 

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C.  20460

OFFICE OF CHEMICAL SAFETY AND

                                                                        
                               	 POLLUTION PREVENTION

  SEQ CHAPTER \h \r 1 MEMORANDUM

Date:	27-May- 2011

SUBJECT:	Tepraloxydim on Imported Crop Subgroup 6C (Dried Shelled Pea
and Bean) and Sunflower Subgroup 20B (PP#0E7788).  Summary of Analytical
Chemistry and Residue Data.

PC Code:  121005	DP Barcode:  D382893

Decision No.: 440435	Registration No.: EPA Reg. No. 8033-13

Petition No.: 0E7788	Regulatory Action: Tolerance Assessment (no S3)

Risk Assessment Type: N/A	Case No.:  N/A

TXR No.: N/A	CAS No.:  149979-41-9

MRID No.  see below  	40 CFR:  §180.573



From:		Amelia M. Acierto, Chemist

		Risk Assessment Branch III 

		Health Effects Division (7509P)

Through:		Stephen Funk, Senior Chemist

		Risk Assessment Branch III

		Health Effects Division (7509P)

To:	       Susan Stanton & James Tompkins, RM 25

	       Herbicide Branch

	       Registration Division (7505P)

MRID Summary Table

MRID No.	Study Type	Comments

48223401

48223401	860.1500 (sunfower field trials)

860.1520 (sunflower processing study)	New DER; 48223401der1 

New DER; 48223401der2 

48223402	860.1500 (dry bean field trials)	New DER; 48223402.der 



Executive Summary

Tepraloxydim 
[2-[1-[[[(2E)-3-chloro-2-propen-1-yl]oxy]imino]propyl]-3-hydroxy-5-(tetr
ahydro-2H-pyran-4-yl)-2-cyclohexen-1-one] is a member of the
cyclohexenone family of chemicals.  It is a selective broad-spectrum,
post-emergence herbicide used to control a variety of annual and
perenial grasses.  Tepraloxydim is a systemic herbicide that enters the
target weed through the foliage and translocates throughout the plant,
inhibiting acetyl-coenzyme A carboxylase (ACCase) activity.  ACCase
plays an important role in fatty acid biosynthesis, and is therefore an
extremely sensitive target.  Inhibition of its activity leads to a wide
range of physiological consequences, including necrosis and eventual
death of the weed.  The metabolite 5-OH-DP contributes 30-50% to the
herbicidal effectiveness of the active ingredient.

  

BASF stated in their submission for beans that the purpose of the study
is to develop residue data to fulfill the requirements of USEPA under
OPPTS 1500 for registration and establish tolerances in/on dry beans and
to fulfill the requirements of PMRA under Directive 98-2, Section 9 and
also Section 10 for dry bean.  A similar statement was found in their
submission for sunflower that the purpose of the study is to develop
residue data to fulfill the requirements of USEPA under OPPTS 860.1500
and 860.1520 for registration and establish tolerances in/on sunflower
and to fulfill the requirements of PMRA under Directive 98-2, Sections 9
and 10 to establish MRLs in Canada for residues of tepraloxydim in
sunflower. 

BASF Corporation, on behalf of Nippon Soda Co. Ltd., has submitted a
petition, PP#0E7788, proposing the establishment of tolerances for the
combined residues of tepraloxydim and its metabolites convertible to GP
(3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and OH-GP
(3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid), calculated
as tepraloxydim, in or on the following imported raw agricultural
commodities (RAC) grown in Canada: 

 

Pea and bean, dried shelled, except soybean, subgroup 6C ......
.....0.10 ppm

Sunflower subgroup 20B
.............................................................. ..0.25
ppm

Tepraloxydim is registered for use in Canada under the trade name
EQUINOX™ EC Herbicide, an emulsifiable concentrate formulation
containing 200 g/L (1.67 lb ai/gal) which is identical to EQUINOX EC
Herbicide, registered in the US (EPA Reg. No. 8033-12) on canola,
cotton, fallow, non-cropland, and soybeans.  The label was amended and
approved by PMRA in April 2010 to include new uses on additional crops
of Subgroup 6C and on sunflower.   The product was previously labeled in
Canada under the trade name ARAMOTM EC Herbicide (Canadian Reg, No.
27603).  BASF has no plans to apply to register EQUINOX in the U.S for
the new uses on dried beans and sunflower.  

Tolerances have been established for plant commodities under 40 CFR
§180.573 (a)(1) for residues of tepraloxydim and its metabolites
convertible to GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and
OH-GP (3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid),
calculated as tepraloxydim, at 0.2 ppm for cotton, undelinted seed; 3.0
ppm for cotton, gin byproducts; 0.10 ppm for flax, seed; lentil, seed;
and pea, dry, seed; 1200.0 ppm for aspirated grain fraction, 6.0 ppm for
soybean, seed and 8.0 ppm for soybean, hulls.   Tolerances have been
established for livestock commodities under §180.573(a)(2) for the
combined residues of tepraloxydim and its metabolites convertible to GP,
OH-GP, and GL (3-(2-oxotetrahydropyran-4-yl)-1,5-dioic acid), calculated
as tepraloxydim, at 0.15 – 0.50 ppm for fat, kidney, meat, and meat
by-products (except kidney) of cattle, goat, hog, horse, and sheep; 0.20
– 0.30 ppm for poultry fat, meat and meat products except liver; 1.00
ppm for poultry liver; 0.20 ppm for eggs, and 0.10 ppm for milk.   A
tolerance with regional registration as defined in §180.1(m) has been 
established under§180.573(c) for the combined residues of tepraloxydim
and its metabolites convertible to GP and OH-GP, calculated as
tepraloxydim, for canola, seed at 0.50 ppm. 

The nature of tepraloxydim in legume and oil seed is adequately
understood based on the available studies in soybean and canola.  HED,
through its Metabolism Assessment Review Committee (MARC), concluded
that tepraloxydim and the metabolites containing the 2-cyclohexen-1-one
moiety are the residues of concern for canola and soybean.  HED has
determined that the tolerance expression should include the combined
residues of tepraloxydim and its metabolites convertible to GP and OH-GP
and concluded that no additional plant metabolism data are required for
new uses on legume and oil seed plants. 

The  nature of the residues of tepraloxydim in livestock is adequately
understood based on the available metabolism data in goat and poultry. 
The residues of concern for livestock commodities are tepraloxydim and
the metabolites containing the 2-cyclohexen-1-one moiety.   HED has
determined that the tolerance expression for livestock commodities
should include the combined residues of tepraloxydim and its metabolites
convertible to GP, OH-GP, and GL.(see Appendix II).  

An adequate gas chromatography/mass spectrometry (GC/MS) enforcement
method, BASF Analytical Method D9701/1, is available for the enforcement
of tolerances for plant commodities.  The method has been reported and
reviewed in detail in conjunction with earlier petitions (PP#8F04945, DP
No. 243962, L Cheng, 10/3/2000 and PP#6E7046, DP #328044, N. Dodd,
6/19/2007).  The method is designed to determine the total residues of
tepraloxydim and its metabolites.  Parent tepraloxydim and related
metabolites containing the 3-tetrahydropyranylpentane-1,5-dione moiety
are converted by oxidation to GP, and GP residues are subsequently
methylated and determined as DMP (dimethyl
3-(tetrahydropyran-4-yl)pentane-1,5-dioate).  Residues of 5-OH-DP and
related 5-hydroxy-metabolites containing the
3-hydroxy-3-tetrahydropyranylpentane-1,5-dione moiety are oxidized to
OH-GP and are subsequently methylated and quantified as OH-DMP (dimethyl
3-hydroxy-3-(tetrahydroxypyran-4-yl)pentane-1,5-dioate).  Ions 168, 182,
and 213 are monitored for DMP, with ion 182 the typical quantiation ion.
 Ions 143 and 175 are monitored for OH-DMP, with ion 143 the typical
quantitation ion.   Residues are reported in terms of parent
equivalents.  The validated limit of quantitation (LOQ) for each of the 
residues of tepraloxydim and 5-OH-DP is 0.05 ppm.   BASF Method D9701/1
has been successfully radiovalidated and has undergone an independent
laboratory validation (ILV).   HED has determined that a tolerance
method validation by the Agency’s analytical laboratory is not
necessary. 

Adequate GC/MS enforcement methods, BASF Analytical Method Nos. 389/0
and 975/1 are available for determining residues in livestock.  The
methods have been reported and also reviewed in detail in conjunction
with the earlier petitions for tolerances for residues of tepraloxydim
in or on imported commodities (PP#8F04945, DP No. 243962, L Cheng,
10/3/2000 and PP#6E7046, DP No. 328044, N. Dodd, 6/19/2007).  The GC/MS
enforcement methods are designed to determine residues of tepraloxydim
and related metabolites, 5-OH-DP and other 5-hydroxy-metabolites, and DL
tetrahydropyran-ring opened metabolites; these metabolites are converted
via oxidation to three common moieties (the glutaric acids GP, OH-GP,
and GL) which are subsequently methylated and quantified as DMP, OH-DMP,
and DML, respectively.  Ions 168, 171, 182, and 213 are monitored for
DMP.  Ions 101, 143, and 175 are monitored for OH-DMP; ions 99, 160,
184, and 227 are monitored for DML.   The usual quantitation ioins are
171, 143, and 160, with the remaining ions being used for confirmation. 
The residues are expressed in terms of parent using molecular weight
conversion factors.    SEQ CHAPTER \h \r 1 The LOQ for residues of
tepraloxydim, 5-OH-DP, and DL are 0.01 ppm each in milk, 0.05 ppm each
in eggs, and 0.05 ppm each in livestock tissues.   HED has determined
that based on the successful radiovalidation and ILV studies on BASF
Analytical Method Nos. 389/0 and 975/1, a tolerance method validation in
the Agency’s analytical laboratory is not necessary.

A liquid chromatography/tandem mass spectrometry (LC/MS/MS) method (BASF
Analytical Method D9704) is available for data collection in plant
commodities.  The method is a confirmatory method for the enforcement
method in plants.  It is a common moiety method and determines the
residues of tepraloxydim and its metabolites containing the
3-tetrahydropyranylpentane-1,5-dione moiety which are converted by
oxidation to GP and determined as GP; and residues of metabolite 5-OH-DP
and related hydroxy metabolites containing the
3-hydroxy-3-tetrahydropyranylpentane-1,5-dione moiety which is oxidized
to OH-GP and determined as OH-GP.  Residues of GP and OH-GP are
expressed as the parent using molecular weight conversion factors.  A
slightly modified method (BASF Analytical Method D9704/1) was used to
analyze the residues of tepraloxydim and its metabolites from the
submitted crop field trials in support of the current petition.   The
validated limit of quantitation (LOQ) for the combined residues of
tepraloxydim and its metabolites in both dry bean seeds and sunflower
seeds is 0.10 ppm (0.05 ppm for tepraloxydim derived from GP, and 0.05
ppm for 5-OH-DP derived from OH-GP).

Feedstuffs associated with sunflower subgroup 20B is sunflower meal
based on Table 1 Feedstuffs, June 2008).  No livestock feedstuffs are
associated with dry beans except for cowpea (seed, forage, and hay). 
These livestock feeds may be fed to livestock in Canada destined for
import into the U.S.  The maximum theoretical dietary burdens of
tepraloxydim to livestock were previously calculated in conjunction with
PP#8F4945 (DP Number 243962, L. Cheng, 10/3/00).   For this petition
(PP#0E7788) a reasonably balanced diet based on Table 1 Feedstuffs (June
2008) was determined.  The established tolerances for livestock
commodities are adequate to support the proposed tolerances.  

Storage stability data were submitted for dry bean and sunflower
commodities.  All samples were stored frozen at <-5°C from collection
to analysis.  Dry bean seed RAC were stored for a maximum of 243 days (8
months), sunflower seed RAC (1x treated) for 176 days (5.8 months),
whole sunflower unprocessed seed (3.86x treated) for 135 days (4.4
month),  meal for 127 days (4.2 months), and refined oil for 167 days
(5.5 months).  Adequate storage stability data for residues of
tepraloxydim and its metabolites are available to support the conditions
and intervals of samples from the residue studies on dry bean and
sunflower.

Adequate field trial data were submitted for the imported commodities
dried bean seed and sunflower seed (the representative crops used in the
subject petition).  Data were collected for dry bean and sunflower seeds
following a single broadcast foliar application of the 200 g/L EC
formulation of tepraloxydim at the 1x target rate of 50 g ai/ha (0.045
lb ai/A).  Dry bean RAC samples were harvested at maturity, at
preharvest interval (PHI) of 53-63 days.   Sunflower RAC samples were
harvested at maturity, at PHI of 58 – 61 days.  The combined residues
of tepraloxydim following a single broadcast foliar application at the
1x rate were <LOQ (<0.10 ppm) in all dry bean seed samples (<0.05 ppm
for tepraloxydim derived from GP and <0.05 ppm for 5-OH-DP, derived from
OH-GP).   The combined residues in sunflower RAC seed samples treated at
the 1x rate  and harvested at PHIs of 58-61 days were also below the LOQ
(<0.10 ppm) except in two samples with detectable residues of 0.10 ppm
and 0.18 ppm.   

Processing data for sunflower seed have been submitted in support of the
current petition.  Residues of tepraloxydim did not concentrate in
sunflower meal and refined oil.  The combined residues and its
metabolites (convertible to GP and OH-GP) in whole, unprocessed
sunflower seed following application at the exaggerated rate of about 3X
 were 0.22 and 0.11 ppm, respectively; residues in meal samples were
0.13 ppm and <0.10 ppm, respectively; residues in refined oil were
non-quantifiable.

There are no Codex MRLs for residues of tepraloxydim.  A Canadian MRL
has been established for residues of tepraloxydim and its metabolites
convertible to 3-perhydropyran-4-ylglutaric acid (GP) and
3-hydroxy-3-perhydropyran-4-ylglutaric acid (OH-GP), expressed as parent
equivalent, in sunflower crop subgroup 20B and dried shelled pea and
bean, except soybean, crop subgroup 6C.  The US tolerance expression for
plants is harmonized with the Canadian expression.  The proposed US
tolerance for subgroup 6C is acceptable for import purposes only, based
on adequate crop field trial data for the representative commodities dry
peas and dry beans.  The proposed import tolerance of 0.25 ppm for
sunflower (subgroup 20B) should be modified to 0.20 ppm to harmonize
with the established Canadian MRL.     

Regulatory Recommendations and Residue Chemistry Deficiencies

HED has examined the residue chemistry database for tepraloxydim. 
Pending submission of  revised Section F, there are no residue chemistry
issues that would preclude establishment of tolerances for residues of
tepraloxydim as follows:

Pea and bean, dried shelled, except soybean, subgroup 6C............
0.10 ppm

Sunflower subgroup 20B
................................................................0.20 ppm

A human health risk assessment is forthcoming.

Note to PM:

The tolerance expression for tepraloxydim in 40 CFR §180.573(a)(1),
(a)(2), and (c) should be stated according to HED’s Interim Guidance
on Tolerance Expression (5/27/09, S. Knizer) as follows:

40 CFR §180.573(a)(1)

 “Tolerances are established for residues of tepraloxydim, including
its metabolites and degradates, in or on the commodities in the table
below.  Compliance with the tolerance levels specified below is to be
determined by measuring only the combined residues of tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propen-1-yl]oxy]imino]propyl]-3-hydroxy-5-(tetr
ahydro-2H-pyran-4-yl)-2-cyclohexen-1-one) and its metabolites
convertible to GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and
OH-GP (3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid),
calculated as tepraloxydim.”

40 CFR §180.573(a)(2)

 “Tolerances are established for residues of tepraloxydim, including
its metabolites and degradates, in or on the commodities in the table
below.  Compliance with the tolerance levels specified below is to be
determined by measuring only the combined residues of tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propen-1-yl]oxy]imino]propyl]-3-hydroxy-5-(tetr
ahydro-2H-pyran-4-yl)-2-cyclohexen-1-one) and its metabolites
convertible to GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid),
OH-GP (3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid), and GL
(3-(2-oxotetrahydropyran-4-yl)-1,5-dioic acid), calculated as
tepraloxydim,”

40 CFR §180.573(c)

 “A tolerance with regional registration, as defined in §180.1(m), is
established for residues of tepraloxydim, including its metabolites and
degradates, in or on the commodities in the table below.  Compliance
with the tolerance levels specified below is to be determined by
measuring only the combined residues of tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propen-1-yl]oxy]imino]propyl]-3-hydroxy-5-(tetr
ahydro-2H-pyran-4-yl)-2-cyclohexen-1-one) and its metabolites
convertible to GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and
OH-GP (3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid),
calculated as tepraloxydim.”

General:

The tolerance for pea and bean, dried shelled, except soybean, subgroup
6C and the tolerance for sunflower subgroup 20B should be footnoted:

“ No domestic registration has been established as of July 31, 2011”

Deficiencies:

860.1500  Crop Field Trial

The new data supplied for dry beans is adequate for support of an import
tolerance.  A dry pea tolerance was established previously (import
only).  The dry pea and dry bean data are adequate to support a subgroup
6C tolerance for import purposes.  

860.1550  Proposed Tolerance

A revised Section F must be submitted to propose  (1) a tolerance of
0.20 ppm for sunflower 

subgroup 20B to harmonize with the established MRL for residues of
tepraloxydim in/on

sunflower in Canada.

860.1650  Submittal of Analytical Reference Standards

The following reference standards for tepraloxydim metabolites in the
National Pesticide 

Standards Repository have expired.  BASF is urged to submit new
standards with new lot numbers or to recertify the current stock and
send new certificates of analysis (COA) by fax to the repository.   The
letter of transmittal should include the assay of the standards, names
of the analytical methods used, a statement of principal impurities,
purification procedures employed, storage requirements, and special
precautions for safe handling.  

BH 620-DML  (expired on 10/1/2010)

BH 620-OH-DMP  (expired on 10/1/2010)

Background

The chemical structure and nomenclature of tepraloxydim and related
compounds included in the tolerance expression for plant commodities are
presented in Table 1 below.  The physicochemical properties of the
technical grade of tepraloxydim are presented in Table 2.

Aramo™ EC herbicide (200 g ai/L EC)

(same as Equinox™ herbicide, EPA Reg. No. 8033-12; 1.67 lb ai/gal EC)

Chemical structure:

Metabolite 	

Common name	Metabolite:  5-OH-DP; BH 620-5-OH-DP

Chemical name
2-[1-[[[(2E)-3-chloro-2-propenyl]oxy]imino]propyl]-3,5-hydroxy-5-(tetrah
ydro-2H-pyran-4-yl)-2-cyclohexen-1-one

Chemical structure:

Oxidation product determined by analytical method 	

Common name	GP; BH 620-GP

Chemical name	3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid

Chemical structure:

Oxidation product determined by analytical method	

Common name	OH-GP; BH 620-OH-GP

Chemical name	3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid

Table 2.	  Physicochemical Properties of Tepraloxydim.

Parameter	Value	Reference

Melting point/range	72.5-74.4 (C	PMRA Proposed Regulatory Decision
Document PRDD2004-01  



pH	3.9

	Density	1.284 g/mL at 20 (C

	Water solubility	0.43 g/L at 20 (C (pH 6.5)

7.25 g/L at 20 (C (pH 9)

	Solvent solubility	Solvent

Acetone

Methanol

2-Propanol

Ethyl acetate

Acetonitrile

Dichloromethane

Toluene

n-Heptane

1-Octanol

Olive oil	g/100 mL at 20 (C

70

33

16

69

77

119

82

1.0

15

8.0

	Vapor pressure	1.1 x 10-7 hPa at 20 (C

2.7 x 10-7 hPa at 25 (C

	Dissociation constant, pKa	pKa = 4.58 at 20 ºC

	Octanol/water partition coefficient, Log(KOW)	pH

pure water

4

7

9	Log Kow

1.5

2.44

0.20

-1.15

	UV/visible absorption spectrum	 λ

204

225

258

290

300	ε (1 x Mol-1 x cm-1)

9.5 x 103

4.6 x 103

1.1 x 104

6.8 x 103

3.1 x 103

	

860.1200 Directions for Use

BASF submitted a label for the 200 g/L (1.67 lb ai/gal) EQUINOX EC
Herbicide which was previously labeled in Canada under the trade name
ARAMOTM EC Herbicide (Canadian Reg, No. 27603).  The emulsifiable
concentrate formulation is identical to EQUINOX EC Herbicide, registered
in the US (EPA Reg. No. 8033-12) on canola, cotton, fallow,
non-cropland, and soybeans.  The label has been amended and approved by
PMRA in April 2010 to include its use on the additional crops in
Subgroup 6C and Sunflower subgroup 20B.  BASF noted that they have no
plans to apply for U.S. registration of EQUINOX use on the additional
Subgroup 6C and on Sunflower subgroup 20C at this time.  

The summary of the proposed use directions for the intended crops is
summarized in Table 3. 

 

Table 3.  Summary of Directions for Use of Tepraloxydim in Canada

Applic. Timing, Type, and Equip.	Formulation

[EPA Reg. No.]	Applic. Rate 

(lb ai/A)

[kg ai/ha]	Max. No. Applic. per Season	Max. Seasonal Applic. Rate

g ai/ha

(lb ai/A)	PHI

(days)	Use Directions and Limitations

Crop Group 6, subgroup 6C, Dried shelled pea and bean (except soybean). 
Includes Lupinus, spp: (grain lupin,sweet, white and white sweet lupin);
Phaseolus, spp. (field bean,kidney bean, lima bean (dry),  navy nean,
pinto bean, tepary bean); Vigna spp (adzuki bean, blackeyed pea,
catjang, cowpea, Chowder pea, moth bean, mung bean, rice bean, southern
pea, urd bean). Broad bean (dry), chickpea, quard, lablab bean; lentil
pea); Pisum spp. (field pea and pigeon pea). 1

Postemergence,

Broadcast, Foliar

Ground equipment	EQUINOX EC Herbicide 2

(1.67 lb ai/gal)

[N/A]	0.045 – 0.046

[0.049-0.052]	NS4	

 50

(0.045)

	60	Add Merge® (0.5% v/v) or DASH HC (0.41% v/v) adjuvant to tank mix. 
Application may be made from emergence to the 7-trifoliate leaf stage
for dry beans and from emergence to 9 leaf for dry pea.  Do not apply
EQUINOX EC herbicide by air.

Sunflower Subgroup 20B (sunflower seed, Calendula; castor oil plant;
chinese tallow tree; euphorbia; evening primrose; jojoba; niger seed;
rose hip; safflower; stokes aster; tallowood; tea oil plant; vernonia;
cultivars, varieties, and/or hybrids of these) 3

Postemergence,

Broadcast, Foliar

Ground Equipment	EQUINOX EC Herbicide

1.67 lb/gal EC

[N/A]	0.029-0.045

[0.033-0.050]	NS4	

 40

(0.036)

	60	Application is made from emergence to 10 leaf stage.  Add Merge®
(0.5% v/v) or DASH HC (0.41% v/v) adjuvant to tank mix.  Application is
made at emergence to 10- leaf stage.  Do not apply EQUINOX EC herbicide
by air.

1 Dry bean variety (of the genera Phaseolus, Lupinus and Vigna) may vary
in their tolerance to herbicides, including to EQUINOX EC herbicide. 
Since not all dry bean varieties have been tested for tolerance to
EQUINOX EC herbicide, first use of EQUINOX EC herbicide should be
limited to a small area of each variety to confirm tolerance prior to
adoption as a general field practice.  Additionally, consult your seed
supplier for information on the tolerance of specific varieties of dry
beans to EQUINOX EC herbicide. 

2 For sale and use in the Prairie provinces and Peace River region of
British Columbia only.

3All types including imazethapyr and imazamox tolerant sunflower with
the CLEARFIELD trait. 

4NS= not specified on label.

Conclusions.  The submitted use directions are sufficient to allow for
evaluation of the available residue data relative to the proposed uses. 
The submitted field trial data reflect the proposed directions for dry
bean; data for sunflower were derived from application rates slightly
higher than the label rate. 

860.1300 Nature of the Residue - Plants

 DP Number 272432, 2/21/01, L. Cheng

 DP Number 272004, 2/2/01, L. Cheng 

 DP Number 365812, 6/19/07, N. Dodd

No new metabolism data were submitted but metabolism data have been
discussed and reviewed in detail in earlier reports (DP Numbers 272004 &
272432, 2/21/01, L. Cheng; DP Number 365812, 6/19/07, N. Dodd).  The
nature of the residues of tepraloxydim in plants is adequately
understood based on the available metabolism data on canola and soybean
which indicate that tepraloxydim is degraded by cleavage of the
chloroallyl side-chain, releasing metabolites such as DP-1 and DP-2 (a
Beckmann rearrangement product).  (Refer to Appendix II for names and
structures of metabolites.)  Tepraloxydim may also be reduced in the
cyclohexenone ring to form N15, hydroxylated at the cyclohexenone ring
to form 5-OH-DP and its related degradates (OH-GP type), and degraded by
oxidative cleavage of the tetrahydropyran ring.  The metabolites DP-2
and N15 may undergo oxidation reaction at the cyclohexenone ring to form
the glutaric acid derivative, GP, which is subsequently degraded to FP. 
DP-1 also may degrade to DP-6 and subsequently to GP.  Metabolism
results from the cyclohexene and tetrahydropyran label studies showed no
evidence of bond cleavage between the two ring structures. 

HED, through its Metabolism Assessment Review Committee (MARC),
concluded that tepraloxydim and those metabolites containing the
2-cyclohexen-1-one moiety are the residues of concern.   It was also
concluded that tolerances for canola, cotton, and soybean are the
combined residues of tepraloxydim and its metabolites convertible to GP
and OH-GP and for dietary risk assessment, the combined residues of
tepraloxydim and its metabolites convertible to GP and OH-GP are used
for canola and cotton commodities, and the combined residues of
tepraloxydim and its metabolites convertible to GP and OH-GP plus DD are
used for soybean commodities.   

Based on the findings on canola and soybeans, HED subsequently
recommended that the residues of concern for flax, dry pea, and lentil
are tepraloxydim and those metabolites containing the 2-cyclohexen-1-one
moiety and that tolerances for flax, dry pea, and lentil should be
established for the combined residues of tepraloxydim and its
metabolites convertible to GP and OH-GP.  

Conclusion.  No new plant metabolism data were submitted with this
petition.  However, the nature of the residue in the pea and bean, dried
shelled, except soybean, subgroup 6C and the sunflower subgroup 20B is
adequately understood based on the available data for leguminous and
oilseed crops (soybean and canola).  Tepraloxydim and the metabolites
containing the 2-cyclohexen-1-one moiety are the residues of concern for
the pea and bean, dried shelled, except soybean, subgroup 6C and the
sunflower subgroup 20B.  HED has determined that the tolerance
expression for the pea and bean, dried shelled, except soybean, subgroup
6C and the sunflower subgroup 20B should include the combined residues
of tepraloxydim and its metabolites convertible to GP and OH-GP.  No
additional plant metabolism data are required for new uses on legume and
oil seed plants. 

860.1300 Nature of the Residue - Livestock

DP Number 272432, 2/21/01, L. Cheng

DP Number 272004, 2/2/01, L. Cheng

DP Number 365812, 6/19/07, N. Dodd

ubstantial residue (≤6% TRR) in any poultry matrix; and metabolite
N15, which accounts for 9-17% TRR in goat liver, is not present in
poultry liver.  In addition, metabolite DP-2 is a major metabolite
(15-22% TRR) in poultry yolks, skin, and fat, but is not present in
goats.  

The metabolism of 5-OH-DP in ruminants and poultry is also similar and
primarily involves dealkoxylation of the side chain to form 5-OH-DP-1
and 5-OH-DP-6, and Beckmann rearrangement with subsequent ring closure
to form 6-OH-DP-2 and 6-OH-DP-4.  In both species, 5-OH-DP is the
principal residue in tissues, eggs, and milk, along with substantial
amounts of the metabolites 5-OH-DP-1 and 6-OH-DP-2.  Although the
metabolic profiles are similar, two notable differences have been
observed.  Metabolite 5-OH-M10, which accounts for 21% TRR in milk, is
not present in any poultry commodity; and 5-OH-DP-6, which is a major
metabolite in most poultry matrices (3-19% TRR), was detected only at a
trace amount in goat liver.  

Conclusions.   The nature of the residues of tepraloxydim in livestock 
is adequately understood based on the available metabolism data in goats
and poultry.   The residues of concern for livestock commodities are
tepraloxydim and the metabolites containing the 2-cyclohexen-1-one
moiety.   HED has determined  that the tolerance expression for
livestock commodities should include  the combined residues of
tepraloxydim and its metabolites convertible to GP, OH-GP, and GL.  No
additional livestock metabolism data are required to support the current
petition.

860.1340 Residue Analytical Methods

Plant commodities

Sunflower 

Sunflower seed and processed commodity samples (refined oil) were
analyzed for combined residues of tepraloxydim and the metabolites
convertible to GP and OH-GP using a slightly modified version of BASF
Analytical Method D9704/1.  Method D9704/1 has been validated on various
crop matrices, including canola seed.   The method was successfully
validated on sunflower seed and oil.  It is an acceptable method for
data collection.

Briefly, residues are extracted from sunflower seed and processed
commodity samples (except refined oil) with methanol (MeOH) and
distilled water by mechanical shaking and then centrifuged. An aliquot
of the extract supernatant is removed and concentrated to remove the
MeOH. Following addition of water and MeOH, calcium hydroxide is added
to precipitate matrix impurities. The filtered extracts are acidified
and salinized, partitioned with dichloromethane, and residues in the
organic layer are evaporated to near dryness. The residues are
re-dissolved in isopropanol and water, adjusted to pH 13-14 with KOH,
and refluxed with hydrogen peroxide to oxidize tepraloxydim and
metabolites to two common moieties (GP and OH-GP). The residues are
cooled, acidified, and then cleaned up on a C18 column eluted with
formic acid:MeOH:water (1:44:55, v/v/v) prior to analysis by liquid
chromatography-tandem mass spectrometry LC-MS/MS.  For refined oil, the
sample is homogenized with hexane and the residues are partitioned into
acetonitrile. The acetonitrile phase is concentrated to dryness, the
residues re-dissolved in isopropanol, and then the method procedures are
followed as described above. MS/MS detection in the negative ionization
mode was used to monitor ion transitions from m/z 215→171 for GP and
m/z 231→127 for OH-GP. 

The analytical method was validated prior to and concurrently with each
sample set by spiking controls with a mixed standard containing each
reference substance.  Concurrent recoveries of tepraloxydim and 5-OH-DP
spiked in control sunflower seed and refined oil samples at 0.05 or 5
ppm ranged from 70 to 110%.  Apparent residues of tepraloxydim and
5-OH-DP were <0.05 ppm (<LOQ) in/on all untreated control sunflower seed
and processed commodity samples.  Recoveries were corrected as necessary
for any apparent residues in the associated controls.

The limit of quantitation (LOQ) for the combined residues of
tepraloxydim was reported as 0.10 ppm for sunflower seed and processed
commodity samples (0.05 ppm for tepraloxdim, derived from GP and 0.05
ppm for 5-OH-DP, derived from OH-GP).

Dry bean

The dry bean (seed) samples were analyzed for combined residues of
tepraloxydim and the metabolites convertible to GP and OH-GP using
Method SOP-PA.0266, which is based on BASF Analytical Method D9704/1.
Method D9704/1 have been validated previously on various crop matrices,
including dry pea seed and bean seed.  It is an acceptable method for
data collection.

nitor ion transitions from m/z 215→171 for GP and m/z 231→127 for
OH-GP.

Method SOP-PA.0266 differed only slightly from the original method in
that (a) the sample extracts were not filtered through #4 Whatman paper
and Celite; (b) a turbovap was used instead of a rotary evaporator; (c)
sample reflux times and volumes for the oxidation step were changed very
slightly; and (d) a vacuum was not used for C18 column sample elution
and evaporation was done until dryness or around 10 mL in a turbovap
instead of dryness in a rotary evaporator.

The limit of quantitation (LOQ) for the combined residues of
tepraloxydim was reported as 0.10 ppm for dry bean seeds (0.05 ppm for
tepraloxydim, derived from GP and 0.05 ppm for 5-OH-DP, derived from
OH-GP).

The performance of the analytical method was evaluated during each
sample set by spiking controls with a mixed standard containing each
reference substance.  Concurrent recoveries of tepraloxydim and 5-OH-DP
spiked in control dry bean seed samples at 0.05 or 5 ppm were 78% and
92% for tepraloxydim and 84% and 104% for 5-OH-DP

860.1360 Multiresidue Methods

DER Reference:  None

See:  DP Number 272432, 2/21/01, L. Cheng

Data depicting the analysis of tepraloxydim and the metabolites 5-OH-DP,
DL, and GP through FDA Multiresidue Protocols have been submitted and
were forwarded to FDA for review.  The multiresidue method testing data
indicate that tepraloxydim and its metabolites are not recovered through
Protocols B, D, E, and F (Sections 302, 303, 304, and 402 of the
Pesticide Analytical Manual, Volume 1 (PAM I).  

860.1380 Storage Stability

Dry bean samples were stored frozen for a maximum of 243 days (8
months).  Sunflower RAC samples were stored for a maximum of 176 days
(5.8 months) and the processed commodities for a maximum of 135 days
(4.4 month) for whole seed, 127 days (4.2 months) for meal, and 167 days
(5.5 months) for refined oil.  Available storage stability indicate that
residues of tepraloxydim and its major metabolites (DP-1, DP-2, GP, and
5-OH-DP) are stable during frozen storage (<-5 ºC) for up to 36 months
in soybean seed and dry pea forage, and for up to 24 months in dry pea
seed and16 months in soybean oil (DP# 243962, L. Cheng, 10/3/2000 and
DP# 328044, N. Dodd, 6/19/2007).  The available data support the storage
conditions and durations of samples from the crop field trials on dry
bean and sunflower.   

The storage intervals and conditions of samples from the crop field
trials submitted to support this petition are presented in Table 4.  

TABLE  4.	Summary of Storage Conditions.  

Matrix	Storage Temperature

(°C)	Maximuml Storage Duration*	Interval of Demonstrated Storage
Stability

Sunflower seed	<-5	176 days

(5.8 months)	 Data are available indicating that residues of
tepraloxydim and (DP-1, DP-2, GP, and 5-OH-DP) are stable during frozen
storage (<-5 ºC) for up to 36 months in soybean seed, up to 24 months
in dry pea seed and 16 months in soybean oil .

Unprocessed whole seed

135 days

(4.4 months)

	Meal

127 days

(4.2 months)

	Refined oil

167 days

(5.5 months)

	Dry bean seed

243 days

(8 months) 

	* From harvest to extraction.  The extracts were analyzed within 2-7
days of extraction.

Conclusions.  Adequate storage stability data for residues of
tepraloxydim and its major metabolites (DP-1, DP-2, GP, and 5-OH-DP) are
available to support the conditions and intervals of samples from the
residue studies on dry bean seeds and sunflower seeds, meal, and oil.

No additional data are required.

860.1400 Water, Fish, and Irrigated Crops

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

860.1460 Food Handling

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

860.1480 Meat, Milk, Poultry, and Eggs

The feedstuff associated with sunflower subgroup 20B is sunflower meal
based on Table 1 Feedstuffs, June 2008).    Sunflower meal (PC) is
potential feed item for poultry, swine, and cattle.  However, the amount
of tepraloxydim residue in sunflower meal will be <0.1 ppm, based on the
sunflower field trials and processing study.  This will be a very minor
residue contribution in the livestock diet compared to other feed items
with significant residues, e.g., soybean meal (PC) at 6 ppm.   The only
feedstuffs associated with dry beans are cowpea seeds, forage, and hay. 
Cowpea  seed is a potential feed item for swine and poultry, and cowpea
hay can be up to 10% of the dairy  cow diet.  These items, because of
the low residue levels, will have an insignificant effect on the
livestock dietary burdens.  The maximum reasonably balance dietary
burdens (MRBDB) were previously estimated as 12.3 ppm for beef cattle,
2.4 ppm for dairy cattle, 2.0 ppm for poultry, and 1.2 ppm for swine
(D328044, N. Dodd, 06/19/2007).  These diets and the resulting livestock
commodity tolerance estimates remain valid.

Conclusions  The established tolerances for livestock commodities listed
under 40 CFR §180.573(a)(2) are adequate to support the requested
tolerances on the pea and bean, dried shelled, except soybean, subgroup
6C and the sunflower subgroup 20B.  Based on the available feeding
studies, the established tolerances for livestock commodities are
adequate to support the proposed tolerances.  Feed items from these
commodities do not impact the MRBDB.

860.1500 Crop Field Trials

DER 48143301   Sunflower

DER 48143302   Dry bean

Sunflower

Five trials were conducted in the U.S and Canada in NAFTA Growing
Regions 5 (North Dakota (Gardner), Wisconsin and Manitoba, one trial
each), 7 (North Dakota,(Eelva), one trial) and 14 (Saskatchewan, one
trial) during the 2007 growing season.  In addition, a processing study
was conducted to determine the potential for concentration of residues
of tepraloxydim in sunflower processed fractions.

At each test location, one untreated control and one treated plot of
sunflower were established.   Each treated plot received one broadcast
foliar application of the 200 g/L (1.67 lb ai/gal) emulsifiable
concentrate (EC) formulation of tepraloxydim at the rate of 49-52 g
a.i./ha (0.044-0.046 lb ai/A).  At one site a third plot was treated at
an exaggerated rate of 147 g a.i./ha (0.131 lb ai/A) to generate samples
for processing (see 860.1520).  The applications were made in
approximately 10-15 gal/A (93-143 L/ha) of water using ground equipment,
and an adjuvant (Merge®, 0.5% v/v) was added to the spray mixture for
all applications.  Merge is a BASF product containing surfactant plus
petroleum hydrocarbons. Sunflower samples (seed) were harvested 58-61
days after treatment. At one site, in addition to the targeted 60±1 day
preharvest interval (PHI), duplicate treated samples were collected at
41, 50, 70 and 80 days after treatment to examine residue decline.

The combined residues of tepraloxydim (and the metabolites convertible
to GP and OH-GP) in/on sunflower seed and processed commodity samples
were quantitated by LC-MS/MS using Method SOP-PA.0266, which is based on
the data collection method BASF Analytical Method D9704/1 for plant
matrices. Acceptable method validation data for sunflower matrices were
obtained for each analyte.  The limit of quantitation (LOQ) for the
combined residues of tepraloxydim was reported as 0.10 ppm in/on
sunflower seed (0.05 ppm for tepraloxydim, derived from GP and 0.05 ppm
for 5-OH-DP, derived from OH-GP).

The results from these trials show that following a single broadcast
foliar application of tepraloxydim at approximately 50 g a.i./ha, the
combined residues of tepraloxydim ranged from <0.10 ppm (less than
combined LOQ) to 0.18 ppm in/on sunflower seed samples harvested at a
PHI of 58-61 days. Only two of the ten treated samples contained
quantifiable residues of tepraloxydim (<0.10 and 0.18 ppm), and these
samples were collected at the trials located in Wisconsin and
Saskatchewan, respectively. Combined residues were also <0.10 ppm in/on
two treated sunflower seed samples harvested 61 days after application
of tepraloxydim at the exaggerated rate of 147 g a.i./ha.

In the residue decline experiment, combined residues of tepraloxydim
were <0.10 ppm in/on duplicate treated seed samples collected at 41, 50,
61, 70 and 80 days after treatment; therefore, the results are
inconclusive with respect to decline at longer sampling intervals.

Dry bean

Five field trials were conducted in NAFTA Regions 5 (ND, SD one trial
each; and MB, two trials) and 5B (QC, one trial) during the 2007 growing
season.  Each test location had one untreated control and one treated
plot.    Each treated plot received one broadcast foliar application of
tepraloxydin emulsifiable concentrate (EC) formulation (200 g/L or 1.67
lb ai/gal) applied at the rate of 50-52 g a.i./ha (0.045 – 0.046 lb
ai/A).  The applications were made using ground equipment in spray
volumes of approximately 94-100 L/ha (10 – 11 al/A) of water. An
adjuvant (Merge® surfactant, 0.5% v/v) was added to the spray mixture
for all applications. Samples of dry bean seed raw agricultural
commodities (RAC) were harvested 53 to 63 days after treatment.  At one
site, additional duplicate treated samples were collected at 70 and 90
days after treatment to determine residue decline.  

The combined residues of tepraloxydim and its metabolites convertible to
GP and OH-GP in/on dry bean seed RAC samples were analyzed by LC-MS/MS
using working method SOP-PA.0266, which is based on BASF Analytical
Method D9704/1 (the data collection method for plant matrices).  The
method is similar to the proposed enforcement method (BASF method D9704
for plant matrices.  Acceptable concurrent method validation data for
dry bean seed were obtained for each analyte.  The validated limit of
quantitation (LOQ) for the combined residues of tepraloxydim is 0.10 ppm
in/on dry bean seed (0.05 ppm for tepraloxydim, derived from GP and 0.05
ppm for 5-OH-DP, derived from OH-GP).

The combined residues of tepraloxydim after a single broadcast foliar
application of 50 g a.i./ha and harvested at PHI 53-63 were <LOQ (<0.10
ppm) in all dry bean seed samples (<0.05 ppm for tepraloxydim derived
from GP and <0.05 ppm for 5-OH-DP, derived from OH-GP).  Residues from
the residue decline studies were non-quantifiable at PHIs of 70 and 90
days. 

Note that field trial data from Canada for dried peas were reviewed
previously and resulted in a dry pea import tolerance (D328044, N. Dodd,
06/19/2007).

Summary of the residue data from the crop field trials for sunflower and
bean is presented in Table 5.

TABLE 5.	Summary of Residue Data from Crop Field Trials with
Tepraloxydim.

Commodity	Total Applic. Rate

(g a.i./ha)	PHI (days)	Residue Levels (ppm)



	n	Min.	Max.	HAFT*	Median

(STMdR)	Mean

(STMR)	Std. Dev.

Total Tepraloxydim (including metabolites convertible to GP and OH-GP)

Sunflower seed	49-52	58-60	10	<0.1	0.18	0.14	<0.1	<0.1	0.05

	147	61	2	<0.1	<0.1	<0.1	<0.1	<0.1	0

Dry bean seed	50-52	53-63	10	<0.1	<0.1	<0.1	<0.1	<0.1	0

1HAFT = Highest average field trial result

Conclusion.  The dry bean and sunflower field trial studies reflecting a
single broadcast foliar application of 200 g/L EC formulation of 
tepraloxydim to dry bean at 50-52 g ai/ha are adequate for the imported
commodities.   A dry pea tolerance (import) of 0.01 ppm was previously
established based on 12 dry pea field trials in Canada (D328044, N.
Dodd, 06/19/2007).  The combined residues of tepraloxydim and
metabolites were below the LOQ (<0.10 ppm; <0.05 ppm each for
tepraloxydim and 5-OH-DP) in all treated dry beans seed samples
harvested at a PHI of 53-63 days.  The results from the residue decline
experiment indicate that residues of tepraloxydim do not increase at
longer PHIs.  The samples were analyzed using an acceptable method.  The
crop field study is supported by adequate storage stability data.  The
dry bean field trial data of the current study and the dry pea field
trial data of the previous study are adequate to support a dry bean and
dry pea subgroup 6C tolerance (import).

860.1520 Processed Food and Feed

 

No processed commodities are associated with dry bean.

A sunflower plot was treated at an exaggerated rate of 147 g a.i./ha
(0.131 lb ai/A); this is equivalent to 3.7x the proposed seasonal
application rate.  An adjuvant (Merge, 0.5% v/v) was added to the spray
mixture.  The application was made in approximately 93-143 L/ha of water
using commercial or simulated commercial ground equipment, and all
sprayers were calibrated prior to each application with the volume/time
method.   

Single untreated control and duplicate RAC sunflower seeds samples from
the plot treated at the exaggerated rate (3.86x) were harvested 61 days
after treatment.  The samples were processed according to simulated
commercial methods.  Combined residues in the duplicate treated RAC
samples 0.11 and 0.22 ppm (tepraloxydim, <0.05 ppm; 5-OH-DP, 0.06 and
0.17 ppm).  In duplicate treated meal samples, the combined residues
were <0.10 and 0.13 ppm (tepraloxydim, <0.05 ppm; 5-OH-DP, 0.05 and 0.08
ppm).  Residues were non-quantifiable in the refined oil. 

The RAC sunflower seed samples were stored frozen from collection to
analysis for a maximum of 176 days (5.8 months).  The whole seed
subsample was stored frozen for a maximum of 135 days (4.4 months). 
Meal and refined oil were stored for 127 days (4.2 months) and 167 days
(5.5 months), respectively.  Freezer storage stability data are
available indicating that residues of tepraloxydim and the metabolites
are stable under frozen storage conditions in/on rapeseed (forage, seed
and straw), dry pea seed and forage, and soybean seed for at least 24
months and soybean oil for 16 months.

The processing data indicate that residues of tepraloxydim did not
concentrate in soybean meal or refined oil.  Results are shown in Table
6.  

.

TABLE 6.	Residue Data from Sunflower Processing Study with Tepraloxydim.

RAC	Processed Commodity	Total Rate

 (g a.i./ha)	PHI

(days)	Tepraloxydim Residues (ppm)	5-OH-DP Residues (ppm)	Total Residues
(ppm)	Processing Factor

Sunflower

(Replicate A)	Whole seed	147	61	<0.05	0.17	0.22	--

	Meal

	<0.05	0.08	0.13	0.6x

	Refined oil

	<0.05	<0.05	<0.1	0.5x

Sunflower

(Replicate B)	Whole seed

	<0.05	0.06	0.11	--

	Meal

	<0.05	<0.05	<0.1	0.9x

	Refined oil

	<0.05	<0.05	<0.1	0.9x



Conclusions.   Based on the RAC samples, residues of tepraloxydim do not
concentrate in sunflower processed fractions (meal and refined oil).

  SEQ CHAPTER \h \r 1 860.1650 Submittal of Analytical Reference
Standards

Information on the availability and expiration dates of the reference
standards for tepraloxydim and related metabolites at the National
Pesticide Standard Repository was provided by the Analytical Chemistry
Branch (e-mail, D. Wright, 4/19/2011).  

Chemical Name			Company			Date Recd	Date Exp

tepraloxydim			Nisso (Nippon Soda Co)			3/6/2006	9/25/2019

BH 620-5-OH-DP,275522)		BASF				11/1/2000	10/1/2012

BH 620-DL				BASF				11/1/2000	10/1/2018

BH 620-DML				BASF				11/1/2000	10/1/2010

BH 620-DMP  318473			BASF				 8/19/2008	  5/1/2015 

BH 620-OH-DMP 318474                              BASF                  
                             11/1/2000	10/1/2010

Metabolites BH 620-DML and BH-OH-DMP are the only standards that have
expired.  The petitioner may replace these with new ones (with different
lot numbers) or may recertify the current stock and send new
certificates of analysis (COA) by fax to the repository at 410-305-2999.
  The letter of transmittal should include the assay of the standards,
names of the analytical methods used, a statement of principal
impurities, purification procedures employed, storage requirements, and
special precautions for safe handling.  Replacement of standards may be
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 Occupational Safety
and Health Administration (OSHA) in 29 CFR 1910.1200.

Analytical Reference Standards can be sent to the attention of either
Theresa Cole or Thuy Nguyen at the following address:

USEPA

National Pesticide Standards Repository/Analytical Chemistry Branch/OPP

701 Mapes Road

Fort George G. Mead, MD 20755-5350

(NOTE: The full 9 digit zip code is mandatory or will be returned) 

860.1850 Confined Accumulation in Rotational Crops

Confined accumulation in Rotational crops to establish tolerances are
not required for import commodities (HED SOP 98.6, Data Requirements for
Import Tolerances, Table 3, 12/3/98).

860.1900 Field Accumulation in Rotational Crops

Rotational crop data are not required to establish tolerances on
imported commodities (HED SOP 98.6, Data Requirements for Import
Tolerances, Table 3, 12/3/98).

860.1550  Proposed Tolerances

BASF Corporation, on behalf of Nippon Soda Company, submitted a petition
(PP#0E7788) proposing the establishment of tolerances for the combined
residues of tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propenyl]oxy]imino]propyl]-3-hydroxy-5-(tetrahy
dro-2H-pyran-4-yl)-cyclohexene-1-one] and its metabolites convertible to
GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and OH-GP
(3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) in or on  pea
and bean, dried shelled, except soybean, subgroup 6C and sunflower
subgroup 20B.

Tolerances for the combined residues of tepraloxydim and its metabolites
convertible to GP and OH-GP are currently established under 40 CFR
180.573(a)(1) from 0.2 ppm to 8.0 ppm in/on cotton undelinted seed and
gin byproducts,  flax seed, lentil seed, dry pea seed, and soybean seed
and hulls.  In addition, tolerances have been established in/on
aspirated grain fraction at 1200 ppm.  A tolerance for a regional
registration is established under 40 CFR 180.573(c) in/on canola seed at
0.50 ppm.  Tolerances for the combined residues of tepraloxydim and its
metabolites convertible to GP, OH-GP, and GL
(3-(2-oxotetrahydropyran-4-yl)-1,5-dioic acid) are currently established
under 40 CFR 180.573(a)(2) in/on livestock commodities at levels ranging
from 0.10 to 1.0 ppm.

There are currently no established Codex maximum residue limits (MRLs)
for residues of tepraloxydim and its metabolites in/on dry pea and bean
and on sunflower seed.

A Canadian MRL has been established for residues of tepraloxydim and its
metabolites convertible to 3-perhydropyran-4-ylglutaric acid (GP) and
3-hydroxy-3-perhydropyran-4-ylglutaric acid (OH-GP), expressed as parent
equivalent in dried shelled pea and bean, except soybean, crop subgroup
6C at 0.1 ppm and  in sunflower crop subgroup 20B and 0.2 ppm.

  

Because the majority of residues were found to be below the LOQ, the
tolerance spreadsheet in the Agency’s Guidance for Setting Pesticide
Tolerances Based on Field Trial Data was not utilized for determining
appropriate tolerance levels. 

The tolerance expression for tepraloxydim in 40 CFR §180.573 (a)(1),
§180.573 (a)(2) and §180.573 (c) should be stated according to HED’s
Interim Guidance on Tolerance Expression (5/27/09, S. Knizer) as
follows:

40 CFR §180.573(a)(1)

 “Tolerances are established for residues of tepraloxydim, including
its metabolites and degradates, in or on the commodities in the table
below.  Compliance with the tolerance levels specified below is to be
determined by measuring only the combined residues of tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propen-1-yl]oxy]imino]propyl]-3-hydroxy-5-(tetr
ahydro-2H-pyran-4-yl)-2-cyclohexen-1-one) and its metabolites
convertible to GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and
OH-GP (3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid),
calculated as tepraloxydim.”

40 CFR §180.573(a)(2)

 “Tolerances are established for residues of tepraloxydim, including
its metabolites and degradates, in or on the commodities in the table
below.  Compliance with the tolerance levels specified below is to be
determined by measuring only the combined residues of tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propen-1-yl]oxy]imino]propyl]-3-hydroxy-5-(tetr
ahydro-2H-pyran-4-yl)-2-cyclohexen-1-one) and its metabolites
convertible to GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid),
OH-GP (3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid), and GL
(3-(2-oxotetrahydropyran-4-yl)-1,5-dioic acid), calculated as
tepraloxydim,”

40 CFR §180.573(c)

 “A tolerance with regional registration, as defined in §180.1(m), is
established for residues of tepraloxydim, including its metabolites and
degradates, in or on the commodities in the table below.  Compliance
with the tolerance levels specified below is to be determined by
measuring only the combined residues of tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propen-1-yl]oxy]imino]propyl]-3-hydroxy-5-(tetr
ahydro-2H-pyran-4-yl)-2-cyclohexen-1-one) and its metabolites
convertible to GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and
OH-GP (3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid),
calculated as tepraloxydim.”

Table 7. 	Tolerance Summary for Tepraloxydim

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

Pea and bean dried shelled, except soybean, subgroup 6C1	0.10	0.10	



Sunflower, subgroup 20B1	0.25	0.20	To harmonize with Canada.

Lentil, seed	0.10	Withdraw	Replaced by subgroup 6C tolerance

Pea, dry, seed	0.10	Withdraw	Replaced by subgroup 6C tolerance.

1 No domestic registration has been established as of July 31, 2011.

Conclusion:   The proposed tolerance for pea and bean dried shelled,
except soybean is acceptable based on the existing dry pea tolerance and
the field trial data submitted herein for dry beans.   US tolerances
exist for lentil and pea, dry, seed and should be deleted upon
establishment of the subgroup 6C tolerances.  The proposed tolerance for
sunflower subgroup 20B should be changed to 0.20 ppm to harmonize with
the MRL for sunflower in Canada.  The commodity definitions must be
revised as shown in Table 7.  The established tolerances for livestock
commodities are adequate to support the requested tolerances.

References

DP Numbers:	243962, 243965, 243967, 262821, 262822, 262825

Subject:	PP#8F04945.  Tepraloxydim on Canola, Cotton, and Soybean. 
Review of Analytical Methods and Residue Data.

From:		L. Cheng

To:		J. Tompkins/V. Walters

Dated:		10/3/00

MRIDs:	44467306-44767351, 44496409-44496411, and 44853401-44853403

DP Number:	272004

Subject:	PP#8F04945.  PC Code 121005.  Tepraloxydim (BAS620 H).  Outcome
of the Second HED Metabolism Assessment Review Committee (MARC) Meeting
Held on 16 January, 2001.

From:		L. Cheng

To:		Y. Donovan

Dated:		2/2/01

MRID:		None

DP Number:	272432

Subject:	PP#8F04945.  Tepraloxydim on Canola, Cotton, and Soybean. 
Review of Analytical Methods and Residue Data.  Amendment to D243962.

From:		L. Cheng

To:		J. Tompkins/V. Walters

Dated:		2/21/01

MRID:		None

DP Numbers:	243962, 243965, 243967, 262821, 262822, 262825

Subject:	PP#8F04945.  Tepraloxydim on Canola, Cotton, and Soybean. 
Review of Analytical Methods and Residue Data.

From:		L. Cheng

To:		J. Tompkins/V. Walters

Dated:		10/3/00

MRIDs:	44467306-44767351, 44496409-44496411, and 44853401-44853403

DP Number:	272004

Subject:	PP#8F04945.  PC Code 121005.  Tepraloxydim (BAS620 H).  Outcome
of the Second HED Metabolism Assessment Review Committee (MARC) Meeting
Held on 16 January, 2001.

From:		L. Cheng

To:		Y. Donovan

Dated:		2/2/01

MRID:		None

DP Number:	272432

Subject:	PP#8F04945.  Tepraloxydim on Canola, Cotton, and Soybean. 
Review of Analytical Methods and Residue Data.  Amendment to D243962.

From:		L. Cheng

To:		J. Tompkins/V. Walters

Dated:		2/21/01

MRID:		None

DP Number:	328044

Subject:	PP#7046.  Tepraloxydim on Imported Dry Peas, Flax, and Lentils.
 Summary of Analytical Methods and Residue Data.  PRIA R29.

From:		N. Dodd

To:		V. Walters

Dated:		6/19/2007

MRID Nos:	46782501, 46782502, 46782503, 46782504, 46782505, 46782506

  SEQ CHAPTER \h \r 1 Attachments:  

Appendix I  – 	International Residue Limit Status Sheet   

Appendix II –	Chemical Name and Structure Table

APPENDIX

International Residue Limits

TEPRALOXYDIM (PC Code 121005; 04/14/2011)

Summary of US and International Tolerances and Maximum Residue Limits 

Residue Definition:

US	Canada	Mexico2	Codex3

40 CFR 180.573:

Plants: tepraloxydim
(2-[1-[[[(2E)-3-chloro-2-propenyl]oxy]imino]propyl]-3-hydroxy-5-(tetrahy
dro-2H-pyran-4-yl)-cyclohexene-1-one) and its metabolites convertible to
GP (3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid) and OH-GP
(3-hydroxy-3-(tetrahydropyran-4-yl)pentane-1,5-dioic acid), calculated
as tepraloxydim 

Livestock: combined residues of tepraloxydim and its metabolites
convertible to GP, OH-GP, and GL
(3-(2-oxotetrahydropyran-4-yl)-1,5-dioic acid), calculated as
tepraloxydim 
Plants:(EZ)-(RS)-2-{1-[(2E)-3-chloroallyloxyimino]propyl}-3-

hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one,

including metabolites convertible to 3-perhydropyran-

4-ylglutaric acid and 3-hydroxy-3-perhydropyran-4-

ylglutaric acid, as parent equivalent

Livestock:(EZ)-(RS)-2-{1-[(2E)-3-chloroallyloxyimino]propyl}-3-

hydroxy-5-perhydropyran-4-ylcyclohex-2-en-1-one,

including metabolites convertible to dimethyl 3-

(perhydropyran-4-yl)glutarate, dimethyl 3-hydroxy-3-

(perhydropyran-4-yl)glutarate and dimethyl 3-(pentan-

5-olid-3-yl)glutarate, as parent equivalent

None

Commodity1	Tolerance (ppm) /Maximum Residue Limit (mg/kg)

	US	Canada	Mexico2	Codex

Pea and bean dried shelled, except soybean, subgroup 6C1	0.10	0.1 Dried
shelled pea and bean, except soybean (Crop subgroup 6C)



Sunflower Subgroup 20B	0.20	0.2 Sunflowers (Crop Subgroup 20B)



























Completed:  M. Negussie;  05/17/2011

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

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

3 * = absent at the limit of quantitation; Po = postharvest treatment,
such as treatment of stored grains.  PoP = processed postharvest treated
commodity, such as processing of treated stored wheat. (fat) = to be
measured on the fat portion of the sample. MRLs indicated as proposed
have not been finalized by the CCPR and the CAC.

 

APPENDIX II.

Chemical Names and Structures of Tepraloxydim, Metabolites, and
Oxidation Products. 1

Common name/code	Chemical name	Chemical structure

Tepraloxydim; BAS 620H; DP 
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ro-2H-pyran-4-yl)-2-cyclohexen-1-one

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DML

	

dimethyl 3-(2-oxotetrahydropyran-4-yl)pentane-1,5-dioate

 

1  This table includes only metabolites and oxidation products
referenced in the subject summary document; refer to DP Number 272004,
2/2/01, L. Cheng for a complete listing of metabolites identified in
metabolism and confined rotational crop studies.

2  This metabolite was identified in methylated extracts of soybean
commodities, indicating that metabolite FP was present in the
unmethylated fractions.

Tepraloxydim	Summary of Analytical Chemistry and Residue Data	DP Number
382893

 PAGE   

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