Document ID: EPA-HQ-OPP-2007-0310-0008
Agency: epa
Document Type: Supporting & Related Material
Title: 
Posted Date: 2007-12-05T05:00Z

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C.  20460

OFFICE OF           

PREVENTION, PESTICIDES

AND TOXIC SUBSTANCES

MEMORANDUM

Date:		September 19, 2007

Subject:		Spinosad.  Petition for a Tolerance for Spice Subgroup (19B),
Except Black Pepper, and Pineapple. Summary of Analytical Chemistry and
Residue Data.  Petition Number 6E7148 

DP Number:	335084	Decision Numbers:	372546

PC Code:	110003	MRID Nos.:  	46998201, 46998202, 46998203, 46998204

40 CFR 180.	495

From: 	  Breann Hanson, Biologist 

	       Alternative Risk Integration and Assessment (ARIA) Team

	       Risk Integration Minor Use and Emergency Response Branch 			   	
	      (RIMUERB)/Registration Division (RD) (7505P)

Through:		William Cutchin, Acting Branch Senior Scientist

		ARIA Team

		RIMUERB/RD (7505P)

		AND

		Donna Davis, Senior Chemist

		Reregistration  Branch 1 (RRB1)

		Health Effects Division (HED) (7509P)

To:		Thomas Bloem, Chemist

			 Registration Action Branch 1 (RAB1)

			 HED (7509P)

Attached please find the summary of analytical chemistry and residue
data to support the establishment of tolerances in/on pineapple and the
spice subgroup (19B), except black pepper.

Executive Summary

Background:  The Interregional Research Project Number 4 (IR-4) has
submitted PP#6E7148 requesting the establishment of tolerances to
support the Section 3 registration of spinosad in/on pineapple and the
spice subgroup (19B), except black pepper, and pineapple.  IR-4 has
proposed tolerances of 1.7 ppm in/on spice subgroup (19B), except black
pepper, 0.02 ppm in/on pineapple and 0.08 ppm in/on pineapple, process
residue. 

Application Scenarios:   Spinosad is intended for application to crops
in the spice subgroup (19B), except black pepper as aerial or ground
foliar applications.  Individual application rates range from 0.063 lb
ai/A – 0.156 lb ai/A and no more than 5 applications may be made per
season.  The minimum retreatment interval (RTI) is 10 days with a
maximum seasonal rate of 0.45 lb ai/A and a 14 day preharvest interval
(PHI).   

Spinosad is intended for application to pineapple as aerial or ground
foliar applications.  Individual application rates range from 0.062 lb
ai/A – 0.1 lb ai/A and no more than 6 applications may be made per
season.  The RTI is 7 days with a maximum seasonal rate of 0.45 lb ai/A
and a 7 day PHI.   

Nature of the Residue - Plant/Livestock:  The nature of the residue in
plants and livestock is adequately understood based on metabolism
studies conducted with apples, cabbage, cotton, tomatoes, turnips,
ruminants (oral and dermal), and poultry (oral).  HED concluded that the
residue of concern in plants and livestock for risk assessment and
tolerance enforcement purposes are spinosyns A and D.

Magnitude of the Residue:  Dill field trial data resulted in combined
residues of spinosyn A and D of < 0.02 ppm to 0.57 ppm on/in treated
dill when the test substance was applied at the proposed application
rate of 0.156 lb ai/A (0.468 lb ai/A/season), treated with 3
applications, using approximately a 14-day PHI.  For one trial treated
with 4 applications, residues were 0.17 ppm. The additional treatment
did not increase residues. The Agency concludes that a spice subgroup
19B, except for black pepper, tolerance of 1.7 ppm is appropriate.  

Pineapple field trial data, conducted in Hawaii (US EPA Region 13),
resulted in residues below 0.020 ppm on/in treated pineapple when the
test substance was applied at the proposed application rate of 0.094 lb
ai/A (0.47 lb ai/A/season) treated with 5 applications, using a 6-7 day
PHI.  For one trial treated with only 4 applications, as the fruit was
ripening earlier than expected, residues were still below 0.020 ppm. 
Field trial data, conducted in Mexico, resulted in residues ranging from
non-detectable (ND) to 0.01 ppm for spinosyn A and ND to < 0.01 ppm for
spinosyn D on/in treated pineapple when the test substance was applied
at the proposed application rate of 0.094 lb ai/A (0.47 lb ai/A/season)
treated with 5 applications, using a 6-7 day PHI.  Field trial data,
conducted in South America, resulted in residues for both spinosyn A and
D ranging from ND to < 0.01 ppm on/in treated pineapple when the test
substance was applied at the proposed application rate of 0.094 lb ai/A
(0.47 lb ai/A/season) treated with 5 applications, using a 3-7 day PHI. 
The Agency concludes that a pineapple tolerance of 0.02 ppm is
appropriate.

In the pineapple processing study a total of approximately 0.85 lb
ai/A/season was applied in order to obtain a sample for processing at an
exaggerated rate of 4 times the currently proposed label rate using a
1-day PHI.  Residues of spinosad in/on juice processed from treated
fruit were less than 0.01 ppm in all samples.  The residue for ground
whole fruit noted in the processing sample was 0.02 ppm following the
additional application of spinosad.  No data were provided for pineapple
process residue; in lieu of providing this data IR-4 proposed a maximum
theoretical concentration factor of 3.8X.   By applying the factor to
the concentration in the whole fruit from an exaggerated rate trial, the
Agency is confident that residues of spinosad in pineapple process
residue will not exceed 0.08 ppm.  Because residues do no appear to
concentrate in pineapple, juice, a separate tolerance for pineapple
juice is not required.

Analytical Enforcement Method: 

Spice Subgroup (19B), except Black Pepper

DowElanco Method 97.05 (03/13/1998) is an immunoassay particle-based
method that has been proposed as an enforcement method.  This method is
substantially similar to existing enforcement methods and is suitable to
enforce the proposed tolerances in/on the spice group (19B), except
black pepper.

Pineapple

Dow AgroSciences Method GRM 03.15 is a high performance liquid
chromatography with ultraviolet absorption detection (HPLC/UV) method
that has been proposed as an enforcement method.  This method is
substantially similar to existing enforcement methods and is suitable to
enforce the proposed tolerances in/on pineapple and pineapple process
residue.  

Recommendations:  The Agency concludes that there are no residue
chemistry deficiencies that would preclude establishment of tolerances
for residues of spinosad in/on pineapple and the spice subgroup (19B),
except black pepper.  Provided there are no issues identified in the
forthcoming Human Health Risk Assessment, the data support the
tolerances for the combined residues of spinsosyn A and D requested by
IR-4 and summarized below.

Spice subgroup (19B), except black pepper	1.7 ppm

Pineapple	0.02 ppm

Pineapple, process residue	0.08 ppm

Because residues do no appear to concentrate in pineapple, juice, a
separate tolerance for pineapple juice is not required.  

The Agency notes that at this time, no additional data are required to
support the proposed new uses, however, should a new use be requested
for pineapple which results in detectable residues in the whole fruit,
additional data on residues in pineapple process residue may be
required.

Background

Spinosad is a fermentation product of Saccharopolyspora spinosa, a
naturally-occurring soil organism.  The product consists of two related
active ingredients:  Spinosyn A and Spinosyn D.  The two active
ingredients differ by one methyl group and are typically present at an
85:15 ratio (A:D).  The registrant indicated that the exact mode of
action is not known but is characterized by excitation of the insect
nervous system, leading to involuntary muscle contractions, prostration
with tremors, and paralysis (effects are consistent with excitation of
the nicotinic acetylcholine receptors).  Spinosad is used for the
control of many foliage feeding pests including lepidopterous larvae,
leafminers, and thrips. 

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

Table 1.  Test Compound Nomenclature

Chemical Structure	

-methyl-α-L-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6-tetradeoxy-
β-D-erythropyranosyloxy)-9-ethyl-2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,1
6a,16b-hexadecahydro-14-methyl-1H-8-oxacyclododeca[b]as-indacene-7,15-di
one

Spinosyn D: 
(2S,3aR,5aS,5bS,9S,13S,14R,16aS,16bR)-2-(6-deoxy-2,3,4-tri-O-methyl-α-L
-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6-tetradeoxy-β-D-erythrop
yranosyloxy)-9-ethyl-2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,16a,16b-hexade
cahydro-4,14-dimethyl-1H-8-oxacyclododeca[b]as-indacene-7,15-dione

CAS name	Spinosyn A: 
2-[(6-deoxy-2,3,4-tri-O-methyl-α-L-manno-pyranosyl)oxy]-13-[[5-(dimethy
lamino)-tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,
10,11,12,13,14,16a,16b-tetradecahydro-14-methyl-1H-as-Indaceno[3,2-d]oxa
cyclododecin-7,15-dione

Spinosyn D: 
2-[(6-deoxy-2,3,4-tri-O-methyl-α-L-manno-pyranosyl)oxy]-13-[[5-(dimethy
lamino)-tetrahydro-6-methyl-2H-pyran-2-yl]oxy]-9-ethyl-2,3,3a,5a,5b,6,9,
10,11,12,13,14,16a,16b-tetradecahydro-4,14-methyl-1H-as-Indaceno[3,2-d]o
xacyclododecin-7,15-dione

CAS #	Spinosyn A:  131929-60-7

Spinosyn D:  131929-63-0

End-use products/(EPs)	Success, EPA Reg. No. 62719-292

Entrust, EPA Reg. No. 62719-282

SpinTor, EPA Reg. No. 62719-294

Table 2.  Physicochemical Properties of the Technical Grade Test
Compound

Melting point/range	Spinosad A: 84-99.5°C

Spinosad D: 161.5-170°C	EPA Fact Sheet

pH (10% slurry of spinosad in water)	7.74

	Density at 20°C	0.512

	Water solubility (ppm)	Spinosad A: 89.4

Spinosad D: 0.495	

	Vapor pressure at 25°C (kPa)	Spinosad A: 3.0 x 10-11

Spinosad D: 2.0 x 10-11

	Dissociation constant (pKa)	not available

	Octanol/water partition coefficient Log(KOW)	

pH 5

pH 7

pH 9	Spinosyn A 2.8

4.0

5.2	Spinosyn D 3.2

4.5

5.2

	UV/visible absorption spectrum	not available

	

860.1200  Directions for Use

The petitioner requested the establishment of tolerances to support the
application of Entrust® (WP; 80% ai; EPA Reg. No. 62719-282), SpinTor®
2SC (2 lbs ai/gal; EPA Reg. No. 62719-294), and Success® (SC; 2 lb
ai/gal; EPA Reg. No. 62719-292) to spice subgroup 19B, except black
pepper, and pineapple.  For resistance management, the labels indicate
that spinosad should not be applied more than 3 times in any 30-day
period or applied less than 10 days apart.  When applied up to 3 times
in succession, spinosad should be rotated with other insect control
products with a different mode of action.  Table 3 is a detailed summary
of the proposed application scenarios.  

Table 3.  Summary of Directions for Use of Spinosad.

Applic. Timing, Type, and Equip. 1	Formulation 2

[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 3

Spice, Subgroup 19B, Except Black Pepper

Foliar applications during fruiting; ground or aerial equipment; when
pests appear	80% WP

[62719-282] 

22.8% 2SC

[62719-294]

22.8% SC

[62719-292]	0.063-0.156	5	0.45	14	The minimum RTI is 10 days.

Pineapple

Foliar applications during fruiting; ground or aerial equipment; when
pests appear	80% WP

[62719-282] 

	0.063 -0.100	6	0.45	7	The minimum RTI is 7 days.

	22.8% 2SC

[62719-294]

	0.062-0.093	6	0.45	7	The minimum RTI is 7 days.

	22.8% SC

[62719-292]

	0.062 – 0.093	6	0.45	7	The minimum RTI is 7 days.

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

2	Unless otherwise specified, the use directions are from the most
recent labels of the respective formulations.

3	Use directions allow for the use of spray adjuvants.

	

Conclusions.  The proposed use directions are adequate for evaluating
the submitted field trials.  The available field trials on dill and
pineapple were conducted at the maximum single and seasonal use rates
and samples were collected at the minimum PHIs specified on the U.S.
labels.  

  SEQ CHAPTER \h \r 1 860.1300 Nature of the Residue - Plants and
Livestock 

The nature of the residue in plants and livestock is adequately
understood based on metabolism studies conducted with apples, cabbage,
cotton, tomatoes, turnips, ruminants (oral and dermal), and poultry
(oral).  HED concluded that the residue of concern in plants and
livestock for risk assessment and tolerance enforcement purposes are
spinosyns A and D (DP#: 243816, G. Herndon, 3/3/1998; DP#: 264984, W.
Donovan, 6/14/2002).

For plants, residue levels of spinosyns A and D declined significantly
with increasing PHI (decreased 40-89% as the PHI increased from 0 to 3
days; decreased 86% to nondetectable as the PHI increased from 0 to
10-48 days).  This decline was accompanied by incremental increases in
nonextractable and polar 14C-residues.  Extensive fractionation and
characterization of nonextractable and polar 14C-residues in selected
crops indicated that most of the radioactivity was degraded to
multicomponent residues of low molecular weight which are subsequently
incorporated into natural plant constituents (DP#: 228434, S. Willett,
1/23/1997; DP#: 243816, J. Herndon, 3/3/1998).

Conclusions:  The nature of the residue in plants and animals is
adequately understood.  No new animal metabolism data is required to
support the requested new uses of spinosad.

860.1340 Residue Analytical Methods – Plants

Adequate plant methods are available for data collection and enforcement
of the proposed tolerances associated with the current petition.  These
methods are listed below.

The Spice Group (19B), except black pepper

46998201.der, B. Hanson, 9/17/2007

The analytical procedure for quantifying residues of spinosad was the
DowElanco method 97.05, “Determination of Residues of Spinosad in
Sorghum Fodder Using a Magnetic Particle-Based Immunoassay Test Kit”
(03/13/1998).  Dill samples were extracted in separate steps with
acetonitrile/water and methylene chloride and passed through a
cyclohexyl sold phase extraction column.  The analytes were then eluted
with triethylamine and dried via nitrogen gas.  The final extract was
assayed with a commercial magnetic-particle immunoassay kit.  Samples of
control spinosad were fortified at levels ranging from 0.02 to 10.0 ppm.
 The limit of quantitation (LOQ) and the limit of detection (LOD) were
calculated to be 0.019 ppm and 0.006 ppm, respectively for dill.   In
conjunction with each field trial, the method was adequately validated
using control samples of each plant matrix fortified with spinosad.  

This method is substantially similar to existing enforcement methods and
is suitable to enforce the proposed tolerances in/on the spice group
(19B), except black pepper.  

Pineapple

46998202.der, B. Hanson, 9/17/2007

46998203.der, B. Hanson, 9/17/2007

46998204.der, B. Hanson, 9/17/2007

The analytical procedure for quantifying residues of spinosad was the
Dow AgroSciences method GRM 03.15 “Method for Determination of
Spinosad in Pineapple (Whole Fruit and Juice) Using High Performance
Liquid Chromotography with Ultraviolet Detection.”  Pineapple samples
were extracted in separate steps with acetonitrile/water and hexane and
purified on a silica gel SPE cartridge.  Quantitation was accomplished
by HPLC/UV.  Control samples were fortified with spinosad at levels
ranging from 0.01 ppm to 5.0 ppm.  In MRID 46998202, the LOQ and the LOD
were calculated to be 0.019 ppm and 0.006 ppm, respectively, for
spinosyn A and as 0.016 ppm and 0.005, respectively, for spinosyn D.  In
MRIDs 46998203 and 46998204, the LOQ was calculated to be 0.01 ppm for
both spinosyn A and spinosyn D.  The statistical LOD and LOQ were
calculated as 0.001 ppm and 0.004 ppm, respectively, for spinosyn A and
as 0.001 ppm and 0.002, respectively, for spinosyn D.  In conjunction
with each field trial, the method was adequately validated using control
samples of each plant matrix fortified with spinosad.  

This method is substantially similar to existing enforcement methods and
is suitable to enforce the proposed tolerances in/on pineapple and
pineapple process residue.  

Conclusions.  The analytical procedures for quantifying residues of
spinosad in both dill and pineapple have been adequately validated for
data collection purposes and are suitable for enforcing the proposed
tolerances on spice subgroup (19B), except black pepper and pineapple. 

860.1340 Residue Analytical Methods – Livestock

No new tolerances for animal commodities are required as a result of the
proposed new uses; therefore a discussion of analytical methods for
livestock commodities is not relevant to this Section 3 request.

860.1360 Multiresidue Methods

Previously-submitted data pertaining to multiresidue methods testing of
spinosyns B and K and N-demethyl spinosyn D in conjunction with
PP#6F4761/6H5754 which were forwarded to Food and Drug Administration
(FDA) for review (S. Willett, 1/23/1997).  The petitioner had also
previously-submitted data pertaining to the multiresidue methods testing
of spinosyns A and D in conjunction with PP#6G04692 which were also
forwarded to FDA (G. Herndon, 5/1/1996).  No new information with
respect to multiresidue methods are required to support the requested
new uses.

860.1380 Storage Stability

46998201.der, B. Hanson, 9/17/2007

46998202.der, B. Hanson, 9/17/2007

46998203.der, B. Hanson, 9/17/2007

46998204.der, B. Hanson, 9/17/2007

The petitioner has submitted storage stability data to support the
requested new uses on pineapple and the spice subgroup (19B), except
black pepper.  The storage intervals and conditions for samples from the
current crop field trials are presented in Table 4.  

Table 4.	Summary of Storage Conditions and Intervals of Samples from
Crop Field Trials.  

Matrix 

	Analyte

	MRID	Storage Temperature (°C)	Actual Storage Duration (days)	Interval
of Demonstrated Storage Stability  (days)

Dill Seed	N/A	46998201	<- 26 to -10	160	165

Pineapple	Spinosyn A	46998202	< -15	321	321

	Spinosyn D

< -15	321	321

Pineapple	Spinosyn A	

46998203	< -20	82	93

	Spinosyn D

< -20	82	93

Pineapple	Spinosyn A	46998204	< -20	62	93

	Spinosyn D

< -20	62	93

Dill (seed) (MRID 46998201) was stored frozen for a maximum of 160 days
at a nominal temperature of -20ºC.  Storage stability samples were
fortified at 1.0 ppm using control tissue samples.  Concurrent storage
stability testing showed that spinosad residues are stable on dill for
up to 165 days with recoveries ranging from 91-113%. 

Pineapple (MRID 46998202) was stored frozen for a maximum of 321 days at
a nominal temperature of -15ºC.  Submitted storage stability studies
show that spinosyn A and D residues are stable on pineapple for up to
321 days with recoveries ranging from 71 - 83%.

Pineapple (MRID 46998203) was stored frozen for a maximum of 82 days at
a nominal temperature of -20ºC.  Submitted storage stability studies
show that spinosyn A and D residues are stable on pineapple for up to 93
days with recoveries averaging 88±3% for spinosyn A and 86±2% for
spinosyn D.

Pineapple (MRID 46998204) was stored frozen for a maximum of 62 days at
a nominal temperature of -20ºC.  Submitted storage stability studies
show that spinosyn A and D residues are stable on pineapple for up to 93
days with recoveries averaging 88±3% for spinosyn A and 86±2% for
spinosyn D.

Conclusions.  Adequate storage stability data are available to support
the samples storage conditions and intervals from the current field
trials.  

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 spinosad.

860.1460 Food Handling

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

860.1480 Meat, Milk, Poultry, and Eggs

No new feeding studies were submitted with this petition although
pineapple processed waste is a feed item.  However, based on the
available processing study information, the low percentage of the diet
at which this feed item is fed, and the much higher tolerances currently
established for other feed items, the Agency concludes that the new use
on pineapple is not likely to results in an increase in the dietary
burden, and therefore, existing animal feeding studies and tolerances
are adequate to support the new use.  

 

860.1500 Crop Field Trials

46998201.der (Dill seed), B. Hanson, 9/17/2007	

46998202.der (Pineapple), B. Hanson, 9/17/2007

46998203.der (Pineapple), B. Hanson, 9/17/2007

46998204.der (Pineapple), B. Hanson, 9/17/2007

IR-4 submitted dill seed and pineapple field trials supporting the
proposed tolerances for the spices subgroup 19B, except black pepper,
and for pineapple.     SEQ CHAPTER \h \r 1 The results from these
studies are summarized in Table 5 and discussed below.

Table 5.	Summary of Residue Data from Recent Crop Field Trials with
Spinosad.

Crop/commodity	Total Rate  (lb ai/A)	PHI (days)	Residue levels (ppm)

	n	Min.	Max.	HAFT 1	Median	Mean	Std. Dev.

Spice Subgroup 19B, Except Black Pepper

Dill	0.422-0.469	13-15	4	<0.02	0.57	0.35	0.07	0.18	0.27

	0.627	14	2	0.17	0.17	0.17	0.17	0.17	-

Pineapple 

Pineapple2 

 (Spinosyn A and D)	0.385-0.476	6-7

	6	<0.02	<0.02	0.01	0.01	0.01	ND

Pineapple3

 (Spinosyn A and D)	0.47  	3-7	6	<0.01	<0.01	0.01	0.01	0.01	ND

Pineapple4 	Spinosyn A	0.47  	3-7	6	<0.01	<0.01	0.01	0.01	0.01	N/A

	Spinosyn D	0.47  	3-7	6	<ND	<0.01	0.01	0.01	0.01	N/A

1	HAFT = Highest Average Field Trial; values of ND, <0.01 and <0.02 are
treated as values of 0.01 ppm.

2	Hawaii filed trial

3	Mexico Field Trial

4	South America Filed Trial 

Spice Subgroup (19B), Except Black Pepper

Dill. Field trials were conducted on dill as a representative crop of
subgroup (19B), except black pepper.

Three trials were conducted in Colorado (US EPA Region 9), Idaho (US EPA
Region 11), and Maryland (US EPA Region 2) during the 2003 growing
season.  At each test location, at least three foliar applications of
Success Naturalyte (22.8% spinosad) were applied at a rate of
approximately 0.156 lb ai/A at 9-11 day intervals for a total of
approximately 0.468 lb/ai/A/season (actual average of 0.446 lb
ai/A/season).  At the Idaho trial, four applications were applied for a
total of approximately 0.624 lb ai/A/season (actual total of 0.627 lb
ai/A/season).  No adjuvants or additives were added to the spray mixture
for any of the above applications.  Dill was harvested at 13-15 days
after final application.  

The results from these trials are shown in Table 6, below.  In these
trials, the maximum residues in/on dill seed (0.57 ppm) did not exceed
the proposed 1.7 ppm tolerance for spice subgroup 19B, except black
pepper.

Table 6.   Residue Data from Crop Field Trials with Spinosad.

Trial ID

(City, State/Year)	Region	

Crop/ Variety	

Commodity or 

Matrix	

Total Rate/Season,

lb ai/A	

PHI

(days)	Residues (ppm)

Sample 1	Sample 2

Fort Colins, CO/ 2003	9	Dill (seed)/

Bouquet	Seed	0.422	13	0.57	0.12

Kimberly, ID/

2003	11	Dill (seed)/

Bouquet	Seed	0.627	14	0.17	0.17

Salisbury, MD/

2003	2	Dill (seed)/

Superdukat	Seed	0.469	15	< 0.02	< 0.02

Pineapple

Pineapple.

Hawaii.  Three trials were conducted in Hawaii (US EPA Region 13) during
the 2003 growing season.  At two of the trials, five broadcast
applications of Success (22.8% spinosad) were applied at a rate of
approximately 0.094 lb ai/A at 7-8 day intervals for a total of
approximately 0.47 lb ai/A/season.  At the third trial, only four
applications were made, as the fruit was ripening earlier than expected,
for a total of approximately 0.376 lb ai/A/season.  No adjuvant was
added to the spray mixture for any of the above applications.  In all
three field trials, pineapple was harvested at 6-7 days after final
application.  

The results from these field trials are shown in Table 7, below.  In
these trials, the maximum residue in/on pineapple (0.01 ppm) did not
exceed the proposed 0.02 ppm tolerance for pineapple.

Table 7.    Residue Data from Crop Field Trials with Spinosad

Trial ID

(City, State/Year)	Region	Crop/ Variety	Commodity or Matrix	Total Rate

(lb ai/A)	PHI

 (days)	Residues (ppm)

03-HI05 Wahiawa, HI/2003	13	Pineapple/

Cayenne	Fruit	0.472	7	< 0.020	< 0.020

03-HI06 Wahiawa, HI/2003	13	Pineapple/

Cayenne	Fruit	0.476	7	< 0.020	< 0.020

03-HI07 Wahiawa, HI/2003	13	Pineapple/

Cayenne	Fruit	0.385	6	< 0.020	< 0.020

Mexico.  Three trials were conducted in Mexico during the 2003 growing
season.  At all trials, five broadcast applications of Success was
applied at a rate of approximately 0.09 lb ai/A at 6-8 day intervals for
a total of approximately 0.47 lb ai/A/season.  No adjuvant was added to
the spray mixture for any of the above applications. In all trials,
pineapple was harvested at 3 and 7 days after final application.

 

The results from these trials are shown in Table 8, below.  In these
trials, the maximum residue in/on pineapple (0.01 ppm) did not exceed
the proposed 0.02 ppm tolerance for pineapple. 

Table 8.	Residue Data from Crop Field Trials with Spinosad

Trial ID

(City, State/Year)	Region	Crop/ Variety	Commodity or Matrix	Total Rate

(lb ai/A)	PHI

 (days)	Residues (ppm)

01-Los Fratellos, Mexico, 2003

	13	Pineapple/

Cayena	Fruit	0.47  	3

	< 0.01

	< 0.01

	7	< 0.01	< 0.01

02-El Kilate, Mexico, 2003

	13	Pineapple/

Cayena	Fruit	0.47  	3

	< 0.01

	 0.01

	7	<0.01	0.01

03-Campo Experimental Papaloapan, Mexico, 2003	13	Pineapple/

Cayena	Fruit	0.47  	3

	< 0.01

	< 0.01

	7	< 0.01	<0.01

South America.   Three trials were conducted in South America during the
2003 growing season.  At all trials, five broadcast applications of
Success was applied at a rate of approximately 0.094 lb ai/A at 7 day
intervals for a total of approximately 0.47 lb ai/A/season.  No adjuvant
was added to the spray mixture for any of the above applications. In all
trials, pineapple was harvested at 3 and 7 days after final application.

 

The results from these trials are shown in Table 9, below.  In these
trials, the maximum residue in/on pineapple (0.01 ppm) did not exceed
the proposed 0.02 ppm tolerance for pineapple. 

Table 9.	Residue Data from Crop Field Trials with Spinosad

Trial ID

(City, State/Year)	Region	Crop/ Variety	Commodity or Matrix	Total Rate

(lb a.i./A)	PHI

 (days)	Residues (ppm)

Spinosyn A	Spinosyn D

01-Buenos Aires, Costa Rica, 2003

	13	Pineapple/

MD-2	Fruit	0.47  	3

7	< 0.01

< 0.01	< 0.01

N.D.

02-Buenos Aires, Costa Rica, 2003	13	Pineapple/

MD-2	Fruit	0.47	3

7	< 0.01

< 0.01	< 0.01

< 0.01

0.85	1	0.02

	03-Guacimo, Costa Rica, 2003	13	Pineapple/

MD-2	Fruit	0.47  	3

7	< 0.01

< 0.01	< 0.01

<0.01

Conclusions.  The submitted field trials on dill and pineapple are
adequate.  Samples of the various RACs were analyzed using an adequate
method and the sample storage conditions and intervals are supported by
the available storage stability data.  The number and locations of field
trials for both dill and pineapple are in accordance with OPPTS
Guideline 860.1500 (with some acceptable deviations). The data represent
the use pattern requested.  Maximum residue limits (MRLs) were
calculated for dill (Appendix II).  MRLs are not required for pineapple.
 ARIA recommends for the requested tolerance of 1.7 ppm in/on dill and
of 0.02 ppm in/on pineapple.

860.1520 Processed Food and Feed

Dill

No processing data are required to support the requested use on the
spice subgroup (19B), except black pepper.

Pineapple

46998204.de2 (pineapple), B. Hanson, 9/17/2007

In the pineapple processing study, which was run concurrently with the
field trial study and is contained in the same study, whole pineapples
were processed using a WALITA juice processor and homogenized to produce
juice.  The juice was not pasteurized or heat stabilized as is common
during commercial pineapple juice production. 

Pineapple and its processed samples were analyzed for residues of
spinosyn A and spinosyn D using the Dow AgroSciences method GRM 03.15. 
Pineapple samples were extracted in separate steps with
acetonitrile/water and hexane and cleaned up on a silica gel SPE column.
 Quantitation was accomplished by HPLC/UV.  Control samples were
fortified with spinosad at levels ranging from 0.01 to 0.1 ppm in both
whole fruit and juice.  The LOQ was calculated to be 0.01 ppm for both
spinosyn A and spinosyn D.  The concurrent recovery of both spinosyn A
and D from pineapple at the lowest level of method validation (LLMV)
averaged 95±4% for spinosyn A and 87±2% for spinosyn D in ground whole
fruit and averaged 101±2% for spinosyn A and 89±3% for spinosyn D in
juice.  

Residues of spinosad in/on juice processed from treated fruit were less
than the method LOQ of 0.01 ppm in all samples.  The residue for ground
whole fruit noted in the processing sample was 0.02 ppm following the
additional application of spinosad with a 1 day PHI.  Residues of
spinosad in juice did not appear to concentrate during processing which
did not include heat stabilization or pasteurization.  

Table 10.	Residue Data from Pineapple Juice Processing Study Spinosad

Trial ID

(City, State/Year)	Region	Crop/ Variety	Commodity or Matrix	Total Rate

(lb ai/A)	PHI

(days)	Residues (ppm)

	Processing Factor

02-Buenos Aires, Costa Rica, 2003	13	Pineapple/

MD-2	Fruit

Juice	0.85

N/A	1

1	0.02

<0.01	NA

< 1

The petitioner has proposed in lieu of providing actual processing data
on pineapple process residue, that the theoretical concentration factor
for pineapple process residue (3.8X) be used to determine the
appropriate tolerance for residues of spinosad on that commodity.  Given
that residues were very low in whole fruit even at exaggerated rates and
below the limit of detection in all trials at the proposed use rates,
and further since pineapple process residue is a feed item that is not
fed in great quantities to livestock, the Agency is willing to use the
theoretical concentration factor in lieu of requiring an additional
processesing study.  By applying the factor to the concentration in the
whole fruit from an exaggerated rate trial, the Agency is confident that
residues of spinosad in pineapple process residue will not exceed 0.08
ppm.  The Agency notes that if a new use on pineapple is requested which
would result in finite residues of spinosad in the pineapple, a new
processing study may be required.  

Conclusions.  No additional processing data are required for the crops
being considered in this report. Residues of spinosad do not appear to
concentrate in pineapple juice.  In lieu of processing data, the Agency
has accepted the use of the theoretical concentration factor to set a
tolerance for residues of spinosad in pineapple process residue,
however, if a new use on pineapple is requested which would result in
finite residues of spinosad in the pineapple, a new processing study may
be required.   ARIA recommends for the requested tolerance of 0.08 ppm
in pineapple, process residues.

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

Analytical reference standards for spinosad are available at the EPA
National Pesticide Standards Repository.

860.1850 /860.1900 Confined/Field Accumulation in Rotational Crops

Based on the results of a confined rotational crop study, the MARC
concluded that the residues of concern in rotational crops are spinosyn
A and D (DP#: 243816, G. Herndon, 3/3/1998; field rotational crop data
have not been submitted).  The confined study was conducted at 0.98 lb
ai/A (2.0x) and indicated that residues are incorporated into the
general carbon pool.  Spinosyns A and D were not detected in the rotated
crops (wheat, lettuce, and radish; PBIs of 30, 120, and 365 days).  

Conclusions.  Since the confined study was conducted at 2.0x the maximum
proposed rate and since spinosyns A and D were not detected, HED
concluded that no rotational crops restrictions are required for the
currently-proposed crops.

860.1550 Proposed Tolerances

There are no residue chemistry data requirements that would preclude the
establishment of permanent tolerance for the combined residues of
spinosad in pineapple commodities and the spice subgroup (19B), except
black pepper.  The Agency concurs with the tolerance levels recommended
by the petitioner provided there are no risk concerns identified in the
forthcoming Human Health Risk Assessment.  The proposed and recommended
tolerances are summarized in the table below.  

There are currently no established Codex, Canadian, or Mexican MRLs for
the combined residues of spinosyn A and D; therefore, harmonization is
not an issue. 

Table 11. 	Tolerance Summary for Spinosad.

Commodity	Proposed Tolerance (ppm)	Recommended Tolerance (ppm)

Spice Subgroup 19B, except Black Pepper	1.7	1.7

Pineapple	0.02	0.02

Pineapple, Process Residues	0.08	0.08

Because residues do no appear to concentrate in pineapple, juice, a
separate tolerance for pineapple juice is not required.  

  SEQ CHAPTER \h \r 1 Attachments: 

Appendix I -	International Residue Limit Status sheet

Appendix II -   MRL Sheet	

Appendix I – International Residue Limit Status Sheet

INTERNATIONAL RESIDUE LIMIT STATUS

Chemical Name: 

Spinosyn
A:(2R,3aS,5aR,5bS,9S,13S,14R,16aS,16bR)-2-(6-deoxy-2,3,4-tri-O-methyl-α
a-L-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6-tetradeoxy-βß-D-ery
thropyranosyloxy)-9-ethyl-2,3,3a,5a,5b,6,7,9,10,11,12,13,14,15,16a,16b-h
exadecahydro-14-methyl-1H-8-oxacyclododeca[b]as-indacene-7,15-dione

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1-methyl-αa-L-mannopyranosyloxy)-13-(4-dimethylamino-2,3,4,6-tetradeoxy
-βß-D-erythropyranosyloxy)-9-ethyl-2,3,3a,5a,5b,6,7,9,10,11,12,13,14,1
5,16a,16b-hexadecahydro-4,14-dimethyl-1H-8-oxacyclododeca[b]as-indacene-
7,15-dione	

Common Name:

spinosad

	

X Proposed tolerance

(Reevaluated tolerance

( Other - recommended tolerances	

Date: 26-July-2007

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

( No Codex proposal step 6 or above

X No Codex proposal step 6 or above for the crops requested	Petition
Number:  6E7148

DP Barcode: D335084

Other Identifier:

Residue definition (step 8/CXL): sum of spinosyn A and spinosyn D
Reviewer/Branch: Breann Hanson

	Residue definition: spinosyn A and D

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

Spice Subgroup 19B, except Black Pepper	1.7

Pineapple	0.02

Pineapple, Process Residues	0.08

Limits for Canada	Limits for Mexico

( No Limits

X No Limits for the crops requested	( No Limits

XNo Limits for the crops requested

Residue definition: sum of spinosyn A and spinosyn D	Residue definition:
 spinosad

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

	Notes/Special Instructions: S. Funk, 07/27/2007.

Appendix II – MRL Sheet

EPA

Spinosad

Dill

13-15 day

Residues

0.570

0.12

0.170

0.17

0.020

0.02

Spinosad	Summary of Analytical Chemistry and Residue Data	DP#: 335084

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