Document ID: EPA-HQ-OPP-2007-0426-0007
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2008-04-09T04:00Z

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C.  20460

OFFICE OF           

PREVENTION, PESTICIDES

AND TOXIC SUBSTANCES

MEMORANDUM

Date:		16-January-2008

Subject:		Buprofezin.  Petition for Application to Low-Growing Berries,
Olives, Leafy Vegetables (except Brassica), and Fruiting Vegetables. 
Summary of Analytical Chemistry and Residue Data.  

Petition #s	7E7207 - low-growing berries, olives, and leafy vegetables
(except Brassica)

7E7253 - fruiting vegetables	DP #s:	340284, 345185

PC Code:	275100	Decision #s:	378399, 382454

40 CFR 180.	511	MRID #s:	47112001, 47112002, 47112003, 47112004

47204701, 47204702 

From:		Tom Bloem, Chemist

		Registration Action Branch 1; Health Effects Division (RAB1/HED;
7509P)

Through:		George F. Kramer, Ph.D., Senior Chemist

		RAB1/HED (7509P)

To:		Daniel Rosenblatt RM 05

		Registration Division (RD; 7505P)

This document was originally prepared under contract by Dynamac
Corporation (1910 Sedwick Road, Building 100, Suite B, Durham, NC 27713;
submitted 10/05/2007).  The document has been reviewed by HED and
revised to reflect current Office of Pesticide Programs (OPP) policies.

HED received a Section 3 registration request for application of
buprofezin to low-growing berries subgroup 13G, olives, leafy vegetables
(except Brassica), and fruiting vegetables.  The following document is
HED’s review of the residue chemistry data submitted in support of
this request and HED’s recommendation concerning the adequacy of these
data to support a Section 3 registration.  

Executive Summary

Background:  Buprofezin is a chitin biosynthesis inhibitor that controls
a variety of Homoptera spp. (planthoppers, leafhoppers, whiteflies, and
scales) through disruption of molting, suppression of oviposition, and
reduction in egg viability.  Buprofezin is registered to Nichino
America, Inc.; the 70% wettable-powder (WP), 70% dry-flowable (DF),
and/or 40% suspension-concentrate (3.6 lb/gal SC) formulations are
currently registered for repeated foliar applications on almonds,
bananas, citrus fruits, cotton, cucurbit vegetables, grapes, lettuce,
peaches, pome fruits, pistachios, snap beans, tomatoes, and various
tropical fruits.  Applications may be made using ground or aerial
equipment, and rates range from 0.25-0.38 lb ai/A for field and
vegetable crops and 0.39-2.0 lb ai/A for perennial fruit crops. 
Tolerances for residues of buprofezin per se ranging from 0.02 - 80 ppm
are currently-established in/on the registered crops (40 CFR 180.511). 
Tolerances have also been established for residues of buprofezin per se,
as a result of secondary residues, in milk (0.01 ppm) and ruminant and
hog fat (0.05 ppm), liver (0.05 ppm), meat (0.05 ppm) and meat
byproducts (0.05 ppm).   

The Interregional Research Project No. 4 (IR-4) is proposing new uses
for buprofezin on olives and members of the low-growing berry subgroup
(13G), expanding the existing use on lettuce to include all leafy
vegetables (except Brassica), and reducing the preharvest interval (PHI)
for tomato from 7 days to 1 day and expanding this use to all fruiting
vegetables.  The following tolerances for residues of buprofezin per se
were also proposed (based on OPPTS 860.1000 Table 1, there are no feed
commodities associated with the proposed crops; therefore, issues
concerning the nature/magnitude of the residue in livestock will not be
discussed):   

Strawberry	2.5 ppm

Bearberry	2.5 ppm

Bilberry	2.5 ppm

Blueberry, lowbush	2.5 ppm

Cloudberry	2.5 ppm

Cranberry	2.5 ppm

Lingonberry	2.5 ppm

Muntries	2.5 ppm

Patrtidgeberry	2.5 ppm

Olive	3.0 ppm

Olive oil 	9.0 ppm

Vegetable, leafy, except Brassica, group 4	25 ppm

Vegetable, fruiting, group 8 	1.8 ppm 

Okra	1.8 ppm

Proposed Uses:  Table 4 is a summary of the proposed application
scenarios.  The proposed label directions are adequate to allow
evaluation of the residue data relative to the proposed use.  Based on
the available residue chemistry data, a revised Section B which
incorporates the following changes should be submitted:  (1) a minimum
retreatment interval (RTI) of 7 days should be specified for all leafy
vegetable crops; (2) the reference to grapes should be removed from the
use directions for olives; (3) the 3.6 lb/gal SC label should be revised
to prohibit the application to all greenhouse grown crops except
tomatoes (Chemistry Science Advisory Council (ChemSAC) minutes the
9-Oct-2002 and 28-Nov-2007 meetings); and (4) the following rotational
crop intervals should be specified:  0 days for all labeled crops, 30
days for leafy vegetables, 60 days for root and tuber vegetables, and
365 days for all other crops.

Nature of the Residue - Plants:  The qualitative nature of buprofezin in
plants is understood based on the available lettuce, cotton, tomato, and
lemon metabolism studies.  Buprofezin was the major residue identified
in the lettuce, cotton, and tomato metabolism studies (all other
identified residues were at <10% total radioactive residues (TRR)).  The
lemon metabolism study provided data for fruit treated 75 and 14 days
prior to harvest and treated only 75 days prior to harvest.  Buprofezin
(66% TRR, PHI = 14 days; 18% TRR, PHI = 75 days) and BF 4 conjugates (6%
TRR, PHI = 14 days; 34% TRR, PHI = 75 days) were the major identified
residues (all other identified residues were <10% TRR).  Based on the
results of these studies, the MARC concluded the following (see next
paragraph also):  (1) tolerance expression for plants will include only
buprofezin; (2) for purposes of risk assessment, the residues of concern
for all proposed and registered commodities (excluding grape juice) will
include only buprofezin; (3) based on the grape processing study, the
residues of concern in grape juice are buprofezin and BF12; and (4)
residues of BF9 and BF12 should be monitored in all future field trial
and processing studies (BF9 and BF12 residue data are requested due to
the potential for these compounds to concentrate in processed
commodities; see Appendix III for structures).  

The MARC has also requested that the petitioner submit orange, apple,
and grape processing studies conducted using the labeled RTI and PHIs
but at 5x the labeled rate.  The processing studies should employ an
analytical method which includes a hydrolysis step and monitors for
residues of BF9, BF12, and BF26 (BF9, BF12, and BF26 are hydrolysis
products of BF4 conjugates).  These data will enable HED to determine
the potential magnitude of BF4 conjugates in the RACs (normalized to 1x)
and determine if the BF4 conjugates, if present, possess different
processing factors than parent.  The need for additional BF4 conjugate
magnitude of the residue data will be determined upon submission and
review of these data.  In the interim, for risk assessment purposes,
residues of BF4 conjugates should be estimated in/on fruit crops and
crops with an extended interval between initial application and harvest
(greater than ~50 days) using the buprofezin:BF4 conjugate residue ratio
from the citrus metabolism study (1.8x) and the buprofezin residues from
the field trials.

Magnitude of the Residue:  The petitioner submitted adequate field trial
and processing studies to support the application of the proposed
formulations to the proposed crops; the number and locations of the
field trials are sufficient and the samples were analyzed using an
adequately validated method (storage intervals were also validated;
Table 7 is a summary of the field trial data).  Based on these data and
the tolerance maximum residue limit (MRL) calculator, HED concludes that
the tolerances listed in Table 1 for residues of buprofezin per se are
appropriate.  A revised Section F is requested.  Provided the petitioner
submits a revised Section B, residues in rotational crops are expected
to be insignificant.

  

Analytical Enforcement Method:  Two gas
chromatography/nitrogen-phosphorus detector (GC/NPD) methods have been
validated by Analytical Chemistry Branch (ACB) and forwarded to Food and
Drug Administration (FDA) for inclusion in Pesticide Analytical Manual
(PAM) Vol. II.  One method (Method BF/02/96) is for determination of
buprofezin per se in lettuce and cucurbit vegetables, and the second
method (Method BF/10/97) is for determination of buprofezin per se in
almonds, cottonseed, citrus fruit, and grapes.   In addition to the
above GC/NPD methods, the petitioner has submitted instructions and
validation data for a GC/mass spectrometry (MS) method for confirmation
of buprofezin residues in plant commodities.  The GC/MS method utilizes
three ions for identification of buprofezin.  This method has also been
forwarded to the FDA for inclusion in PAM Vol. II.  

The data collection methods were similar to the enforcement methods. 
Since adequate method validation and concurrent recovery data were
attained in the field trial studies, HED concludes that the current
enforcement methods are adequate for enforcement of the tolerances
recommended as part of the current petition.  

FDA Multiresidue Methods:  The petitioner submitted data concerning the
behavior of buprofezin through FDA multiresidue testing Protocols C –
F.  Acceptable results were attained for buprofezin under the GC
conditions specified in Protocol C.  Acceptable recoveries of buprofezin
were attained from tomatoes using Protocol D Method 302 E1 without the
optional Florisil column and Protocol E Method 303 E1 with Florisil
cleanup C1 or C2.  Acceptable recoveries of buprofezin were attained
from cottonseed using Protocol F Method 304 E5 with Florisil cleanup C1
or C2.  This information has been forwarded to FDA for inclusion in PAM
I.

Recommendations:  Provided the petitioner submits revised Sections B and
F, HED concludes that the residue chemistry database is sufficient for
an unconditional registration for the proposed crops and establishment
of the tolerances listed in Table 1 for residues of buprofezin per se. 
A human-health risk assessment will be prepared as a separate document. 
HED notes that the currently established lettuce (head and leaf) and
tomato tolerances may be deleted.   

Table 1.  HED-Recommended Tolerances for Residues of Buprofezin per se.

Commodity	Recommended Tolerance (ppm)

Bearberry 	2.5

Bilberry	2.5

Blueberry, lowbush	2.5

Cloudberry	2.5

Cranberry	2.5

Lingonberry	2.5

Muntries	2.5

Partridgeberry	2.5

Strawberry	2.5

Olive	3.5

Olive, oil	4.8

Vegetable, leafy, except Brassica, group 4 (except head lettuce and
radicchio)
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●Revised Section B

●Revised Section F

Background

Buprofezin is an insecticide which shows a high level of activity
against Homoptera spp. (planthoppers, leafhoppers, whiteflies, and
scales).  Its mode of action is through the inhibition of chitin
biosynthesis, which results in the death of nymphs at molting, the
suppression of oviposition in adults, and the reduced viability of eggs.
 The nomenclature and physicochemical properties of buprofezin are shown
in Tables 2 and 3.

Common name	  SEQ CHAPTER \h \r 1 Buprofezin

Company experimental name	BF1

IUPAC name
2-tert-butylimino-3-isopropyl-5-pheyl-3,4,5,6-tetrahydro-3H-1,3,5-thiadi
azin-4-one

CAS name	
2-[(1,1-dimethylethyl)imino]tetrahydro-3(1-methylethyl)-5-phenyl-4H-1,3,
5-thiadiazin-4-one

CAS registry number	69327-76-0

End-use product (EP)	3.6 lb/gal SC (Courier 40SC Insect Growth
Regulator; EPA Reg. No. 71711-20)

Table 3.  Physicochemical Properties of Buprofezin.

Parameter	Value	Reference

Melting range	  SEQ CHAPTER \h \r 1 104-106 °C	D280879, B. Kitchens,

6-Jun-2002

pH	test substance is not dispersible with water

	Density	1.18 g/cm3

	Water solubility (25 °C)	0.382 g/liter at 25 °C

	Solvent solubility (25 °C)	520 g/liter - chloroform; 320 g/liter -
toluene; 240 g/liter acetone; 20 g/liter hexane

	Vapor pressure (25 °C)	1.68 x 10-2 Pa

	Dissociation constant, pKa	does not dissociate

	Octanol/water partition coefficient, Log(KOW)	4.31 at 20 °C

	UV/visible absorption spectrum	not available

	

860.1200 Directions for Use

There are currently three end-use products for buprofezin registered to
Nichino America, Inc. for use on food/feed crops, including a 70% WP
(APPLAUD( 70WP, EPA Reg. No. 71711-15), a 70% DF (APPLAUD( 70DF, EPA
Reg. No. 71711-21), and a 3.6 lb/gal SC (Courier 40SC, EPA Reg. No.
71711-20).  The 70% WP and/or 70% DF formulations are registered for
uses on almonds, pistachios, bananas, pome fruits, stone fruit, citrus
fruits, grapes, and various tropical fruits, and the 3.6 lb/gal SC
formulation is registered for uses on cotton, cucurbit vegetables,
lettuce, snap beans, and tomatoes.  IR-4 is proposing the following:  a
new use for the 70% DF on olives to control scales; a new use for the
3.6 lb/gal SC on low-growing berries subgroup 13G to control whiteflies;
expanding the existing use for the 3.6 lb/gal SC on lettuce to include
all leafy vegetables (except Brassica); and reduction in the tomato PHI
from 7 days to 1 day for the 3.6 lb/gal SC and expanding this use to all
fruiting vegetables.  

Proposed 70% DF and 3.6 lb/gal SC labels were provided.  The labels
indicate that application through irrigation equipment is prohibited and
indicate the following rotational crop restrictions:  (1) crop listed on
the label may be planted at any time; (2) small grain crops and leafy
vegetable may be planted 30 days after application; and (3) all other
crops may be planted 60 days following application.  Table 4 is a
summary of the proposed use directions.

Table 4.  Summary of Directions for Use of Buprofezin.

App. Timing, Type, 

and Equip.	Formulation

[EPA Reg. No.]	App. Rate

(lb ai/A)	Max. No. App. per Season	Max. Seasonal App. Rate (lb ai/A)	PHI

(days)	Use Directions and Limitations

Bearberry, Bilberry, Lowbush Blueberry, Cloudberry, Cranberry, 

Lingonberry, Muntries, Partridgeberry, and Strawberry

Broadcast foliar, during fruiting.  Ground equipment.	3.6 lb/gal SC

[71711-20]	0.25- 0.38	2	0.76	2	Apply by ground/air equipment  in
80-120/≥5 GPA1; a minimum RTI of 10 days is specified

Leafy Vegetables (except Brassica)

Broadcast foliar, during vegetative development.  Ground or air
equipment.	3.6 lb/gal SC

[71711-20]	0.25-0.38	2/crop cycle

4/year	0.76/crop

1.53/year	7	Apply by ground/air equipment in ≥20/≥5 GPA; a minimum
7-day RTI is specified for lettuce.

Olive

Broadcast foliar, during fruit development.  

Ground equipment	70% DF

[71711-21]	1.51- 2.01	2	4.11	21	Apply by ground/air equipment in
111-150/≥5 GPA; a minimum 50-day RTI is specified.

Fruiting Vegetables (eggplant, groundcherry, okra, pepino, pepper 
(including bell pepper, 

chili pepper, cooking pepper, pimento, and sweet pepper) and tomato)

Broadcast foliar; Ground or air equipment.	3.6 lb/gal SC

[71711-20]	0.25-0.38	2	0.76	1	Apply by ground/air equipment in 
≥20/≥5 GPA; for greenhouse-grown tomatoes apply in a minimum of 20
GPA; a minimum 5-day RTI is specified.

1  GPA = gallons per acre

Conclusions.  The label directions are adequate to allow evaluation of
the residue data relative to the proposed use.  Based on the available
residue chemistry data, a revised Section B which incorporates the
following changes should be submitted:  (1) a minimum RTI of 7 days
should be specified for all leafy vegetable crops; (2) the reference to
grapes should be removed from the use directions for olives; (3) the 3.6
lb/gal SC label should be revised to prohibit the application to all
greenhouse grown crops except tomatoes (Chemistry Science Advisory
Council (ChemSAC) minutes the 9-Oct-2002 and 28-Nov-2007 meetings); and
(4) the following rotational crop intervals should be specified:  0 days
for all labeled crops, 30 days for leafy vegetables, 60 days for root
and tuber vegetables, and 365 days for all other crops.

860.1300 Nature of the Residue - Plants

MARC Decision, D264546, 4/20/2000, T. Bloem; MARC Decision, D273214,
3/13/2001, T. Bloem; TXR No. 0052261, 12/10/2003, T. Bloem

The qualitative nature of buprofezin in plants is understood based on
the available lettuce, cotton, tomato, and lemon metabolism studies. 
Buprofezin was the major residue identified in the lettuce, cotton, and
tomato metabolism studies (all other identified residues were at <10%
TRR). The lemon metabolism study provided data for fruit treated 75 and
14 days prior to harvest and treated only 75 days prior to harvest. 
Buprofezin (66% TRR, PHI = 14 days; 18% TRR, PHI = 75 days) and BF 4
conjugates (6% TRR, PHI = 14 days; 34% TRR, PHI = 75 days) were the
major identified residues (all other identified residues were <10% TRR).
 Based on the results of these studies, the MARC concluded the following
(see next paragraph also):  (1) tolerance expression for plants will
include only buprofezin; (2) for purposes of risk assessment, the
residues of concern for all proposed and registered commodities
(excluding grape juice) will include only buprofezin; (3) based on the
grape processing study, the residues of concern in grape juice are
buprofezin and BF12; and (4) residues of BF9 and BF12 should be
monitored in all future field trial and processing studies (BF9 and BF12
residue data are requested due to the potential for these compounds to
concentrate in processed commodities; see Appendix III for structures). 

The MARC has also requested that the petitioner submit orange, apple,
and grape processing studies conducted using the labeled RTI and PHIs
but at 5x the labeled rate.  The processing studies should employ an
analytical method which includes a hydrolysis step and monitors for
residues of BF9, BF12, and BF26 (BF9, BF12, and BF26 are hydrolysis
products of BF4 conjugates).  These data will enable HED to determine
the potential magnitude of BF4 conjugates in the RACs (normalized to 1x)
and determine if the BF4 conjugates, if present, possess different
processing factors than parent.  The need for additional BF4 conjugate
magnitude of the residue data will be determined upon submission and
review of these data.  In the interim, for risk assessment purposes,
residues of BF4 conjugates should be estimated in/on fruit crops and
crops with an extended interval between initial application and harvest
(greater than ~50 days) using the buprofezin:BF4 conjugate residue ratio
from the citrus metabolism study (1.8x) and the buprofezin residues from
the field trials.

860.1340 Residue Analytical Methods

D261869, 4/24/2000, T. Bloem; D269588, 10/19/2000, T. Bloem; D278952,
11/8/2001, T. Bloem; D324423, 12/14/2005, T. Bloem

Enforcement Methods:  Two GC/NPD methods have been validated by ACB and
forwarded to FDA for inclusion in PAM Vol. II.  One method (Method
BF/02/96; see below for description) is for determination of buprofezin
per se in lettuce and cucurbit vegetables, and the second method (Method
BF/10/97; see below for description) is for determination of buprofezin
per se in almonds, cottonseed, citrus fruit, and grapes (see below for
summaries of these methods).   In addition to the above GC/NPD methods,
the petitioner has submitted instructions and validation data for a
GC/MS method for confirmation of buprofezin residues in plant
commodities.  The GC/MS method utilizes three ions for identification of
buprofezin.  This method has also been sent to the FDA for inclusion in
PAM Vol. II. 

The data collection methods were similar to the enforcement methods. 
Since adequate method validation and concurrent recovery data were
attained in the field trial studies, HED concludes that the current
enforcement methods are adequate for enforcement of the tolerances
recommended as part of the current petition.  The following is a summary
of the data collection methods.    

Data Collection Methods:  The strawberry, olive, tomato, and pepper
field trial and the olive processing studies submitted as part of the
current petition monitored for residues of buprofezin per se using
Method BF/10/97 (see below for description).  The method was adequately
validated prior to and in conjunction with the analysis of field trial
and processing study samples.  The lowest level of method validation
(LLMV) was 0.05 ppm for buprofezin in strawberries, olives, olive oil,
tomato, and pepper.  The statistically calculated limits of quantitation
(LOQs) were 0.017 ppm for strawberry, 0.028 ppm for olives, 0.033 ppm
for olive oil, 0.052 ppm for tomato and 0.052 ppm for pepper and the
calculated limits of detection (LODs) were 0.006-0.017 ppm.

The celery and spinach field trial studies monitored for residues of
buprofezin, BF9, and BF12 using Method BF/05/94 (see below for
description).  The method was adequately validated prior to and in
conjunction with the analysis of field trial samples.  The validated LOQ
was 0.01 ppm each analyte in celery and spinach; LODs were not reported.

The petitioner has previously submitted and HED reviewed lettuce and
tomato field trial studies which monitored for residues of buprofezin,
BF9, BF12, and/or BF26.  As indicated above, the employed methods were
similar the current enforcement method and included adequate method
validation and concurrent recovery data (tomato - D340901, T. Bloem,
9/7/2007; lettuce - D261869, T. Bloem, 4/24/2000; D271597, T. Bloem,
1/30/2001; D296493, T. Bloem, 12/17/2003; D328454, T. Bloem, 2/28/2007).
 The validated LOQ was 0.01 ppm for each analyte; LODs were not
reported. 

Method BF/02/96:  Residues are extracted with acetone, concentrated to
the aqueous phase, and acidified by dilution with 1M HCl.  The acidic
extract is partitioned with hexane (discarding the hexane fraction) and
then neutralized and buffered to pH 7.  Residues are partitioned into
ethyl acetate/hexane (1:1, v/v) and concentrated to dryness.  Residues
are redissolved in toluene and determined by GC/NPD using external
standards (determines buprofezin per se).  The method has a reported LOQ
of 0.05 ppm.

Method BF/10/97:  Residues are extracted with acetone, concentrated to
the aqueous phase, and acidified by dilution with 1M HCl.  The acidic
extract is partitioned with hexane, discarding the hexane phase after
back extraction with 1M HCl.  The acidic aqueous partitions are combined
and residues of buprofezin are partitioned into dichloromethane. 
Residues are dried with sodium sulfate, concentrated to dryness, and
redissolved in hexane.  Residues are eluted through a Florisil column
with ethyl acetate/hexane (2:8, v/v).  Residues are concentrated to
dryness, redissolved in toluene, and analyzed by GC/NPD, using external
standards (determines buprofezin per se).  The reported LOQ is 0.05 ppm.
 

Method BF/05/94:  Residues are extracted with acetone, concentrated to
the aqueous phase, and acidified by dilution with 1M HCl.  The acidic
aqueous extract is initially partitioned against hexane (BF9 residues
partition into hexane).  Residues of BF9 are dried by filtering through
sodium sulfate, cleaned up by elution though a Florisil column using
ethyl acetate:hexane (20:80, v/v), and concentrated to dryness.  The
remaining acidic extract is neutralized using NaOH and buffered to pH 7.
 Residues of buprofezin and BF12 in this fraction are partitioned into
50% ethyl ether/hexane, and concentrated to dryness.  Residues of all
analytes were dissolved in toluene, combined and analyzed by GC/NPD,
combined and analyzed by GC/NPD, using external standards (determines
buprofezin, BF9, and BF12).  The validated LOQ is 0.01 ppm each analyte;
LODs were not reported. 

860.1360 Multiresidue Methods

D262532, 2/4/2000, T. Bloem

The petitioner submitted data concerning the behavior of buprofezin
through FDA multiresidue testing Protocols C – F.  Acceptable results
were attained for buprofezin under the GC conditions specified in
Protocol C.  Acceptable recoveries of buprofezin were attained from
tomatoes using Protocol D Method 302 E1 without the optional Florisil
column and Protocol E Method 303 E1 with Florisil cleanup C1 or C2. 
Acceptable recoveries of buprofezin were attained from cottonseed using
Protocol F Method 304 E5 with Florisil cleanup C1 or C2.  This
information has been forwarded to FDA (D262532, 2/4/2000, T. Bloem).

860.1380 Storage Stability

47112001.de2

Storage stability studies were conducted in conjunction with the
strawberry, olive, olive oil, and pepper field trial or processing
studies.  Control samples of strawberries, olives, olive oil, and
peppers were fortified with buprofezin per se at 0.50 ppm and placed in
frozen storage for 326 days, 241 days, 51 days, and 269 days,
respectively.  The resulting corrected percent recoveries were adequate.
 However, the studies did not include a zero day analysis to validate
the concentration on the samples at the beginning of the storage
interval (required by the OPPTS 860.1380 guidelines).  Therefore, the
stability of buprofezin in/on strawberry, olive, olive oil, and pepper
when placed in frozen storage can not be determined from these data.  

The storage intervals and conditions of samples from the crop field
trial and processing studies submitted to support this petition are
presented in Table 5.  A summary of the available storage stability data
for buprofezin and Metabolites BF9, BF12 and BF23 are presented in Table
6.  Based on the currently available data, HED concludes that the
storage intervals and conditions used in the field trial and processing
studies are validated.    

Table 5.  Summary of Samples Storage Conditions and Intervals from
Submitted Crop Field Trials and Processing Study.  

Matrix	Storage Temperature (°C)	Actual Storage Duration (Days)

Strawberry	frozen	46-276

Olive Fruit

184-238

Olive oil

47

Spinach

45-196

Celery

24-220

tomato

≤74

pepper

≤251

Table 6.  Demonstrated Stability of Buprofezin and its Metabolites (BF9,
BF12 and BF23) in Plant and Livestock Commodities during Frozen Storage
(months).

Commodity	Validated Storage interval (months)

	Buprofezin	BF9	BF12	BF23

Almonds	12	12	12	--

Almond, hulls	2.6	2.6	2.6	-

Apples	6.9	--	--	--

Avocadoes	7.2	--	--	--

Bananas	2.2	2.2	2.2	--

Beans, snap	6	--	--	--

Cottonseed	44.5	--	--	--

Cottonseed oil	47	--	--	--

Grapes	21	12	12	--

Grape, juice	--	--	12	--

Grape, raisin	2.3	--	--	--

Lettuce	31.4	31.4	31.4	--

Lychees	6.9	--	--	--

Orange juice	6.9	--	--	--

Orange oil	15.3	--	--	--

Peach	14.2	--	--	--

Pears	4.1	--	--	--

Potato tubers	29	29	29	--

Tomatoes	29.2	29.2	29.2	--

Tomato juice, paste and dry pomace	6	6	6	--

Wheat forage and hay	29	29	29	--

Wheat grain	29	122	<12 	--

Wheat straw	29	122	122

	Beef fat and liver	10	--	--	--

Milk	10	12	--	12

1  D271597, 1/30/2001, T. Bloem; D273252, 3/20/2001, T. Bloem; D285400,
10/9/2002, T. Bloem; D296492, 12/17/2003, T. Bloem; D293230, 1/7/2004,
T. Bloem; D336916, 2/28/2007, T. Bloem

2  Acceptable corrected recoveries were obtained at 12 months for BF9
from stored wheat grain (87%) and straw (80%) and for BF12 from stored
wheat straw (80%).

860.1500 Crop Field Trials

47112001.der (strawberry); 47112002.de1 (olive); 47112003.der (spinach);
47112004.der (celery); 47204701.der (tomato); 47204702.der (pepper);
D261869, 4/24/00, T. Bloem; D296493, 12/17/03, T. Bloem (head and leaf
lettuce); D340901, 7/9/07, T. Bloem (tomato)

IR-4 submitted field trial data reflecting the use of buprofezin
formulated as a 70% WP on olives; 3.6 lb/gal SC on strawberry, lettuce
(head and leaf), spinach, celery, and peppers (bell and non-bell); and
70% WP and 3.6 lb/gal SC on tomatoes.    SEQ CHAPTER \h \r 1 The results
from these studies are discussed below and the residue data are
summarized in Table 7.  HED notes that residue decline data were only
provided for strawberry, lettuce, and tomato and BF9
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●The tomato (46567301.der; PHI of 1 to 3 days), lettuce (D261869,
4/24/00; PHI of 7 to 14 days), and strawberry (47112001.der; PHI of 1 to
10 days) residue decline data all indicated a reduction in buprofezin
per se residues as the PHI increased.  In addition, previously submitted
citrus (D273252, 3/20/01, T. Bloem), cottonseed (D273252, 3/20/01, T.
Bloem), and apple (46007203.der) residue decline data also indicated a
decrease in buprofezin per se residues as the PHI increased.

●BF9 and BF12 residue data were requested due to the potential for
these compounds to concentrate in processed commodities at rates
different from that of parent and thereby lead to significant residues
in the processed commodity (this was demonstrated in grape juice for
BF12). Based on OPPTS 860.1000 Table 1, tomato and olive are the only
proposed crops which possess processed commodities.  The tomato field
trial and processing studies monitored for BF9 and BF12; however, the
olive field trial and processing studies monitored for only buprofezin
per se. For the following reasons, HED concludes that additional olive
residue data are unnecessary:  (1) the chemical structure for BF9 and BF
12 indicates that they are likely to be more polar than parent and
therefore would have oil processing factors less than that of parent and
(2) a cottonseed processing study did not demonstrate concentration of
BF9 in cottonseed oil (BF12 residue data was not provided; D273252,
3/20/01, T. Bloem). 

Table 7.	  Summary of Residue Data from Crop Field Trials with
Buprofezin.

Crop matrix	Total App. Rate  (lb ai/A)	Analyte	PHI (days)	Residue Levels
(ppm)1,2

n	Min.	Max.	HAFT3	Median	Mean	Std. Dev.

Strawberry (proposed use = 2 x 0.38 lb ai/A; 2-day PHI)

Strawberry	0.676-0.707	Buprofezin	2-4	18	0.10	1.20	1.15	0.44	0.58	0.31

Olive (proposed use = 2 x 2.01 lb ai/A; 21-day PHI)

Olives	4.23-4.33	Buprofezin	21-23	8	0.41	1.66	1.60	1.10	1.07	0.43

Leafy Vegetables (except Brassica; proposed use = 2 x 0.38 lb ai/A;
7-day PHI)

Spinach	0.758-0.778	Buprofezin	7	12	0.71	18.10	16.70	6.74	7.18	5.05

BF9

12	<0.01	<0.01	<0.01	<0.01	<0.01	--

BF12

12	<0.01	<0.01	<0.01	<0.01	<0.01	--

Celery	0.746-0.794	Buprofezin	7	12	0.35	12.00	11.25	2.97	4.10	3.59

BF9

12	<0.01	0.04	0.04	0.01	0.01	0.01

BF12

12	<0.01	<0.01	<0.01	<0.01	<0.01	--

Lettuce, leaf4	1.525	Buprofezin	7	9	1.18	11.49	11.49	6.08	6.12	4.00

	10	9	0.67	7.81	7.81	4.02	4.07	2.87

	14	9	0.13	5.49	5.49	2.23	2.37	2.07

BF9	7, 10,  and 14	24	<0.01	<0.01	<0.01	<0.01	<0.01	--

BF12

24	<0.01	<0.01	<0.01	<0.01	<0.01	--

Lettuce, head

(with wrapper leaves)4	1.525	Buprofezin	7	11	0.27	4.41	4.41	2.02	1.99
1.12

	10	11	0.14	4.30	4.30	0.48	0.95	1.16

	14	11	0.02	4.56	4.56	0.50	0.82	1.29

BF9	7, 10,  and 14	30	<0.01	<0.01	<0.01	<0.01	<0.01	--

BF12

30	<0.01	<0.01	<0.01	<0.01	<0.01	--

Lettuce, head

(without wrapper leaves)4	1.525	Buprofezin	7	9	0.03	1.33	1.33	0.17	0.33
0.43

	10	9	0.01	0.46	0.46	0.03	0.10	0.15

	14	9	0.01	0.29	0.29	0.03	0.07	0.09

BF9	7, 10,  and 14	30	<0.01	<0.01	<0.01	<0.01	<0.01	--

BF12

30	<0.01	<0.01	<0.01	<0.01	<0.01	--

Fruiting Vegetables (proposed use = 2 x 0.38 lb ai/A; 1 day PHI)

Bell pepper	0.746-0.787	Buprofezin	1	16	0.10	0.96	0.86	0.31	0.34	0.24

Non-bell pepper	0.761-0.785	Buprofezin	1	6	0.10	1.10	1.05	0.48	0.56	0.42

Tomato6	0.747-0.826	Buprofezin	1	56	0.016	0.539	0.471	0.098	0.129	0.102

	0.752-0.763	BF9	1	8	<0.01	<0.01	<0.01	<0.01	<0.01	--

	0.752-0.763	BF12	1	8	<0.01	<0.01	<0.01	<0.01	<0.01	--

	0.747-0.788	BF26	1	6	<0.01	<0.01	<0.01	<0.01	<0.01	--

1  Residues are expressed in terms of each analyte.

2  The validated LOQ is 0.01 ppm for each analyte in leafy vegetable
crops;  the validated LOQ for BF9, BF12, and BF26 in tomato is 0.01 ppm;
 the LLMV for the remaining crop/analyte combinations is 0.05 ppm.  For
calculation of median, mean and standard deviation, the method LOQ was
assumed for residue values <LOQ.

3  HAFT = Highest-Average Field Trial.

4  Residue values for lettuce were obtained from an earlier HED review
(D261869, 4/24/00, T. Bloem).

5  Although the lettuce field trials were conducted at 2x the maximum
seasonal rate, the single application rates used in the field trials
(~0.38 lb ai/A) were equivalent to 1x maximum single rate, and HED has
concluded that the two earliest applications would not contribute
substantially to overall residue levels (D296493, 12/17/03, T. Bloem). 
Therefore, the available lettuce data are acceptable for supporting the
maximum labeled rate 0.77 lb ai/A/crop.

6  This summary includes tomato field trials submitted as part of the
current petition as well as tomato field trials submitted and reviewed
as part of an earlier petition (D340901, 9/7/2007, T. Bloem).  

Leafy Vegetables (except Brassica) Group 4:  The petitioner submitted
adequate spinach, celery, and lettuce (head and leaf) field trial data
(see below for summary).  The field trials were conducted using the
proposed application scenario (spinach and celery) or were conducted
using an application scenario which HED has determined to be adequate
given the proposed application scenario (lettuce; see below).  The
number and locations of the field trials are in accordance with OPPTS
860.1500 for a leafy vegetables (except Brassica; group 4) registration.
 HED notes that the proposed label indicates a 7-day RTI for lettuce but
does not indicate a RTI for the remaining leafy vegetables (except
Brassica) group 4; HED requests that a revised label be submitted which
indicates a 7-day RTI for all group 4 crops.  Based on the residue data
and the tolerance MRL harmonization spreadsheet, spinach, celery, head
lettuce, and leaf lettuce tolerances for residues of buprofezin per se
of 25 ppm, 15 ppm, 6.0 ppm, and 35 ppm, respectively, were recommended. 
Provided a revised Section B is submitted and since the recommended leaf
lettuce tolerance is >5x the recommended head lettuce tolerance and
based on the SOP 200.1 (Guidance for Translation of Field Trial Data
from Representative Commodities in the Crop Group Regulation to other
Commodities in Each Crop Group/Subgroup), HED concludes that the
following tolerances for residues of buprofezin per se are appropriate: 
Leafy vegetables, except Brassica, group 4 (except head lettuce and
radicchio) - 35 ppm; lettuce, head - 6.0 ppm; and radicchio - 6.0 ppm.  
    

Spinach (47112003.der):  In 6 field trials conducted in EPA Zones 1
(n=1), 2 (n=1), 6 (n=1), 9 (n=1), and 10 (n=2) during 2004, a 3.6 lb/gal
SC formulation of buprofezin was applied to spinach as two broadcast
foliar applications during vegetative development, at rates of
0.374-0.393 lb ai/A (RTIs of 7 days; total rate of 0.758-0.778 lb ai/A;
1x proposed single/seasonal rate). Applications were made using ground
equipment at volumes of 14-31 GPA and did not include the use of any
spray adjuvants.  Single control and duplicate treated samples of
spinach were harvested from each trial at 7 days after the final
application (DAT).  The harvested samples were analyzed for residues of
buprofezin, BF9, and BF12 using an adequately validated method (storage
interval has also been validated).  Residues of buprofezin were
0.71-18.10 ppm in/on 12 samples of spinach harvested at 7 DAT.  Average
buprofezin residues were 7.18 ppm and the HAFT residue was 16.70 ppm. 
Residues of BF9 and BF12 were each <LOQ (<0.01 ppm) in/on all samples of
spinach.  No residue decline trials were conducted.

Celery (47112004.der):  In 6 field trials conducted in EPA Zones 3
(n=1), 5 (n=1), and 10 (n=4) during 2004, a 3.6 lb/gal SC formulation of
buprofezin was applied to celery as two broadcast foliar applications
during vegetative development at rates of 0.373-0.410 lb ai/A (RTIs of 7
days; total rate of 0.746-0.794 lb ai/A; 1x proposed single/seasonal
rate).  Applications were made using ground equipment at volumes of
18-50 GPA and did not include the use of any spray adjuvants.  Single
control and duplicate treated samples of celery were harvested from each
trial at 7 DAT.  The harvested samples were analyzed for residues of
buprofezin, BF9, and BF12 using an adequately validated method (storage
interval has also been validated).  Residues of buprofezin were
0.35-12.0 ppm in/on 12 samples of celery harvested at 7 DAT.  Average
buprofezin residues were 4.10 ppm and the HAFT residue was 11.25 ppm. 
Residues of BF9 were all <LOQ in/on 9 samples, and were 0.01-0.04 ppm
in/on the remaining 3 samples.  Residues of BF12 were <LOQ in/on all 12
samples of celery.  A residue decline trial was not conducted.

Lettuce (leaf and head; D261869, 4/24/00; D296493, 12/17/03):  During
the 1994 and 1995 growing season, ten head lettuce field trials were
conducted in EPA Zones 1 (n=1), 2 (n=1), 3 (n=1), 5 (n=1), 6 (n=1), 9
(n=1), and 10 (n=4), and eight leaf lettuce field trials were conducted
in EPA Zones 1 (n=1), 3 (n=1), 6 (n=1), and 10 (n=5).  In each test,
buprofezin (3.6 lb /gal SC) was applied to head or leaf lettuce as four
broadcast foliar applications at ~0.38 lb ai/A/application (RTIs of 4-6
days, total rate of 1.52 lbs ai/A;  1x/2x proposed single/seasonal
rate).  Applications were made using ground equipment with spray volumes
of 19-95 GPA.  Single control and treated samples of either leaf lettuce
or head lettuce (with and without wrapper leaves) were harvested from
each test at 7, 10, and 14 DAT and analyzed for residues of buprofezin,
BF9 and BF12 using an adequately validated method (storage interval has
also been validated).  Residues of buprofezin were 1.18-11.54 ppm in/on
leaf lettuce and 0.27-4.41 ppm in/on head lettuce (with wrapper leaves)
harvested at 7 DAT.  Residue data from samples harvested at 10 and 14
DAT indicate that residues of buprofezin declined steadily in both leaf
and head lettuce as the PHI increased.  Residues of the metabolites BF9
and BF12 were <LOQ (<0.01 ppm) in/on all samples of leaf and head
lettuce harvested at 7, 10 or 14 DAT.  Although the available leaf and
head lettuce fields were conducted at 2x the maximum seasonal rate, HED
has previously concluded that these data will adequately support the 1x
seasonal rate on lettuce (D296493, 12/17/03, T. Bloem).  After
considering the rates of residue decline observed in the leaf and head
lettuce field trials and the RTIs specified on the label, the Agency
concluded that the majority of buprofezin residues in/on lettuce
resulted from the final two applications which were made at 1x rates.

HED notes that one of the leaf lettuce and one of the head lettuce field
trials were side-by-side comparisons of the 70WP and 3.6 lb /gal SC
formulations; since the petitioner is not requesting registration of the
70WP formulation, the 70WP data are not discussed.  

Fruiting Vegetables Group 8:  The petitioner submitted adequate tomato
and pepper (bell and non-bell) field trial data (see below for summary).
 The number and locations of the field trials are in accordance with
OPPTS 860.1500 for a fruiting vegetable (group 8) registration.  The
pepper field trials were conducted using the proposed application
scenario.  The tomato field trials employed the proposed application
rate (single and seasonal) and PHI but employed a RTI of 24-30 days
rather than the proposed 5-day RTI.  This issue was brought to the
ChemSAC via a direct inquiry from IR-4 to the ChemSAC chair (issue was
discussed by the ChemSAC prior to HED review of the data).  The ChemSAC
concluded the following (min_359.7-11-07.doc):  

The tomato residues resulted in a calculated tolerance of 0.45 ppm;
whereas the pepper residues resulted in a calculated tolerance of 1.8
ppm.  If it is assumed that the entire residue on the tomatoes in this
study resulted from the second application, then it follows that
shortening the application interval so that the two sprays were applied
just a few days apart would, at worst, result in twice the residue on
the harvested fruit.  Doubling the calculated tomato tolerance produces
a figure that is still below the calculated tolerance resulting from the
pepper data, which I propose should cover the entire crop group. 

ChemSAC agrees with IR-4’s proposal to establish a fruiting vegetable
crop group tolerance for buprofezin based on the residue data for
peppers.  The SAC further notes that even without trying to adjust
residues to account for the desired shorter reapplication interval, the
tomato residues are within 5X of the residue in pepper and therefore
within the range typically deemed appropriate for allowing a crop group
tolerance.  

HED notes that the 1.8 ppm pepper tolerance mentioned in the ChemSAC
minutes was calculated by IR-4 and is based on combined bell and
non-bell pepper residue data.  However, HED does not combine bell and
non-bell pepper data when establishing a pepper or fruiting vegetable
tolerance; rather, HED calculates a bell pepper and a non-bell pepper
residue and based on these tolerances determines if a pepper tolerance
or separate bell and non-bell tolerances are appropriate.  Based on the
residue data and the tolerance MRL harmonization spreadsheet, tomato,
bell pepper, and non-bell pepper tolerances for residues of buprofezin
per se of 0.45 ppm, 1.3 ppm, and 4.0 ppm, respectively, were
recommended.  Since the recommended non-bell pepper tolerance is >5x the
recommended tomato tolerance and based on the SOP 200.1 (Guidance for
Translation of Field Trial Data from Representative Commodities in the
Crop Group Regulation to other Commodities in Each Crop Group/Subgroup)
and since okra will be added to the fruiting vegetable crop group
(non-bell pepper data may be translated to okra), HED concludes that the
following tolerances for residues of buprofezin per se are appropriate: 
fruiting vegetable (except non-bell pepper) - 1.3 ppm; Pepper, non-bell
- 4.0 ppm; and Okra - 4.0 ppm.  

Tomato (47204701.der, 46689301.der, and 46567301.der):  Eighteen
field-grown tomato field trials were conducted during 2003 and 2005 (EPA
Zones 2 (n=2), 3 (n=3), 5 (n=1), and 10 (n=12); n=2 for cherry
tomatoes).  In addition, three greenhouse-grown tomato field trials (all
conducted on small tomato variety) were conducted in 2005 in EPA Zones 1
(n=1), 10 (n=1), and 12 (n=1).  The treated plots at each trial received
2 applications of the 3.6 lb ai/gal SC (n=17) or 70% WP (n=11)
buprofezin formulations at ~0.38 lb ai/acre (RTI = 24-30 days; total
rate of ~0.76 lb ai/A; 1x the proposed single/seasonal rate).  HED notes
that all of the greenhouse and 4 of the field-grown tomato trials were
side-by-side comparisons of the SC and WP formulations (the remaining 4
WP trials were not comparisons with the SC formulation).  All
applications were broadcast foliar sprays conducted with ground
equipment (21-201 GPA) and did not include an adjuvant.  Tomato samples
were harvested 1 DAT.  The tomato samples were analyzed for residues of
buprofezin, BF9, BF12, and/or BF26 using an adequately validated method
(storage interval has also been validated).  Residues of buprofezin per
se in tomato following two application of the 3.6 lb ai/gal SC or 70% WP
ranged from 0.016-0.539 ppm.  Residues of BF9, BF12, and BF26 were <LOQ.
 The side-by-side SC and WP residue data indicated that following 2
applications at 0.38 lb ai/acre (RTI = 26-30 days; PHI = 1 days),
residues of buprofezin per se do not vary with formulation; therefore,
the WP data were included in the residue statistics indicated above and
in the tolerance calculation.  Residues of BF9, BF12, and BF26 were <LOQ
in/on all the field trials (see D340901, 7/9/07, T. Bloem). 

Pepper (bell and non-bell; 47204702.der):  Eight bell pepper (EPA Zones
2 (n=2), 3 (n=2), 5 (n=1), 6 (n=1), and 10 (n=2)) and three non-bell
pepper (EPA Zones 3 (n=1), 6 (n=1), and 10 (n=1)) field trials were
conducted during 2004.  The trials consisted of a control plot and a
treated plot.  The treated plots received 2 applications of the 3.6 lb
ai/gal SC buprofezin formulation at 0.373-0.397 lb ai/acre (RTI = 4-6
days; total rate of 0.746-0.787 lb ai/A; 1x the proposed single/seasonal
rate).  All applications were broadcast foliar sprays conducted with
ground equipment (31-41 GPA) and did not include an adjuvant.  Pepper
samples were harvested 1 DAT.  The harvested samples were analyzed for
residues of buprofezin per se using an adequately validated method
(storage interval has also been validated).  Residues of buprofezin per
se in bell and non-bell pepper samples ranged from 0.10-0.96 ppm
(average = 0.34 ppm) and 0.10-1.10 ppm (average = 0.56 ppm),
respectively. 

 

Low-growing berry, subgroup 13G:  HED has revised crop group 13 to
include several additional subgroups and crops that were previously
excluded from the group (ChemSAC minutes min_314.4-19-06.doc).  Details
of the changes may be found in a memo from B. Schneider dated 3/28/06,
entitled “Crop Grouping – Part II:  Analysis of the USDA IR-4
Petition to Amend the Crop Group Regulation 40 CFR § 180.41 (c)(13) and
Commodity Definitions [40 CFR § 180.1(h)] Related to Crop Group 13
Berry.”  This document indicates that strawberry is the representative
commodity for the low-growing berry subgroup 13G which is comprised of
bearberry, bilberry, lowbush blueberry, cloudberry, cranberry,
lingonberry, muntries, partridgeberry, and strawberry (crops included on
the proposed label).  The petitioner submitted adequate strawberry field
trial data (see below for summary).  The strawberry field trials were
conducted using the proposed application rate and PHI for low-growing
berry (subgroup 13G) but employed a PHI of 2-4 days (PHI = 2 days (n=2);
PHI > 2 days (n=7)) rather than consistently employing the proposed
2-day PHI (residue decline data resulted in a 0.60 ppm decline in
residues as the PHI increased from 1 to 10 days).  An additional
strawberry field trial in EPA Zone 1 is required to fulfill the
geographical requirements suggested in OPPTS 860.1500 for a strawberry
registration, and, therefore, by inference a low-growing berry (subgroup
13G) registration.  Since three strawberry field trials were conducted
in Region 2 with one of these trials on the Region 1 border and since
only a single field trial in Region 2 is suggested in OPPTS 860.1500 for
strawberry registration, HED concludes that an additional strawberry
field trial is unnecessary.  Using the MRL harmonization spreadsheet, a
tolerance of 2.5 ppm for residues of buprofezin per se is recommended. 
Since the recommended tolerances is greater than 2x the highest residue
value from the field trials, HED concludes that the proposed 2-day PHI
is acceptable and that a that a 2.5 ppm low-growing berry (subgroup 13G)
tolerance for residues of buprofezin per se is appropriate.  

Strawberry (47112001.der):  In 9 field trials conducted in EPA Zones 2
(n=3), 3 (n=1), 5 (n=1), 10 (n=3) and 12 (n=1) during 2003-2004, a 3.6
lb/gal SC formulation of buprofezin was applied to strawberries as two
broadcast foliar applications during fruiting, at rates of 0.335-0.356
lb ai/A (RTIs of 6-10 days; total rate of 0.676-0.707 lb ai/A; 1x the
proposed single/seasonal rate).  Applications were made using ground
equipment at volumes of 80-120 GPA and did not include the use of any
spray adjuvants.  Single control and duplicate treated samples of
strawberries were harvested from each trial at 2-4 DAT.  At two trial
sites, samples were collected at approximately 1, 3, 7, and 10 DAT to
assess residue decline.  The harvested samples were analyzed for
residues of buprofezin per se using an adequately validated method
(storage interval has also been validated).  Residues of buprofezin per
se were 0.10-1.20 ppm in/on 18 samples of strawberries harvested at 2-4
DAT.  Average residues were 0.58 ppm and the HAFT residue was 1.15 ppm. 
In the residue decline trials, average residues declined from 0.90 ppm
at 1 DAT to 0.30 ppm by 10 DAT.

Olive:  The petitioner submitted adequate olive field trial data (see
below for summary).  The field trials were conducted using the proposed
application scenario.  The number and locations of the field trials are
in accordance with OPPTS 860.1500 for an olive registration.  HED notes
that the field trial data employed application of the 70WP formulation
rather than the requested 70DF formulation; however, HED concludes that
the DF and WP formulations are sufficiently similar to permit residue
translation.  Based on the olive residue data and the tolerance MRL
harmonization spreadsheet, HED concludes that a 3.5 ppm olive tolerance
for residues of buprofezin per se is appropriate.  

Olive (47112002.de1):  In 4 field trials conducted during 2004 in EPA
Zone 10, a 70% wettable-powder (WP) formulation of buprofezin was
applied to olives as two broadcast foliar applications during fruit
development, at rates of 2.11-2.17 lb ai/A (RTIs of 49-51 days; total
rate of 4.23-4.33 lb ai/A; 1x the proposed single/seasonal rate). 
Applications were made using ground equipment at volumes of 111-150 GPA
and did not include the use of any spray adjuvants.  Single control and
duplicate treated samples of olives were harvested from each trial at
21-23 DAT.  The harvested samples were analyzed for residues of
buprofezin per se using an adequately validated method (storage interval
has also been validated).  Residues of buprofezin per se were 0.14-1.66
ppm in/on 8 samples of olives harvested at 21-23 DAT.  Average residues
were 1.07 ppm and the HAFT residue was 1.60 ppm.  No residue decline
trial was conducted.

860.1520 Processed Food and Feed

47112002.de2 (olive); D273252, 3/20/01, T. Bloem (tomato)

The only proposed crops defined in OPPTS 860.1000 as having processed
commodities are olive and tomato.  The following paragraphs are
summaries of the currently available processing data for these crops. 
HED notes that the olive processing study monitored for only buprofezin
(tomato processing study monitored for buprofezin, BF9, and BF12);  HED
concludes that an additional olive processing study monitoring for
residues of BF9 and BF12 is unnecessary for the reasons specified in the
introduction to OPPTS 860.1500 section (page 10).      

Tomato (D273252, 3/20/01, T. Bloem):  The petitioner previously
submitted a tomato processing study in which tomatoes were treated with
four broadcast foliar applications of buprofezin (3.6 lb/gal SC) at 0.93
lb ai/A (2.5x) for a total application rate of 3.72 lb ai/A (4.9x; RTI =
6 days).  The samples were harvested 7 DAT and analyzed for residues of
buprofezin, BF9, and BF12 using an adequately validated method (storage
interval has also been validated).  Residues of BF9 and BF12 were
insignificant when compared to that of buprofezin and therefore will not
be further discussed.  Residues of buprofezin in/on the unprocessed and
processed commodities resulted in a reduction factor for juice (0.1x)
and purée (0.6x) and a concentration factor for wet pomace (23.2x), dry
pomace (33.9x), and paste (1.2x).  Based on the tomato HAFT residue
(0.942; HAFT multiplied by 2 to account for the 28-day RTI employed in
the field trials rather than the proposed 5-day) and the concentration
factors from the processing study, the maximum buprofezin residue
expected in/on wet pomace, dry pomace, and paste are 21.85 ppm, 31.93
ppm, and 1.13 ppm, respectively.  HED does not set tolerances in/on
tomato wet or dry pomace.  Since the HED-recommended tolerance for
tomato is 1.3 ppm, a separate tomato paste tolerance is unnecessary.  

Olive:  The petitioner submitted an adequate olive processing study
monitoring for residues of buprofezin per se in whole fruit and olive
oil following application at 5.3x the proposed seasonal application
rate.  The resulting data indicated yielded a 3.0x olive oil processing
factor for residue of buprofezin per se.  Based on the olive HAFT (1.60
ppm) and the 3.0x processing factor, HED concludes that an olive oil
tolerance for residues of buprofezin per se of 4.8 ppm is appropriate
(1.60 ppm x 3.0 = 4.8 ppm).

Olive Processing Study (47112002.de2):  In a field trial conducted
during 2004 in EPA Zone 10, a 70% WP formulation of buprofezin was
applied to olives as two broadcast foliar applications during fruit
development, at rates of 10.8 lb ai/A (RTIs of 49-51 days; total rate of
21.6 lb ai/A; 5.4x/5.3x the proposed single/seasonal rate). 
Applications were made using ground equipment at volumes of ~150 GPA and
did not include the use of any spray adjuvants.  Single bulk control and
treated samples of olives were harvested from each trial at 21 DAT, and
the olives were processed into oil using simulated commercial
procedures.  The resulting samples were analyzed for residues of
buprofezin per se using an adequately validated method (storage interval
has also been validated).  Following two broadcast foliar applications
of buprofezin (WP) totaling 21.6 lb ai/A, residues of buprofezin per se
were 10.2 ppm in olives harvested at 21 DAT and 31.0 ppm in processed
olive oil.  The processing factor for buprofezin residues in olive oil
is 3.0x.  The maximum theoretical processing factor for olive oil is
10x.

860.1850 & 1900 Confined and Field Accumulation in Rotational Crops

MARC Decision, D264546, 4/20/00, T. Bloem; MARC Decision, D273214,
3/13/2001, T. Bloem; MARC Decision, TXR No. 0052261, 12/10/2003, T.
Bloem; D261869, 4/24/00, T. Bloem; D336916, 2/28/2007, T. Bloem

Adequate confined and field rotational crop studies are available. 
Buprofezin, BF9, and BF12 were the major residues identified in the
confined rotational crop study; the field rotational crop study
monitored for residues of buprofezin, BF9, and BF12 with only buprofezin
per se found at levels >LOQ (see below for summary).  Pending the
submission of storage stability data and based on the data from the
confined and field studies, the MARC concluded that buprofezin per se
was the residue of concern in rotational crops.  The petitioner has
submitted the requested storage stability data and these data validated
the storage interval for all commodities from the field rotational crop
study with the exception of BF9 and BF12 in wheat grain and wheat straw.
 The storage stability data indicated the potential for declines of >30%
in residues of BF9 and BF12 in wheat grain and straw stored for the
intervals incurred in the field rotational crop study (D336916,
2/28/2007, T. Bloem).  Therefore, BF9 and BF12 can not be eliminated as
residues of concern in rotational crops. 

The buprofezin field rotational crop study employed four bare soil
applications at ~0.38 lb ai/A, for a total of 1.52 lb ai/A.  This use
rate represents 1x/1x the proposed single/yearly application rate for
leafy (except Brassica) vegetable and 1x/2x the proposed single/seasonal
rate for fruiting vegetable and strawberry (these are the only proposed
crops which are rotated).  A total of 8 tests were conducted, with 2
tests each in CA, AZ, FL and CA.  Rotational crops of carrots (n=4),
head lettuce (n=4), leaf lettuce (n=1), mustard greens (n=4), radishes
(n=3), sugar beets (n=3), turnips (n=2), and wheat (n=4) were planted 30
days after the final application.  Plants were harvested at maturity and
analyzed for residues of buprofezin, BF9, and BF12 using an adequate
analytical method.  Residues of BF9 and BF12 were <LOQ in/on all of the
rotated crops, and residues of buprofezin were <LOQ in all samples
except carrots (<0.01 (n=2), 0.03, and 0.05 ppm), leaf lettuce (0.05
ppm; petitioner indicated the sample was contaminated with soil), and
wheat straw (<0.01 (n=3) and 0.02 ppm).  However, as indicated above,
the BF9 and BF12 wheat straw/grain storage intervals were not validated.
  Based on a linear regression of the storage stability data and the
storage intervals employed in the field rotational crop study, HED
expects that only 51% and 70% of BF9 in wheat straw and grain and 59%
and 37% of BF12 in wheat straw and grain were measured in the field
study.  Assuming LOQ residues and correcting for degradation, the
following BF9 and BF12 residues were calculated:  wheat straw - BF9 and
BF12 residues of 0.020 ppm and 0.017 ppm; wheat grain - BF9 and BF12
residues of 0.014 ppm and 0.027 ppm.  

ain (TRRs ≤0.068 ppm), residues in the extractable and nonextractable
fractions were such that residue identification was not required.  

Based on the observed increase in BF12 residues in wheat straw between
the 30-day and 174-day PBIs in the confined study, the results of the
storage stability study, and because HED defaults the recommended PBI
for those crops not represented in the field rotational crop study to
the most conservative PBI, HED concludes that the following rotational
crop restrictions are appropriate for buprofezin:  0 days for all
labeled crops, 30 days for leafy vegetables, 60 days for root and tuber
vegetables, and 365 days for all other crops. 

860.1550 Proposed Tolerances

Table 8 is a summary of the proposed and HED recommended tolerances for
residues of buprofezin per se.  Except for tomato, there are currently
no established Codex, Canadian, or Mexican MRLs for residues of
buprofezin per se in/on the proposed commodities.  For tomato, there are
Codex and Mexican MRLs for residues of buprofezin per se of 1 ppm and
0.5 ppm, respectively.  HED notes that the MRL harmonization tolerance
calculator recommended for 0.45 ppm tomato tolerance; however, this
tolerance is based on residue data which employed a ~28-day RTI rather
than the proposed 5-day RTI.  Therefore, the recommended 0.45 ppm
tolerance may be to low and HED concluded that it would be more
appropriate to set the tomato tolerance based on the bell pepper residue
data (see OPPTS 860.1500 for further information).  Since the
international tomato MRLs are less than the EPA recommended tolerance,
harmonization is not possible.  

Table 8.  Tolerance Summary.

Commodity	Proposed 

Tolerance (ppm)	HED-Recommended Tolerance (ppm)	Comments

Bearberry 	2.5	2.5	--

Bilberry	2.5	2.5

	Blueberry, lowbush	2.5	2.5

	Cloudberry	2.5	2.5

	Cranberry	2.5	2.5

	Lingonberry	2.5	2.5

	Muntries	2.5	2.5

	Partridgeberry	2.5	2.5

	Strawberry	2.5	2.5

	Olive	3.0	3.5	Increase tolerance to 3.5 ppm.

Olive, oil	9.0	4.8	Decrease tolerance to 4.8 ppm.

Vegetable, leafy, except Brassica, group 4 (except head lettuce and
radicchio)	25	35	Increase proposed tolerance to 35 ppm and change
commodity definition.

Lettuce, head	--	6.0	Propose a tolerance.

Radicchio	--	6.0	Propose a tolerance.

Vegetable, fruiting, group 8 (except non-bell pepper)	1.8	1.3	Decrease
tolerance to 1.3 ppm and change commodity definition.

Pepper, non-bell	--	4.0	Propose a tolerance.

Okra	1.8	4.0	Propose a tolerance.

  SEQ CHAPTER \h \r 1 RDI: RAB1 Chemists (28-Nov-2007)

T. Bloem:S10945:Potomac Yard 1:703-605-0217:7509P:RAB1

  SEQ CHAPTER \h \r 1 Appendix I - International Residue Limit Status
sheet

Appendix II - Tolerance Assessment Calculations 

Appendix III - Chemical Structures

Template Version September 2005

Appendix I - International Residue Limit Status sheet

INTERNATIONAL RESIDUE LIMIT STATUS

Chemical Name:
2-[(1,1-dimethylethyl)imino]tetrahydro-3(1-methylethyl)-5-phenyl-4H-1,3,
5-thiadiazin-4-one 	Common Name:

Buprofezin

	( Proposed tolerance

( Reevaluated tolerance

X Other - HED recommended tolerances	Date: 11/21/07

Codex Status (Maximum Residue Limits)	U. S. Tolerances

( No Codex proposal step 6 or above

(No Codex proposal step 6 or above for the crops requested	Petition
Number:  7E7207

DP Number:  340284

Other Identifier:

Residue definition:   buprofezin (fat soluble)

(Scheduled for periodic review in 2008)	Reviewer/Branch: Tom Bloem/RAB1

	Residue definition: buprofezin

Crop (s)	MRL (mg/kg)	Crop(s) 	Tolerance (ppm)

Tomato	1	Low-growing berry, subgroup 13G	2.5

Olive	3.5

Olive, oil	4.8

Vegetable, leafy, except Brassica, group 4 (except head lettuce and
radicchio)	35

head lettuce and radicchio	6.0

fruiting vegetable (except non-bell pepper)	1.3

pepper, non-bell	4.0

okra	4.0

Limits for Canada	Limits for Mexico

√  No Limits

( No Limits for the crops requested	(   No Limits

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	Notes/Special Instructions: S.Funk, 11/17/2007.

Appendix II –  Tolerance Assessment Calculations.  

Appendix III - Chemical Structures

compound	structure

buprofezin; 

BF9

BF12

BF4

  SEQ CHAPTER \h \r 1 BF 26

 

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Buprofezin	Summary of Analytical Chemistry and Residue Data	DP Number: 
340284

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