Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 3 of 29 would be deleted and replaced with a tolerance of 0.5 0 ppm in sugar beet. All commod ities in

subgroup 1 B would then be labeled with a 1

- day PHI. IR

- 4 has also proposed an e xpansion of

the established regional citrus registration to a national registration. T here would then be no

need to maintain the tolerances in citrus currently under 40CFR § 180.544 [ c ] (t olerances with

regional registrations )

. IR

- 4 collected additional citrus fruit field trial data for this purpose.

With t hese results, and the previously submitted citrus data ( MRID # 47556401 )

, IR

- 4 has

proposed the establishment of ge neral (national) tolerances in citrus fruit s ( g roup 10

- 10) at 1.9

ppm, in citrus oil (except lemon) at 100 ppm, and in lemon oil at 45 ppm. The established citrus

tolerances with regional registrations under 40CFR § 180.544 [ c ] would be deleted.

The prop osed label directions for use on citrus fruit s stipulate repeated foliar applications

, commencing when pests are first observed on the flushing leaves. Use r at es are 0.12

- 0.25 lb ai

per acre ( lb ai/A ) per application, up to a maximum of 1.0 lb ai/A per season. The minimum re

treatment interval (RTI) is 14 days ; t he minimum PHI i s 1 day. The proposed label directions for

use on root vegetables ( subgroup 1 B ) stipulate repeated foliar applications commencing at egg

hatch, or when first signs of feeding ar e observed. Use r at es are 0.12

- 0.25 lb ai per acre ( lb ai/A )

per application, up to a maximum of 1.0 lb ai/A per season ( 0 .5 lb ai/A per season on radishes)

. The minimum RTI is not specified; t he minimum PHI is 1 day. The label states that a pplications

may include the use of an adjuvant for the proposed uses, and may be made using ground or

aerial equipment on root vegetables; only ground applications are allowed on citrus fruit s

.

B ased on acceptable metabolism studies in cotton, apples, grapes and r ice , t he nature of

methoxyfenozide residues in primary crops is adequately understood

. HED concluded that the

residue of concern (ROC) for both the tolerance expression and the risk assessment in primary

crops (and drinking water) is methoxyfenozide. The qualitative nature of methoxyfenozide

residues in livestock is also adequately understood

, based on available ruminant and poultry

meta bolism studies. HED determined that the ROC is the parent compound in milk and

ruminant tissues (except meat byproducts), and in poultry meat and fat. The ROCs in meat

byproducts and eggs are methoxyfenozide and its m etabolite

, RH

- 141,518. The

methoxyfe nozide assessment team concurs with the previous finding s regarding residues of

concern.

Adequate methods are available for enforcing the current tolerances f or methoxyfenozide

i n primary crops, and animal commodities. Depending on the plant commodit y, the limit s of

quantitation (LOQ s ) for methoxyfenozide in primary crop commodities are 0.01 0

- 0.05 0 ppm. In

the submitted carrot and radish field trial studies, residues of methoxyfenozide were determined

via one of the tolerance enforc ement methods

, Method TR 34

- 98

- 87 ( Rohm and Haas Technical

Report #34

- 98

- 87 ) , with minor modifications

. This method utilizes high performance liquid

chromatography (HPLC)

, with either tandem mass spectrometric detection (LC/MS/MS) for

analysis of carrots, or ultraviolet detection (HPLC /UV) for analysis of radishes. In the submitted

citrus field trial and orange processing stud ies , residues of methoxyfenozide were determined via

LC/MS/MS

, using Dow AgroSciences Method GRM 02.25 ( modified)

. The methods were

adequate ly va lidated in conjunction with the analysis of field trial and processing study samples.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 4 of 29 The lowest level s of method validation (LLMV s ) were 0.01 0 ppm in carrot s and radish es, and

0.05 0 ppm in each citrus commodity.

Adequate multiresidue method testing data are available for the parent and its regulated

metabolites. B ased on the se data, the FDA m ultiresidue m ethods are not suitable for analysis of

methoxyfenozide or its regulated metabolites.

In conjunction with the field trial and processing stud ies , the petitioner submitted

adequate storage stability data supporting the storage conditions and duration s of the various

requested commodities . The se data indicate that methoxyfenozide is stable at ≤

- 20°C for

interva ls of up to 5 1 8 days in carrot roots

, 253 days in radish roots

, 629 days in citrus fruits, 405

days in orange dried pulp

, and 403 days in orange juice. However, the data f o r orange oil

indicate d that there is the potential for a 24% decline in methoxyfenozide residues after 400 days

of storage. Therefore, the residue data for citrus oil w ere corrected to account for decline during

storage.

A dequate field trial residue data are available for the representative commodities (carrot

and radish) to support the establishment of a crop subgroup tolerance in root vegetables

, except

sugar beet (subgroup 1 B ), pending submission of a revised Section B p r ohib iting the use of

agricultural adjuvants (for enhanced deposition, redistribution and weatherabil ity) in tank mixes

applied to subgroup 1 B crops . T he submitted carrot and radish field trial s d id not include the use

of an y adjuvant s

. The field trial data support a tolerance of 0.3 0 ppm in carrots , and a tolerance

of 0.9 0 ppm in radishes ; these tolerance levels vary by less than 5X . Ergo, the revocation of the

established tolerance of 0.5 ppm in root vegetables ( subgroup 1A )

, concomitant with the

establishment of tolerance s in sugar beet at 0.5 0 ppm , and in root vegetables

, except sugar beet

(su bgroup 1 B ), at 0. 9 0 ppm is appropriate

.

Adequate field trial residue data are also available for the representative commodities

( oranges, lemons and grapefruit ) to support the establishment of a crop group tolerance in citrus

fruits (group 10

- 10)

. The current and previously submitted citrus field trial data adequately

represent the number and geographic distribution for grapefruit, the number for lemons, and the

geographic distribution for oranges, but not the number for oranges or geographic distri bution for

lemons recommended in OCSPP Residue Chemistry Test Guideline 860.1500. The guideline

recommends 8 orange trials in Zone 3, but only 5 were conducted. The guideline recommends 4

lemon trials in Zone 10 and 1 in Zone 3, but all 5 were conducted in Zone 10; however, HED

considers the lemon field trial data adequate. Additionally, given that 20 of the 23 recommended

citrus field trials were conducted, and that the HAFT (for all citrus) came from the original

orange trials in Zone 10 (submitted wit h the previous petition for the regional use), and that all

the required field trials for Zone 10 have been submitted, HED concludes that the data are

adequate to support the proposed use (and national registration) of methoxyfenozide on citrus

fruits. Th e field trial data support tolerances of 0.7 0 , 1.5 and 3.0 ppm in grapefruit, lemons and

oranges, respectively ; these tolerance levels vary by less than 5X . Ergo, a tolerance of 3.0 ppm

in citrus fruits (group 10

- 10) is appropriate.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 5 of 29 The submitted orange processing study is adequate

, and indicates that methoxyfenozide

residues do not concentrate in juice (<0.2 X )

, and concentrated o nly slightly in dried pulp (1.1X )

. T herefore separate tolerances are not required in these citrus commodi ties. However,

methoxyfenozide residues concentrated by 56 X in orange oil, when samples were corrected for

potential residue decline during storage. Based on the processing factor for oil

, and the highest

average field trial ( HAFT ) residues i n orange s (1 .67 ppm , from the previously submitted citrus

field trials ) , the maximum expected residues in oil would be 93.5 ppm. Therefore, the revocation

of the established regional tolerance of 100 ppm in citrus oil

, concomitant with the establishment

of a national tolerance in citrus oil at 100 ppm is appropriate

. Because of the commercial

importance of lemon oil, and the significantly lower HAFT in lemons (0.792 ppm, from the

previously submitted citrus field trials), the petitioner has proposed a tolerance of 45 ppm in

lemon oil. However, the Agency does not set tolerances in the oils of the various specific citrus

fruits . Therefore, the establishment of a tolerance in lemon oil is precluded

.

Adequate livestock feeding studies are available for methoxyfenoz ide , and tolerances for

livestock commodities were recently re assessed in conjunction with petitions for uses on grass es

, peanut s

, a lfalfa and c lover

. Because the currently proposed uses will not alter the dietary burden

of methoxyfenozide residues to liv estock, reassessment of livestock tolerances is not required for

this petition.

The nature of methoxyfenozide residues in rotational crops is a dequately understood,

based on the adequate confined accumulation study. Methoxyfenozide is extensively

meta bolized in rotational crops. HED has determined that the ROCs (for risk assessment) in

rotational crops are methoxyfenozide and its m etabolites d esignated as RH

- 152,067, RH

131,157, RH

- 152,071

, and the free and conjugated forms of m etabolite RH

- 117,236 , including

its glucose conjugate ( RH

- 151,055) and its malonylglycosyl conjugate ( RH

- 152,072 ). Adequate

limited and extensive rotational crop field trials are available for methoxyfenozide, and these

field trials support the rotational crop restrictions c urrently on methoxyfenozide labels. There

are currently no tolerances in rotational crops.

An analytical reference standard for methoxyfenozide, with an expiration date of 17

October 2014 , is currently available in the EPA National Pesticide Standards Repository

(NPSR)

.

There are no Canadian maximum residue levels ( MRLs ) in any of the currently proposed

commodities. Codex MRLs are established in citrus fruits at 0.7 mg/kg, in carrots at 0.5 mg/kg,

and in radishes at 0.4 mg/kg. Harmonization of to lerances in the currently requested

commodities is not possible, as the US and Codex use patterns differ. Additionally, the

max imum residues in citrus fruits, and in radishes are greater than the corresponding Codex

MRLs

. HED’s recommended tolerances were determin ed using the Organization for Economic

Cooperation and Development ( OECD) tolerance calculation procedures (except for those in

citrus oil)

.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 6 of 29 Regulatory Recommendations and Residue Chemistry Def iciencies

HED has examined the residue chemistry database for methoxyfenozide . Pending

submission of revised Section s B and F

, there are no residue chemistry issues that would

preclude granting a registration for the proposed uses of methoxyfenozide ( as Intrepid 2F ) . The

submitted data support the following tolerances for residues of methoxyfenozide in/on the

following commodities , at the levels listed below.

Fruit, citrus, group 10

- 10

................................ ................................ ....... 3.0 ppm

Citrus

, oil

................................ ................................ ............................... 100 ppm

Beet, sugar

................................ ................................ ............................ 0.5 0 ppm

Vegetable, root, except sugar beet, subgroup 1B

................................ . 0. 9 0 ppm

860.1200 Directions for Use

The product label for Intrepid 2F ( EPA Reg istration # 62719

- 442) should be amended to

s pecify that adjuvants may not be added to spray mixtures applied to root vegetables

, except

sugar beet (subgroup 1 B )

. The petitioner s ho u ld also submit a revised Section B p r ohibiting the

use of agricultural adjuvants in tank mixes applied to subgroup 1 B crops.

860.1550 Proposed Tolerances

The petitioner s ho u l d submit a revised Section F to reflect the revis ions to tolerances and

commodity definitions , as presented above and in Table 9

.

Note to RD : According to HED’s Interim Guidance on Tolerance Expressions (S.

Knizner; 27 May 2009), the tolerance express ion for methoxyfenozide cited in 40CFR

§180. 544 [a] [1] should be revised to state:

Tolerances are established for residues of methoxyfenozide, including

its metabolites and degradates, in or on the commodities listed in the

table below. Compliance with the tolerance levels specified below is to

be determined by measuring only methoxyfenozide ( 3

- methoxy

- 2

- methylbenzoic acid 2

- (3,5

- dimethylbenzoyl)

- 2

- (1,1

- dimethylethyl)

hydrazide ) in or on the commodity.

Note to RD : A previous residue chemistry summary document for methoxyfenozide

( D358341; D. Rate; 10 June 2009 ) refers to rotational crop tolerances cited in 40CFR

§180.544[d][1 and 2]. As mentioned above, there are currently no tolerances listed in that

section. H ED recommends that RD investigate the disposition of these previously listed

tolerances.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 7 of 29 Background

Methoxyfenozide is a diacylhydrazine insecticide used on a variety of crops for control of

armyworms and other lepidopterous pest species. Methoxyfen ozide mimics the action of the

molting hormone of lepidopterous larvae, causing the larvae to undergo an incomplete and

premature molt, which ultimately results in their death. Methoxyfenozide is currently registered

to Dow AgroSciences. The nomenclature and physicochemical properties of methoxyfenozide

are presented below in Tables 1 and 2 , respectively

.

TABLE 1 Methoxyfenozide Nomenclatur e.

Chemical structure

Common name Methoxyfenozide

Company experimental name RH

- 2485

Molecular formula C 22 H 28 N 2 O 3 Molecular weight 368.47

IUPAC name N

- tert

- butyl

- N′

- (3

- methoxy

- o

- toluoyl)

- 3,5

- xylohydrazide

CAS name 3

- methoxy

- 2

- methylbenzoic acid 2

- (3,5

- dimethylbenzoyl)

- 2

- (1,1

- dimethylethyl)hydrazide

CAS registry number 161050

- 58

- 4

End

- use product (EP) 2 lb ai /gal F (Intrepid 2F

, EPA Registration # 62719

- 442)

TABLE 2 Physicochemical Properties of Methoxyfenozide.

Parameter Value Reference

Melting point/range ( oC ) 206.1

- 208 D231303; H. Podall; 19 M ay 1997

pH 7.0

Density (g/ cm 3 ) 0.740 ± 0.0081

Water solubility (mg/L at 20oC) 3.3

Solvent solubility (g/L at 20oC) N

- heptane 1.87

Xylene 3.38

1,2

- dichloroethane 36.72

Methanol 192.92

2

- Propanol 50.22

Vapor pressure ( 25oC ) 1.33 x 10

- 5 Pa

Dissociation constant, pK

a None

Octan ol/water partition coefficient

( Log [ K OW ] ) 3.72 ± 0.04

UV/visible absorption (max) ε 55313 at 203 nm European Commission; SANCO/10384/202

–

rev. 4 ; 7 October 2004Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 8 of 29 860.1200 Directions for Use

Methoxyfenozide is currently registered for use on a wide variety of food and feed crops

as a 2 lb/gal F formulation (Intrepid 2F, EPA Reg istration # 62719

- 442 ). I R

- 4 is proposing new

uses for this formulation on citrus fruits (crop group 1 0

- 10 ), and revised uses on root vegetables

, except s ugar be ets (subgroup 1B )

. Draft supplemental labels for the Intrepid 2F were provided,

and the proposed use directions are summarized in Table 3 ( below )

.

TABLE 3 Summary of Use Directions for Methoxyfenozide

. Applic ation Type,

Timing and

Equip ment 1 Formulation

[EPA

Reg istration #] Use

Rate

(lb ai/A) Max # of

Uses per

Season Max imum

Seasonal Use

Rate (lb ai/A) PHI

( D ays) Use Directions and

Limitations

Citrus Fruits

, C rop G roup 10

- 10

Foliar applications

at first sign of pests

on flushing leaves

. Ground equipment

only. 2 lb/gal F

[62719

- 442] 0.12

-

0.25 N S 2 1.0 1 The m inimum RTI is

14 days

. Apply in a

minimum of 2 0 GP A 3

.

Root Vegetables, Except Sugar Beet, Crop Subgroup 1B

Foliar applications

at egg hatch, or first

sign of feeding

damage. Ground or

aerial equipment. 2 lb/gal F

[62719

- 442] 0. 12

-

0.25 NS 1.0 1 The minimum RTI is

not specified

. Apply

in a minimum of 10

GP A . Maximum

s easonal use rate on

radish es is 0.5 lb ai/A.

1. The main label prohibits applications throug h any type of irrigation system. The supplemental labels allow for

the inclusion of adjuvants in the spray mix.

2. NS = Not S pecified

. However, based on the lowest single use rate, and maximum seasonal use rates, the implied

maximum number of uses per season would be 4 on radishes, 8 on citrus fruits, and 8 on all root vegetables

other than radishes.

3. GPA = Gallons Per Acre.

Concl usion s: The supplemental label directions are adequate to allow for evaluation of

the residue data relative to the submitted field trials. The available field trial data support the

proposed use directions , except with respect to the use of adjuvants

. T he product label for

Intrepid 2F should be amended to s pecify that adjuvants may not be added to spray mixtures

applied to root vegetables

, except sugar beet (subgroup 1 B ).

860.1300 Nature of the Residue

- Plants

HED Memo; D 258034; W. Wassell ; 23 J uly 1999

D 251225; W. Wassell ; 2 7 J uly 1999

D 259989; W. Wassell; 8 A ugust 2000

The nature of methoxyfenozide residues in primary crops is adequately understood, based

on acceptable metabolism studies in cotton, apples, grapes and rice. Methoxyfenozide does not

undergo extensive metabolism in primary crops. HED has determined that the ROC, for both theMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 9 of 29 tolerance expression and risk assessment in primary crops (and drinking water)

, is the parent

compound only, methoxyfenozide

.

860.130 0 Nature of the Residue

- Livestock

HED Memo; D258034; W. Wassell; 23 July 1999

The nature of the residue in livestock is adequately understood, based on the available

metabolism studies in lactating goats

, and laying hens. HED has determined that the ROC in

milk and ruminant tissues (other than liver and kidney) is parent compound; in ruminant liver

and kidney it is methoxyfenozide and its RH

- 141,518 metabolite. The ROC in poultry meat

(muscle) and fat is parent methoxyfenozide. The ROC in eggs, poul try liver, and poultry meat

byproducts is methoxyfenozide and its metabolite

, RH

- 141,518.

860.1340 Residue Analytical Methods

DERs for MRIDs # 47556401, 4840260 1 to

- 03

Enforcement M ethods for P lant C ommodities

The following HPLC/UV or LC/MS methods are available for enforcing tolerances of

methoxyfenozide i n primary crops: Method TR 34

- 96

- 88 for cotton commodities; Method TR

34

- 98

- 87 for pome fruits; Method TR 34

– 00

- 38 for corn commodities; Method TR 34

- 00

- 107

for tree nuts; Method TR 34

- 00

- 109 for stone fruits; and Method TR 34

- 99

- 74 for leafy and

Brassica ( C ole) vegetables, fruiting vegetables, grapes and raisins. Adequate method validation,

radiovalidation, and independent laboratory validation (ILV) data have been provided for these

met hods. Successful petition method validation (PMV) trials were conducted on Methods TR

34

- 96

- 88 and TR 34

- 98

- 87, and the Biological and Economic Analysis Division’s (BEAD’s)

Analytical Chemistry Branch (ACB) concluded that PMV trials were not required for the other

methods

, as they are sufficiently similar to the validated methods.

For each of these methods, residues of methoxyfenozide are extracted with acidic

aqueous methanol, filtered

, and diluted with 10% sodium chloride. Extract s are then purified by

sequential liquid

- liquid partitioning with hexane and dichloromethane (DCM). Residues in the

DCM fraction are further purified by elution through one or more of the following column types:

basic alumina, silica gel, carbon, Florisil, or C 18 . Residue s in the final eluate are concentrat ed,

re

- dissolved in acetonitrile (ACN)/ water, and analyzed by reverse

- phase HPLC using UV (240

nm) or MS (m/z 367) with external standards. The LOQ s for methoxyfenozide are 0.01 0

- 0.05 0

ppm

, depending on the plant commod ity.

Data C ollectio n M ethods for Plant C ommodities

Citrus Fruits: Res idues of methoxyfenozide in citrus fruits (oranges, lemons and

grapefruits) , and processed orange commodities (MRID #47556401) were determined using a n

LC/MS/MS method which is a modified version of Dow AgroSciences Method GRM 02.25,

Determination of Residue of Methoxyfenozide in High Moisture Crops by LiquidMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 10 of 29 Chromatography with Tandem Mass Spectrometry Detection

. This method was previously

reviewed in conjunction with a petition for use on soybeans (D316528; W. Cutchin; 25 April

2006). The major modifications to the method included:

1) The use of vacuum for filtration instead of centrifuge,

2) an increase of the sample size from 0.050 g to 1.00 g,

3) the addition of a concentration step prior to solid

- phase extraction

(SPE) cleanup,

4) a change to the configuration of the SPE column, and

5) the substitution of PFP

- Propyl phase for the SB

- C 8 phase HPLC

column, and use of 10 mM ammonium acetate instead of formic

acid in the mobile phase.

A brief description of the method follows. Methoxyfenozide residues were extracted

with 90% methanol/ 10% 0.1 N hydrochloric acid, then filtered, and concentrated. An aliquot was

then diluted with water, and residues we re purified using a Phenomenex Strata

- X SPE cartridge.

After loading, the SPE cartridge was washed with 60% water/40% methanol/0.1% formic acid

solution, and residues were then eluted with ACN . Residues were concentrated to dryness

, and

reconstituted in 50% ACN /50% 10 mM ammonium acetate. The samples were then analyzed by

LC/MS/MS using external standards and the m/z 339→149 ion transition for quantitation of

residues. The LLMV in citrus fruits wa s 0.05 0 ppm. The reported LOQ s for methoxyfenozide

were 0.021, 0.018, 0.009 and 0.067 ppm in orange fruit, pulp

, juice and oil, respectively. T he

reported limit s of detection ( LOD s ) were 0.007, 0.006, 0.003 and 0.022 ppm for orange fruit,

pulp , juice and oil, respectively. The above method was validated prior to

, and in conjunction

with

, the analysis of field trial samples. Control samples of oranges were fortified with

methoxyfenozide at 0.05 0

- 5. 0 ppm for method validation

, and at 0.05 0

- 0.50 ppm for concurrent

validation.

Samples of citrus fruits (MRID #48 402 601) were analyzed for methoxyfenozide using a

modified version of Dow AgroSciences Method GRM 02.25. Modifications (provided in the

study) were made to improve the performance of the method

. Briefly, samples were

homogenized with 90% methanol/10% 0.1 N HCl, then shaken and centrifuged. An aliquot of

the extract was diluted with water

, and purified with a n SPE plate. The plate was washed with

60% water/40% methanol/0.1% formic acid

, and eluted with ACN . The eluate was evaporated

to dryness

, and the r esidues were reconstituted in a 70% water/30% ACN mobile phase

containing 0.1% formic acid. The purified extract was analyzed by LC/MS/MS. Based on

recoveries of samples fortified at the LLMV, the LOD and LOQ in citrus fruits were sta ted as

0.0072 and 0.022 ppm, respectively.

Carrots: Residues of methoxyfenozide in carrots were determined using Rohm and Haas

Technical Report #34

- 98

- 87, Tolerance Enforcement Method for Parent RH

- 2485 in Pome Fruit

. Minor modifications which were i mplemented to improve efficiency did not negatively affect the

performance of the method. Residues were extracted from carrots by blending and shaking with

methanol/0.1 N hydrochloric acid. The extract was purified by partitioning with hexane andMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 11 of 29 DCM . Qu antification was achieved via LC/MS/MS. The method was validated at 0.010, 0.10,

and 1.0 ppm of methoxyfenozide prior to sample analysis. The LOD and LOQ for

methoxyfenozide were reported as 0.0028 and 0.0084 ppm, respectively. During sample

analysis, u ntreated carrot roots were fortified with methoxyfenozide at 0.010, 0.10 and 1.0 ppm

for determination of concurrent recover ies

.

Radishes: Residues of methoxyfenozide in radishes were determined using Rohm and

Haas Technical Report #34

- 98

- 87, Toleranc e Enforcement Method for Parent RH

- 2485 in Pome

Fruit . Minor modifications which were implemented to improve efficiency did not negatively

affect the performance of the method. Residues were extracted from radish es by blending with

methanol/0.1 N hydrochloric acid. The extract was purified by partitioning with hexane and

DCM, a nd was further subjected to SPE cleanup using a silica gel column

, followed by a carbon

column. Residues were quantified via HPLC / UV

. The method was validated at 0.01 0 , 0 .10 and

1.0 ppm o f methoxyfenozide prior to sample analysis

. The LOD and LOQ for methoxyfenozide

were reported as 0.0034 and 0.010 ppm, respectively. The method suitability was dem onstrated

by concurrent recoveries, using samples fortified with methoxyfenozide at 0.10 ppm

.

Conclusion s: The available methods are adequate for enforcing the established and

r ecommended tolerances

. R esidues in citrus fruit and root vegetable commodities from the field

trial and processing studies were determined using adequate data collection methods.

860.1360 Multiresidue Methods

PP#8F5004 & PP#8F5006; D 249438, D 249458, D251218 & D 251225 ; W. Wassell ; 27 July 1999

Data concerning the recovery of methoxyfenozide using the FDA multiresidue method

protocols ( PAM Vol ume I ) were previously submitted to

, and reviewed by

, HED.

Methoxyfenozide was not recoverable by any of these procedures. The data were forwarded to

FDA for evaluation

, and the updating of PAM Volume I

.

8 60.1380 Storage Stability

DERs for MRI Ds # 47556401, 48402602 and

- 03

The storage durations and conditions for sa mples from the crop field trial and processing

stud ies submitted to support th e current petition are presented in Table 4.

Citrus Fruits: Samples of oranges, lemons and grapefruits from the c it r us field trials

were stored at <

- 20°C for durations of up to 658 days prior to extraction for analysis ( see Table

4, below) . To support this storage duration , a concurrent freezer storage stability s tudy was

conducted using control samples of oranges fortified with methoxyfenozide at 1.0 0 ppm. A 0

- day analysis was not conducted on the fortified samples prior to storage. The fortified samples

were stored for a maximum interval of 629 days under the same conditions (<

- 20oC) as the field

trial samples. At the end of the analytical phase, the stored samples were analyzed in triplicate

,Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 12 of 29 along with control samples freshly fortified with methoxyfenozide at 1.0 0 ppm. The average

recovery from the stored f resh citrus samples (corrected for concurrent recoveries) was 99%.

Although the field trial samples were stored for slightly longer (658 days ) than the fortified

samples in the storage stability study , the difference was relatively minor (29 additional da ys,

<5% longer than the interval of the storage stability study ), so the storage stability data support

the storage conditions and durations of the samples from the citrus field trials.

Samples of orange fruit, dried pulp, juice and oil fr om the c i t rus processing stud y were

stored at ≤

- 20 oC for durations of up to 420 days prior to analysis ( see Table 4, below ). To

support these storage durations , a concurrent freezer storage stability study was conducted using

control samples of orange f ruit, dried pul p, juice and oil

, each fortified with methoxyfenozide at

1.0 0 ppm. A 0

- day analysis was not conducted on the fortified samples prior to storage. The

fortified samples were stored under the same conditions (≤

- 20oC) as the processing samples. At

the end o f the analytical phase, the stored samples were analyzed in triplicate

, along with control

samples freshly fortified with methoxyfenozide. The average recovery from the stored orange

fruit, dried pulp, juice and oil samples (corrected for concurrent recoveries) were 99, 103, 109,

and 76%, respectively. These data indicate that methoxyfenozide is stable at

- 20°C for intervals

of up to 629 days in orange fruit

, 405 days in orange dried pulp

, and 403 days in orange juice

. However, the 76% recovery from oil after 400 days indicates that some breakdown of residues

may occur in frozen oil. However, the actual rate of decline c ould not be determined as the

stored oil sample wa s only analyzed at one time point. These data support the sample storage

conditions and durations for the c i t rus processing stud y; however, residues in oil we corrected to

account for possible decline during storage.

Carrots: The maximum storage dura tion for carrot samples was 491 days ( see Table 4,

below) . Carrot storage stability samples were fortified with methoxyfenozide at 1.00 ppm.

Storage stability samples were analyzed 518 days after fortification. Recoveries of

methoxyfenozide from carrot samples fortified at 1.00 ppm averaged 90 ± 3 % (n = 3).

Radishes: R adish samples were stored frozen for durations of up to 253 days a f ter

collection ( see Table 4, below)

. A freezer storage stability study was conducted using radish

samples fortified with 1.00 ppm methoxyfenozide

, and stored for 468 days. The concurrent

recovery of methoxyfenozide was 75% (n = 1). R ecoveries fr om stored radish samples fortified

with methox yfenozide at 1.00 ppm ranged from 75

- 77% (76 ± 1%, n= 3) , so the average

recovery (corrected for concurrent recover y ) was 101%

.

TABLE 4 Summary of Storage Conditions.

Matrix Storage Temperature

(°C) Actual Storage Duration

( D ays) * Interval of Demonstrated

Storage Stability ( D ays)

Orange fruit <

- 20 658 629

Lemon fruit 621

Grapefruit 657

Orange d ried p ulp 411 405

Orange j uice 413 403

Orange o il 420 400Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 13 of 29 TABLE 4 Summary of Storage Conditions.

Matrix Storage Temperature

(°C) Actual Storage Duration

( D ays) * Interval of Demonstrated

Storage Stability ( D ays)

Carrot roots

- 37 to 0.2 491 518

Radish roots

- 37 to

- 6 253 468

* Interval from harvest to extraction for analysis.

Conclusion s: The available storage stability data are adequate

, and support the storage

conditions and durations for samples from the submitted root vegetable and citrus fruit field

trials

, and the orange processing stud y

. Based on the decline in residues observed in cit rus oil

during frozen storage ( 24% decrease after 13 months), the residue data for citrus oil will be

corrected to account for decline during storage.

860.1400 Water, Fish, and I rrigated Crops

There are no proposed uses that are relevant to this guideline topic.

860.1460 Food Handling

There are no proposed uses that are relevant to this guideline topic.

860.1480 Meat, Milk, Poultry, and Eggs

Adequate livestock feeding studies are available for methoxyfenozide ( D 269969; M.

Nelson ; 7 A ugust 20 02 ), and methoxyfenozide residues in animal commodities were recently

re assessed in conjunction with petitions for uses on citrus fruits (regional registration), dried

shelled peas and beans (except soybeans), popcorn, and pomegranate ( D358341; D. Rate; 10

June 2009 ). The maximum reasonably balanced dietary burdens ( M RB DB s ) of

methoxyfenozide residues to livestock were calculated at that time to be 3 5 ppm for beef cattle,

5 4 ppm for dairy cattle, 7.7 ppm for poultry

, and 0.2 ppm for swine

.

The only new livestock feedstuffs associated with the currently proposed uses are citrus

dr ied pulp, and carrot culls. Based on recent changes in Agency guidance on calculating

M RBDBs ( ChemSAC memo randum; 30 June 200 8 ), citrus dried pulp is generated in Florida

(fresh market culls in California and Texas are disposed of as wet pulp). It is fed to beef and

dairy cattle, an d is used at a maximum of 10% in premixed ration supplements. Wet pulp is

applied to local fields for livestock foraging. Carrot culls are generated in carrot growing areas,

and are fed to local growing beef cattle, dairy cattle, and sheep. They are fed at a maximum of

10% in dairy cattle diets, and at <5% (not used, essentially) in beef cattle and sheep diets.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 14 of 29 Conclusions: As the recommended tolerances in these livestock feedstuffs are 3 ppm or

less, and because the feedstuffs are fed local ly , and do not comprise substantial portions of

livestock diets (≤10%) , they will not significantly alter the dietary burden to livestock f r om

methoxyfenozide residues . Ergo, reassessment of livestock tolerances is not required for this

petition.

860.1500 Cro p Field Trials

DERs for MRIDs # 4840260 1 to

- 03

Citrus Fruit s (Crop Group 10

- 10)

Oranges, grapefruit and lemons : IR

- 4 has submitted field trial data for residues of

methoxyfenozide i n citrus fruits . 14 field trials were conducted (7 on oranges, 4 on grapefruit,

and 3 on lemons) in the US

, encom passing EPA regions 3 (FL; 5 orange

, and 3 grapefruit), 6

(TX ; 1 orange), and 10 (CA; 1 orange, 1 grapefruit, 3 lemon) during the 2008 growing season.

The number and geographic locations of the submitted trials

, in combination with previously

reviewed citrus data (MRID # 47556401)

, do not satisfy the data requirements of OCSPP Residue

Chemistry Test Guideline 860.1500 for a national registration.

At each of the trial sites

, methoxyfenozide (as Intrepid 2F ) was applied to citrus trees as 4

foliar directed applications at rates of approximately 0.25 lb ai/A each, for total seasonal use

rates of approximately 1.0 lb ai/A. A n on

- ionic surfactant (NIS) or crop oil concentrate (COC)

adjuvant was included in each tank mix at all trial sites . The applications were made at 12

- to

15

- day RTI s

, and marketable citrus fruit was collected at a PHI of 1 day. Additional samples

( for the determination of residue decline characteristics) were also collected from the CA69

or ange trial at 3

- , 7

- and 14

- day PHIs.

The results from the current field trials (see Table 5, below) show that the maximum

methoxyfenozide residue in citrus fruit w as 0.658 ppm following total seasonal applications of

approximately 1.0 lb ai/A

, with a PHI of 1 day. The residue decline trial showed that t here was

no significant decline in residues over 14 days. The LLMV was 0.05 0 ppm. The reported LOD

and LOQ were 0.0072 ppm and 0.022 ppm, respectively.

TABLE 5 Summary of Residue Data from Citrus Field Trials with Methoxyfenozide.

Commodity Total Use

Rate (lb ai/A) PHI

( D ays) Residue Levels (ppm)

n Min. Max. HAFT * Median Mean Std. Dev.

Field Trials from Current Submission (MRID # 48402601)

Orange fruit 1.00

- 1.02 1 14 0.195 0.658 0.543 0.277 0.311 0.12

3 2 0.213 0.229 0.221 0.221 0.221

---

7 2 0.159 0.190 0.175 0.175 0.175

---

14 2 0.188 0.294 0.241 0.241 0.241

--- Grapefruit fruit 0.99

- 1.01 1 8 0.136 0.312 0.283 0.246 0.226 0.06

Lemon fruit 0.99

- 1.02 1 6 0.191 0.388 0.349 0.308 0.291 0.07Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 15 of 29 TABLE 5 Summary of Residue Data from Citrus Field Trials with Methoxyfenozide.

Commodity Total Use

Rate (lb ai/A) PHI

( D ays) Residue Levels (ppm)

n Min. Max. HAFT * Median Mean Std. Dev.

Field Trials from Previous Submission (MRID #47556401 )

Orange fruit 1.00

- 1.01 1 4 0.140 1.72 1.670 0.894 0.912 0.876

Lemon fruit 1.00 1 4 0.374 0.933 0.792 0.529 0.591 0.259

Grapefruit fruit 1.00

- 1.02 1 4 0.112 0.278 0.254 0.173 0.184 0.083

All c itrus f

ruits 1.00

- 1.02 1 12 0.112 1.72 1.670 0.326 0.562 0.571

* HAFT = Highest Average Field Trial.

Conclusions: The current and previously submitted citrus field trial data adequately

represent the number and geographic distribution for grapefruit, the number for lemons, and the

geographic distribution for oranges, but not the number for oranges or geographic distribution for

lemons recommended in OCSPP Residue Chemistry Test Guideline 860.1500. The guide line

recommends 8 orange trials in Zone 3, but only 5 were conducted. The guideline recommends 4

lemon trials in Zone 10 and 1 in Zone 3, but all 5 were conducted in Zone 10 ; however, HED

considers the lemon field trial data adequate

. Additionally , given that 20 of the 23 recommended

citrus field trials were conducted, and that the HAFT (for all citrus) came from the original

orange trials in Zone 10 (submitted with the previous petition for the regional use), and that all

the required field trials for Zo ne 10 have been submitted, HED concludes that the data are

adequate to support the proposed use (and national registration) of methoxyfenozide on citrus

fruits. The field trial data support tolerances of 0.7 0 , 1.5 and 3.0 ppm in grapefruit, lemons and

ora nges, respectively ; these tolerance levels vary by less than 5X . Ergo, a tolerance of 3.0 ppm

in citrus fruits (group 10

- 10) is appropriate. A revised Section F should be submitted requesting

a tolerance that concurs with HED’s recommendation.

Root V egetables, Except Sugar Beet (Crop Subgroup 1B)

Carrots: IR

- 4 has submitted field trial data for residues of methoxyfenozide i n carrots.

Eight field trials were conducted in the US, encompassing EPA regions 3 (FL; 1 trial), 5 (MI and

WI; 1 trial each), 6 (TX; 1 trial) and 10 (CA and NM; 3 trials and 1 trial , respectively ) during the

2007

- 2008 growing season s

.

At each of the trial site s

, methoxyfenozide (as Intrepid 2F ) was applied to carrot plants as

4 foliar applications at a target rate of 0.25 lb ai/A , for total seasonal use rates of approximately

1.0 lb ai/A. Foliar broadcast applications were used at all trial sites except CA64, FL19 and

NM07 (at these sites, foliar directed applications were made). Applications were made at 12

- to

16

- day RTI s

, and marketable carrots w ere collected at a PHI of 1 day. At trial CA48

, a dditional

samples were also collected at PHIs of 0, 3, 6, 7 and 10 days for the determination of residue

decline characteristics . No spray adjuvant s w ere used for any of the applic ations at any of the

field trial sites

.

The results from these trials (see Table 6, below) show that the maximum

methoxyfenozide residue in carrot roots was 0.13 ppm following total seasonal applications of

approximately 1.0 lb ai/A , with a PHI of 1 day . All control samples contained <0.01 0 ppmMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 16 of 29 methoxyfenozide except for one sample at 0.0107 ppm from field trial FL19. T he residue

decline trial showed that methoxyfenozide decreased with increasing PHI s

.

TABLE 6 Summary of Residue Data fr om C ar ro t Field Trials with Methoxyfenozide.

Commodity Total Use Rate

(lb ai/A) PHI

(Days) Residue Levels (ppm)

n Min. Max. HAFT* Median Mean Std. Dev.

Carrot roots 1.03 0 2 0.103 0.112 0.1075 0.1075 0.1075

--

1.007

- 1.03 1 16 0.0266 0.130 0.1245 0.0743 0.0737 0.0303

1.03 3 2 0.0716 0.0802 0.0759 0.0759 0.0759

--

1.03 6 2 0.0695 0.0805 0.0750 0.0750 0.0750

--

1.03 7 2 0.0388 0.0399 0.0394 0.0394 0.0394

--

1.03 10 2 0.0537 0.0604 0.0571 0.0571 0.0571

--

* HAFT = Highest Average Field Trial.

Radishes: IR

- 4 has submitted field trial data for residues of m ethoxyfenozide i n r adish es

. F ive field trials were conducted in the US

, encompassing EPA region s 1 ( NY ; 1 trial), 3 ( FL ; 2

trials)

, 5 ( WI ; 1 trial) and 10 ( CA ; 1 trial) during the 2007

- 2008 growing season s

.

At each of the trial site s

, methoxyfenozide (as Intrepid 2F ) was applied to radish plants as

2 foliar applications at a target rate of 0.25 lb ai/A , for total seasonal use rates of approximatel y

0.5 lb ai/A. Foliar broadcast applications were used at all trial sites except FL20 and FL21,

where foliar directed applications were made. Applications were made at 13

- to 15

- day RTI s

, and marketable r adish es w ere collected at a PHI of 1 day. A t tria l CA47

, a dditional samples

were also collected at PHIs of 0, 3, 5, 7 and 9 days for the determination of residue decline

characteristics. No spray adjuvants were used for any of the applications at any of the field trial

sites.

The results from these trials (see Table 7, below) show that the maximum

methoxyfenozide residue in radish roots was 0.601 ppm following total seasonal applications of

approximately 0 .50 lb ai/A , with a PHI of 1 day . All control samples contained <0.010 p pm

methoxyfenozide. The residue decline trial showed that t here was no significant decline in

residues over 9 days.

TABLE 7 Summary of Residue Data from Radish Field Trials with Methoxyfenozide.

Commodity Total Use Rate

(lbs ai/A) PHI

(Days) Residue Levels (ppm)

n Min. Max. HAFT* Median Mean Std. Dev.

Radish r oots 0.496 0 2 0.0 384 0.0445 0. 0415 0.0 414 0. 0415

--

0.496

- 0.520 1 10 0.0442 0.601 0.4525 0.1098 0.1894 0.1766

0.496 3 2 0.0643 0.0648 0.0646 0.0645 0.0646

--

0.496 5 2 0.0561 0.0676 0.0619 0.0619 0.0619

--

0.496 7 2 0.0487 0.0557 0.0522 0.0522 0.0522

--

0.496 9 2 0.0402 0.0486 0.0444 0.0444 0.0444

--

* HAFT = Highest Average Field Trial.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 17 of 29 Conclusions: The c a rr o t and r a dis h field trial data adequately represent the number s and

geographic distribution s recommended in OCSPP Residue Chemistry Test Guideline 860.1500.

The field trial data support a tolerance of 0.3 0 ppm in carrots , and a tolerance of 0.9 0 ppm in

radishes ; these tolerance levels vary by less than 5X . Ergo, a t olerance of 0.9 0 ppm in root

vegetables

, except sugar beet (subgroup 1 B ), is appropriate. A revised Section F should be

submitted requesting a tolerance that concurs with HED’s recommendation. The petitioner

s ho u ld also submit a revised Section B p r ohibi ting the use of agricultural adjuvants in tank mixes

applied to subgroup 1 B crops.

860.1520 Processed Food and Feed

DER for MRID # 47556401

In conjunction with the citrus fruit field trials, IR

- 4 submitted a processing study with

oranges treated at approximately 1 X the seasonal use rate. The study is discussed in the text, and

the processing factors for methoxyfenozid e residues in orange fruit, dried pulp, juice and oil are

summarized in Table 8 (below)

.

TABLE 8 Summary of Processing Factors for Methoxyfenozide in Citrus Commodities

.

RAC Processed Commodity Processing Factor

Orange Fruit (RAC) N ot applicable

. Dried p ulp 1.1 X

Orange j uice <0.2 X

O range o il 56 X

In a field trial conducted in CA during 2006 , methoxyfenozide ( as Intrepid 2F ) was

applied to orange trees at fruit maturity as a single foliar directed spray at the rate of 0.995 lb

ai/A. This application rate is roughly 4 X the maximum proposed single use rate , and 1X the

maximum total seasonal use rate. The a pplication w as made using ground equipment in a

volume of 100 GP A, and no adjuvants were used in the spray mix

. Single control and treated

bulk samples of o range s were harvested at a PHI of 3 days , and whole fruits were proc essed into

dried pulp, juice, and oil using commercial processing procedures.

Samples of orange whole fruit, dried pulp, juice and oil were stored at ≤

- 20oC for 13.4

-

13.8 months prior to analysis. The available storage stability data indicate that met hoxyfenozide

is stable in frozen citrus fruit, pulp and juice for this duration, but the study also showed a

potential decline of 24% in methoxyfenozide residues in oil after 13.1 months of frozen storage.

Therefore, the residues in oil were corrected to account for this decline.

Methoxyfenozide residues were determined using an adequate LC/MS /MS method ( Dow

AgroSciences Method GRM 02.25 , modified ) , which was validated in conjunction with the

analysis of processing study samples. The LLMV was 0.05 0 ppm for each matrix , and the

reported LOQs were 0.021 ppm in whole fruit, 0.018 ppm in dried pulp, 0.009 in juice, and 0.067Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 18 of 29 ppm in oil. The reported LODs were 0.007, 0.006, 0.003 and 0.022 ppm, respectively for whole

fruit, pulp

, juice and oil.

Following a single foliar application of methoxyfenozide at approximately 1.0 lb ai/A,

methoxyfenozide residues were 0.245 ppm in orange fruit

, 0.269 ppm in dried pulp, <0.05 ppm

in juice , and 10.4 ppm in oil . When corrected for potential decline during f rozen storage,

original residues in oil were 13.68 ppm. These data indicate that methoxyfenozide residues wer e

reduced in orange juice (<0.2X )

, and concentrated only slightly in dried pulp (1.1 X ). However,

residues concentrated substantially in citrus oi l (56 X ) . The theoretical citrus processing factors

are 2 X for juice and dried pulp , and 1000X for oil.

Conclusions: The citrus processing study is adequate and indicates that separate

tolerances are not required in orange juice and dried pulp. However, a se parate tolerance is

required in citrus oil. Based on the 56 X processing factor for oil

, and the HAFT residue of 1.67

ppm (from the previously submitted citrus field trials) in citrus fruits, the maximum expected

residue in oil is 93.5 ppm. Therefore, a tolerance in citrus oil at 100 ppm is appropriate.

Because of the commercial importance of lemon oil, and the significantly lower HAFT in lemons

(0.792 ppm, from the previously submitted citrus field trials), the petitioner has proposed a

tolerance of 45 ppm in lemon oil. However, the Agency does not set tolerances in the oils of the

various specific citrus fruits. Therefore, the establishment of a tolerance in lemon oil is

precluded. A revised Section F should be submitted requesting a toleranc e that concur s with

HED ’s recommendation.

860.1650 Submittal of Analytical Reference Standards

The analytical standard for methoxyfenozide (RH

- 112485) , with an expiration date of 17

October 2014 , is currently available in the EPA ’s NPSR (personal communication from Dallas

Wright of BEAD/ACB; 10 January 2011). Upon expiration of the current standard (and/or its 3

metabolites) , the registrant is required to resubmit a reasonable amount of the analytical

reference standard for methoxyfenozide

. The reference standard should be sent to the ACB,

which is located at Fort Meade, MD. It should be sent to the attention of either Theresa Cole or

Thuy Nguyen at the address listed below, along with a le tter of transmittal. Please note that the

full 9

- digit Zip Code is mandatory, or the mail will be returned to the registrant.

USEPA

National Pesticide Standards Repository

Analytical Chemistry Branch/BEAD/OPP

701 Mapes Road

Fort George G. Mea de, MD 20755

- 5350

The letter of transmittal should in clude the assay of the standard , name of the analytic al

method used, a statement of principal impurities, purification procedures employed, storage

requirements, and special precautions for safe handli ng. Replacement of standards may beMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 19 of 29 required periodically if supplies are exhausted

, or if decomposition occurs during storage.

Material Safety Data Sheets (MSDSs) must accompany all analytical standards as specified by

the Occupational Safety and Health Administration (OSHA) in 29CFR § 1910.1200. In addition

to the parent compound, 3 metabolites ( included in risk assessment) are currently available in the

NPSR , as listed below with their respective expiration date s.

M ethoxyfenozide metabolite J (RH

- 151055) 15 July 2014

M ethoxyfenozide metabolite RH

- 117236 3 September 2013

M ethoxyfenozide metabolite RH

- 141518 26 July 2013

860.1850 Confined Accumulation in Rotational Crops

HED Memo; D258034; W. Wassell; 23 July 1999

D251225; W. W assell; 27 July 1999

The nature of methoxyfenozide residues in rotational crops is adequately understood,

based on the available confined rotational crop study . Following three soil appli cations of

[ 14 C ]

- methoxyfenozide at rates totaling 2.0 lb ai/A

, total radioactive residues accumulated at

≥0.01 ppm in mustard, rad ishes, and wheat planted 31, 91 and 364 days after the last application.

Methoxyfenozide was highly me tabolized in rotational cr ops by oxidation, demethylation and

hydroxylation to non

- conjugated metabolites, which were then conjugated with biomolecules

, yielding bound residues and precursors in the sugar synthesis pathway.

HED concluded that t he ROCs in rotational crops include methoxyfenozide, its free

phenol metabolite (RH

- 117,236), conjugated forms of the phenol metabolite (RH

- 151,055 and

RH

- 152,072), and the metabolites RH

- 152,067

, RH

- 131,157 and RH

- 152,071. For enfor cement

purposes, the tolerance definition for rotated crops includes parent only in high

- moisture crops

, and the combined residues of parent and metabolites RH

- 151,055

, RH

- 152,072 and RH

- 117,236

in low

- moisture crops. Metabolites RH

- 152,067

, RH

- 131,157 and RH

- 152,071 are also to be

taken into account in risk assessments. There are currently no tolerances in rotational crops.

860.1900 Field Accumulation in Rotational Crops

D 322948; D. Rate ; 2 J une 2009

Label directions for methoxyfenozi de currently list rotational crop restriction s specify ing

that crops with registered uses may be replanted at any time, and all other food or feed crops may

be replanted 7 days after the last application. Adequate limited and extensive rotational crop

fie ld trials are available that support these rotational crop restrictions

. There are currently no

tolerances in rotational crops.

Note to RD : A previous residue chemistry summary document for methoxyfenozide

( D358341; D. Rate; 10 June 2009 ) refers to rotational crop tolerances cited in 40CFR

§180.544[d][1 and 2]. As mentioned above, there are currently no tolerances listed in thatMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 20 of 29 section. HED recommends that RD investigate the disposition of these previously listed

tolerances.

860.15 50 Proposed Tolerances

Note to RD : According to HED’s Interim Guidance on Tolerance Expressions (S.

Knizner; 27 May 2009), the tolerance expression for methoxyfenozide cited in 40CFR

§180. 544 [a] [1] should be revised to state:

Tolerances are establish ed for residues of methoxyfenozide, including

its metabolites and degradates, in or on the commodities listed in the

table below. Compliance with the tolerance levels specified below is to

be determined by measuring only methoxyfenozide (3

- methoxy

- 2

- methy lbenzoic acid 2

- (3,5

- dimethylbenzoyl)

- 2

- (1,1

- dimethylethyl)

hydrazide) in or on the commodity.

For purposes of the tolerances expression, HED previously determined that the ROC is

methoxyfenozide in primary crops, and in livestock commodities (except meat byproducts and

eggs)

. The ROCs in eggs and meat byproducts are the parent and Metabolite RH

- 141,518. The

tolerances proposed by IR

- 4 in the current petition are listed in Table 9 (below), alongside

HED’s recommended tolerances.

Adequate field tr ial residue data are available for the representative commodities (carrot

and radish) to support the establishment of a crop subgroup tolerance in root vegetables

, except

sugar beet (subgroup 1 B ), pending submission of a revised Section B re stricting tank mixes with

agricultural adjuvants (for enhanced deposition, redistribution and weatherability) to use on

citrus fruit s only. T he submitted carrot and radish field trial s do not reflect the use of an

adjuvant. The field trial data support a tolerance of 0 .3 0 ppm in carrots , and a tolerance of 0.9 0

ppm in radishes ; these tolerance levels vary by less than 5X . Ergo, the revocation of the

established tolerance of 0.5 ppm in root vegetables ( subgroup 1A ), concomitant with the

establishment of tolerances in su gar beet at 0.5 0 ppm , and in root vegetables

, except sugar beet

(subgroup 1 B ), at 0.9 0 ppm is appropriate. A revised Section F should be submitted requesting a

tolerance that concurs with HED’s recommendation. The petitioner s ho u ld also submit a revised

Section B p r ohibiting the use of agricultural adjuvants in tank mixes applied to subgroup 1 B

crops.

Adequate field trial residue data are also available for the representative commodities

(oranges, lemons and grapefruit) to support the establishment of a crop group tolerance in citrus

fruits (group 10

- 10)

. The current and previously submitted citrus field trial data adequately

represent the number and geographic distribution for grapefruit, the number for lemons, and the

geographic distribution for ora nges, but not the number for oranges or geographic distribution for

lemons recommended in OCSPP Residue Chemistry Test Guideline 860.1500. The guideline

recommends 8 orange trials in Zone 3, but only 5 were conducted. The guideline recommends 4Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 21 of 29 lemon tri als in Zone 10 and 1 in Zone 3, but all 5 were conducted in Zone 10; however, HED

considers the lemon field trial data adequate. Additionally, given that 20 of the 23 recommended

citrus field trials were conducted, and that the HAFT (for all citrus) came from the original

orange trials in Zone 10 (submitted with the previous petition for the regional use), and that all

the required field trials for Zone 10 have been submitted, HED concludes that the data are

adequate to support the proposed use (and nation al registration) of methoxyfenozide on citrus

fruits. The field trial data support tolerances of 0.7 0 , 1.5 and 3.0 ppm in grapefruit, lemons and

oranges, respectively; these tolerance levels vary by less than 5X. Ergo, a tolerance of 3.0 ppm

in citrus fr uits (group 10

- 10) is appropriate. A revised Section F should be submitted listing the

correct commodity definition, and requesting a tolerance that concurs with HED’s

recommendation.

The submitted orange processing study is adequate , and indicates that methoxyfenozide

residues do not concentrate in juice (<0.2X), and concentrated only slightly in dried pulp (1.1X).

Therefore separate tolerances are not required in these citrus commodities. However,

methoxyfenozide residues concentr ated by 56X in orange oil, when samples were corrected for

potential residue decline during storage. Based on the processing factor for oil, and the HAFT

residues in oranges (1.67 ppm), the maximum expected residues in oil would be 93.5 ppm.

Therefore, t he revocation of the established regional tolerance of 100 ppm in citrus oil,

concomitant with the establishment of a national tolerance in citrus oil at 100 ppm is appropriate.

Because of the commercial importance of lemon oil, and the significantly lowe r HAFT in lemons

(0.792 ppm, from the previously submitted citrus field trials), the petitioner has proposed a

tolerance of 45 ppm in lemon oil. However, the Agency does not set tolerances in the oils of the

various specific citrus fruits. Therefore, the establishment of a tolerance in lemon oil is

precluded. A revised Section F should be submitted listing the correct commodity definition,

and requesting a tolerance that concur s with HED’s recommendation.

There are no Canadian MRLs in any of the curr ently proposed commodities. Codex

MRLs are established in citrus fruits at 0.7 mg/kg, in carrots at 0.5 mg/kg, and in radishes at 0.4

mg/kg. Harmonization of tolerances in the currently requested commodities is not possible, as

the US and Codex use patte rns differ. Additionally, the maximum residues in citrus fruits, and in

radishes are greater than the corresponding Codex MRLs . HED’s recommended tolerances were

determin ed using the OECD tolerance calculation procedures (except for those in citrus oils)

. See Appendix II for the tolerance calculation data sets.

TABLE 9 Tolerance Summary for Methoxyfenozide.

Commodity Established/ [ Proposed ]

Tolerance (ppm) Recommended

Tolerance (ppm) Comments ; C orrect Commodity

D efinition

Tolerances L isted U nder 40CFR § 180.544 [ a ][ 1 ]

Vegetable, root, subgroup 1A 0.5 None

Beet, sugar [ 0.5 ] 0.5 0

Vegetable, root, except sugar

beet, subgroup 1B [ 0.8 ] 0.9 0

Fruit, citrus, group 10 [ 1.9 ] 3.0 Fruit, citrus, group 10

- 10

Citrus

, oil ( except lemon ) [ 100 ] 100 Citrus, oilMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 22 of 29 TABLE 9 Tolerance Summary for Methoxyfenozide.

Commodity Established/ [ Proposed ]

Tolerance (ppm) Recommended

Tolerance (ppm) Comments ; C orrect Commodity

D efinition

Lemon, oil [ 45 ] None The Agency does not set tolerances

in the oils of the various specific

citrus fruits.

Tolerances Listed Under 40CFR § 180.544 [ c ]

Fruit, citrus, group 10 10 None Regional registration, for use in

states west of the Mississippi River. Citrus

, oil 100 None

References

PP#8F5004 & PP#8F5006; Methoxyfenozide. Conclusions of the 13/JUL/1999 Meeting

of the Metabolism Assessment Review Committee

. ; D 258034; W. Wassell ; 23 J uly 1999.

PP# 8F5004 & PP#8F5006: Methoxyfenozide on Cotton and the Pome Fruit Crop

Group. Evaluation of Metabolism Data, Residue Data, and Analytical Methodology. ; D 251225,

D251218, D249458

, D 249438 ; W. Wassell ; 27 J uly 1999.

PP9F06033: Section 3 Request for Use of Methoxyfenozi de on Grapes and Fruiting

Vegetables. Review of Analytical Methods and Residue Chemistry Data. ; D 259989; M. Doherty ;

8 August 2000.

PP#0F06213: Methoxyfenozide in/on Field Corn and Sweet Corn; Poultry Tolerances;

and, Higher Tolerances on Other Selected Animal Commodities. Residue Chemistry Review. ;

D 269969 ; M. Nelson ; 7 August 2002

.

Methoxyfenozide in/on Various Rotational Crops. Residue Chemistry Review. ; D 269986,

D 274542 ; M. Nelson ; 7 August 2002

.

METHOXYFENOZIDE Supplemental Human Health Risk Assessment for: PP#9F06033

- Fruiting Vegetables (except Cucurbits) Crop Group; Grapes; Raisins; PP#9F06062

- Leafy and

Cole (Brassica) Vegetables Crop Groups; PP#0F06201

- Rotational Crops; PP#0F06213

-

Fie ld and Sweet Corn; Higher Milk/Fat /Mbyp; Add Poultry/Eggs; PP#1F06259

- Stone Fruits

Crop Group; Prune; PP#1F06287

- Tree Nuts Crop Group, including Pistachio; Almond Hulls;

PP#2E06382

- Globe Artichoke; and PP#2E06408

- Lychee, including Longan, Spanish Lime,

Pulasan, and Rambutan. ; D 259549; M. Nelson ; 7 August 2002

.

Methoxyfenozide. Use on Sweet Potato, Blueberry, Dry Bean, Grass, Peanut, Green

Onion, Avocado, Gu ava, Alfalfa and Clover. Summary of Analytical Chemistry and Residue

Data. Petition Numbers 6E7086, 7E7218, & 6F7135. ; D 331948; W. Cutchin; 18 December

2007.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 23 of 29 Revisions of Feedstuffs in Table 1 of OPPTS Test Guideline 860.1000 and Guidance on

Constructing Maximum Reasonably Balanced Diets (MRBD) ; Chemistry Science Advisory

Council ( ChemSAC ) memorandum; 30 June 2008

.

Methoxyfenozide. Pe tition for Uses and Tolerances on the Citrus Crop (Group 10),

Dried Shelled Peas and Beans, except Soybean (Subgroup 6C), Popcorn, and Pomegranate.

Summary of Analytical Chemistry and Residue Data. ; D358341; D. Rate; 10 June 2009

.

Methoxyfenozide. Re gistrant’s Response to Conditional Registrations for Uses and/or

Tolerances on Leaf Vegetables, Rotational Crops, Stone Fruits, and Poultry Commodities.

Summary of Analytical Chemistry and Residue Data. Petition Numbers: 9F06062, 0F06201,

0F06213, 1F0625 9. ; D 322948, D 295721, D 2889 2 4, D 295680 ; D. Rate ; 2 J une 2009

.

Attachments

Appendix I

- International Residue Limit Status sheet

Appendix II

- Tolerance Assessment CalculationsMethoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 24 of 29 Appendix I International Residue Limit Status S heet

Methoxyfenozide (PC Code 121027 )

Summary of US Tolerances, and International Maximum Residue Limits.

Residue Definitions

US Canada Mexico 1 Codex

40CFR §180.544

Plant s: Methoxyfenozide (3

- methoxy

- 2

- methylbenzoic acid 2

- (3,5

- dimethylbenzoyl)

- 2

- (1,1

- dimethylethyl)hydrazide).

Livestock: Combined residues of

methoxyfenozide and its glucuronide

metabolite, RH

- 141,518 (3

- [2

- (1,1

- dimethylethyl)

- 2

- (3,5

- dimethylbenzoyl)

- hydrazino]carbonyl

- 2

- methylphenyl

- β

- D

glucopyranuronic acid). Plants/Livestock:

Methoxyfenozide (3

- methoxy

- 2

- methylbenzoic acid 2

- (3,5

- dimethylbenzoyl)

- 2

- (1,1

- dimethylethyl)hydrazide).

Livestock kidney/liver:

Methoxyfenozide , and its

metabolite

, 3

- {[2

- (1,1

- dimethylethyl)

- 2

- (3,5

- dimethylbenzoyl)

- hydrazino]carbonyl}

- 2

- methylphenyl

- β

- D

glucopyranuronic acid

. Methoxyfenozide

(t he residue is fat

soluble, but is

not class ifi ed as

fat

- soluble with

respect to its

distribution in

milk )

.

Commodity 2 Tolerance

(ppm) 3 Maximum Residue Limit (mg/kg)

US Canada Mexico 1 Codex

Fruit, citrus, group 10

- 10 3.0 0.7 in citrus fruits

Citrus, oil 100

Vegetable, root, e xcept sugar

beet

, subgroup 1B. 0.9 0 0.5 in carrot

, 0.4 in radish

Sugar, beet 0.5 0 0.3 in sugar beet

Completed: M. Negussie, 7 December 20 1 1

. 1. Mexico adopts US tolerances

, and/or Codex MRLs

, for its export purposes.

2. Includes only commodities of interest for this action.

3. Tolerance values are those recommended by HED, not those proposed by the petitioner.Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 25 of 29 Appendix II Tolerance Assessment Calculations

Figure II

- 1 Dataset and Tolerance Calculation for Methoxy fenozide Residues in Carrot s

.

Residues (mg/kg)

0.084

0.054

0.125

0.027

0.069

0.083

0.047

0.097

Methoxyfenozide

Carrot

USA

1.00 lb ai/A, 1

- day PHI

Total number of data (n) 8

Percentage of censored data 0%

Number of non

- censored data 8

Lowest residue 0.027

Highest residue 0.125

Median residue 0.076

Mean 0.073

Standard deviation (SD) 0.031

Correction factor for censoring (CF) 1.000

Proposed MRL estimate

- Highest residue 0.125

- Mean + 4 SD 0.197

- CF x 3 Mean 0.220

Unrounded MRL 0.220

Rounded MRL 0.3Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 26 of 29 Figure I I

- 2 Dataset and Tolerance Calculation for Methoxyfenozide Residues in

Radishes

.

Residues (mg/kg)

0.108

0.453

0.046

0.267

0.074

Methoxyfenozide

Radish

USA

0.50 lb ai/A, 1

- day PHI

Total number of data (n) 5

Percentage of censored data 0%

Number of non

- censored data 5

Lowest residue 0.046

Highest residue 0.453

Median residue 0.108

Mean 0.190

Standard deviation (SD) 0.170

Correction factor for censoring (CF) 1.000

Proposed MRL estimate

- Highest residue 0.453

- Mean + 4 SD 0.871

- CF x 3 Mean 0.569

Unrounded MRL 0.871

Rounded MRL 0.9

High uncertainty of MRL estimate.

[Small dataset]Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 27 of 29 Figure II

- 3. Dataset and Tolerance Calculation for Methoxyfenozide Residues in

Orange s.

Residues (mg/kg)

0.323

0.258

0.207

0.250

0.314

0.543

0.280

0.154

1.670

Methoxyfenozide

Orange

USA

1.00 lb ai/A, 1

- day PHI

Total number of data (n) 9

Percentage of censored data 0%

Number of non

- censored data 9

Lowest residue 0.154

Highest residue 1.670

Median residue 0.280

Mean 0.444

Standard deviation (SD) 0.472

Correction factor for censoring (CF) 1.000

Proposed MRL estimate

- Highest residue 1.670

- Mean + 4 SD 2.333

- CF x 3 Mean 1.333

Unrounded MRL 2.333

Rounded MRL 3Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 28 of 29 Figure II

- 4 Dataset and Tolerance Calculation for Methoxyfenozide Residues in Lemon s.

Residues (mg/kg)

0.321

0.204

0.349

0.391

0.792

Methoxyfenozide

Lemon

USA

1.00 lb ai/A, 1

- day PHI

Total number of data (n) 5

Percentage of censored data 0%

Number of non

- censored data 5

Lowest residue 0.204

Highest residue 0.792

Median residue 0.349

Mean 0.411

Standard deviation (SD) 0.224

Correction factor for censoring (CF) 1.000

Proposed MRL estimate

- Highest residue 0.792

- Mean + 4 SD 1.307

- CF x 3 Mean 1.234

Unrounded MRL 1.307

Rounded MRL 1.5

High uncertainty of MRL estimate.

[Small dataset]Methoxyfenozide Summary of Analytical Chemistry and Residue Data DP Barcode D396397

Page 29 of 29 Figure II

- 5 Dataset and Tolerance Calculation for Methoxyfenozide Residues in

Grapefruit

.

Residues (mg/kg)

0.283

0.216

0.263

0.141

0.254

0.115

Methoxyfenozide

Grapefruit

USA

1.00 lb ai/A, 1

- day PHI

Total number of data (n) 6

Percentage of censored data 0%

Number of non

- censored data 6

Lowest residue 0.115

Highest residue 0.283

Median residue 0.235

Mean 0.212

Standard deviation (SD) 0.069

Correction factor for censoring (CF) 1.000

Proposed MRL estimate

- Highest residue 0.283

- Mean + 4 SD 0.488

- CF x 3 Mean 0.636

Unrounded MRL 0.636

Rounded MRL 0.7

High uncertainty of MRL estimate.

[Small dataset]