9.6x; median 3.4).

Dill Seed
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IR-4 has submitted field trial data for chlorantraniliprole on dill seed.  Two dill seed trials were conducted in Zones 2 (NC; 1 trial) and 11 (ID; 1 trial).

Each trial consisted of one untreated plot and one treated plot.  At each trial location, the treated plot received two foliar broadcast applications of a 1.67 lb ai/gal suspension concentrate (SC) formulation of chlorantraniliprole (Coragen(R) 20SC) at 0.098-0.105 lb ai/A/application for a total seasonal rate of 0.199-0.203 lb ai/A.  Applications were made at a 3- to 4-day retreatment interval (RTI) using ground equipment in spray volumes of 22-45 gal/A with a nonionic surfactant (NIS) included in each spray mix.  Samples of dill seed were harvested at a preharvest interval (PHI) of 1 day.

Samples were analyzed for residues of chlorantraniliprole using LC/MS/MS based on DuPont-13294.  The limit of quantitation (LOQ; determined as the lowest level of method validation, LLMV) was 0.01 ppm in/on green onion and dill seed.  The method was adequate for data collection based on acceptable method validation and concurrent recovery data.  The fortification levels used in method validation and concurrent method recovery were adequate to bracket expected residue levels.  Recoveries and residues in treated samples were not corrected for residues in controls.

Samples were stored frozen (-38 to -0.6 °C) from collection to analysis for 665-737 days (21.9-24.2 months) for dill seed.  Samples were analyzed within 0-5 days of extraction.  To support the sample storage intervals, a concurrent storage stability study was conducted with the field trial study.  The data demonstrate that residues of chlorantraniliprole were stable in/on dill seed, stored frozen for up to 797 days (26.2 months); no 0-day data were provided.  HED has concluded (see minutes of 6/19/13 Chemistry Science Advisory Council (ChemSAC) meeting) that data for 0-day fortified samples are desirable for storage stability studies but are not mandatory

Following two foliar broadcast applications of the 1.67 lb ai/gal SC formulation of chlorantraniliprole at a total rate of 0.199-0.203 lb ai/A, residues of chlorantraniliprole (and per trial averages) in/on dill seed, respectively, harvested at a 1-day PHI, were 15.4-24.3 (17.0-19.8) ppm.

Peanut
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DuPont  has submitted field trial data for chlorantraniliprole on peanuts.  Six peanut trials were conducted in the United States in NAFTA Growing Zones 2 (GA, 3 trials), 3 (FL, 1 trial), 6 (TX, 1 trial), and 8 (TX, 1 trial) during the 2011 growing season.  The number and distribution of trials are adequate, per the recommendations of D381810 (S. Funk, 01/30/2011).

Each field trial included one control plot and one treated plot.  At each site, the treated plot received two foliar broadcast applications of a 1.67 lb ai/gal (200 g ai/L) suspension concentrate (SC) formulation of chlorantraniliprole (DPX-E2Y45 20SC) at 0.099-0.102 lb ai/A/application (111-115 g ai/ha/application) for a total rate of 0.200-0.203 lb ai/A (224-228 g ai/ha).  Applications were made with a 5- or 6-day retreatment interval (RTI), starting 6-7 days prior to harvest.  Applications were made using ground equipment in a spray volume of 13-25 gal/A (117-234 L/ha); an adjuvant was added to the spray mixture.  Samples of peanuts were harvested 1 day after the last application of chlorantraniliprole. Peanut forage/hay was not collected, but alfalfa may be translated to cover peanut hay (S. Funk, D381810, 01/30.2011).

Samples of peanut nutmeats were analyzed for residues of chlorantraniliprole using LC/MS/MS method.  The limit of quantitation (LOQ), based on the lowest level of method validation (LLMV) was 0.01 ppm for chlorantraniliprole in/on peanut nutmeats.  The method was adequate for data collection based on acceptable method validation and concurrent recoveries.  The fortification levels used for concurrent recoveries were adequate to bracket expected residue levels.

Peanut samples were stored frozen at approximately 20 °C from collection to extraction for up to 3.3 months; samples were analyzed 0-1 days after extraction.  Adequate storage stability studies are available which demonstrate that residues of chlorantraniliprole are stable at approximately 20 C for at least 24 months in diverse crops, including water-, oil-, protein-, and starch-containing commodities as represented by fruits, a fruiting vegetable, a root crop, a non-oily grain, and an oilseed (DP# 336941, L. Cheng, 2/25/2008).  These data are adequate to support the storage intervals and conditions of samples from the submitted field trial study.

Following two foliar broadcast applications of a 1.67 lb ai/gal SC formulation of chlorantraniliprole at a total rate of 0.20 lb ai/A, residues (and per trial averages) of chlorantraniliprole were <0.01 (<LOQ)-0.046 (<0.01-0.034) ppm in/on nutmeats harvested at a 1-day PHI.

Peanut hay was not collected or analyzed.  It was previously decided that the results for alfalfa hay may be translated to peanut hay (D361791, D. Rate, 01/08/2010).  Peanut and alfalfa have similar proposed use patterns except for the PHI; a 0-day PHI exists for alfalfa and a 1-day PHI is proposed for peanuts.  Residues on alfalfa hay ranged from 8.0 to 47 ppm from the foliar application of an SC formulation at a total application rate of  0.2 lb ai/acre (0.1 lb ai/acre X 2) and a 0-day PHI.

Rice
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DuPont has submitted field trial data for chlorantraniliprole on rice and crayfish.  A total of 3 crop field trials were conducted during the 2011 growing season in NAFTA Growing Zone 4 (LA, 2 trials; MO, 1 trial). The number and distribution of trials meet the conditions set in D361791 (D. Rate, 01/08/2010).  The trials were requested to confirm the tolerance of 0.15 ppm set for rice based on exaggerated (4X) field trials with chlorantraniliprole.

Each field trial included one control plot and one treated plot.  Seeds for each treated plot received one seed treatment of an undiluted 5.21 lb ai/gal flowable concentrate (FS) formulation of chlorantraniliprole (DPX-E2Y45-456) at a rate of 0.204 lb ai/100 lb seed.  Based on seeding rates, the field application rate was 0.08 lb ai/A (90 g ai/ha).  Seeds were planted 103-113 days after they had been treated.  Mature rice was harvested 231-238 days after treatment, which was 118-135 days after planting.

Samples of rice grain were analyzed for residues of chlorantraniliprole using LC/MS/MS methods, which was modified from Method DuPont-13294 (for rice grain). The limit of quantitation (LOQs), based on the lowest levels of method validation (LLMVs), was  0.010 ppm for chlorantraniliprole in/on rice grain. The method is adequate for data collection based on acceptable concurrent recoveries. The fortification levels used for concurrent recoveries were adequate to bracket expected residue levels.

Rice grain samples were stored frozen at approximately -20 °C from harvest to extraction for up to 3.2 months ; samples were analyzed 1-8 days after extraction.  Adequate storage stability studies are available which demonstrate that residues of chlorantraniliprole are stable at approximately -20 C for at least 24 months in diverse crops, including water-, oil-, protein-, and starch-containing commodities as represented by fruits, a fruiting vegetable, a root crop, a non-oily grain, and an oilseed (DP# 336941, L. Cheng, 2/25/2008). These data are adequate to support the storage intervals and conditions of samples from the submitted field trial study.

Following a single treatment of rice seed with a 5.21 lb ai/gal FS formulation of chlorantraniliprole at a rate of 0.204 lb ai/100 lb seed (equivalent to 0.08 lb ai/A), residues (and per trial averages) of chlorantraniliprole were <0.010-0.016 (<0.010-0.015) ppm in/on rice grain harvested 118-135 days after planting.

Strawberry
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DuPont has submitted field trial data for chlorantraniliprole on strawberries.  A total of 8 crop field trials were conducted during the 2011 growing season in NAFTA Growing Zones 1 (NY), 2 (GA), 3 (FL), 5 (IA and MN, 1 trial each), 10 (CA, 2 trials), and 12 (BC).  The number and distribution of trials meets the requirements of OCSPP 860.1500 and also fulfills the requests for confirmatory trials for strawberry (D361791, D. Rate, 01/08/2010).  There is an existing tolerance of 1.0 pm for berry, low growing, subgroup 13-07G.

Each field trial included one control plot and one treated plot.  The treated plot received two foliar broadcast applications of a 1.67 lb ai/gal (200 g ai/L) suspension concentrate (SC) formulation of chlorantraniliprole (Chlorantraniliprole 20SC) at 0.097-0.106 lb ai/A/application (109-119 g ai/ha/application) for a total rate of 0.19-0.21 lb ai/A (217-235 g ai/ha).  Applications were made with a 6- to 7-day retreatment interval (RTI), beginning 7 or 8 days prior to harvest.  Applications were made using ground equipment in a spray volume of 14-50 gal/A (131-466 L/ha); an adjuvant was added to the spray mixture.  Mature fruit was harvested 1 day after the last application of chlorantraniliprole.

Samples were analyzed for residues of chlorantraniliprole using a liquid chromatography/tandem mass spectrometry (LC/MS/MS) method, modified Method DuPont-13294.  The limit of quantitation (LOQ), based on the lowest level of method validation (LLMV), was 0.010 ppm for chlorantraniliprole in/on strawberries.  The method was adequate for data collection based on acceptable method validation and concurrent recoveries.  The fortification levels used for concurrent recoveries were adequate to bracket expected residue levels.

Strawberries were stored frozen at approximately -20 °C from harvest to extraction for up to 6.8 months; samples were analyzed 1-4 days after extraction.  Adequate storage stability studies are available which demonstrate that residues of chlorantraniliprole are stable at approximately -20 C for at least 24 months in diverse crops, including water-, oil-, protein-, and starch-containing commodities as represented by fruits, a fruiting vegetable, a root crop, a non-oily grain, and an oilseed (DP# 336941, L. Cheng, 2/25/2008).  These data are adequate to support the storage intervals and conditions of samples from the submitted field trial study.

Following two foliar broadcast applications of a 1.67 lb ai/gal SC formulation of chlorantraniliprole at a total rate of 0.2 lb ai/A, residues (and per trial averages) of chlorantraniliprole were 0.18-0.69 (0.18-0.68) ppm in/on strawberries harvested at a 1-day PHI.

Coffee
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DuPont has submitted field trial data for chlorantraniliprole on coffee.  One coffee trial was conducted in the United States in Growing Zone 13 (HI) during the 2011 growing season.  The trial fulfills the requests for confirmatory data for coffee (D361791, D. Rate, 01/08/2010). A trial in region 13 was requested to meet the requirement of five trials.  Also,  the use of adjuvant was requested.  There is an existing tolerance of 0.4 ppm for coffee green beans.

The field trial included one control plot and one treated plot.  The treated plot received two foliar broadcast applications of a 35% (w/w) water-dispersible granule (WG) formulation of chlorantraniliprole (DPX-E2Y45-436) at 0.01 lb ai/A/application (111-112 g ai/ha/application) for a total rate of 0.2 lb ai/A (223 g ai/ha).  Applications were made with a 14-day retreatment interval (RTI), starting 21 days prior to harvest.  Applications were made using ground equipment in a spray volume of 57.1-57.4 gal/A (534-537 L/ha); an adjuvant was added to the spray mixture.  Samples of mature coffee cherries were harvested 7 days after the last application of chlorantraniliprole, and coffee beans were collected 7 days later following the standard procedure for producing beans from cherries.

Samples were analyzed for residues of chlorantraniliprole using a LC/MS/MS method, modified Method DuPont-13294.  The limit of quantitation (LOQ), based on the lowest level of method validation (LLMV), was 0.010 ppm for chlorantraniliprole in/on coffee beans.  The method was adequate for data collection based on acceptable concurrent recoveries.  The fortification levels used for concurrent recoveries were adequate to bracket expected residue levels.

Coffee green bean samples were stored frozen at approximately -20 °C from collection to extraction for 0.7 month; samples were analyzed 0-1 days after extraction.  Adequate storage stability studies are available which demonstrate that residues of chlorantraniliprole are stable at approximately -20 C for at least 24 months in diverse crops, including water-, oil-, protein-, and starch-containing commodities as represented by fruits, a fruiting vegetable, a root crop, a non-oily grain, and an oilseed (DP# 336941, L. Cheng, 2/25/2008).  These data are adequate to support the storage intervals and conditions of samples from the submitted field trial study.

Following two foliar broadcast applications of a 35% WG formulation of chlorantraniliprole at a total rate of 0.2 lb ai/A, residues of chlorantraniliprole were <0.010 ppm in/on coffee green beans produced from coffee cherries harvested at a 7-day PHI.

Cucumber
49076101.der

IR-4 has submitted greenhouse trial data for chlorantraniliprole on cucumber.  Three greenhouse trials were conducted in the United States during the 2008 growing season in the NAFTA Growing Zones 2 (MD; 1 trial), 3 (FL; 1 trial), and 9 (CO; 1 trial).  The number of trials is in accordance with recommendations of ChemSAC for greenhouse use where a field use exists with the same use rate and PHI (ChemSAC Minutes, 09/24/2008).

Each trial consisted of one untreated plot and one treated plot.  The cucumbers were grown in pots or in rockwool cubes.  At each trial location, the treated plot received two foliar directed applications of a 1.67 lb ai/gal suspension concentrate (SC) formulation of chlorantraniliprole (Coragen(R) 20SC) at 0.098-0.122 lb ai/A/application for a total seasonal rate of 0.197-0.229 lb ai/A.  Applications were made at a 3-day retreatment interval (RTI) using ground equipment in spray volumes of 35.7-50.2 gal/A with a nonionic surfactant (NIS) or a nonionic surfactant/ organosilicone surfactant (NIS/OSS) included in each spray mix.  Samples of mature cucumbers were harvested at a preharvest interval (PHI) of 1 day.

Samples were analyzed for residues of chlorantraniliprole using a LC/MS/MS method based on DuPont-13294.  The limit of quantitation (LOQ; determined as the lowest level of method validation, LLMV) was 0.01 ppm in/on cucumbers.  The method was adequate for data collection based on acceptable method validation and concurrent recovery data.  The fortification levels used in method validation and concurrent method recovery were adequate to bracket expected residue levels.  Recoveries and residues in treated samples were not corrected for residues in controls.

Samples were stored frozen (-37 to -0.2 °C) from collection to analysis for 525-562 days (17.3-18.5 months).  Samples were analyzed on the day of extraction.  To support the sample storage intervals, a concurrent storage stability study was conducted with the greenhouse study.  The data demonstrate that residues of chlorantraniliprole were stable in/on cucumbers stored frozen for up to 572 days (18.8 months); no 0-day data were provided.  HED has concluded (see minutes of 6/19/13 Chemistry Science Advisory Council (ChemSAC) meeting) that 0-day fortified samples are desirable for storage stability study but are not mandatory.

Following two foliar directed applications of the 1.67 lb ai/gal SC formulation of chlorantraniliprole at a total rate of 0.197-0.229 lb ai/A, residues of chlorantraniliprole (and per trial averages) in/on cucumbers harvested at a 1-day PHI were 0.0210-0.0738 (0.0257-0.0697) ppm.

Tomato
49076102.der

IR-4 has submitted greenhouse trial data for chlorantraniliprole on tomato.  Four greenhouse trials were conducted in the United States during the 2007 growing season in the NAFTA Growing Zones 2 (NJ and TN; 2 trials), 6 (TX; 1 trial), and 9 (CO; 1 trial).  The number of trials is in accordance with recommendations of ChemSAC for greenhouse use where a field use exists with the same use rate and PHI (ChemSAC Minutes, 09/24/2008).

Each trial consisted of one untreated plot and one treated plot.  At each trial location, the treated plot received two foliar directed applications of a 1.67 lb ai/gal suspension concentrate (SC) formulation of chlorantraniliprole (Coragen(R) 20SC) at 0.099-0.106 lb ai/A/application for a total seasonal rate of 0.199-0.209 lb ai/A.  Applications were made at a 4- to 6-day retreatment interval (RTI) using ground equipment in spray volumes of 50-94 gal/A.  Adjuvants were not added to the spray mix.  Samples of mature tomatoes were harvested at a preharvest interval (PHI) of 1 day.

Samples were analyzed for residues of chlorantraniliprole using a LC/MS/MS method based on DuPont-13294.  The limit of quantitation (LOQ; determined as the lowest level of method validation, LLMV) was 0.01 ppm in/on tomatoes.  The method was adequate for data collection based on acceptable method validation and concurrent recovery data.  The fortification levels used in method validation and concurrent method recovery were adequate to bracket expected residue levels.  Recoveries and residues in treated samples were not corrected for residues in controls.

Samples were stored frozen (-37 to -2 °C) from collection to analysis for 77-229 days (2.5-7.5 months).  Samples were analyzed within 0-2 days of extraction.  To support the sample storage intervals, a concurrent storage stability study was conducted with the greenhouse study.  The data demonstrate that residues of chlorantraniliprole were stable in/on tomatoes stored frozen for up to 235 days (7.7 months); no 0-day data were provided.  HED has concluded (see minutes of 6/19/13 Chemistry Science Advisory Council (ChemSAC) meeting) that 0-day fortified samples are desirable for storage stability study but are not mandatory.

Following two foliar directed applications of the 1.67 lb ai/gal SC formulation of chlorantraniliprole at a total rate of 0.199-0.209 lb ai/A, residues of chlorantraniliprole (and per trial averages) in/on tomatoes harvested at a 1-day PHI were 0.0101-0.102 (0.0126-0.0963) ppm.

Cherry, Papaya, Lychee
49076103.der

Conditional registrations for the use of chlorantraniliprole on tropical fruit crops were established.  A tolerance of 4.0 ppm for larger, slow-growing tropical fruits and a tolerance of 2.0 ppm for smaller, fast-growing tropical fruits were established. The tolerances for tropical fruit are based on the translation of stone fruit data (D361791, D. Rate, 01/08/2010; ChemSAC Minutes 10/01/2008 and 11/17/2008).   Residue decline studies were requested for cherry, lychee, and papaya.

IR-4 has submitted residue decline field trial data for chlorantraniliprole on cherries, lychee, and papaya.  Three field trials were conducted in the United States during the 2009 growing season.  One cherry trial was conducted in NAFTA Growing Zone 11 (WA; 1 trial); one lychee trial was conducted in Zone 13 (FL; 1 trial); and one papaya trial was conducted in Zone 13 (HI; 1 trial).

Each trial consisted of one untreated plot and one treated plot.  At each trial location, the treated plot received two foliar directed applications of a 35% water dispersible granule (WG) formulation of chlorantraniliprole (Altacor(R)) at 0.099-0.105 lb ai/A/application for a total seasonal rate of 0.199-0.207 lb ai/A.  Applications were made at a 9- to 10-day retreatment interval (RTI) using ground equipment in spray volumes of 76-198 gal/A with an nonionic surfactant (NIS) included in each spray mix.  Samples of mature fruit were harvested at preharvest intervals (PHIs) of 1, 3, 6/7, 9/10, and 13/14/15 days.

Samples were analyzed for residues of chlorantraniliprole using a LC/MS/MS method based on DuPont-13294.  The limit of quantitation (LOQ; determined as the lowest level of method validation, LLMV) was 0.01 ppm in/on cherries, lychee, and papaya.  The method was adequate for data collection based on acceptable method validation and concurrent recovery data.  The fortification levels used in method validation and concurrent method recovery were adequate to bracket expected residue levels.  Recoveries and residues in treated samples were not corrected for residues in controls.

Samples were stored frozen (-37 to -0.6 °C) from collection to analysis for 712-726 days (23.4-23.9 months) for cherries, 713-725 days (23.5-23.8 months) for lychee, and 710-723 days (23.4-23.8 months) for papaya.  Samples were analyzed within 1-9 days of extraction.  To support the sample storage intervals, a concurrent storage stability study was conducted with the field trial study.  The data demonstrate that residues of chlorantraniliprole were stable in/on cherries stored frozen for up to 802 days (26.4 months); no 0-day data were provided.  HED has concluded (see minutes of 6/19/13 Chemistry Science Advisory Council (ChemSAC) meeting) that 0-day recovery data for fortified samples are desirable for storage stability studies but are not mandatory.

Following two foliar directed applications of the 35% WG formulation of chlorantraniliprole at a total rate of 0.199 lb ai/A, residues of chlorantraniliprole (and per trial averages) in/on cherries harvested at 1-, 3-, 6-, 10-, and 15-day PHIs, respectively, were: 0.151-0.192 (0.171), 0.135-0.162 (0.148), 0.105-0.120 (0.112), 0.132-0.151 (0.141), and 0.0994-0.129 (0.114) ppm.

Following two foliar directed applications of the 35% WG formulation of chlorantraniliprole at a total rate of 0.200 lb ai/A, residues of chlorantraniliprole (and per trial averages) in/on lychee harvested at 1-, 3-, 6-, 9-, and 13-day PHIs, respectively, were: 0.402-0.500 (0.451), 0.306-0.442 (0.374), 0.363-0.386 (0.374), 0.239-0.313 (0.276), and 0.308-0.337 (0.322) ppm.

Following two foliar directed applications of the 35% WG formulation of chlorantraniliprole at a total rate of 0.207 lb ai/A, residues of chlorantraniliprole (and per trial averages) in/on papaya harvested at 1-, 3-, 7-, 10-, and 14-day PHIs, respectively, were: 0.284-0.292 (0.288), 0.204-0.224 (0.214), 0.196-0.211 (0.203), 0.164-0.196 (0.180), and 0.137-0.142 (0.139) ppm.

The half-lives were calculated based on the assumption of first order kinetics and a slope m determined by least squares straight line fit of ln average concentration versus time (days); t 1/2 = ln 2/m for all sampling intervals.  The half-lives ranged from 14 to 32 days.  These results confirm that very small fruit (cherry) and tropical fruits have approximately the same half-lives as stone fruits (median 33, minimum 19 days) and pome fruits (median 23, minimum 11 days) (D361791, D. Rate, 01/08/2010; ChemSAC Minutes 10/01/2008 and 11/17/2008) .  This validates the previous decision to translate the stone fruit tolerance to tropical fruits and to reduce the PHI for some tropical fruits from 10 days to 1 day with a 2x correction applied to the stone fruit tolerance.  The half-lives show that residues will not exceed a doubling (2x) with a reduction from 10 days to 1 day in the PHI.

Therefore, the proposal to reduce the PHI for papaya and passionfruit from 10 days to 1 day with an increase in the tolerances from 2 ppm to 4 ppm is acceptable.

Table <IP_ADDRESS>         Residue Data from Cherry, Lychee, and Papaya Field Trials with Chlorantraniliprole.
                                   Trial ID
                         (City, State, Province; Year)
                                     Zone
                                    Crop;
                                    Variety
                                   Commodity
                                  Total Rate
                                   (lb ai/A)
                                      PHI
                                    (days)
                Residues Chlorantraniliprole (ppm) [Average][1]
                                Cherry Trials
Prosser, WA; 2009 (WA03)
                                      11
                              Cherry; Sweetheart
                                     Fruit
                                     0.199
                                       1
                             0.151, 0.192 [0.171]

                                       3
                             0.135, 0.162 [0.148]

                                       6
                             0.105, 0.120 [0.112]

                                      10
                             0.151, 0.132 [0.141]

                                      15
                             0.129, 0.0994 [0.114]
                                 Half life[1]
                                    31 days
                                 Lychee Trials
Homestead, FL; 2009 (FL69)
                                      13
                               Lychee; Brewster
                                     Fruit
                                     0.200
                                       1
                             0.402, 0.500 [0.451]

                                       3
                             0.306, 0.442 [0.374]

                                       6
                             0.386, 0.363 [0.374]

                                       9
                             0.313, 0.239 [0.276]

                                      13
                             0.337, 0.308 [0.322]
                                 Half life[1]
                                    32 days
                                 Papaya Trials
Hilo, HI; 2009 (HI01)
                                      13
                                Papaya; Rainbow
                                     Fruit
                                     0.207
                                       1
                             0.292, 0.284 [0.288]

                                       3
                             0.204, 0.224 [0.214]

                                       7
                             0.211, 0.196 [0.203]

                                      10
                             0.196, 0.164 [0.180]

                                      14
                             0.137, 0.142 [0.139]
                                 Half life[1]
                                    14 days
1 Assumes first order kinetics and a slope m determined by least squares straight line fit of ln average concentration versus time (days); t 1/2 = ln 2/m.

Table <IP_ADDRESS>.  Summary of Residues from Field Trials with Chlorantraniliprole
                                 Crop Matrix
                                    Analyte
                                 Applic. Rate
                                 (lb ai/acre)
                                  PHI (days)
                                     n[*]
                                Residues (ppm)

                                   Min.[†]
Max.[†]
                                    LAFT[*]
                                   HAFT[*]
                                   Median[*]
                                    Mean[*]
                                     SD[*]
    Peanut  Proposed Use = 0.20 lb ai/acre total application rate. 1 day PHI
                                    Nutmeat
                             Chlor-antra-niliprole
                                     0.20
                                       1
                                       6
                                   <0.01
0046
                                   <0.01
                                     0.034
                                     0.01
                                     0.014
                                     0.010

Rice    Proposed Use = 0.08 lb ai/acre total application rate, at-plant application
                                     Grain
                             Chlor-antra-niliprole
                                     0.08
                                   125- 135
                                       3
                                   <0.010
0.016
                                   <0.010
                                     0.015
                                     0.012
                                     0.012
                                     0.02
Berry, low growing, subgroup 13-07G.  Proposed Use = 0.20 lb ai/acre total application rate. 1 day PHI
                               Strawberry fruit
                             Chlor-antra-niliprole
                                      0.2
                                       1
                                       8
                                     0.18
0.69
                                     0.18
                                     0.68
                                     0.23
                                     0.30
                                     0.17
   Coffee.  Proposed Use = 0.20 lb ai/acre total application rate. 7 day PHI
                               Coffee green bean
                             Chlor-antra-niliprole

                                      0.2

                                       7
                                       1
                                   <0.010
                                   <0.010
                                   <0.010
                                   <0.010
                                     0.01
                                     0.01
                                      NA
Cucumber.  Proposed Use = =0.20 lb ai/acre total application rate in greenhouse. 1 day  PHI
                                   Cucumber
                                     fruit
                             Chlor-antra-niliprole
                                  0.20- 0.23
                                       1
                                       3
                                    0.0210
0.0738
                                    0.0257
                                    0.0697
                                    0.0296
                                    0.0417
                                    0.0244
Tomato.  Proposed Use  =0.20 lb ai/acre total application rate in greenhouse. 1 day  PHI
                                 Tomato fruit
                             Chlor-antra-niliprole
                                   0.20-0.21
                                       1
                                       4
                                    0.0101
                                     0.102
                                    0.0126
                                    0.0963
                                    0.0314
                                    0.0429
                                    0.0378
Onion, green, subgroup 3-07B. Proposed use = 0.20 lb ai/acre total application rate per crop. 1 day PHI
                                  Green onion
                             Chlor-antra-niliprole
                                     0.20
                                       1
                                       5
                                     0.371
                                     1.50
                                     0.406
                                     1.49
                                     0.717
                                     0.811
                                     0.406
                               Green onion, dry
                             Chlor-antra-niliprole
                                     0.20
                                       1
                                       5
                                     0.900
                                     11.1
                                     1.00
                                     10.8
                                     2.66
                                     4.44
                                     4.11
                          Dill seed. Proposed Use =
                                   Dill seed
                             Chlor-antra-niliprole
                                     0.20
                                       1
                                       2
                                     15.4
                                     24.3
                                     17.0
                                     19.8
                                     18.4
                                     18.4
                                      N/A
† Values based on total number of samples.
[*] Values based on per-trial averages.  LAFT = Lowest Average Field Trial, HAFT = Highest Average Field Trial, SD = Standard Deviation.  For computation of the LAFT, HAFT, median, mean, and standard deviation, values < LOQ are assumed to be at the LOQ.

Conclusions.

The greenhouse tomato trials are adequate to cover the use on fruiting vegetables in greenhouses, per the decision of ChemSAC (Minutes of the ChemSAC Meeting, 09/29/2010).  The greenhouse cucumber trials are adequate to cover the use on cucumber grown in greenhouses.  In both instances, the existing tolerances will encompass the expanded use (See 6.0).

The strawberry field trials were conducted according to the label for crop subgroup 13-07G.  The existing tolerance for this subgroup will encompass the use on strawberry (See 6.0).  The data fulfill the condition or registration requirement for strawberry (D361791, D. Rate, 01/08/2010).

The peanut field trials provide adequate data to support a tolerance on peanut nutmeat.  The number and distribution of trials are adequate, per the recommendations of D381810 (S. Funk, 01/30/2011).  Alfalfa hay results may be translated to peanut nutmeat.

The rice seed treatment trials are adequate to confirm the existing tolerance and fulfill a condition of registration requirement (D316791, D. Rate, 01/08/2010).   See 6.0.

The single residue decline studies on cherry, papaya, and lychee completes the condition of registration data requirement for decline data on (tropical) fruits of small and large size (D316791, D. Rate, 01/08/2010).  The request to decrease the PHI for papaya and passionfruit from 10 days to 1 day with increases in the tolerances from 2 ppm to 4 ppm is acceptable.

5.3.2	Field Rotational Crops (860.1900)
DP#404708, S. Funk, 09/10/2013 (PP#2E8064)
DP#382293, S. Funk, 02/28/2011 (PP#0F7763)
DP#353542, L. Cheng, 6/18/2008 (PP#7F7181)
DP#336941, L. Cheng, 2/25/2008 (PP#7F7181)
Minutes of the April 9, 2008 Meeting of the HED Chemistry SAC (ChemSAC min_388.4-9-08)
DP#361791, D. Rate, 01/08/2010 (PP#9F7513)
DP#384485, D. Rate, 12/01/2010

Chlorantraniliprole is the major residue in all rotational crop commodities studied.  No new field rotational crop data were presented

Acceptable studies pertaining to limited field accumulation in rotational crops were reviewed in PP#7F7181 (DP#353542, L. Cheng, 6/18/2008).  HED concluded that these data are adequate for estimation of the magnitude of residues of chlorantraniliprole in root, leafy, and cereal grain crops when grown rotationally in fields previously treated with chlorantraniliprole at total seasonal rates of 0.9-2.7x.  Generally, residues at or above the LOQ (0.010 ppm) may occur on rotated leafy crops and on the tops of root vegetables at plantback intervals of 30-130 days, ranging between 0.01 and 0.2 ppm, whereas residues on grain and root vegetables are anticipated to be below the LOQ.  Chlorantraniliprole residues (>0.01 ppm) are also possible in livestock feedstuffs of rotated grain crops (forage, straw, hay), ranging from 0.02 to 0.2 ppm for plantback intervals (PBIs) ranging from 30-240 days.  These data suggested that rotational crop tolerances are required, and that the petitioner needs to conduct extensive field rotational crop trials.  HED previously concluded that until the requested data are submitted, a restriction should be imposed on the proposed labels to prohibit the rotation to any crop not on the label (DP#336941, L. Cheng, 2/25/2008).

The petitioner subsequently submitted proposals and justification requesting no rotational crop restrictions for chlorantraniliprole and for the establishment of tolerances for inadvertent residues for a number of crops.  The submission was brought to HED's ChemSAC for discussion on April 9, 2008.  Based on the available data, the ChemSAC determined that a 30-day plant-back interval is appropriate for all crops requested (bulb vegetables, peanuts, sugar cane, asparagus, okra, strawberry, crop groups 6, 15, 16, 17, 18)  except Crop Groups 1 and 2, for which a 0-day PBI is allowable.

Time-limited tolerances, with expiration date of 4/10/14, were previously established for indirect or inadvertent residues of chlorantraniliprole in/on:  cereal grain forage, fodder and  straw (Crop Group 16) at 0.20 ppm; leek at 0.20 ppm; green onion at 0.20 ppm; Welsh onion at 0.20 ppm; peanut hay at 0.20 ppm; and shallot fresh leaves at 0.20 ppm.  These have been recommended for removal upon relevant primary crop (crop group) tolerances.

Subsequently the addition of the following oilseed rotational crops with a reduction of the PBI from 12 months to 30 days was made (D384485, D. Rate, 12/01/2010): borage, calendula, castor oil plant, Chinese tallowtree, cuphea, echium euphorbia, evening primrose, flax, gold of pleasure, meadowfoam, niger seed, safflower, stokes aster, sunflower, sweet rocket, and veronica.  The 30-day PBI was subsequently extrapolated to all rotated oilseeds, based on rotated cereal grain and soybean seed data (D397571, S.Funk, 05/01/2012).

Conclusions.

Adequate field rotational crop studies have been conducted previously to support appropriate plant-back intervals for those crops with no primary uses.  Additional data are not required.

5.3.3	Processed Food and Feed (860.1520)

No new processing studies were provided.  Peanuts in the only commodity addressed herein for which the required processing study has not been conducted/reviewed .  DuPont previously requested a waiver from the peanut processing study based on a translation of the results of the cottonseed processing study (D382293, S. Funk, 02/30/2011).   In the cottonseed processing study (MRID 46979734), delinted cottonseed was mechanically cracked and the hulls separated from the kernels.  The kernels were dried to 12% moisture content, heated, flaked, and expanded/extruded under steam to collets.  The collets are extracted with solvent (hexane).  The miscella (crude oil and hexane) is separated, the crude oil is heated to remove residual hexane, and the oil is refined by alkali treatment.

A very similar commercial process is used with peanuts, although as a first step peanuts may be subjected to mechanical pressure to remove some oil.   The resulting press cake is extracted with hexane, and the oil fractions are combined and purified with alkali treatment.

 In the cotton processing study, average residues of chlorantraniliprole were 0.016 ppm in cotton seed harvested 21 days after treatment with the 35WG at a total rate of 0.40 lb ai/A.  Average residues after processing were 0.004, 0.012 and 0.033 ppm in refined oil, meal and hulls, respectively. The results of the cotton processing study show that chlorantraniliprole upon processing does not concentrate in refined oil (0.25x) or meal (0.75x) but concentrates in hulls (2.1x) (D336941, L Cheng, 02/25/2008).

The oil content of peanuts is 45  -  52% (Agricultural Marketing Resource Center, Iowa State University).  The oil content of cottonseed is 18  -  26% (Table 4, OECD Guidance Document on Magnitude of the Pesticide Residues in Processed Commodities,  ENV/JM/MONO(2008)23, 07/29/2008).  As the commercial processing procedures for cottonseed and peanut are similar and peanut yields more oil than cottonseed for a given weight of commodity, the cottonseed processing results may be translated to peanut.  Concentration of chlorantraniliprole will not occur in peanut oil (0.25x) or peanut meal (0.75x).

Conclusions:

The cottonseed processing study may be translated to peanuts.  Concentration of chlorantraniliprole from peanut to oil is not anticipated.  The concentration/reduction factors are 0.25x for peanut oil and 0.75x for peanut meal.

5.3.4	Meat, Milk, Poultry and Eggs (860.1480)

An acceptable ruminant feeding study (MRID 46895504) was previously submitted in connection with PP#7F7181 (DP#336941, L. Cheng, 2/25/2008).   An acceptable poultry feeding study was previously submitted (D404708, S. Funk, 09/10/2013)   No new feeding study data were submitted.

<IP_ADDRESS>	Dietary Burden

Peanut meal and peanut hay are the only new feed item associated with the current submissions.  Peanut meal is a protein concentrate fed to dairy cattle (10%), poultry (25%), and swine (15%).  Peanut hay is a roughage fed only to dairy cattle (15%).  The dietary burdens (D404708, S.Funk, 09/10/2013) will not change as a result of these new feeds. Other feed items already considered contribute more to the total dietary burden.

<IP_ADDRESS>	Estimated Secondary Residues in Livestock

The estimated secondary residue in livestock remain unchanged from the latest calculation (D404708, S.Funk, 09/10/2013).

Conclusions:

The dietary burdens of poultry, swine, and ruminants remain unchanged.  The existing tolerances for meat, milk, poultry, and eggs are adequate.

5.3.5.	Food Handling (860.1460)

There are no food handling uses related to the current submissions.

5.3.6	Water, Fish, and Irrigated Crops (860.1400)

48930701.der
Crayfish

DuPont has submitted field trial data for chlorantraniliprole on rice and crayfish.  A total of 3 crop field trials were conducted during the 2011 growing season in North Atlantic Free Trade Agreement (NAFTA) Growing Zone 4 (LA, 2 trials; MO, 1 trial).  A previous request to waive the study was denied (D361791, D. Rate, 01/08/20100.

Each field trial included one control plot and one treated plot.  Seeds for each treated plot received one seed treatment of an undiluted 5.21 lb ai/gal flowable concentrate (FS) formulation of chlorantraniliprole (DPX-E2Y45-456) at a rate of 0.204 lb ai/100 lb seed.  Based on seeding rates, the field application rate was 0.08 lb ai/A (90 g ai/ha).  Seeds were planted 103-113 days after they had been treated.  Mature rice was harvested 231-238 days after treatment, which was 118-135 days after planting.  Crayfish were collected from the plots, when possible, at the following intervals after planting rice:  51-52 days (early first season), 76-77 days (mid first season), 103 days (late first season), and 279 or 318 days (normal harvest).

Samples of crayfish were analyzed for residues of chlorantraniliprole and its metabolite IN-ECD73 (in crayfish only) a using a LC/MS/MS method, which was modified from Method DuPont-24137 (for crayfish).  The limits of quantitation (LOQs), based on the lowest levels of method validation (LLMVs), were 0.010 ppm for chlorantraniliprole in crayfish and 0.010 ppm for IN-ECD73 in crayfish.  The fortification levels used for concurrent recoveries were adequate to bracket expected residue levels.

Crayfish samples were stored frozen at approximately -20 °C from harvest to extraction for up to 9.9 months; samples were analyzed 1-8 days after extraction.  Storage stability data generated concurrently with the field trial study demonstrate that residues of chlorantraniliprole and IN-ECD73 were stable in/on crayfish for up to 10 months of frozen storage.  These data are adequate to support the storage intervals and conditions of samples from the submitted trial study.

Following a single treatment of rice seed with a 5.21 lb ai/gal FS formulation of chlorantraniliprole at a rate of 0.204 lb ai/100 lb seed (equivalent to 0.08 lb ai/A), residues (and per trial averages) of chlorantraniliprole and IN-ECD73 were all below the LOQ (<0.010 ppm each) in/on all samples of crayfish collected 51-52, 76-87, 103-122, and 279-318 days after rice was planted.

Conclusions

The rice seed treatment reflects the proposed maximum application rate.  Adequate concurrent storage stability data were presented to support the residue data, and an adequate data collection analytical method was utilized.  The lack of residues (<0.01 ppm chlorantraniliprole) in crayfish at sampling intervals of 51 to 318 days after rice planting shows no bioaccumulation of chorantraniliprole.  The existing tolerance of 8.0 ppm may be reduced to 0.01 ppm.

6.0	Tolerance Derivation

Tolerance estimates for rice grain (3 trials), peanut (6 trials), strawberry (8 trials), coffee green beans (5 trials), greenhouse cucumber (5 trials), greenhouse tomato (4 trials), and green onions (5 trials) were made by use of the OECD tolerance calculation procedures.  The statistical goal of the tolerance calculation procedures is to produce an MRL proposal in the region of the 95[th] percentile of the underlying residues distribution.  The existing tolerances for rice grain, strawberry (berry low growing subgroup 13-07H), coffee green beans, cucurbit vegetables group 9, and fruiting vegetables group 8-10 were confirmed, that is, the tolerance estimates obtained from the new field trial data sets were the same as or lower than the existing tolerances.

The tolerance estimate for peanut nutmeats was 0.06 ppm.  No analyses were conducted for peanut hay, but it was previously decided (D361791, D. Rate, 01/08/2010). that alfalfa hay may be translated to peanut hay.  The animal feed nongrass group 18 (including alfalfa) hay tolerance is 90 ppm.

The green onion tolerance estimate of 3.0 ppm may be used for the onion, green, subgroup 3-07B.

The conversion of green onions to dried onions has an median processing factor of 3.4.  That factor applied to the green onion highest field trial residue, 1.49 ppm, yields a tolerance estimate of 5 ppm for dried onions.  The dried onion may be used as a surrogate for dried chive, a representative commodity of crop subgroup 19A. The existing tolerance for the herb subgroup 19A is 90 ppm, and is based on the extrapolation of alfalfa hay to dried basil.  The 90 ppm will be retained, as it represents possible residue levels in dried basil, the other representative commodity for subgroup 19A.

Two dill seed trials were conducted.  Where only two trials are conducted, the OECD calculation spreadsheet is not applicable.  The residue estimate is taken as 5 X mean, or 5 X 19.4.  The tolerance estimate for the spices subgroup 19B is 90 ppm.  This replaces the existing estimate of 14.0 ppm (D361791, D. Rate, 01/08/2010).  Note that the registrant petitioned for 40 ppm.

The crayfish study (n = 3 trials) included samples taken from 50  -  318 days after planting of treated rice seeds.  All samples of crayfish contained no residues at the LOQ of 0.01 ppm. The existing tolerance of 8 ppm was based on the use of a fish bioconcentration study and the estimated residues in water, sediment, and rice straw.  Therefore, the tolerance may be lowered to 0.01 ppm.

The tolerances for papaya and passion fruit will be increased from 2 ppm to 4 ppm.  This reflects a requested decrease in the PHI from 10 days to 1 day.  The residue decline study with cherry, leechee, and papaya shows that the half-life is in excess of 10 days and that, therefore, a doubling of the tolerance will be adequate (D361791, D. Rate, 01/08/2010).

Appendix A.  International Residue Limits Table

Table A1.  Summary of US and International Tolerances and Maximum Residue Limits of Chlorantraniliprole
                              Residue Definition
                                      US
                                    Canada
                                   Mexico[b]
                                     Codex
40CFR§180.628.  For plant and animal commodities: chlorantraniliprole, 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide
3-bromo- N -[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide.

Chlorantraniliprole
(fat soluble)
                                 Commodity[a]
                Tolerance (ppm) /Maximum Residue Limit (mg/kg)

                                      US
                                    Canada
                                   Mexico[b]
                                     Codex
Crayfish
0.01

None
Fruit, pome, group 11-10
1.2
0.4 (listed as individual commodities: apple, etc)

0.4
Fruit, stone, group 12-12, except cherry, Chickasaw plum, and damson plum
4.0
2.5 (listed as individual commodities: peach, etc)

1
Nut, tree, group 14-12
0.02
0.02
(listed as individual commodities:  almond, chestnut, etc)

0.02
Papaya
4.0
None

None
Passionfruit
4.0
None

None
Peanut, nutmeat
0.06
0.06 (pending)

None
Peanut, hay
90
None

None
Onion, green, subgroup 3-07B
3.0
3.0 (pending)(listed as individual commodities: green onion, etc)

None
Spice subgroup 19B
90
None

None
Completed:  10/30/2013
a	Includes only commodities of interest for this action.  Tolerance values should be the HED recommendations and not those proposed by the applicant.
b	Mexico adopts US tolerances and/or Codex MRLs for its export purposes.

Appendix B.  OECD MRL Calculation Procedure Inputs/Outputs

Tree Nuts

Almond
                                    Almond
                              Chlorantraniliprole
                                      US
                                      GAP

Total number of data (n)
                                       6
Percentage of censored data
                                     100%
Number of non-censored data
                                       0
Lowest residue
                                     0.010
Highest residue
                                     0.010
Median residue
                                     0.010
Mean
                                     0.010
Standard deviation (SD)
                                     0.000
Correction factor for censoring (CF)
                                     0.333

Proposed MRL estimate

- Highest residue
                                     0.010
- Mean + 4 SD
                                     0.010
- CF x 3 Mean
                                     0.010
Unrounded MRL
                                     0.010

Rounded MRL
                                     0.01

 High uncertainty of MRL estimate.
[Small dataset and high level of censoring]
`
                               Residues (mg/kg)
                                       n
                                   < 0.01
                                       6

Pecan
                              Chlorantraniliprole
                                     pecan
                                      US
                                      GAP

Total number of data (n)
                                       6
Percentage of censored data
                                      67%
Number of non-censored data
                                       2
Lowest residue
                                     0.010
Highest residue
                                     0.015
Median residue
                                     0.010
Mean
                                     0.012
Standard deviation (SD)
                                     0.002
Correction factor for censoring (CF)
                                     0.556

Proposed MRL estimate

- Highest residue
                                     0.015
- Mean + 4 SD
                                     0.021
- CF x 3 Mean
                                     0.019
Unrounded MRL
                                     0.021

Rounded MRL
                                     0.02

 High uncertainty of MRL estimate.
[Small dataset and high level of censoring]

                               Residues (mg/kg)
                                       n
                                   < 0.01
                                       4
                                     0.014
                                       1
                                     0.015
                                       1

Rice

Three trials were conducted to confirm a 0.15 ppm tolerance on grain set from exaggerated (4X) trials.  The existing tolerance for rice grain is 0.15 ppm.  The estimate from the present three trials is 0.04 ppm.  The tolerance is confirmed as adequate.

                              chlorantraniliprole
                                     rice
                                      USA
                                seed treatment

Total number of data (n)
                                       3
Percentage of censored data
                                      0%
Number of non-censored data
                                       3
Lowest residue
                                     0.010
Highest residue
                                     0.015
Median residue
                                     0.012
Mean
                                     0.012
Standard deviation (SD)
                                     0.003
Correction factor for censoring (CF)
                                     1.000

Proposed MRL estimate

- Highest residue
                                     0.015
- Mean + 4 SD
                                     0.022
- CF x 3 Mean
                                     0.037
Unrounded MRL
                                     0.037

Rounded MRL
                                     0.04

 High uncertainty of MRL estimate.
[Small dataset]
                               Residues (mg/kg)
                                       n
                                     0.01
                                       1
                                     0.012
                                       1
                                     0.015
                                       1

Peanut

                              Chlorantraniliprole
                                    Peanut
                                      USA
                            2X0.1 lb ai/A, 1 d PHI

Total number of data (n)
                                       6
Percentage of censored data
                                      67%
Number of non-censored data
                                       2
Lowest residue
                                     0.010
Highest residue
                                     0.034
Median residue
                                     0.010
Mean
                                     0.014
Standard deviation (SD)
                                     0.010
Correction factor for censoring (CF)
                                     0.556

Proposed MRL estimate

- Highest residue
                                     0.034
- Mean + 4 SD
                                     0.053
- CF x 3 Mean
                                     0.024
Unrounded MRL
                                     0.053

Rounded MRL
                                     0.06

 High uncertainty of MRL estimate.
[Small dataset and high level of censoring]

                               Residues (mg/kg)
                                       n
                                   < 0.01
                                       4
                                     0.012
                                       1
                                     0.034
                                       1

Strawberry  (Berry, low growing, subgroup 13-07G)

                              Chlorantraniliprole
                                  Strawberry
                                      USA
                            2X-0.1 lb ai/A, 1 d PHI

Total number of data (n)
                                       8
Percentage of censored data
                                      0%
Number of non-censored data
                                       8
Lowest residue
                                     0.180
Highest residue
                                     0.680
Median residue
                                     0.235
Mean
                                     0.298
Standard deviation (SD)
                                     0.169
Correction factor for censoring (CF)
                                     1.000

Proposed MRL estimate

- Highest residue
                                     0.680
- Mean + 4 SD
                                     0.972
- CF x 3 Mean
                                     0.893
Unrounded MRL
                                     0.972

Rounded MRL
                                       1

                               Residues (mg/kg)
                                       n
                                     0.18
                                       1
                                      0.2
                                       1
                                     0.21
                                       1
                                     0.23
                                       1
                                     0.24
                                       2
                                      0.4
                                       1
                                     0.68
                                       1

Coffee Green Bean

The existing tolerance for coffee green beans is 0.4 ppm.  An addition trial was conducted to assess the effect of adjuvant and to fulfill the requirement for five trials.   The combined data yields a tolerance estimate of 0.4 ppm.  This confirms the existing tolerance.

The initial 4 trials were conducted at 0.7x the label rate (MRID 47588222).  The residues were corrected to 1x by the use of proportionality.

                              Chlorantraniliprole
                                    Coffee
                                      US
                            0.2 lb ai/acre, 7 d PHI

Total number of data (n)
                                       5
Percentage of censored data
                                      20%
Number of non-censored data
                                       4
Lowest residue
                                     0.010
Highest residue
                                     0.160
Median residue
                                     0.140
Mean
                                     0.122
Standard deviation (SD)
                                     0.063
Correction factor for censoring (CF)
                                     0.867

Proposed MRL estimate

- Highest residue
                                     0.160
- Mean + 4 SD
                                     0.376
- CF x 3 Mean
                                     0.317
Unrounded MRL
                                     0.376

Rounded MRL
                                      0.4

 High uncertainty of MRL estimate.
[Small dataset]

                               Residues (mg/kg)
                                       n
                                   < 0.01
                                       1
                                    0.14[1]
                                       2
                                    0.16[1]
                                       2
[1] Adjusted to 1x application rate.

Cucumber (Greenhouse)

The tolerance estimate for cucumbers from greenhouse use is 0.15 ppm.  The existing tolerance for vegetable, cucurbit, group 9 is 0.5 ppm, which is within 5X of the estimate for greenhouse use on cucumber.

                              Chlorantraniliprole
                             Cucumber (greenhouse)
                                      USA
                             0.2 lb ai/A, 1 d PHI

Total number of data (n)
                                       3
Percentage of censored data
                                      0%
Number of non-censored data
                                       3
Lowest residue
                                     0.026
Highest residue
                                     0.070
Median residue
                                     0.030
Mean
                                     0.042
Standard deviation (SD)
                                     0.024
Correction factor for censoring (CF)
                                     1.000

Proposed MRL estimate

- Highest residue
                                     0.070
- Mean + 4 SD
                                     0.139
- CF x 3 Mean
                                     0.125
Unrounded MRL
                                     0.139

Rounded MRL
                                     0.15

 High uncertainty of MRL estimate.
[Small dataset]
                               Residues (mg/kg)
                                       n
                                    0.0257
                                       1
                                    0.0296
                                       1
                                    0.0697
                                       1

Tomato (Greenhouse)

The tolerance estimate for tomato from greenhouse use is 0.20 ppm.  The existing tolerance for vegetable, fruiting, group  8-10 is 1.4 ppm.  The existing tolerance for the crop group is adequate for tomatoes from greenhouse use.  While the existing tolerance is >5X from the new estimate, the existing tolerance also reflects the use of adjuvants.

                              Chlorantraniliprole
                              Tomato (Greenhouse)
                                      USA
                            0.2 lb ai/A, 1 day PHI

Total number of data (n)
                                       4
Percentage of censored data
                                      0%
Number of non-censored data
                                       4
Lowest residue
                                     0.013
Highest residue
                                     0.096
Median residue
                                     0.031
Mean
                                     0.043
Standard deviation (SD)
                                     0.038
Correction factor for censoring (CF)
                                     1.000

Proposed MRL estimate

- Highest residue
                                     0.096
- Mean + 4 SD
                                     0.194
- CF x 3 Mean
                                     0.129
Unrounded MRL
                                     0.194

Rounded MRL
                                      0.2

 High uncertainty of MRL estimate.
[Small dataset]

                               Residues (mg/kg)
                                       n
                                    0.0126
                                       1
                                    0.0203
                                       1
                                    0.0424
                                       1
                                    0.0963
                                       1

Green Onion

                              Chlorantraniliprole
                                  Green Onion
                                      USA
                            2X0.1 la ai/A, 1 d PHI

Total number of data (n)
                                       5
Percentage of censored data
                                      0%
Number of non-censored data
                                       5
Lowest residue
                                     0.406
Highest residue
                                     1.490
Median residue
                                     0.717
Mean
                                     0.811
Standard deviation (SD)
                                     0.406
Correction factor for censoring (CF)
                                     1.000

Proposed MRL estimate

- Highest residue
                                     1.490
- Mean + 4 SD
                                     2.435
- CF x 3 Mean
                                     2.432
Unrounded MRL
                                     2.435

Rounded MRL
                                       3

 High uncertainty of MRL estimate.
[Small dataset]

                               Residues (mg/kg)
                                       n
                                     0.406
                                       1
                                     0.653
                                       1
                                     0.717
                                       1
                                     0.787
                                       1
                                     1.49
                                       1

Dried Green Onion

Dried green onion will be used as a representative of chives (D361791, D. Rate, 01/08/2010), which in turn is a representative commodity for herb subgroup 19A.  Five trials were conducted with residues of  6.25, 1.00, 2.66, 10.8, and 1.48 ppm, which provided processing factors of 9.6x, 2.5x, 3.4x, 7.2x, and 2.1x.   The median processing factor, 3.4x, applied to the green onion highest average field trial (HAFT), 1.49 ppm, yields a tolerance estimate of 5 ppm.  This contrasts to the existing tolerance of 90 ppm for dried herbs subgroup 19A.  The existing tolerance will be retained, based on the previous translations and the lack of field trial data for the other representative commodity, basil (fresh and dried).  Note that the registrant has not requested a change to this tolerance.

Dill Seed

Dill seed is one of the two representative commodities for the spices subgroup 19B.  The other is black pepper.  Two trials were conducted, and therefore the OECD MRL calculation spreadsheet cannot be used.  In such situations, the tolerance estimate is taken as 5 X Mean, or 5 X 19.4 = 92 ppm.  The tolerance estimate for the spices subgroup 19B is 90 ppm.  This replaces the existing estimate of 14.0 ppm (D361791, D. Rate, 01/08/2010).