Document ID: EPA-HQ-OPP-2006-0522-0006
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2007-09-26T04:00Z

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C.  20460

OFFICE OF           

PREVENTION, PESTICIDES

AND TOXIC SUBSTANCES

MEMORANDUM

	Date:	03/30/07

	Subject:	Pyraclostrobin.  PP#’s 5F7002 and 5E7014.  Petition for
Tolerances on Cotton and 	

		Belgian Endive, and An Increased Tolerance on the Berries Crop Group.
Submission 

		of Requested Field Trial Data on Mustard Greens (PP#3F6581).   
Submission of 		

		Additional Field Trial Data on Fruiting Vegetables (PP#0F6139),
Cucurbit 

		Vegetables (PP#0F6139), Sunflower (PP#2F6431), Mint (PP#2F6431), and 	

		Grape(PP#0F6139).  Summary of Analytical Chemistry and Residue Data. 
(Reg. 	

		No. 7969-198)

DP Barcodes:	337807, 327899, 337817, 338448

	Decision Numbers:	362283, 363131, 363593

PC Code:	099100	MRID Nos.:	46512002, 46512003, 46637701, 46665501,
46665502, 46665504, 46665505, 46665506, 46685901, 46685902, 46713801

40 CFR 180.	582

Chemical Class:	Strobilurins

	From:	Jerry B. Stokes, Chemist

		Reregistration Branch 4

		Health Effects Division (7509P)

	Through:	Susan V. Hummel, Senior Scientist

		Reregistration Branch 4

		Health Effects Division (7509P)

		

	To:	Barry O’Keefe

		Registration Branch 3

		Health Effects Division (7509P)

		Barbara Madden PM-5

		Risk Integration Minor Use, and Emergency Response Branch

		Registration Division (7505P)

		John Bazuin, PM-22

		Fungicide Branch

		Registration Division (7505P)

This document was originally prepared under contract by Dynamac
Corporation (1910 Sedwick Road, Building 100, Durham, NC 27713;
submitted 11/17/2006).  The document has been reviewed by the Health
Effects Division (HED) and revised to reflect current Office of
Pesticide Programs (OPP) policies. Note: This review and accompanying
DERs have MRIDs that contain residue data for both pyraclostrobin and
boscalid.  Only pyraclostrobin is be discussed in this summary memo and
the accompanying DERs..

Executive Summary

Pyraclostrobin is a strobilurin fungicide registered to BASF Corporation
(BASF) for use on a variety of field, vegetable, fruit and nut crops. 
It is formulated as water-dispersible granules (WDG) or an emulsifiable
concentrate (EC) and is applied as foliar applications using ground or
aerial equipment at maximum seasonal rates of 0.3-3.0 lb ai/A.  The 20%
WDG formulation is also registered for use as a seed treatment on the
variety of crops.

Permanent tolerances are established for the combined residues of
pyraclostrobin (carbamic acid, [2-[[[1-(4-chlorophenyl)-1H-
pyrazol-3-yl]oxy]methyl]phenyl]methoxy-, methyl ester) and its
desmethoxy metabolite (methyl
2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]phenyl carbamate), BF
500-3, expressed as parent compound, in/on numerous plant commodities
[40 CFR §180.582(a)(1)].  The established tolerances for plant
commodities range from 0.02 ppm in/on wheat grain to 29 ppm in/on leafy
vegetables, except Brassica, and include tolerances on the berries crop
group (1.3 ppm), Brassica leafy greens (16 ppm), cucurbit vegetables
(0.5 ppm), fruiting vegetables (1.4 ppm), peppermint and spearmint (8.0
ppm),  sunflower (0.3 ppm), and grape (2.0 ppm).  Tolerance have also
been established on livestock commodities for the combined residues of
pyraclostrobin and its metabolites convertible to
1-(4-chlorophenyl)-1H-pyrazol-3-ol, BF 500-5, and
1-(4-chloro-2-hydroxyphenyl)-1H-pyrazol-3-ol, BF 500-8, expressed as
parent compound [40 CFR §180.582(a)(2)].  The established tolerances
for livestock commodities range from 0.1 to 1.5 ppm; no tolerances are
established for poultry commodities.

In the current petition, BASF is proposing the use of pyraclostrobin
(WDG) on cotton as a combination of an in-furrow application at planting
and up to three broadcast foliar applications during boll development,
each at 0.2 lb ai/A, for a total of 0.8 lb ai/A/season.  The proposed
pre-harvest interval (PHI) for cotton is 30 days.  BASF is also
proposing the use of the 23.6% WDG formulation of pyraclostrobin as a
seed treatment on cotton at 0.01 lb ai/100 lb seed.  SEQ CHAPTER \h \r 1
  In conjunction with these uses, BASF is proposing permanent tolerances
for the combined residues of pyraclostrobin and BF 500-3 at 0.4 ppm
in/on undelinted cottonseed and at 30 ppm in/on cotton gin byproducts.

BASF has also submitted field trials on mustard greens in response to
deficiencies cited in an earlier petition (PP#3F6581, D281042, L. Cheng,
7/26/04) and supplemental field trials on berries, cucurbit vegetables,
fruiting vegetables, mint, sunflower, and grape.  These field trials
were conducted to support the use of pyraclostrobin on these crops in
Canada.  Adequate field trial data supporting the use of pyraclostrobin
on these crops in the U.S. have been previously reviewed (PP#0F6139,
D269668, L. Cheng, 11/28/01; PP#3F6581, D281042, L. Cheng, 7/26/04). 
Based on the new field trial data on berries, BASF is also requesting an
increased in the current tolerance on berries from 1.3 to 4.0 ppm.  

The Interregional Research Project No. 4 (IR4) has submitted field trial
data for the use of pyraclostrobin (WDG) on Belgian endive (MRID
46713801) (PP#5E7014). At each test location, Belgian endive received
two root spray applications of Pristine® Fungicide (EPA Reg. No.
7969-199) at two application rates prior to cold storage and prior to
forcing.  One set of endive was treated at rates of approximately 0.0055
lb pyraclostrobin per 875 lb roots (+ 0.011 lb boscalid per 875 lb
roots) (1X).  (This memo will only discuss the pyraclostrobin
residues.).  An additional set was treated at the 2X rate. Belgian
endive was harvested at 19 to 21 days.  In  PP#5E7014, the petitioner
also submitted data (MRID 46665505) to support a proposed postharvest
use of pyraclostrobin on pome fruit (crop group 11) and stone fruit
(crop group 12).   However, IR4 has since informed RD (letter to RD,
November 2006) that they not longer will support the proposed
postharvest use on pome or stone fruit.  

For purposes of tolerances and dietary risk assessment, HED has
concluded that the residues of concern in plant commodities include
pyraclostrobin and it desmethoxy metabolite, BF 500-3 (D278044, L.
Cheng, 10/9/01), and the residues of concern in livestock commodities
include pyraclostrobin and its metabolites convertible to
1-(4-chlorophenyl)-1H-pyrazol-3-ol (BF 500-5) and
1-(4-chloro-2-hydroxyphenyl)-1H-pyrazol-3-ol (BF 500-8).  

  SEQ CHAPTER \h \r 1 Adequate residue analytical methods are available
for determining the residues of concern in both plant and animal
commodities.  These methods were successfully validated by an
independent laboratory and validated using radiolabeled samples from
metabolism studies.  The proposed enforcement methods have been
forwarded to ACB/BEAD for petition method validations.  Residues in
plant commodities from the current field trials and cotton processing
study were determined using an adequate LC/MS/MS method (BASF Method
D9908, MRID 46710001(currently under HED review)), which is similar to
the proposed enforcement method.  The method was adequately validated in
conjunction with the field trial analyses.  For each analyte, the
validated limit of quantitation (LOQ) is 0.02 ppm, and the estimated
limit of detection (LOD) is 0.004-0.005 ppm.

Adequate cattle and poultry feeding studies are available for
pyraclostrobin and were reviewed in earlier petitions.  Considering the
proposed and established tolerances on livestock feedstuffs, and using
Agency guidance for calculating dietary exposures of livestock, the
potential dietary exposure of livestock to pyraclostrobin residues was
calculated to be 4.7 ppm for beef cattle, 11.9 ppm for dairy cattle, and
0.20 ppm for poultry, and 0.19 ppm for swine. With regards to the
current tolerances for livestock commodities, the existing tolerances
are adequate for milk, meat, fat, meat byproducts (except liver), and
liver of cattle, goats, horses, and sheep, and the current tolerances
for liver could be lowered to 1.0 ppm.  Also, the existing tolerances
for hog commodities can be deleted as quantifiable residues are unlikely
to occur in hogs [40 CFR §180.6(a)(2)] based on the dietary burden
proposed in Table 5.   As stated previously, tolerances are still not
required for poultry commodities.

The submitted cotton, mustard greens, and Belgian endive field trials
and the supplemental field trials on berries, cucurbit vegetables,
grape, sunflower, and mint are adequate and support the proposed or
existing uses of pyraclostrobin on these crops.  Together with the
previously submitted field trials, the number and geographic
distribution of the field trials on these crops are adequate, and the
appropriate samples were collected at the proposed PHIs.  Samples were
analyzed using an adequate method, and the sample storage intervals are
supported by the available storage stability data.  Although no field
trials were conducted supporting the proposed seed treatment on cotton,
no additional cotton field trial data are required as the use rate for
the seed treatment is negligible compared to the use rates for the
in-furrow and foliar applications.

 

The submitted cottonseed processing study is adequate and indicates that
residues do not concentrate in cotton meal, hulls or oil (<0.3x). 
Processing study requirements for grape, mint, plum, tomato and
sunflower have been adequately addressed in previous petitions.

 

Adequate confined and limited field rotational crops studies are
available.  Tolerances for rotated crops are not required, and the
available data support the 14-day plant-back interval specified on
current labels. 

  SEQ CHAPTER \h \r 1 Regulatory Recommendations and Residue Chemistry
Deficiencies

No deficiencies were noted in the subject petition that would preclude
establishing permanent tolerances for pyraclostrobin on the proposed
commodities.  HED  SEQ CHAPTER \h \r 1  recommends establishing
permanent tolerances for pyraclostrobin at 0.3 ppm in/on undelinted
cottonseed and at 30 ppm in/on cotton gin byproducts.  The additional
berry data also support increasing the current tolerance on the berries
crop group from 1.3 to 4.0 ppm.  A human health risk assessment is
forthcoming.

Background

Pyraclostrobin belongs to the strobilurin class of fungicides, which are
synthetic analogs of a natural antifungal substance that inhibits spore
germination, mycelial growth, and sporulation of fungi on leaf surfaces.
 Pyraclostrobin is currently registered to BASF Corporation as WDG and
EC formulations for use on a wide variety of crops.  Permanent
tolerances are established for the combined residues of pyraclostrobin
and its desmethoxy metabolite (BF 500-3), expressed as parent, in/on
numerous plant commodities at levels ranging from 0.02 ppm in/on wheat
grain to 29 ppm in/on leafy vegetables, except Brassica [40 CFR
§180.582(a)(1)]. 

BASF has submitted at new petition (PP#5F7002) proposing the use of
pyraclostrobin (EC) on cotton along with tolerances for residues in/on
cotton seed (0.4 ppm) and cotton gin byproducts (30 ppm).  Under this
petition, BASF is also requesting an increase in the current tolerance
for the Berries Crop Group from 1.3 to 4.0 ppm, based on new berry field
trial data generated in support of the use on berries in Canada.  BASF
has also submitted additional field trial data on mustard greens in
response to deficiencies cited by the Agency in an earlier petition for
use on Brassica leafy greens (PP#3F6581, D281042, L. Cheng, 7/26/04),
which required an additional three field trials on mustard greens in
Zones 2, 3 and 10.

In addition to the above data, BASF has also submitted supplemental
field trials on cucurbit vegetables, fruiting vegetables, mint,
sunflower and grape, which were conducted to support the use of
pyraclostrobin on these crops in Canada.  Adequate field trial data
supporting the use of pyraclostrobin in the U.S. on these crops or crop
groups were previously reviewed, (PP#0F6139, D269668, L. Cheng,
11/28/01; PP#3F6581, D281042, L. Cheng, 7/26/04), and U.S. tolerances
have been established for pyraclostrobin residues in/on cucurbit
vegetables (0.5 ppm), fruiting vegetables (1.4 ppm), peppermint and
spearmint (8.0 ppm), sunflower (0.3 ppm), and grape (2.0 ppm).

The Interregional Research Project No. 4 (IR-4) has submitted field
trial data for the use of pyraclostrobin (WDG) on Belgian endive (MRID
46713801) (PP#5E7014). At each test location, Belgian endive received
two root spray applications of Pristine® Fungicide (EPA Reg. No.
7969-199) at two application rates prior to cold storage and prior to
forcing.  One set of endive was treated at rates of approximately 0.0055
lb pyraclostrobin per 875 lb roots (+ 0.011 lb boscalid per 875 lb
roots) (1X).  (This memo will only discuss the pyraclostrobin
residues.).  An additional set was treated at the 2X rate. Belgian
endive was harvested at 19 to 21 days.  The petitioner has proposed a
tolerance of 11.0  ppm  for pyraclostrobin residues in/on Belgian
endive.  However, HED used the MRL calculator and recommends a tolerance
of  6.0 ppm for the proposed use.  In  PP#5E7014, the petitioner also
submitted data (MRID 46665505) to support a proposed postharvest use of
pyraclostrobin on pome fruit (crop group 11) and stone fruit (crop group
12).   However, IR4 has since informed RD (letter to RD, November 2006)
that they not longer will support the proposed postharvest use on pome
or stone fruit.  

The nomenclature and physicochemical properties of pyraclostrobin are
presented below in Tables 1 and 2.

TABLE A.1.	Pyraclostrobin Nomenclature.

Compound	

Common name	Pyraclostrobin

Company experimental name	BAS 500 F

IUPAC name	methyl
N-{2-[1-(4-chlorophenyl)-1H-pyrazol-3-yloxymethyl]phenyl}(N-methoxy)
carbamate

CAS name	methyl
[2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]phenyl]methoxycarbam
ate

CAS registry number	175013-18-0

End-use products (EP)	2 lb/gal EC (Headline® Fungicide; EPA Reg. No.
7969-186, 23.6 % a.i.)

20% WDG (Cabrio® Fungicide; EPA Reg. No. 7969-187)

12.8% WDG (Pristine® Fungicide; EPA Reg. No. 7969-199) 1

1	This formulation is a MAI which also contains 25.2% of boscalid.

TABLE A.2.	Physicochemical Properties of Technical Grade Pyraclostrobin.

Parameter	Value	References 1

Melting point/range	63.7-65.2 C	D269848 & D274191

pH	Not reported	D269848 & D274191

Density	1.285 g/cm3 at 20 C	D269848 & D274191

Water solubility at 20 C	2.41 mg/L (deionized water)

1.9 mg/L (pH 7)

2.3 mg/L (pH 4)

1.9 mg/L (pH 9)	D269848 & D274191

Solvent solubility	acetone (≤160 mg/L); methanol (11 mg/L); 2-propanol
(3.1 mg/L); ethyl acetate (≤160 mg/L); acetonitrile (≤76 mg/L);
dichloromethane (≤110 mg/L); toluene (≤100 mg/L); n-heptane (0.36
mg/L); 1-octanol (2.4 mg/L); olive oil (2.9 mg/L); DMF (≤62 mg/L).
D269848 & D274191

Vapor pressure	2.6 x 10-10 hPa  at 20 C

6.4 x 10-10 hPa at 25 C	D269848 & D274191

Dissociation constant, pKa	Does not dissociate in water.	D269848 &
D274191

Octanol/water partition coefficient, Log(KOW) at room temperature	3.80
at pH 6.2

λmax = 275 nm	D269848

1	Product Chemistry data were reviewed by the Registration Division
(D269848 and D274191, 5/3/01, 5/15/01, and 6/7/01, S. Malak).

860.1200  Directions for Use

BASF is proposing   SEQ CHAPTER \h \r 1 new uses of pyraclostrobin for
the control of fungal diseases in cotton. The formulations being
proposed for these uses include a 2.09 lb/gal EC (Headline® Fungicide,
EPA Reg. No. 7969-186) for the in-furrow and broadcast foliar
applications to cotton, and a 20% WDG (Cabrio® Fungicide; EPA Reg. No.
7969-187) for the seed treatment.  These formulations are currently
registered to BASF for use on a wide variety of food and feed crops at
seasonal rates of 0.3-3.0 lb ai/A.  The petitioner provided example
labels containing the proposed use directions for cotton, which are
summarized in Table 3.  For comparison of the existing uses with the
required field trials on mustard greens and the supplemental field
trials on Belgian endive, berries, cucurbit vegetables, fruiting
vegetables, grape, mint, and sunflower, the approved use directions for
these crops are also summarized in Table 3.

Table 3.  Summary of Directions for Use of Pyraclostrobin.

Applic. Timing, Type, and Equip. 1	Formulation

[EPA Reg. No.]	Applic. Rate 

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

(lb ai/A)	PHI

(days)	Use Directions and Limitations 2

Belgian endive

Root spray applications during crop development; groundl equipment 	2.09
lb/gal EC

[7969-186]	0.0055 lb/

875 lb roots	2	0.011 lb/ 

875 lb roots	19-21	The minimum RTI 11 days.

Berry Group

Broadcast foliar applications during fruiting; ground or aerial
equipment	20% WDG

[7969-187]

12.8% WDG

[7969-199]	0.18	4	0.72	0	For aerial applications, use a minimum of 5
gal/A

The minimum RTI is 7 days.

Cotton

Seed treatment	20% WDG

[7969-187]	0.01 lb ai/100 lb seed	NA	0.80	NA	Apply in a minimum of 5
gal/A

In-furrow application at planting; ground equipment	2.09 lb/gal EC

[7969-186]	0.20 3	1

30	For aerial applications, use a minimum of 5 gal/A

 The minimum RTI is 7 days.

Broadcast foliar applications during crop development; ground or aerial
equipment

0.20	3

	Cucurbit Vegetables

Broadcast foliar applications from flowering to fruiting; ground or
aerial equipment	20% WDG

[7969-187]	0.20	6	1.20	0	For aerial applications, use a minimum of 5
gal/A The minimum RTI is 7 days.

Fruiting Vegetables

Broadcast foliar applications during crop development and fruiting;
ground or aerial equipment	20% WDG

[7969-187]

12.8% WDG

[7969-199]	0.20	6	1.20	0	For aerial applications, use a minimum of 5
gal/A The minimum RTI is 7 days.

Grape

Broadcast foliar applications during fruit development; ground or aerial
equipment	12.8% WDG

[7969-199]	0.10	6	0.55	14	The minimum RTI is 10 days

Mint

Broadcast foliar applications during crop development; ground or aerial
equipment 	2.09 lb/gal EC

[7969-186]	0.20	4	0.80	14	The minimum RTI is 7 days.

For aerial applications, use a minimum of 5 gal/A

Mustard Greens

Broadcast foliar applications; ground or aerial equipment	20% WDG

[7969-187]

12.8% WDG

[7969-199]	0.20	4	0.8	3	The minimum RTI is 7 days.

For aerial applications, use a minimum of 5 gal/A

Sunflower

Broadcast foliar applications during plant growth; ground or aerial
equipment	2.09 lb/gal EC

[7969-186]

12.8% WDG

[7969-199]	0.20	2	0.40	21	The minimum RTI is 7 days.

For aerial applications, use a minimum of 5 gal/A

1	Ground application may be made through the following types of
irrigation systems:  center pivot, lateral move, end tow, side wheel
roll, traveler, big gun, solid set, or hand move. 

2	Use directions allow for the use of spray adjuvants, and specify a 14
day plant-back interval for rotational crops without registered uses for
pyraclostrobin.

3	The in-furrow application rate for cotton is equivalent to 0.013 lb
ai/ 1,000 ft row.

Conclusions.  The proposed use directions for the in-furrow and foliar
applications to cotton are adequate and reflect the use patterns from
the available cotton field trials.  In addition, the requested seed
treatment use on cotton is approved although no seed treatment trials
were conducted.  Based on the pounds of cottonseed typically used for
planting (13-18 lb seed/acre) and the maximum seed treatment rate (0.01
lb ai/100 lb seed), the seed treatment would be equivalent to
0.001-0.002 lb ai/A, which is negligible compared to the proposed
maximum seasonal use rate of 0.8 lb ai/A.

The proposed use directions for root applications to Belgian endive are
adequate and reflect the use patterns from the available Belgian endive
field trials.  In addition, the submitted field trials on mustard
greens, berries, cucurbit vegetables, grape, mint, and sunflower were
conducted at the maximum seasonal use rates (1x) currently listed on the
registered end-use products, and with the exception of mint, sample were
collected at the minimum PHIs specified on the U.S. labels.  In the mint
field trial, samples were collected at 7 DAT; whereas the use directions
on the U.S. label specifies a 14-day PHI.

Only the fruiting vegetable (tomato and pepper) field trials were
conducted at <1x rates. Although the maximum single application rate
(0.2 lb ai/A) was used for each application to tomato and peppers, only
three applications were made for a total of 0.6 lb ai/A, which is 0.5x
the approved maximum seasonal rate for fruiting vegetables.  However,
sufficient tomato and pepper field trials are already available to
support the existing use on fruiting vegetables.

860.1300 Nature of the Residue - Plants

HED Metabolism Committee Decision Memo; D278044, L. Cheng, 10/9/01

Adequate grape, potato, and wheat metabolism studies are available for
pyraclostrobin (PP#0F6139, D269668, 11/28/01, L. Cheng).  The results of
these studies indicate that the metabolism of pyraclostrobin is similar
in the three crops investigated.  The HED Metabolism Assessment Review
Committee (MARC) discussed the results of these studies on 9/20/01, and
concluded that the nature of the residue in plants is understood.  For
the purpose of tolerance and risk assessment, the terminal residues of
concern in plants consist of pyraclostrobin and its desmethoxy
metabolite (BF 500-3).

860.1300 Nature of the Residue - Livestock

HED Metabolism Committee Decision Memo; D278044, L. Cheng, 10/9/01

Adequate ruminant and poultry metabolism studies are available for
pyraclostrobin (PP#0F6139, D269668, 11/28/01, L. Cheng).  The HED MARC
has determined that for the purpose of tolerance and risk assessment,
the residues of concern in livestock commodities consist of
pyraclostrobin and its metabolites convertible to
1-(4-chlorophenyl)-1H-pyrazol-3-ol (BF 500-5) and
1-(4-chloro-2-hydroxyphenyl)-1H-pyrazol-3-ol (BF 500-8).



 

BAS 500-5	

 

BAS 500-8	

 

860.1340 Residue Analytical Methods

  SEQ CHAPTER \h \r 1 

Plant commodities.  Two adequate methods were proposed for enforcing
tolerance for residues of pyraclostrobin and BF 500-3 in/on plant
commodities: a LC/MS/MS method (BASF Method D9808), and an HPLC/UV
method (BASF Method D9904).  The validated method LOQ for both
pyraclostrobin and BF 500-3 is 0.02 ppm in all tested plant matrices,
for a combined LOQ of 0.04 ppm.  Adequate independent method validation
and radiovalidation data were submitted for both methods (D269668,
11/28/01, L. Cheng), and both methods were forwarded to ACB/BEAD for a
petition method validation (D269850, 11/8/00, L. Cheng).

 

Samples from the current crop field trials and cotton processing study
were analyzed for residues of pyraclostrobin and BF 500-3 using the
LC/MS/MS method (BASF Method D9908, MRID 46710001 (currently under HED
review)).  For all commodities, except cottonseed oil, residues were
extracted with methanol:water:2N HCl (70:25:5) and filtered.  For oil
samples, residues were extracted with hexane, partitioned into
acetonitrile, concentrated, and redissolved in methanol:water:2N HCl
(70:25:5).  Residues from all samples were then cleaned up by
partitioning into cyclohexane.  Residues of pyraclostrobin and BF 500-3
were determined by LC/MS/MS, using external standards.  For each
analyte, the validated method LOQ is 0.02 ppm and the LOD is 0.004-0.005
ppm.

Based on the concurrent method validation data, Method D9908 is adequate
collecting data on residues of pyraclostrobin and BF 500-3 in berries,
cotton commodities, cucurbit vegetables, fruiting vegetables, grape,
mint, mustard greens, and sunflower seed. 

Livestock commodities.  Two methods have also been proposed for
enforcing tolerances for  livestock commodities:  HPLC/UV method 439/0
and Method 446 (consisting of GC/MS method 446/0 and LC/MS/MS method
446/1).  The HPLC/UV method determines residues of pyraclostrobin per
se.  Method 446 has a hydrolysis step, and determines residues of
pyraclostrobin and its metabolites as BF 500-5 and BF 500-8.  The
validated method LOQs for BF 500-5 type residues, in parent equivalents,
are 0.01 ppm for milk and 0.05 ppm for tissues, and the validated LOQs
for BF 500-8 type residues, in parent equivalents, are 0.01 ppm for milk
and 0.05 ppm for tissues.  Independent method validation data for the
HPLC/UV and LC/MS/MS methods are acceptable (D269668, 11/28/01, L.
Cheng).  Radiovalidation data submitted for the GC/MS and LC/MS/MS
methods are adequate for liver and milk, and marginal for muscle. 
Method 446 has been forwarded to ACB/BEAD for petition method
validation.  As poultry tolerances are not currently necessary, an
enforcement method for poultry commodities is not required at the
present time.

860.1360 Multiresidue Methods

Data pertaining to the multiresidue methods testing of pyraclostrobin
and its desmethoxy metabolite were reviewed (PP#0F6139, D269668,
11/28/01, L. Cheng).  Pyraclostrobin was successfully evaluated through
several of the FDA protocols, while recovery of BF 500-3 was
unsuccessful in all protocols.  Pyraclostrobin was completely recovered
through Protocol D (in grape) and E (in grape), and partially recovered
through Protocol F (in peanut).  Metabolite BF 500-3 had poor peak shape
and inadequate sensitivity with Protocol C columns, and therefore, was
not further analyzed under Protocol D, E, and F.  The results of the
multiresidue testing for pyraclostrobin were forwarded to FDA on 1/4/02
for the purpose of updating PAM, Volume I.

860.1380 Storage Stability

Adequate storage stability studies are available indicating that
pyraclostrobin and metabolite BF 500-3 are relatively stable at
≤-10ºC in fortified samples of grape juice (juices), sugar beet tops
(leafy vegetables), sugar beet roots (root crop), tomato (fruit/fruiting
vegetable), and wheat grain (non-oily grain) and wheat straw (dry feed)
for up to 25 months, and in fortified samples of peanut nutmeats
(oilseed) and peanut oil for up to 19 months (D269668, L. Cheng,
11/28/01).  

The storage intervals and conditions for samples from the current crop
field trials and cottonseed processing study are presented in Table 4.  

Table 4.	Summary of Storage Conditions and Intervals of Samples from
Crop Field Trial and Cotton Processing Study.  

Matrix 	MRID	Storage Temperature (C)	Actual Storage Duration (months)
Interval of Demonstrated Storage Stability  (months)

Red raspberry	46637701	<-10	6.0	25

Blueberry

	5.9

	Cucumber	46512002	<-10	7.6	25

Cantaloupe

	4.3

	Squash

	5.9

	Sunflower Seed	46512003	<-10	4.0	19

Tomato	46665501	<-10	4.9	25

Pepper

	4.7

	Mint (tops, leaves, stems)	46665502	<-10	5.9	25

Grape	46665504	<-10	4.4	25

Peach	46665505	<-10	5.7	25

Plum

	6.0

	Cherry

	6.6

	Belgian endive	46713801	< - 10	6.6	18

Mustard greens	46665506	<-10	8.7	25

Undelinted cottonseed	46685901	<-10	6.7	19

Cotton gin byproducts

	6.7	25

Cottonseed hulls	46685902	<-10	5-7	25

Cottonseed meal

	4.8	19

Cottonseed oil

	5.3-6.9	19

Conclusions.  Adequate storage stability data are available to support
the samples storage conditions and intervals from the current field
trials for cotton and Belgian endive, and for the cottonseed processing
study.  The storage stability data on tomato support the berry, fruit
vegetable, grape, and cucurbit vegetable field trials, and the storage
stability data on sugar beet tops support the mustard greens and mint
field trials.  The storage stability data on peanut nutmeats and oil
support the residue data on sunflower seeds and cotton seed and oil, and
the storage stability data on wheat straw support the data on cottonseed
hulls and gin byproducts.

860.1400 Water, Fish, and Irrigated Crops

This guideline requirement is not relevant to the current petition as
there are no aquatic uses being proposed for pyraclostrobin.

860.1460 Food Handling

This guideline requirement is not relevant to the current petition as
there are no food handling uses being proposed for pyraclostrobin.

860.1480 Meat, Milk, Poultry, and Eggs

Adequate feeding studies were reviewed in conjunction with an earlier
pyraclostrobin petition (D269668, 11/28/01, L. Cheng).  In the ruminant
feeding study, dairy cows were dosed orally for 28 days with
pyraclostrobin at levels equivalent to 8.8, 27.2, and 89.6 ppm in their
diet, and in the poultry feeding study, laying hens were dosed orally
for 30 days with pyraclostrobin at levels equivalent to 0.28, 0.88, and
3.01 ppm in their diet. 

The current tolerances for livestock commodities were established based
on results from the available feeding studies and the Agency’s
estimated dietary burdens for pyraclostrobin residues, which were
previously calculated to be 36.3 ppm for beef cattle, 35.4 ppm for dairy
cattle, and 0.35 ppm for poultry (D269668, 11/28/01, L. Cheng). 

 

The new livestock feedstuffs included in the current petition are
cottonseed, hulls, meal and gin byproducts.  The potential dietary
exposure of livestock to pyraclostrobin residues has been recalculated
below in Table 5 using recent Agency guidance on calculating dietary
exposure from “reasonably balanced” livestock diets to include all
feedstuffs with existing tolerances and those proposed.  Based on these
recalculated dietary exposure levels and the residue data from the
ruminant feeding study, the existing tolerances are adequate for milk,
meat, fat, meat byproducts (except liver), and liver of cattle, goats,
horses, and sheep.  In fact, the current tolerances of 1.5 ppm for liver
of cattle, goats, horses, and sheep could be reasonably lowered to 1.0
ppm.  

In addition, the existing tolerances for hog commodities can be deleted
as quantifiable residues are unlikely to occur in hog [40 CFR
§180.6(a)(2)] as residues of pyraclostrobin and its metabolites were
<LOQ in meat, fat, kidney and liver of cattle dosed at 8.8 ppm, which is
46x the calculated dietary burden for swine.  As noted in earlier
pyraclostrobin petitions (D269668, 11/28/01, L. Cheng), the data from
the poultry feeding and metabolism studies indicates that tolerances for
residues in poultry commodities are not required at the present time.



Table 5. Livestock dietary burdens for pyraclostrobina.

	%  Diet b	Residue (ppm)

Feedstuff	Type	Tolerance, ppm	% Dry Matter	Beef	Dairy	Poultry	Swine	Beef
	Dairy 	Poultry 	Swine 

barley hay	R	25	88	10	25	-	-	2.8	7.1	-	-

cotton gin byproducts	R	30.	90	5	-	-	-	1.7	-	-	-

legume, hay (cowpea)	R	25	86	-	15	-	-	-	4.4	-	-

barley, grain	CC	0.4	88	50	45	20	20	0.23	0.20	0.08	0.08

corn, field, grain	CC	0.1	88	20	-	60	65	0.023	-	0.06	0.065

	

cotton, undekinted seed	PC	0.3	85

15

0.053

sunflower (meal)	PC	0.3	92	15

20	15	0.049

0.06	0.045

Totals

100	100	100	100	4.8	11.8	0.20	0.19

a    All data are based on Table 1 Feedstuffs (October 2006), a revision
of feedstuffs data found in Table 1 (180.1000 OPPTS Test Guidelines). 
Residue levels for beef and dairy are corrected for moisture content and
are determined by formula: tolerance / %DM  x  % in diet.  Residue
levels for poultry and swine are considered “as-is” and are
determined by formula: tolerance  x   % in diet.  R: roughage; CC:
carbohydrate concentrate;  PC:  protein concentrate.

b   Typical compositions of daily rations for the animals of choice for
Table 1 data  follow: 

Feedlot beef  have a daily ration of 15-40 %  R, 45-80 %  CC, and 5-15 %
 PC.  As the slaughter time (last 3 months) gets closer, then the beef
cattle are fed higher amounts of CC (up to 80 %), and lower amounts of 
R (15-20 %) and PC (5-10 %).  The average life span for feedlot beef is
16-18 months   Most of feedlot beef are slaughtered in 4 major centers
located in the Midwest and the processed meat is “boxed” and shipped
to distributors for sale to local grocers.  Commercial ground beef
(75-93 % lean) is produced from the combination of feedlot beef (60-70 %
lean) and other lean meat sources, i.e., beef cows and bulls from
cow-calf operations, imported lean meat trimmings, and non-lactating
dairy cows. 

High volume milk-producing lactating dairy cows have a daily ration of
45 % R, 40-45 % CC, and 10-15 % PC.  Dairy cows usually produce 2-3
calves before slaughter. The average life span of the lactating dairy
cow is 3-4 years.  Upon slaughter, much of the meat is used in ground
beef and processed foods e.g., deli meats, soups, frozen
dinners/entrees.

A laying hen that will give a steady egg production is fed 75-80 % CC
and 20-25 % PC.   The life span can be up to 18 months.  In general,
laying hens are not processed and marketed as whole or cut-up chickens.
Much of the layer meat is used in processed food products, e.g., deli
meats, soups, canned chicken, etc.  (Note:  The laying hen is the animal
of choice.  Frying and rotisserie chickens come from the broiler, a fast
food chicken, weighing 3.5-4.0 lb.), and an animal that is raised in a
very short time.  The average life span is 38-42 days.  The broiler diet
contains 85-90 % CC and 10-15 % PC.    

A marketable hog diet that will give steady growth would have 80-85 % CC
and 15-20 % PC.  Most of the US hog production is confined to “mega”
operations.  Animals are born in in-house nurseries, and simply moved to
connecting buildings as the animal grows until slaughter (250 lb
finished animal in 6 months). These animals provide meat for the
“fresh pork” market.

Note:  These guidelines are not to be used for pesticide residues that
bioaccumulate.  Contact Health Effects Division, OPP, EPA for these
types of pesticides.

860.1500 Crop Field Trials

46512002.der (Cucurbit vegetables)	46512003.der (Sunflower)	46637701.der
(Berries) 46665501.der (Fruiting vegetables)	46665502.der (Mint)
46665504.der Grape)

46665506.der (Mustard greens)	46685901.der (Cotton)

BASF submitted cotton field trials supporting a new use for
pyraclostrobin (EC) on cotton, along with previously requested field
trials on mustard greens supporting the existing use on Brassica leafy
greens.  In addition, BASF submitted supplemental field trials from the
U.S. and Canada on berries, cucurbit vegetables, fruiting vegetables,
grape, mint and sunflower.  These field trials were conducted to support
uses on these crops in Canada.    SEQ CHAPTER \h \r 1 The results from
these studies are summarized in Table 6 and discussed below, along with
the previously reviewed data on the above crops.

Table 6.	Summary of Residue Data from Crop Field Trials with
Pyraclostrobin.

Crop/commodity	Total Applic. Rate  (lb ai/A)	PHI (days)	Combined
Pyraclostrobin Residues (ppm) 1

	n	Min.	Max.	HAFT 2	Median	Mean	Std. Dev.

Berries (0.72 lb ai/A total application rate, 0-day PHI)

Red raspberries	0.73-0.75	0	6	0.76	1.33	1.28	1.01	1.04	0.22

Blueberries	0.73-0.75	0	12	1.11	2.52	2.33	1.55	1.73	0.50

Overall Berries	0.73-0.75	0	18	0.76	2.52	2.33	1.32	1.50	0.54

Cotton (0.80 lb ai/A total application rate, 30-day PHI)

Undelinted, seed	0.80-0.85	29-33	24	<0.04	0.17	0.15	0.03	0.05	0.04

Gin byproducts 3	picker	0.80-0.85	29-30	6	2.04	25.06	20.35	3.38	8.60
9.60

	stripper

30-32	6	1.05	2.00	1.91	1.74	1.59	0.42

Cucurbit Vegetables (1.2 lb ai/A total application rate, 0-day PHI)

Cucumber	1.17-1.20	0	8	0.053	0.186	0.180	0.102	0.106	0.057

Cantaloupe	1.18-1.20	0	4	0.099	0.379	0.338	0.202	0.218	0.143

Squash	1.16-1.20	0	8	0.094	0.213	0.190	0.126	0.131	0.037

Cucurbits	1.16-1.20	0	20	0.053	0.379	0.338	0.118	0.139	0.082

Fruiting Vegetables (1.2 lb ai/A total application rate, 0-day PHI)

Tomato	0.54-0.58	0	14	0.096	0.366	0.304	0.178	0.192	0.086

Pepper	0.55-0.61	0	6	0.092	0.701	0.689	0.344	0.375	0.268

Fruiting Vegetables	0.54-0.61	0	20	0.092	0.701	0.689	0.207	0.247	0.177

Grape (0.55 lb ai/A total application rate, 14-day PHI)

Grape	0.56-0.57	13-14	8	0.56	1.93	1.86	1.28	1.30	0.48

Mustard Greens (0.80 lb ai/A total application rate, 3-day PHI)

Mustard greens	0.8	0	10	5.5	14.4	12.6	8.3	8.9	2.5

3	6	1.4	5.5	5.1	3.7	3.4	1.7

7	6	1.0	2.3	2.2	1.9	1.7	0.6

14-15	6	0.18	1.2	1.0	0.31	0.5	0.4

Sunflower (0.40 lb ai/A total application rate, 21-day PHI)

Seed	0.40	21	2	<0.04	<0.04	<0.04	0.02	0.02	NA

Mint (0.80 lb ai/A total application rate, 14-day PHI)

Mint tops	0.91-0.92	7	4	2.25	3.65	3.55	2.96	2.96	0.69

1	Residues of pyraclostrobin and BF 500-3 are expressed in parent
equivalents, and the LOQ is 0.02 ppm for each analyte or 0.04 ppm for
the combined residues.  For purposes of calculating median and mean and
standard deviation, ½ LOQ (0.01 ppm) was used for residue values of
each analyte that were <LOQ. 

2	HAFT = Highest Average Field Trial.

3	Samples of gin byproducts were obtained from trials harvested using
mechanical picker (3 tests) and strippers (3 tests).

4	A sixth application was inadvertently applied to cherries.

Brassica Leafy Green, Subgroup 5B

Mustard Greens.  The Agency previously reviewed residue data from five
mustard green field trials conducted in Zones 2, 4, 5, 6 and 10 during
2001 (PP#3F6581, D281042, L. Cheng, 7/26/04).  In each trial,
pyraclostrobin (20% WDG) was applied to mustard greens as four broadcast
foliar applications at 0.2 lb ai/A, at RTIs of with a 6 to 8 days, for a
total of 0.8 lb ai/A/season (1x rate).  Applications were made using
ground equipment at 12-31 gal/A, and included the use of a spray
adjuvant.  Samples of mustard greens were harvested 0, 3, 7, 10, and 14
DAT; the label specified PHI is 3 days.  Samples were analyzed using an
adequate LC/MS/MS method (BASF Method Number D9908), and the sample
storage conditions and intervals (6.6 months) were supported by the
available storage stability data.  

In these five field trials, the combined pyraclostrobin residues were
1.13-13.40 ppm in/on 10 samples of mustard greens harvested at the
labeled 3-day PHI.  The HAFT residues were 12.95 ppm and average
residues were 7.13 ppm.  Based on these data, the Agency established a
16 ppm tolerance for pyraclostrobin residues in/on Brassica leafy
greens.  However, the Agency also requested data from three additional
field trials in Zones 2, 3, and 10.

In response to this request, BASF submitted field trial data from six
mustard green field trials conducted in Zones 2, 3 and 10 during 2004
and 2005.  In each test, pyraclostrobin (20% or 12.8% WDG) was applied
to mustard greens as four broadcast foliar applications at 0.2 lb ai/A
during vegetative crop development, for a total rate of 0.8 lb ai/A (1x
rate).  Applications were made RTIs of 6-8 days using ground equipment
at 13-32 gal/A, and each application included the use of a non-ionic
surfactant at 0.25% of the spray volume.  For the 2004 tests, single
control and duplicate treated samples of mustard greens were harvested
at 0 days after the last application (0 DAT).  For the 2005 tests,
single control and duplicate treated samples of mustard greens were
harvested at 0, 3, 7, and 14-15 DAT, with the exception of the CA test
in which 0-DAT samples were not collected.   Samples were stored frozen
for up to 8.7 months prior to analysis, an interval supported by
available storage stability data.  Samples were analyzed for residues of
pyraclostrobin and BF 500-3 using an adequate LC/MS/MS method (BASF
Method D9908), which has a LOQ of 0.02 ppm for each analyte.  

In these tests, combined pyraclostrobin residues in/on mustard greens
were 5.5-14.4 ppm at 0 DAT and declined steadily to 0.18-1.20 ppm at
14-15 DAT.  At the label-specified preharvest interval of 3 days,
combined residues were 1.4-5.5 ppm.  Average combined residues were 8.9
ppm at 0 DAT, 3.4 ppm at 3 DAT, 1.7 ppm at 7 DAT, and 0.5 ppm at ~14
DAT.

Belgian Endive

Adequate field trial data are available supporting the use of
pyraclostrobin on Belgian endive.  Filed trials were conducted in
California.  The trials represent NAFTA growing region 10.  The number
of trials and geographic representation are adequate for Belgian endive.
 Two root spray applications of BAS 510 and BAS 500 F were made at two
application rates prior to cold storage and prior to forcing.  One set
of endive was treated at rates of approximately 0.0055 lb pyraclostrobin
per 875 lb roots (+ 0.011 lb boscalid per 875 lb roots).  Another set
was also treated at rates 2X rates of approximately 0.011 lb
pyraclostrobin per 875 lb roots (+0.022 lb boscalid per 875 lb roots). 
Only the pyraclostrobin residues are discussed in this memo.

The maximum storage interval for treated samples in this study was 198
days (see Table C.2). The storage stability for pyraclostrobin in/on
Belgian endive was not determined in this study.  However, in a
previously submitted storage stability study pyraclostrobin residues
were shown to be stable for 18 months.  Pyraclostrobin residues in/on
Belgian endive treated at the 1X rate ranged from 0.05 to 2.90 ppm (1.55
± 1.24).  Also, pyraclostrobin residues ranged from 1.48 to 7.96 ppm in
samples treated at the 2X rate.   Based on the field trial data, HED
recommends a pyraclostrobin tolerance in/on Belgian endive of 6.0 ppm.

Fruiting Vegetables, Group 8

Tomato and Peppers.  Adequate field trial data are available supporting
the use of pyraclostrobin (EC or WDG) on fruiting vegetables in the U.S.
(PP#0F6139, D269668, 11/28/01, L. Cheng).  In a total of 24 field trials
conduct in the U.S. during 1998 and 1999, pyraclostrobin (20% WDG or 2
lb/gal EC) was applied to Bell peppers (6 tests), non-Bell peppers (3
tests), and tomato (15 tests) as six broad foliar applications at
0.19-0.22 lb ai/A during fruit development at RTIs of 6-9 days, for a
total of 1.19-1.24 lb ai/A (1x rate).  Applications were made using
ground equipment in 14-41 gal/A, and included the use of a spray
adjuvant.  Single control and duplicate treated samples of peppers or
tomato were harvested from each test immediately following the last
application (0 DAT).  Samples were stored frozen for up to 6 months
prior to analysis for residues of parent and BF 500-3 using BASF Method
D9808.    SEQ CHAPTER \h \r 1 Combined residues were   SEQ CHAPTER \h \r
1 <0.04-<0.30 ppm in/on Bell peppers, <0.14-0.99 ppm in/on non-Bell
(chili) peppers, and <0.08-<0.25 ppm in/on tomato.  Based on these
studies, the Agency established a 1.4 ppm tolerance on the fruiting
vegetables crop group.

BASF has subsequently submitted additional field trials supporting the
use of pyraclostrobin on fruiting vegetables in Canada.  In a total of
ten field trials conducted in the U.S. and Canada during 2004,
pyraclostrobin (12.8% WDG) was applied to tomato (7 tests), Bell peppers
(2 tests) and non-Bell peppers (1 test) as three broadcast foliar
applications at 0.17-0.23 lb ai/A (0.19-0.26 kg ai/ha) during fruit
development at RTIs of 6-8 days, for totals of 0.54-0.61 lb ai/A/season
(0.5x the maximum U.S. rate; 0.61-0.68 kg ai/ha).  All applications were
made using ground equipment at 23-36 gal/A (214-341 L/ha), and included
the use of a non-ionic surfactant at 0.25% of the spray volume.  Single
control and duplicate treated samples of mature tomato or peppers were
harvested from each test at 0 DAT.  Samples were stored frozen for up to
4.9 months prior to analysis for residues of parent and BF 500-3 using
BASF Method D9808.  The method LOQ and LOD is 0.02 and 0.04 ppm for each
analyte in fruiting vegetables.

 

In the 2004 tests conducted at a 0.5x rate, combined residues were
0.096-0.366 ppm in/on tomato and 0.092-0.701 ppm in/on peppers.  Average
residues were 0.192 and 0.375 ppm for tomato and peppers, respectively,
and HAFT residues were 0.304 and 0.689 ppm.  Residues in the 2004 tests
were similar to the earlier studies and did not exceed the existing U.S.
tolerance of 1.4 ppm.

Cucurbit Vegetables, Group 9

Cucumber, Squash and Melon.   Adequate field trial data are available
supporting the use of pyraclostrobin (EC or WDG) on cucurbit vegetables
in the U.S. (PP#0F6139, D269668, 11/28/01, L. Cheng).  In a total of 19
field trials conduct in the U.S. during 1998, pyraclostrobin (2 lb/gal
EC) was applied to cucumber (8 tests), summer squash (5 tests), and
muskmelon (6 tests) as six broad foliar applications at 0.19-0.21 lb
ai/A during flowering and fruit development at RTIs of 6-10 days, for a
total of 1.19-1.23 lb ai/A (1x rate).  Applications were made using
ground equipment in 12-30 gal/A, and included the use of a spray
adjuvant.  Single control and duplicate treated samples of cucumber,
squash or melon were harvested from each test immediately following the
last application (0 DAT).  Samples were stored frozen for up to 10.5
months and then analyzed for residues of parent and BF 500-3 using BASF
Method D9808.    SEQ CHAPTER \h \r 1 Combined residues were <0.08-0.16
ppm in/on cantaloupe, <0.04-<0.43 ppm in/on cucumber, and <0.07-<0.22
ppm in/on summer squash.  Based on these studies, the Agency established
a 0.5 ppm tolerance on the cucurbit vegetables crop group.

 

BASF has subsequently submitted additional field trials supporting the
use of pyraclostrobin on cucurbit vegetables in Canada.  In a total of
ten field trials conducted in the U.S. and Canada during 2004,
pyraclostrobin (20% WDG) was applied to cucumber (4 tests), muskmelon (2
tests) and summer squash (4 tests) as six broadcast foliar applications
at 0.19-0.21 lb ai/A from vegetative development through fruiting at
RTIs of 6-8 days, for totals of 1.16-1.20 lb ai/A (1x rate; 1.31-1.35 kg
ai/ha).  All applications were made using ground equipment at 25-32
gal/A, and included the use of a non-silicone based adjuvant at 0.25% of
the spray volume.  Single control and duplicate treated samples of
mature cucurbit vegetables were harvested from each test on the same day
as the final application (0 DAT).  Samples were stored frozen for up to
7.5 months prior to analysis for residues of parent and BF 500-3 using
BASF Method D9808.  The method LOQ and LOD is 0.02 and 0.04 ppm for each
analyte in cucurbits.

 

In these tests, combined pyraclostrobin residues were <0.053-<0.186 ppm
in/on 8 samples of cucumber, <0.099-0.379 ppm in/on 4 samples of
muskmelon, and <0.094-<0.213 ppm in/on 8 samples of summer squash. 
Average combined residues were 0.106 ppm for cucumber, 0.218 ppm for
muskmelon, and 0.131 ppm for summer squash.  Residues in the 2004 tests
were similar to the earlier studies and did not exceed the existing U.S.
tolerance of 0.5 ppm.

Berries, Group 13

Blueberries and Raspberries.  Adequate field trial data are available
supporting the use of pyraclostrobin (WDG) on the berries crop group in
the U.S. (PP#0F6139, D269668, 11/28/01, L. Cheng).  In a total of nine
field trials conduct in the U.S. during 1999, pyraclostrobin (20% WDG)
was applied to red raspberries (3 tests) and blueberries (6 tests) as
four broad foliar applications during fruit development at 0.18-0.19 lb
ai/A at RTIs of 6-7 days, for a total of 0.72-0.74 lb ai/A (1x rate).
Applications were made using ground equipment in 50-102 gal/A, and
included the use of a non-silicone spray adjuvant.  Single control and
duplicate treated samples of blueberries and raspberries were harvested
from each test immediately following the last application (0 DAT). 
Samples were stored frozen for up to 3 months and then analyzed for
residues of parent and BF 500-3 using BASF Method D9808.  C  SEQ CHAPTER
\h \r 1 ombined pyraclostrobin residues were <0.12-0.69 ppm in/on
highbush blueberries and <0.46-0.97 ppm in/on red raspberries.  Based on
these residues, the Agency established a 1.3 ppm tolerance on the
berries crop group.

To support the use of pyraclostrobin on berries grown in Canada, BASF
recently submitted additional data from three raspberry field trials
conducted in Zones 5, 5B, and 12, and six blueberry field trials were
conducted in Zones 1A and 5 during 2004.  At each test location,
pyraclostrobin (12.8% WDG) was applied as four broadcast foliar
applications at 0.17-0.19 lb ai/A during fruit development at RTIs of
6-8 days, for totals of 0.73-0.75 lb ai/A (1x rate, 0.82-0.84 kg ai/ha).
 Applications were made using ground equipment at 29-85 gal/A (267-798
L/ha), and included the use of a non-ionic surfactant at 0.25% of the
spray volume.  Single control and duplicate treated samples of mature
berries were harvested from each test at 0 DAT.  Samples were stored
frozen for up to 6 months prior to analysis, and analyzed using BASF
Method D9908, which was adequately validated in conjunction with the
field trial analyses.  The method LOQ and LOD is 0.02 and 0.004 ppm for
each analyte in berries.

In the 2004 field trials, combined pyraclostrobin residues were
0.76-1.33 ppm in/on six samples of red raspberries and 1.11-2.52 ppm
in/on 12 samples of blueberries.  Combined residues averaged 1.04 and
1.73 ppm for raspberries and blueberries, respectively, and HAFT
residues were 1.28 and 2.33 ppm.  For all nine berry tests, combined
residues averaged 1.50 ppm.  As residue in these field trials exceeded
the current U.S. tolerance for the berries crop group, BASF has proposed
increasing the tolerance for berries to 4.0 ppm.

Grape.  Adequate grape field trial data are available supporting the use
of pyraclostrobin (WDG or EC) on grape in the U.S. (PP#0F6139, D269668,
11/28/01, L. Cheng).  In 13 field trials conducted in CA(8), NY(2),
OR(2) and WA (1) during 1997 and 1998, pyraclostrobin (EC) was applied
to grape as six broadcast foliar applications during fruit development
at 0.15-0.16 lb ai/A/application at RTIs of 6-15 days, for a total of
0.90-0.91 lb ai/A (1.6x rate).  Applications were made using ground
equipment as either concentrate (45-53 gal/A) or dilute (235-294 gal/A)
sprays, and included the use of a spray adjuvant.  Single control and
treated samples of grape were collected from each test at 14 DAT. 
Samples were stored frozen for up to 15.5 months and analyzed using BASF
Method D9808.  Combined pyraclostrobin residues in/on grape from the
1997/98 field trials were 0.23-1.92 ppm in/on grape.  

Adequate data are also available from 12 grape field trials conducted in
CA(8), NY(2), and WA(2) during 1999.  In these trials, pyraclostrobin
(20% WDG) was applied to grape as three broadcast foliar applications
during fruit development at 0.18-0.19 lb ai/A/application at RTIs of
13-14 days, for at total of 0.53-0.55 lb ai/A (1x seasonal rate). 
Applications were made using ground equipment at 50-79 or 100-159 gal/A,
and included the addition of a non-silicone spray adjuvant.   Single
control and duplicate treated samples of grape were collected from each
test at 14 DAT.  Samples were stored frozen for up to 10 months, and
analyzed using BASF Method D9808.  Combined pyraclostrobin residues
in/on grape from the 1999 field trials were 0.10-1.31 ppm in/on grape.  

In the recent four field trials conducted in the U.S. and Canada during
2004, pyraclostrobin (12.8% WDG) was applied to grape as three broadcast
foliar applications at 0.19 lb ai/A/application during berry development
at RTIs of 13-14 days, for totals of 0.56-0.57 lb ai/A (1x rate,
0.63-0.64 kg ai/ha).  All applications were made using ground equipment
at 83-153 gal/A (776-1430 L/ha), and included the use of a non-ionic
surfactant at 0.25% of the spray volume.  Single control and duplicate
treated samples of mature grape were harvested 13 or 14 DAT.  Samples
were stored at <-10ºC for up to 4.4 months prior to analysis, and
analyzed for residue of pyraclostrobin and BF 500-3 using a LC/MS/MS
method (BASF Method D9908), which was adequately validated in
conjunction with the field trial analyses.  The method LOQ and LOD for
each analyte is 0.02 and 0.004 ppm, respectively.

Following three foliar applications at a 1x rate, residues in/on grape
harvested at 13-14 DAT were 0.52-1.70 ppm for pyraclostrobin and
0.04-0.23 ppm for BF 500-3, for combined residues of 0.56-1.93 ppm.  The
highest average field trial (HAFT) combined residues were 1.86 ppm, and
average combined residues were 1.30 ppm.  Residues in/on grape from in
the 2004 field trials were similar to the earlier studies and did not
exceed the existing U.S. tolerance of 2.0 ppm.

Miscellaneous Commodities

Cotton.  In twelve trials conducted in Zones 2, 4, 6, 8 and 10 during
2004, pyraclostrobin (20% WDG) was applied to cotton four times; first
as an in-furrow application at planting at 0.20-0.21 lb ai/A, followed
by three broadcast foliar applications during boll development at
0.20-0.24 lb ai/A at RTIs of 5-9 days, for a total of 0.80-0.85 lb
ai/A/season (1x proposed rate).  All applications were made using ground
equipment at 5-10 gal/A for the in-furrow application and at 11-39 gal/A
for the foliar applications.  Foliar applications included the use of a
non-silicone surfactant at 0.25% of the spray volume.  Single control
and duplicate treated cotton samples were harvested by hand (1 site), or
by mechanical picker (7 sites) or stripper (4 sites) at 29-33 DAT. 
Samples of undelinted seeds were collected from all sites, and cotton
gin byproducts (gin trash) were collected from six sites (3 stripper and
3 picker).  All samples were stored at <-10 ºC for up to 6.6 months
prior to analysis, an interval which is supported by the available
storage stability data.

Samples of cottonseed and gin byproducts were analyzed for residue of
pyraclostrobin and BF 500-3 using a LC/MS/MS method (BASF Method D9908),
which was adequately validated in conjunction with the field trial
analyses.  The method LOQ and LOD for each analyte is 0.02 and 0.005
ppm, respectively.

At maturity (29-33 DAT), residues in/on 24 treated samples of undelinted
cotton seed were <0.02-0.14 ppm for pyraclostrobin and <0.02-0.028 ppm
for BF 500-3, for combined residues of <0.04-0.17 ppm.  Average combined
residues were 0.05 ppm in/on undelinted seeds, and HAFT residues were
0.15 ppm.  Residues in/on gin trash were generally higher for cotton
harvested using a picker than for cotton harvested using a stripper. 
Following harvest with a picker, combined residues in/on six samples of
gin trash were 2.04-25.06 ppm and averaged 8.60 ppm.  Following harvest
with a stripper, combined residues in/on six samples of gin trash were
1.05-2.00 ppm and averaged 1.59 ppm.

No field trials were submitted to support the proposed seed treatment
use for pyraclostrobin (20% WDG) on cotton at 0.01 lb ai/100 lb seed. 
However, no seed treatment trials are required as the amount of
pyraclostrobin applied as a seed treatment is negligible compared to the
in-furrow and foliar applications.  Based on the pounds of cottonseed
typically used for planting (13-18 lb seed/acre), the maximum seed
treatment rate would be equivalent to 0.001-0.002 lb ai/A, compared to
seasonal rate (0.8 lb ai/A) for the combined in-furrow and foliar
applications.

Mint.  Adequate field trial data are available supporting the use of
pyraclostrobin (WDG or EC) on mint grown in the U.S. (D281042, 7/26/04,
L. Cheng).  In 5 field trials conducted in Zones 5 and 11 in the U.S.
during 2001, pyraclostrobin (20% WDG) was applied to mint as four
broadcast foliar applications during crop development at 0.2 lb ai/A at
RTIs of 6-8 days, for at total of 0.8 lb ai/A (1x rate).   Single
control and duplicate treated samples of mint (leaves and stems) were
collected from each test at 7 and 14-15 DAT.  Samples were stored frozen
for up to 4 months and were analyzed for residues of pyraclostrobin and
BF 500-3 using BASF Method Number D9908.  Combined residues were
2.51-11.78 ppm at 7 DAT and 1.82-7.40 ppm at ~14 DAT.  Based on the
residue data for the specified 14-day PHI, the Agency established 8 ppm
tolerances for peppermint and spearmint.

 

To support the use of pyraclostrobin on mint grown in Canada, BASF
submitted additional data from two mint field trials conducted in Canada
(Zone 7) during 2004.  In these tests, pyraclostrobin (12.8% WDG) was
applied to mint as four broadcast foliar applications at 0.22-0.23 lb
ai/A during crop development at RTIs of 7 days, for totals of 0.91-0.92
lb ai/A (~1.2x rate, 1.02-1.03 kg ai/ha).  All applications were made
using ground equipment at 31-34 gal/A (290-318 L/ha), and included the
use of a non-ionic surfactant at 0.25% of the spray volume.  Single
control and duplicate treated samples of mint tops were harvested from
each test at 7 DAT.  The labeled PHI for mint in the U.S. is 14 days. 
Samples were stored frozen for up to 5.9 months prior to analysis and
analyzed for residue of pyraclostrobin and BF 500-3 using BASF Method
D9908, which was adequately validated in conjunction with the field
trial analyses.  The method LOQ and LOD for each analyte is 0.02 and
0.004 ppm, respectively.

Following four foliar applications totaling 0.91-0.92 lb ai/A (1.2x
rate), Combined pyraclostrobin residues were 2.48-3.65 ppm at 7 DAT. 
Combined residues averaged 2.96 ppm, and HAFT residues were 3.55 ppm.  
Although samples from the Canadian tests were collected at a shorter PHI
(7 days) than specified on the U.S. label (14 days), residues from the
Canadian tests were still below the current U.S. tolerance of 8 ppm.

Sunflower.  Adequate field trial data are available supporting the use
of pyraclostrobin (WDG or EC) on sunflower grown in the U.S. (D281042,
7/26/04, L. Cheng).  In 7 field trials conducted in Zones 5, 7, 8, and
14 during 2001, pyraclostrobin (20% WDG) was applied to sunflower as two
broadcast foliar applications during seed development at 0.2 lb ai/A at
RTIs of 6-8 days, for at total of 0.4 lb ai/A (1x rate).  Single control
and duplicate treated samples of mature sunflower seeds were collected
from each test at 20-21 DAT.  Samples were stored frozen for up to 2
months and were analyzed for residues of pyraclostrobin and BF 500-3
using BASF Method Number D9908.  Combined residues were <0.04-0.25 ppm
in/on sunflower seeds at ~21 DAT.  Based on these residue data, the
Agency established a 0.3 ppm tolerance for sunflower.

In the supplemental sunflower field trial conducted in Zone 5 during
2004, pyraclostrobin (12.8% WDG) was applied as two broadcast foliar
applications to sunflower at 0.2 lb ai/A during seed development at a
RTI of 6 days, for a total of 0.4 lb ai/A (0.45 kg ai/ha).  Applications
were made using ground equipment at 24-25 gal/A, and included the use of
a non-ionic surfactant at 0.25% of the spray volume.  Single control and
duplicate treated samples of seed were harvested at 21 DAT.  Samples
were stored frozen for up to 4 months and analyzed for residues of
pyraclostrobin and BF 500-3 using BASF Method D9908, which was validated
in conjunction with the field trial analyses.  The method LOQ and LOD
for each analyte is 0.02 and 0.004 ppm, respectively.  In this field
trial, combined residues were <0.04 ppm in/on the two samples of seed
harvested at 21 DAT.  Residues did not exceed the established 0.3 ppm
tolerance for sunflower.

Conclusions.  The required field trials on cotton and mustard greens and
the supplemental field trials on Belgian endive, berries, cucurbit
vegetables, grape, sunflower, and mint are adequate and support the
proposed or existing uses of pyraclostrobin on these crops.  Together
with the previously submitted field trials, the number and geographic
distribution of the field trials on these crops are adequate, and the
appropriate samples were collected at the proposed PHIs.  

Although the cotton field trials were conducted using the 20% WDG
formulation and the proposed use on cotton is for the 2/lb/gal EC
formulation, the cotton field trial data for the WDG will support the
use of the EC formulation, as previously submitted side-by-side field
trials using tomato, cucumber and grape have shown that residues
resulting from the two types of formulations are similar.

The submitted supplemental field trials on fruiting vegetables (tomato
and peppers) were also adequate, but are not useful for assessing the
current U.S. tolerance as the field trials were conducted at 0.5x the
maximum seasonal use rate on existing U.S. labels.  However, sufficient
tomato and pepper field trials are already available to support the
existing use on fruiting vegetables.  

860.1520 Processed Food and Feed

46685902.der (cotton)

Adequate processing studies on grape, mint, plum, tomato and sunflower
have been previously reviewed (D269668, 11/28/01, L. Cheng; and D281042,
7/26/04, L. Cheng) under other petitions.  The available mint and
sunflower processing studies indicate that pyraclostrobin residues do
not concentrate in mint oil (0.01x) or sunflower meal and oil (0.03x). 
In the grape processing study, combined residues did not concentrate in
juice (0.01x), but concentrated by 3.4x in raisins.  Based on HAFT
residues of 1.92 ppm for grape, the maximum expected residues in raisins
were determined to be 6.53 ppm.  Therefore, the Agency established a
separate 7.0 ppm tolerance for grape, raisins.

In the tomato processing study, residues did not concentrate in puree
(0.6x), but concentrated by 2.1x in tomato paste.  However, a separate
tolerance for tomato paste is not required as the maximum expected
residues in paste (0.638 ppm) are below the 1.4 ppm tolerance for
fruiting vegetables.

Cotton.  For the new cotton processing study, pyraclostrobin (20% WDG)
was applied to cotton in a single trial as a combination of an in-furrow
application at 1.0 lb ai/A followed by three broadcast foliar
applications during boll development at 1.0 lb ai/A/application, for a
total of 4.0 lb ai/A/season (5x maximum proposed rate).  Single control
and duplicate treated samples of raw cotton were harvested using a
mechanical picker at 30 DAT.  The cotton samples were ginned to yield
undelinted cottonseeds (RAC), which were then processed using simulated
commercial procedures into hull, meal, and crude and refined oil.  Prior
to analysis, samples of cottonseed and each processed commodity were
stored frozen for up to 7 months, an interval supported by the available
storage stability data.  Cotton seed commodities were analyzed for
residues of parent and BF 500-3 using a LC/MS/MS method (BASF Method
D9908), which was validated in conjunction with the analysis of treated
samples.  The method LOQ and LOD is 0.02 and 0.005 ppm for each analyte.

 

Following applications at a 5x rate, combined pyraclostrobin residues
in/on undelinted cottonseed at 30 DAT were 0.106 and 0.176 ppm and
averaged 0.14 ppm.  Combined residues were <0.04 ppm in/on all cotton
processed commodities, for processing factors of <0.3x for each
commodity.  The maximum theoretical processing factor for undelinted
cottonseed is 6.3x (oil).

Conclusions.  Adequate processing studies have been previously reviewed
for grape, mint, plum, tomato and sunflower.  These studies in indicate
that pyraclostrobin residues do not concentrate in grape juice, tomato
puree, mint oil, and sunflower meal and oil.  Residues can concentrate
in tomato paste (2.1x) and prunes (1.3x), but separate tolerances were
not required as the maximum expected residues in these commodities are
below the tolerances for the respective RACs.  Residues have also been
shown to concentrate in raisins (3.4x), and a separate tolerance of 7.0
ppm has been established to cover the maximum expected residues in
raisins.  The new cotton processing study is also adequate and indicates
that residues do not concentrate in cottonseed hulls, meal or oil.

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

Analytical reference standards for pyraclostrobin and BF 500-3 are
available at the EPA National Pesticide Standards Repository.

860.1850 Confined Accumulation in Rotational Crops

An adequate confined rotational crop study is available on
pyraclostrobin (PP#0F6139, D269668, L. Cheng, 11/28/01; D314519, L.
Cheng, 05/05/05).  The confined study indicates that the metabolism of
pyraclostrobin in rotated crops is similar but more extensive than that
in primary crops.  Pyraclostrobin undergoes demethoxylation to yield BF
500-3, followed by further degradation to medium polar and polar
metabolites, and subsequent conjugation reactions and incorporation into
natural products.  The MARC (D278044, L. Cheng, 10/09/01) concluded that
the residues of concern in rotational crops consist of pyraclostrobin
and metabolite BF 500-3.

860.1900 Field Accumulation in Rotational Crops

An adequate limited field rotational crop study is available (PP#0F6139,
D269668, L. Cheng, 11/28/01) reflecting six broadcast foliar
applications of pyraclostrobin (EC) to cucumber at 0.19-0.20 lb
ai/A/application and RTIs of 6-8 days, for a total of 1.2 lb
ai/A/season.  This rate is 1x the maximum use rate of any rotated crop. 
Average residues of pyraclostrobin and BF 500-3 were each <LOQ in/on RAC
samples from all representative rotational crops (radish, cabbage and
wheat) planted 14 days following the final application to the primary
crop.  These data indicate that the label specified 14-day plant-back
restriction is acceptable for all crops that are not registered for
direction application.

860.1550 Proposed Tolerances

For purposes of both the tolerance expression and dietary risk
assessment, HED has concluded that the residues of concern in plant
commodities include pyraclostrobin and it desmethoxy metabolite, BF
500-3 (D278044, L. Cheng, 10/9/01), and the residues of concern in
livestock commodities include pyraclostrobin and its metabolites
convertible to 1-(4-chlorophenyl)-1H-pyrazol-3-ol (BF 500-5) and
1-(4-chloro-2-hydroxyphenyl)-1H-pyrazol-3-ol (BF 500-8).  

Tolerances for plant commodities are currently established for the
combined residues of pyraclostrobin and BF 500-3, expressed as parent,
in plant commodities at levels ranging from 0.02 ppm in/on wheat grain
to 29 ppm in/on leafy vegetables, except Brassica [40 CFR
§180.582(a)(1)].  Tolerances for livestock commodities are established
for the combined residues of pyraclostrobin and its metabolites
convertible to BF 500-5 or BF 500-8, each expressed as parent, at levels
ranging from 0.1 ppm in milk, meat, and fat to 1.5 ppm in liver of
cattle, goats, hogs, horses, and sheep [40 CFR §180.582(a)(2)].  No
tolerances are established for poultry commodities.    

The tolerances proposed by BASF for the current petition are listed in
Table 7, along with the Agency’s recommended tolerance levels.  As the
majority of cottonseed samples from the cotton field trials had residues
below the combined LOQ (0.04 ppm), the recommended tolerance level for
undelinted seeds were not determined using the Tolerance/MRL
Harmonization Spreadsheet.  Rather, the recommended tolerance of 0.3 ppm
is based on the maximum combined residues observed in seeds (0.17 ppm). 
Tolerances for Belgian endive, cotton gin byproducts and the berries
crop group were both determined using the Tolerance/MRL Harmonization
Spreadsheet as combined residues were readily quantifiable in these
commodities.  For the berries crop group, residue values from both the
earlier and new berry field trials were used to calculate the
appropriate tolerance, and the data from raspberries and blueberries
were pooled as residue levels were similar on both types of berries. 
The residue datasets used for the tolerance calculations and the
supporting spreadsheet outputs are presented in Appendix II.  The
calculated tolerances were 6.0 ppm for Belgian endive, 30 ppm for cotton
gin byproducts and 4.0 ppm for the berries crop group.

Results from the requested mustard greens field trials and the
supplemental field trials on cucurbit vegetables, fruiting vegetables,
grape, sunflower, and mint indicate that no changes are necessary in the
existing tolerances for these crops.  For each crop, the combined
residues in the new field trials were below the established tolerances. 

With regards to the current tolerances for livestock commodities, the
existing tolerances are adequate for milk, meat, fat, meat byproducts
(except liver), and liver of cattle, goats, horses, and sheep, and the
current tolerances for liver could be lowered to 1.0 ppm.  Also, the
existing tolerances for hog commodities can be deleted as quantifiable
residues are unlikely to occur in hogs [40 CFR §180.6(a)(2)] based on
the dietary burden proposed in Table 5.   As stated previously,
tolerances are still not required for poultry commodities.

The Codex Alimentarius Commission, Mexico and Canada have not
established any maximum residue limits (MRLs) for residues of
pyraclostrobin in or on raw agricultural commodities, although a variety
of MRLs are pending in Canada (Appendix I).  Therefore, there are no
questions of compatibility of U.S. tolerances with International MRLs at
the present time.

Table 7. 	Tolerance Summary for Pyraclostrobin.

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

Belgian endive

	6	6	Tolerance calculated using available residue data and Tolerance/MRL
Harmonization Spreadsheet.

Berry, group 13	1.3	4.0	Tolerance calculated using available residue
data and Tolerance/MRL Harmonization Spreadsheet.

Brassica, leafy greens, subgroup 5B	16	16	No change in the established
tolerance is required.  Combined residues in the new mustard green field
trials (1.13-13.40 ppm) were below the established tolerance.

Cotton, undelinted seed	0.4	0.3	Tolerance should be set at 0.3 ppm based
on maximum combined residues of 0.17 ppm.

Cotton, gin byproducts	30	30	Tolerance calculated using available
residue data and Tolerance/MRL Harmonization Spreadsheet.

Grape	2.0	2.0	No change in the established tolerance is required.  The
combined residues in the supplemental field trials (0.56-1.93 ppm) were
below the established tolerance.

Peppermint	8.0	8.0	No change in the established tolerance is required. 
The combined residues in the supplemental field trials (2.25-3.55 ppm)
were below the established tolerance.

Spearmint	8.0	8.0

	Sunflower	0.3	0.3	No change in the established tolerance is required. 
Combined residues in the supplemental field trial (<0.04 ppm) were below
the established tolerance.

Vegetable, cucurbit, group 9	0.5	0.5	No change in the established
tolerance is required.  The combined residues in the supplemental field
trials (0.053-0.379 ppm) were below the established tolerance.

Vegetable, fruiting, group 8	1.4	1.4	No change in the established
tolerance is required.  The combined residues in the supplemental field
trials (0.092-0.701 ppm) were below the established tolerance.

References

DP Barcodes:	D316741

Subject:	Pyraclostrobin.  Cabrio® EG Fungicide/BAS 516 04F Seed
Treatment Fungicide (7969-187) Seed Treatment Uses: Barley, Brassicas,
Bulb Vegetables, Corn, Cucurbits, Legume Vegetables, Peanut, Rye, Sugar
Beet, Sunflower and Wheat. 

From:	L. Cheng

To:	J. Bazuin/C. Giles-Parker

Dated:	9/22/05  SEQ CHAPTER \h \r 1 

MRIDs:	None

DP Barcodes:	D314519

Subject:	Pyraclostrobin.  Storage Dates for Confined Rotational Crop
Study  SEQ CHAPTER \h \r 1 .

From:	L. Cheng

To:	J. Bazuin/C. Giles-Parker

Dated:	  SEQ CHAPTER \h \r 1 05/05/05

MRIDs:	46469501

DP Barcodes:	D281042, D286732, D287729, D288459, D290342, D290343,
D290369, D292440, D293088, D293684, D295893, and D298178

Subject:	Pyraclostrobin.  PP#3F06581, 2F06431, 2E6473, 3E6548, 3E6553,
3E6774, and 2F06139.  Petitions for the establishment of permanent
tolerances to allow uses on corn (field, sweet, and pop), hops, mint,
pome fruits, edible-podded legume vegetables, succulent peas, sunflower,
Brassica leafy greens, soybeans, succulent beans, broccoli, cabbage,
lettuce (head and leaf), spinach, celery, turnip greens, and the import
commodities mango and papaya.  Application for amended Section 3
registration for citrus (reduced PHI).  Petitioner’s response to data
deficiencies identified in PP#0F06139 regarding storage stability data,
dried shelled peas and beans (reduced PHI), and uses on dry and
succulent peas.  Summary of Analytical Chemistry and Residue Data.	 

From:	L. Cheng

To:	C. Giles-Parker/J. Bazuin

Dated:	7/26/04

MRIDs:	45596211, 45623406, 45623407, 45623408, 45623410, 45645801,
45645802, 45645803, 45645804, 45702901, 45765401, 45832001, 45858801,
45858802, 45903601, 45903602, 46033901-04, 46084401-04, 46109101,
46109102

DP Barcodes:	D278385, D282532, D286787, D287829

Subject:	  SEQ CHAPTER \h \r 1 PP#1F06313.  BAS 510 F (Common Name:
Boscalid), New Fungicide Active Ingredient.  Residue Chemistry Summary
Document.	

From:	M. Nelson

To:	M. Rodriguez/C. Giles-Parker

Dated:	  SEQ CHAPTER \h \r 1 08/15/03

MRIDs:	45405021-28, 45405101-28, 45405202-45405204, 45623401-13, and
45643801

DP Barcodes:	D269668, D272771, D272789, D274095, D274192, D274471,
D274957, D275843, and D278429

Subject:	PP#0F06139.  Pyraclostrobin on Various Crops:  Bananas
(import), Barley, Berries, Bulb Vegetables, Citrus Fruits, Cucurbit
Vegetables, Dried Shelled Pea & Bean (except Soybean), Fruiting
Vegetables, Grape, Grass, Peanut, Pistachio, Root Vegetables (except
Sugar Beet), Rye, Snap Beans, Stone Fruits, Strawberry, Sugar Beet, Tree
Nuts, Tuberous and Corm Vegetables, and Wheat.  Review of Analytical
Methods and Residue Data.  EPA File Symbols:  

From:	L. Cheng

To:	C. Giles-Parker/J. Bazuin

Dated:	11/28/01

MRIDs:	45118428-451184-37, 45118501-45118512, 45118514-45118537,
45118601-45118625, 45160501, 45272801, 45274901, 45321101, 45367501,
45399401, and 45429901

DP Barcode:	D278044

Subject:	PP# 0F06139.  PC Code 099100.  Pyraclostrobin.  Outcome of the
HED Metabolism Assessment Review Committee (MARC) Meeting Held on
September 20, 2001.

From:	L. Cheng

To:	Y. Donovan

Dated:	10/09/01

MRIDs:	None

DP Barcode:	D269850

Subject:	PP# 0F06139.  Pyraclostrobin (BAS 500F) in or on Various Crops.
Request for Tolerance Method Validation (TMV) Trial.

From:	L. Cheng

To:	F. D. Griffith, Jr.

Dated:	11/8/00

MRIDs:	45118505, 45118504, 45118509, 45118510, 45118501, 45118503,
45118507, 45118514

  SEQ CHAPTER \h \r 1 Attachments:  

Appendix I - International Residue Limit Status sheet

Appendix II - Tolerance Assessment Calculations

RDI:  SVHummel 04/10/07

Petition Number(s):  5F7002, 5E7014, 3F6581, 2F6431, 0F6139

Dp Barcodes (s):  337807, 327899, 337817, 338488

PC Code:  099100

Template Version September 2005

Appendix I – International Residue Limits

No Codex proposal step 6 or above

(No Codex proposal step 6 or above for the crops requested 	Petition
Number: 5F7002, 5E7014

DP Barcode: 337807, 337817

Other Identifier: 

Residue definition (step 8/CXL):   	JStokes/HED/RRB4

	Residue definition: Combined residues of pyraclostrobin and BF 500-3,
expressed as parent

Crop (s)1	MRL (mg/kg)	Crop(s)	Proposed Tolerance (ppm)

Cotton, undelinted seed	0.4

Cotton, gin byproducts	30

Berries, group 13	4.0

Beligan endive	6.0

	Limits for Canada	Limits for Mexico

( No Limits

( No Limits for the crops requested	( No Limits

(  No Limits for the crops requested

Residue definition:  Cyhalothrin-lambda	Residue definition:   
Lambda-cyhalothrin

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

	Notes/Special Instructions:

Appendix II - Tolerance Assessment Calculations.

The Agency’s Guidance for Setting Pesticide Tolerances Based on Field
Trial Data was utilized for determining appropriate tolerance levels for
cotton gin byproducts and berries (group 13) as the combined residues of
pyraclostrobin and BF 500-3 were readily quantifiable (>LOQ) in/on 
these commodities. 

The datasets used to establish the crop group tolerance consisted of
field trial data representing applications of the appropriate
formulations at ~1x maximum proposed maximum use rates.  As specified by
the Guidance for Setting Pesticide Tolerances Based on Field Trial Data
SOP, the field trial application rates were within 25% of the maximum
label application rate, and the PHIs were consistent with the
appropriate stage of maturity and the proposed PHI for each commodity. 

 

The values for combined pyraclostrobin residues were used to calculate
the appropriate tolerances for Belgian endive (Table II-1), cotton gin
(Table II-2) and the berries crop group (Table II-3).  As residue levels
in blueberries and raspberries were similar, the data from both types of
berries were pooled to calculate the group tolerance.  The datasets for
each commodity were entered into the tolerance spreadsheet and visual
inspection of the lognormal probability plots indicates that the berry
data set is reasonably lognormal (Figure II-5); however, the data set
for Belgain endive and cotton gin trash do not appear to be lognormal
(Figures II-3 and II-5, respectatively).  The calculated tolerances were
6.0 ppm for Belgian endive, 30 ppm for cotton gin byproducts and 4.0 ppm
for berries (Figures II-2, II-4, and II-6).  



Table II-1.	Combined Residues of Pyraclostrobin and BF 500-3 in/on
Belgian endive.

Regulator:	EPA

Chemical:	Pyraclostrobin

Crop:	Belgian endive

PHI:	19-21 days

App. Rate:	0.0055 lb pyraclostrobin per 875 lb roots

Submitter:	BASF Corporation

MRID Citation:	MRID

	Combined Residues

	0.092

	0.060

	1.890

	1.870

	2.753

	2.903

Figure II-1.	Lognormal probability plot of pyraclostrobin field trial
data for Belgain endive harvested 19-21 days following one application
at  0.0055 lb pyraclostrobin per 875 lb roots

Figure II-2.	Tolerance spreadsheet summary of pyraclostrobin field
trial data on Belgian enduve following one application of
pyraclostrobin.

	Regulator:	EPA

Chemical:	Pyraclostrobin

Crop:	Beligan endive

PHI:	19-21 days

App. Rate:	0.0055 lb/876 lb roots

Submitter:	IR-4

	n:	6

min:	0.06

max:	2.90

median;	1.88

average:	1.59

	95th Percentile	99th Percentile	99.9th Percentile

EU Method I

Normal	4.0	5.0	6.0

	(7.0)	(8.0)	(--)

EU Method I

Log Normal	14	50	190

	(560)	(6300)	(--)

EU Method II

Distribution-Free

6.0

California Method

μ + 3σ

6.0

UPLMedian95th

25

Approximate Shapiro-Francia Normality Test Statistic	0.7644

	0.05 >= p-value > 0.01 : Reject lognormality assumption



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瑹⵭܀Byproducts.

Regulator:	EPA

Chemical:	Pyraclostrobin

Crop:	Gin Trash (all)

PHI:	29-32 days

App. Rate:	0.8-0.82 lb ai/A

Submitter:	BASF Corporation

MRID Citation:	MRID 46685901

	Combined Residues

	2.90

	3.85

	2.04

	2.12

	1.82

	2.00

	1.08

	1.05

	1.66

	1.93

	15.64

	25.06

Figure II-3.	Lognormal probability plot of pyraclostrobin field trial
data for cotton gin byproducts from cotton harvested ~30 days following
the last of four applications totaling 0.80-0.85 lb ai/A.

Figure II-4 Tolerance spreadsheet summary of pyraclostrobin field trial
data on cotton gin byproducts following four applications of
pyraclostrobin (WDG).



Table II-3	Combined Residues of Pyraclostrobin and BF 500-3 in/on
Blueberries and Red Raspberries.

Regulator:	EPA

Chemical:	Pyraclostrobin

Crop:	Blueberry	Raspberry

PHI:	0 days

App. Rate:	0.72-0.75

Submitter:	BASF Corporation

MRID Citation:	MRIDs 45118605 & 46637701

	Combined Residues	Combined Residues

	0.32	0.64

	0.38	0.97

	0.47	0.46

	0.56	0.53

	0.57	0.49

	0.69	0.82

	0.30	1.23

	0.44	1.33

	0.29	0.87

	0.37	0.94

	0.12	0.76

	0.29	1.08

	1.47

1.48

1.11

1.32

1.27

1.24

1.61

1.96

2.32

2.35

2.13

2.52

	Figure II-5.	Lognormal probability plot of pyraclostrobin field trial
data for berries harvested 0 days  following four broadcast foliar
applications totaling 0.73-0.75 lb ai/A.

Figure II-6	Tolerance spreadsheet summary of pyraclostrobin field trial
data on berries following four broadcast foliar applications of
pyraclostrobin (WDG).

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