Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; 0423718



### UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C. 20460



## MEMORANDUM

Date: 12-November-2014 O FF IC E O F CH E M I CA L SA F E T Y AND

POLL U TION PR E V E NTI O N



### Subject: Azoxystrobin. 

### Pet i t i on for the Establishment of Permanen t To l erances o n I mported
Pear, Imported Tea, and Imported Coffee. Pet i t i on for the Establishment of

Pe r manent Tolerance on Ti Palm and for Crop Group Co n vers i ons fo r Stone Fru i t Group 12-12 and Tree N u t Group 14-12. Summary of Analytica l Chemistry and

Residue Data.

From: PCCode: 128810

Decision No.:486446, 

### 4qs1t./'l

Petition No.: 3E8228; 4E83 I 9

Risk Assessm e nt Type: NA

TXR No.: NA

MRID No.: See Below



### Steve Funk, Senior Chemist

Risk Assessment Branch III (RABIII)

H ealth Effects D i vision ( H ED; 7509P) DP Barcode: D423334; D423718 Registration No.: NIA Regu l atory Action: Tolerance Petition

Case No.: N I A

CASNo.: 131860-33-8 40CFR§180.507



### Through : Christine O l inger, Branch Chief**~ ,/;~** **·** 

### '

Risk Assessment B r anc h I II (RABII I )**~ ~**  

### · Health Effects Division (HED; 7509P)

To: Shaunta Hill/Shaja Joyner, RM#20 Fungicide Branch Registration Division (7505P)

Note: T he DERs were originally prepared under contract by Versar, lnc. (6850 Versar Center, Springfield, VA
22151; submitted 5 1 23 1 12)

. T he document has been reviewed by the Hea l th Effects Division (HED) and revised to
reflect current Office of Pesticide Programs (OPP).



### Page 1 of 25Azoxystrobin Summary of Analytical Chemistry and Residue Dat a Barcode 0423334; 04 23718

OCSPP 860 MR I D Number T itle

Series

Guideline

860. 1 500 49227501 C. Ellis, 2013

, Azoxystrobin

- Residue Study on Pears in

South Korea in 2012, S 12-03087 ,U npuslished study prepared by Eurofins Agro Science Services

, Ltd., 134 p (A I 29 I 3A 50000)

860.1500 49227502 N. Smith,, 2013, Azoxystrobin SC (A l 3364A}- Compilation of

Residue Data in or on Tea, TKO 185024

, Unpublished study prepared by Syngenta Crop Protection

, LLC

, 1 1 0 p. (Al 3364A 50000)

860.1500 49227503 K. Mickelson, 2012, Azoxystrobin and Cyproconazole (Al2910C)

860.1520

- Magnitude of the Residues in or on Coffee: Final Report, TK0046957,
67650, unpublished study prepared by International Agricultural Research, In c., Morse Laboratories, Inc

., 381 p. (A 1291 OC 50005)



### P age 2of25Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 3 of 25 Table of Contents

1.0 Executive Summary

................................ ................................ ................................ ............ 5

2.0 Regulatory Recommendations

................................ ................................ ............................ 5

2.1 Data Deficiencies/Data Needs

................................ ................................ .......................... 5

2.2 Tolerance Considerations

................................ ................................ ................................ . 5

2.2.1 Enforcement Analytical Method

................................ ................................ ............... 6

2.2.2 Recommended Tolerances

................................ ................................ ........................ 6

2.2.3 Revisions to Petitioned

- For Tolerances

................................ ................................ .... 7

2.2.4 International Harmonization

................................ ................................ ..................... 7

3.0 Introduction

................................ ................................ ................................ ......................... 7

3.1 Chemical Identity

................................ ................................ ................................ ............. 8

3.2 Physical/Chemical Characteristics

................................ ................................ ................... 8

3.3 Pesticide Use Pattern/Directions for Use (860.1200)

................................ ....................... 9

4.0 Metabolite/Degradate Residue Profile

................................ ................................ .............. 10

4.1 Nature of the Residue

................................ ................................ ................................ ..... 10

4.1.1 Summary of Plant Metabolism (860.1300)

................................ ............................. 11

4.1.2 Summary of Livestock Metabolism (860.1300)

................................ ..................... 11

4.1.3 Summary of Confined Rotational Crops (860.l850)

................................ ............... 11

5.0 Residue Profile

................................ ................................ ................................ .................. 11

5.1 Residue Analytical Methods (860.1340)

................................ ................................ ........ 11

5.1.1 Data Collection Methods

................................ ................................ ........................ 12

5.1.2 Multi

- Residue Methods (860.1360)

................................ ................................ ........ 12

5.1.3 Tolerance Enforcement Methods

................................ ................................ ............ 13

5.1.4 Submittal of Analytical Reference Standards (860.1650)

................................ ...... 13

5.2 Storage Stability (860.1380)

................................ ................................ .......................... 13

5.3 Residue Data

................................ ................................ ................................ .................. 15

5.3.1 Crop Field Trials (860.1500)

................................ ................................ .................. 15

5.3.2 Field Rotational Crops (860.1900)

................................ ................................ ......... 17

5.3.3 Processed Food and Feed (860.1520)

................................ ................................ ..... 17

5.3.4 Meat, Milk, Poultry and Eggs (860.1480)

................................ .............................. 18

5.3.4.1 Dietary Burden

................................ ................................ ................................ 19

5.3.4.2 Estimated Secondary Residues in Livestock

................................ ................... 19

5.3.5. Food Handling (860.1460)

................................ ................................ ...................... 19Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 4 of 25 5.3.6 Water, Fish, and Irrigated Crops (860.1400)

................................ .......................... 19

6.0 Tolerance Derivation

................................ ................................ ................................ ........ 19

Appendix A. International Residue Limits Table

................................ ................................ ........ 21

Appendix B. OECD MRL Calculation Procedure Inputs/Outputs

................................ .............. 22Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 5 of 25 1.0 Executive Summary

Axoxystrobin fungicide is currently registered for use on a variety of field, vegetable, fruit, and nut crops as well as on ornamental plants and turf. End

- u se products of azoxystrobin are typically formulated as water dispersible granular (WDG)

, suspension concentrate (SC; previously referenced as flowable concentrate), and soluble emulsion (SE) formulations. These products may be applied as in

- furrow at

- planting or postemergence foliar applications using ground or aerial equipment at maximum seasonal rates of 0.40

- 2.0 lb ai/A. Azoxystrobin is also registered for seed treatment of many food/feed crops as well as for postharvest uses on bananas/plantains a nd citrus fruits.

The residue chemistry data base is adequate. The nature of the residue in plants, rotational crops,

and livestock is adequately understood. Acceptable metabolism studies have been conducted on primary crops of grapes, peanuts, and wheat as well as on representative rotational crops. Acceptable metabolism studies on goats and laying hens are also available. The residues of concern in/on primary and rotational crop commodities, for tolerance expression and risk
assessment purposes, are a zoxystrobin and its Z

- isomer ( R230310)

. The residue of concern in

livest ock is parent azoxystrobin only. There are adequate existing storage stability data to validate the storage conditions and durations of samples from the submitted studies.

The current proposal ( 3E8228 ) from Syngenta Crop Protection is for import tolerances with no domestic registrations (uses) for tea, coffee, and pear. Relevant crop field trial studies from non

US locations and specimen labels were supplied in support of the t olerance requests. A coffee processing study was also submitted.

Additionally, IR4 has petitioned ( 4E8321 ) to establish a tolerance for Ti palm based on the existing data for crop subgroup 1A and crop subgroup 2 and has petitioned for conversion of the

s tone fruit crop group to 12

- 12 and the tree nut group to 14

- 12. No new data were submitted.

2.0 R egulatory R ecommendations

There are no residue chemistry considerations that would preclude establishing the

recommended tolerances for azoxystrobin on pear

, coffee

, and tea

. All are for import tolerances with no domestic registrations. Additionally, there are no residue chemistry consideration that would preclude establishing the recommended tolerance for Ti palm and establishing the crop group conversions for stone fruit group 12

- 12 and tree nut group 14

- 12. The specific tolerance

recommendations are discussed in Section 2.2.

2.1 Data Deficiencies/Data Needs

None

.

2.2 Tolerance ConsiderationsAzoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 6 of 25 2.2.1 Enforcement Analytical Method

PP#s 5F4541 & 6F4762; DP # 235342, 5/30/97, C. Stafford PP#7F4864; DP#s 249657 and 249668, 1/25/99, D. Dotson PP#s 6F7106 & 7F7198; DP#s 334571 & 340016, 3/12/08, W. Cutchin PP#5F4541; DP#s 218318 and 218448, 3/19/96, J. Garbus



### A GC/NPD method, RAM 243/04, is available for the enforcement of tolerances for residues of azoxystrobin and its Z

- isomer in crop commodities. The method has undergone method validation by the Analytical Chem istry Branch ( ACB ) / Biological and Economic Analysis Division ( BEAD ). The method was revised to incorporate comments made by BEAD, and the revised method (designated RAM 243, dated 5/15/98) has been submitted to FDA for inclusion

in Pesticide Analytical Manual (PAM)

, Volume II. The LOQ is 0.01 ppm for each analyte in

crop c ommodities.

Data have previously been submitted pertaining to the multiresidue methods testing of azoxystrobin in conjunction with the grape petition (PP#5F4541). The data indicate that azoxystrobin could not be recovered through application of the multiresidue proto cols. These

data have been forwarded to FDA for inclusion in PAM I.

Azoxystrobin may be determined by QuEChERS.

2.2.2 Recommended Tolerances

The residue definition (40CFR§180.507) complies with the recommendation of the S. Knizner

5/27/09 m emo. No change is needed. For compliance in plant commodities , the sum of azoxystrobin and its Z

- isomer is determined.

Table 2.2.2 . Tolerance Summary for Azoxystrobin Commodity Proposed Tolerance (ppm) HED

- Recommended

Tolerance (ppm) Comments

( correct commodity definition ) Coffee, bean, green 0.03 0.0 3 Coffee, green bean

Asian Pear 0.07 0.07 Pear, Asian

Tea 10.0 20.0 Tea, dried

Ti palm, leaves 50 50.0 Ti, leaves Translation of existing group 2 (leaves of root and tuber vegetables) tolerance.

Ti palm , root s 0.5 0.5 Ti, roots Translation of existing subgroup 1A (root vegetable) tolerance. Stone Fruit Group 12 Revoke Revoke Crop Group conversion to 12

- 12 Fruit, Stone, Group 12

- 12 2.0 2.0 Crop Group conversion

. Harmonization with Codex.
Nut, Tree, Group 14 Revoke Revoke Crop Group conversion to 14

- 12 Nut, tree, group 14

- 12 0.02 0.02 Nut, tree, group 14

- 1 2 , except pistachio

. Crop Group conversion. Pistachio remains at a higher tolerance (0.50 ppm)Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 7 of 25 2.2.3 Revisions to Petitioned

- For Tolerances

The proposed tolerance of 10.0 ppm for tea is insufficient, as the trials were conducted at 50% of the label maximum rate. Correction by proportionality to the maximum label rate provides a tolerance recommendation of 20 ppm.

2.2.4 Internatio nal Harmonization

The residue definitions for plants and livestock are not harmonized with Codex; t he US and the

Canadian residue definition s include both the predominant E isomer and the minor Z isomer

whereas t he Codex includes only the E isomer.

A Co dex MRL has been established for coffee beans at 0.03 mg/kg, but no MRLs have been established for pear or tea. Codex recommended an increase in its coffee bean tolerance from 0.02 to 0.03 ppm in 2013. The recommended US tolerance for coffee is harmonized with Codex. No MRLs have been established in Canada for tea, coffee, or pears. The International Residue Limits (IRL) table is found in Appendix A

.

Codex has not established an MRL for ti palm leaves or roots. Canada has not established a tolerance for ti palm leaves or roots. There is no issue of harmonization.

For the crop group conversions, Codex has established an MRL for stone fruit at 2 mg/ kg. Canada has a tolerance for peach at 0.8 ppm. For purposes of harmonization with Codex, the stone fruit group 12

- 12 will be increased to 2.0 ppm from the curren t tolerance of 1.5 ppm for stone fruit group 12.

Codex has established an MRL of 0.01 mg/k g for tree nuts. Canada has established tolerances of 0.02 ppm for the various tree nuts, which is harmonized with the US. The US crop group tolerance is based on a residue definition of azoxystrobin plus the z

- isomer (R230310). Residue s were <0.01 ppm for each component in the almond and pecan trials. Therefore, the tolerance estimate is 0.02 ppm, the sum of the components. The Codex residue definition is parent only, which support the 0.01 mg/kg MRL. The US tolerance cannot be harmonized with Codex.

2.3 Label Recommendations

There are no domestic uses proposed for coffee, tea, or pear and therefore no domestic labels. Adequate summaries of appropriate foreign labels were provided. A proposed master label was provided for ti palm and for the stone fruit group and tree nut group conversions. No changes to the proposed label are needed.

3.0 Introduction

Azoxystrobin is a broad

- spectrum fungicide and belongs to a class of pesticidal compounds called β

- methoxyacrylates, which are derived from the na turally occurring strobilurins (Group 11 fungicide). The biochemical mode of action is inhibition of electron transport.Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 8 of 25 3.1 Chemical Identity

Table 3.1

. Azoxystrobin Nomenclature.

Compound

Common name Azoxystrobin

Company experimental name ICIA5504 (Zeneca), R215504 (Syngenta)

IUPAC name methyl ( 2 E )

- 2

- {2

- [6

- (2

- cyanophenoxy)pyr i midin

- 4

- yloxy]phenyl}

- 3

- methoxyacrylate

CAS name methyl ( α E )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS registry number 131860

- 33

- 8

End

- use products (EP) None for current petition.

Regulated metabolite, Z

isomer

Common name Azoxystrobin, Z

- isomer

Company experimental name R230310

Chemical name methyl ( 2 Z )

- 2

- {2

- [6

- (2

- cyanophenoxy)pyr i midin

- 4

- yloxy]phenyl}

- 3

- methoxyacrylate



### 3.2 Physical/Chemical CharacteristicsAzoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 9 of 25 Table 3.2

. Physicochemical Properties of Technical Grade Azoxystrobin.

Parameter Value Reference

Melting point/range 114

- 116oC DP#s 218318 and 218448, 3/19/96, J. Garbus pH 6.4

Density 1.25 g/cm 3

Water solubility (20°C) pH 5.2 6.7 mg/L pH 7.0 6.7 mg/L pH 9.2 5.9 mg/L

Solvent solubility (20°C) Hexane 0.057 mg/L

Octanol 1.4 mg/L

Methanol 20 mg/L

Toluene 55 mg/L

Acetone 86 mg/L Ethyl Acetate 130 mg/L

Acetonitrile 340 mg/L

Dichloromethane 400 mg/L

Vapor pressure (20°C) 1.1x10

- 13 kPa (8.2x10

- 13 mm Hg)

Dissociation constant, pK
a Not dissociable

Octanol/water partition coefficient, Log(K OW ) log P = 2.5



### 3.3 Pesticide Use Pattern/ Directions for Use (860.1200)

Table 3.3 . Summary of Proposed Directions for Use of ChemicalName 1

.

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

Rate g ai/ha [lb ai/acre] Max. No.

Applic. per

Season Max. Seasonal

Applic. Rate g ai/ha [ lb ai/A ] PHI

(days) Use Directions and

Limitations

Coffee

Foliar with ground equipment. AmistarZtra

SC (200 g/L
azoxystro

bin; 80 g/L Cyprocon

azole)

Colombia 100

- 150

[0. 0 89

- 0.14 ] 3 450 2
[ 0

. 40 ] 15 Start application 90 days after principal flowering followed by 2 consecutive applications with a 45 day interval.

Use a mixture volume of 50 cc per tree after diluting 1.8 ml of commercial product to 1

liter of water . Apply when the coffee crop (leaves, branches, and fruits) is dry. The reentry interval is 4

hours.

Asian Pear

Foliar Azoxystro

bin Amistar

WP 10% (South Korea) 450 3

[0.40] 5 2250 [2.0] 7 Apply at beginning of infestation with a 10 day

retreatment interval.Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 10 of 25 Tea

Foliar Amistar 20

SC ( 0.22 kg/L ) 4 110

– 4 40

[0.09 8

- 0. 39 ] 3 1320 [1. 17 ] 14 Dilution rate 1 g product per 1 L water. Apply

mixture at a maximum

of 4000 L/ha.

Ti Palm

Foliar Abound

Flowable (reg no 100

- 1098) (2.08 lb/gal) 112

- 370

[0.10

- 0.33] Not

specified 2240

[2.00] 0

Soil Abound

Flowable (reg no 100

- 1098) (2.08 lb/gal) 0.0065

-

0.013 lb

ai/1000

row feet Not

specified 2240

[2.00] 0 Band application

between rows.

Use for soilborne/seedling

disease control. Apply in a minimum of 10 gallons per acre

1 Based on foreign label translations provided in Section B of the petition . There are no domestic registrations for the proposed new uses on coffee, pear, and tea

. 2 Calculated based on a maximum of 8333 trees per ha.

3 1 g product is diluted to 1 liter. Calculated from an application of 4500 liters spray solution per ha.

4 Density 1.1 g/cm 3

.



### C onclusions

.

Label translations provided as Section B of the petition are adequate to allow evaluation of the residue data relative to the propo sed use. For the foreign uses (pear, coffee, tea) , label

deficiencies are not addressed.

For the crop group conversions (stone fruit, tree nuts), the master label (registration number 100

- 1098) is acceptable. The list of stone fruits and tree nuts included in the new groups have been correctly provided. The use directions remain unchanged. For Ti palm, the proposed label is

ade quate, and there are no deficiencies.

4.0 Metabolite/Degradate Residue Profile

4.1 Nature of the Residue

Table 4.0. Summary of Metabolites and Degradates to be included in the Risk Assessment and

Tolerance Expression for Azoxystrobin 1

Matrix Residues included in Risk

Assessment Residues included in Tolerance Expression

Plants Primary Crop Azoxystrobin + Z

- isomer Azoxystrobin + Z

- isomer

Rotational Crop Azoxystrobin + Z

- isomer Azoxystrobin + Z

- isomer

Livestock Ruminant Azoxystrobin Azoxystrobin

Poultry Azoxystrobin Azoxystrobin Drinking Water Azoxystrobin Not Applicable

1 HED Metabolism Assessment Review Committee Decision Memo; DP# 251683, 12/30/98, W. WassellAzoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 11 of 25 4.1.1 Summary of Plant Metabolism (860.1300)

PP#5F4541; DP#s 218318 and 218448, 3/19/96, J. Garbus PP#6F4762; DP#s 230634, 230635, 230636, and 230637; 4/25/97; L. Kutney



### Adequate metabolism studies on grapes, peanuts, and wheat were submitted in conjunction with earlier azoxystrobin petitions, PP# s 5F4541 and 6F4762. Azoxystrobin undergoes photochemical isomerization to produce the Z

- isomer and is extensively metabolized in plants. The parent compound undergoes cleavage of the ether linkages between the phenylacrylate and pyrimidinyl rings and th e cyanophenyl and pyrimidinyl rings, with subsequent oxidation, hydrolysis, and/or reduction of the primary metabolites to form numerous secondary metabolites. Azoxystrobin is systemic. HED has determined that the residues of concern in/on plants for

tol erance expression and risk assessment purposes are azoxystrobin and its Z

- isomer.

4.1.2 Summary of Livestock Metabolism (860.1300)

PP#5F4541; DP#s 218318 and 218448, 3/19/96, J. Garbus PP#6F4762; DP#s 230634, 230635, 230636, and 230637; 4/25/97; L. Kutne y HED Metabolism Assessment Review Committee Decision Memo; DP# 251683, 12/30/98, W. Wassell



### The nature of the residue in livestock is adequately understood based on acceptable metabolism studies conducted on goats and laying hens. HED has determined that the residue of concern in

livesto ck is parent azoxystrobin only.

Note that this topic is not relevant to the current submission, as pears, tea, and coffee do not have

livestock feed items. Ti palm roots/leaves are not recognized as significant feed items.

4.1.3 Summary of Confined Rotational Crops (860.l850)

PP#6F4762 ; DP#s 230634, 230635, 230636, and 230637 , L. Kutney, 4/25/97 PP#9F6058; DP# 260134, 9/6/00, M. Nelson



### Adequate confined studies have previously been presented in PP#6F4762 and re

- evaluated in

PP#9F6058. Azoxystrobin is metabolized via four pathways: (i) hydrolysis of the ester, followed by conjugation to glucose or malonylglucose; (ii) reduction of th e side chain double bond followed by conjugation to glucose or malonylglucose; (iii) cleavage of the ether linkage to form

two

- ring compounds followed by further conjugation; and (iv) mineralization to 14 

### C

- carbon dioxide which is incorporated into natural products. Rotational crops were found to contain a larger amount of conjugated metabolites than found in the primary crop metabolism studies, and these conjugated metabolites were conjugates of primary crop metabolites

HED has concluded that the residue s of concern in rotational crops are parent and the Z

- isomer.

Note that this topic is not relevant to the current requests for import tolerances

.

5.0 Residue Profile

5.1 Residue Analytical Methods (860.1340)Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 12 of 25 5.1 .1 Data Collection Methods

49227501.der

49227502.der

49227503.der



### For pear and coffee

, s amples were analyzed for residues of azoxystrobin and its Z

- isomer (R23010) using a standard high performance liquid chromatography method with tandem mass spectrometry detection (LC/MS/MS), Method RAM 305/03. S amples were extracted twice with acetonitrile (ACN):water (90:10, v:v). After centrifugation, the combined extract s w ere cleaned

up on a C18 solid phase extraction (SPE) column for analy sis. Transitions monitored were

404.1/372.1 and 404.1/344.0. Matrix matched standards were used. A cceptable con current recoveries were reported for pear samples at fortification levels of 0.01 and 0.10 pp m (90

- 112% azoxystrobin, 84

- 91% Z

- isomer) , thus validating the method. Acceptable method validation and concurrent recoveries were reported for green coffee bean samples at fortification levels of 0.01 and 1.0 ppm (87

- 116% azoxystrobin, 89

- 118% Z

- isomer), thus validating the method. The limit of quantitation (LOQ ; determined as the lowest level of method validation, LLMV ) was 0.01

ppm for each analyte; the LOQ for combined residues was 0.02 ppm , for both coffee beans and pear fruits

.

For tea, non

- standard high performance liquid chromatography method s with UV detection ( HP LC/ UV 235nm ) were used at two different laboratories. Samples were extracted with organic solvent, concentrated, and purified by sequential solid

- phase extractions (S PE). The final eluate s

w ere concentrated to dryness and redissolved in ACN:water (1:1, v:v) for HPLC/UV analysis. Acceptable concurrent recoveries were reported for tea samples fortified with azoxystrobin and

its Z

- isomer (R230310) at 0.4 ppm each (JACC location; 82

- 92% ) and with azoxystrobin at 1.6 ppm (92

- 101%) and 10 ppm (JFRL location ), thus validating the methods. Samples were analyzed for only azoxystrobin. The LOQ was 0.4 ppm or 1.6 ppm, depending on the laboratory.

Conclusions.

Method RAM 305/ 03 has been adequately validated as a data collection method for coffee and

pears. This method has been used previously for data collection (D397692, M. Negussie, 03/21/2013). The HPLC/UV method for tea was validated at relatively high concentrations and

was not used to determine the Z

- isomer.

5.1.2 Multi

- Residue Methods (860.1360)

PP#5F4541; DP#s 218318 and 218448, 3/19/96, J. Garbus



### Data have previously been submitted pertaining to the multiresidue methods testing of azoxystrobin in conjunction with the grape petition (PP#5F4541). The data indicate that azoxystrobin could not be recovered through application of the multiresidue protocols. These

data have been forwarded to FDA for inclusion in PAM I.

Azoxystrobin may be determined by QuEChERS. Adequate recoveries and precision have been demonstrated for acidic, dry (cereal), sugar containing, and water containing matrices at fortifications of 0.01 to 0.25 ppm (DIN EN 15662 (2009

- 02); Foods of plant or igin

-Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 13 of 25 Determination of pesticide residues using GC

- MS and/or LC

- MS/MS following acetonitrile extraction/partitioning and clean

- up by dispersive SPE

- QuEChERS

- method ).

Conclusions

.

US FDA MRMs are not suitable for the determination of azoxystrobin.

5.1 .3 Tolerance Enforcement Methods

PP#s 5F4541 & 6F4762; DP# 235342, 5/30/97, C. Stafford PP#7F4864; DP#s 249657 and 249668, 1/25/99, D. Dotson PP#s 6F7106 & 7F7198; DP#s 334571 & 340016, 3/12/08, W. Cutchin



### Crop commodities : A GC/NPD method, RAM 243/04, is available for the enforcement of tolerances for residues of azoxystrobin and its Z

- isomer in crop commodities. The method has undergone method validation by the Analytical Chem istry Branch ( ACB ) / Biological and

Economic A nalysis Division ( BEAD ). The method was revised to incorporate comments made by BEAD, and the revised method (designated RAM 243, dated 5/15/98) has been submitted to

FDA for inclusion in Pesticide Analytical Manual (PAM)

, Volume II. The LOQ is 0.01 ppm for each analyte in crop commodities.

Conclusions.

An adequate residue analytical method i s available for tolerance enforcement in crop

commodities.

5.1.4 Submittal of Analytical Reference Standards (860. 1650)

Referen ce standards are available from the EPA National Pesticide Standards Repository (Email from T. Cole, 10/14/2014). The azoxystrobin standard expires 07/26/2018, and the Z

- isomer standard expires 08/31/2018.

5.2 Storage Stability (860.1380)

DER References:

48 601201 .der (including MRID 4860102)

48601203.der PP#7F4864; DP#s 248887 and 249671, 10/14/98, D. Dotson, et al. PP#7F4864; DP#s 249657 and 249668, 1/25/99, D. Dotson



### Adequate storage stability data are available indicating that azoxystrobin and its Z

- isomer are reasonably stable under frozen conditions in/on fortified samples of diverse crops. In previous studies, residues were determined to be stable for 2 years in/on apple, banana, carrot, cucumber, grape, leaf lettuce, rape seed, peach, winter whe at straw, wheat forage, and wine. Over the 2

- year period, residues of both azoxystrobin and its Z

- isomer decreased by up to 20% in winter wheat grain and by up to 27% (azoxystrobin only) in tomato, peanut, and pecan, but all recoveries were >70%; residues in these crops were stable (without decrease) for up to 6

- 8 months of storage.Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 14 of 25 Previous studies conducted on processed commodities demonstrated that fortified residues of azoxystrobin and its Z

- isomer were generally stable under frozen conditions in peanut oil and meal, tomato juice and paste, and wheat bran for up to 1 year, and in soybean meal, corn grits, and orange oil, juice and pulp for at least two years.

A concurrent storage stability w as conducted to support the tea field trial study . Control samples of each commodity were fortified with azoxystrobin or the Z

- isomer and placed in storage under the same frozen conditions as the treated samples for the same storage durations; no 0

- day da ta were provided.

Table 5.2.1. Stability of Azoxystrobin In Tea Leaves Following Storage at

- 20 o C
Commodity Spike

level (ppm) Storage interval

(days) Recovered

residues ( % ) Mean

Recovered

Residues ( % ) Corrected %

recovery

Azoxystrobin

Dried tea leaves 1.0 67 93.3, 92.2 92.8 106

76 80.8, 76.3 78.6 87.0

83 90.3, 88.6 89.7 105

83 74.7, 74.0 74.4 96.4

2 108 89, 88 88 91

119 84,83 84 87

122 84, 83 84 87

122 94,92 93 96

Z

- Isomer (R230310)

Dried tea leaves 1.0 67 95.8, 95.6 95.7 114

76 80.7, 79.8 80.2 101

83 95.2, 93.6 94.4 116

83 74.7, 74.0 74.4 96.4

Table B.5. 2.2 . Summary of Storage Conditions.

Matrix Storage Temperature (°C) Actual Storage Duration 1 Interval of Demonstrated Storage Stability

Pear ≤

- 18 42

- 66 days (1.4

- 2.2 months) Residues of azoxystrobin and R230310 are stable

for up to 2 years in various crops including apples stored frozen (<

- 18 °C). 2

Tea, Dried

Leaves - 20 79

– 113 days (2.6

– 3.7 months) Azoxystrobin is stable for up to 4.0 months. The Z

isomer is stable for up to 3 months. Concurrent storage stability (see Table 5.2.1 )
Coffee, green

beans - 20 31

- 57 days (1.0

- 1.9 months) 71 days (2.6 months) beans for processing Residues of azoxystrobin and R230310 are stable

for up to 2 years in various crops including oil seed rape stored frozen (<

- 18 °C). 2

Coffee, dry

roasted bean - 20 28 days (0.9 months)

Coffee, instant

- 20 21 days (0.7 month)

1 Interval from harvest to analysis. The petitioner indicated samples were analyzed within 7 days of extraction for pear, 0

- 3 days

for coffee. Extraction dates not provided for tea.

2 DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98

. 

### ConclusionsAzoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 15 of 25 The storage stability data are adequate to support the field trials and coffee processing study. Stability for up to two years of frozen storage has been demonstrated for high water (lettuce, apple), high acid (orange), high oil (rape seed), and high starch (wheat) commodities. Stability

has not been demonstrated in a high protein commodity (such as pulses).

5.3 Residue Data

5.3.1 Crop Field Trials (860.1500)

49227501.der

49227502.der

49227503.der1



### Asian Pear

Syngenta Crop Protection, LLC has submitted field trial data for azoxystrobin on Asian pears. Eight pear field trials were conducted in South Korea during the 2012 growing season. All pears were contained in paper/wax paper bags according to local practi ces and regulations for this crop in South Korea. The bags were placed on the pears well in advance of the first application and remained in place until harvest. Each trial consisted of one untreated plot and one treated plot. At all trial locations, the treated plot received five foliar broadcast applications of a 10% wettable powder (WP) formulation of azoxystrobin (A12913A) at 0.359

- 0.475 lb ai/A/application ( 402

- 532 g ai/ha/application) for total rates of 1 .978

- 2.081 lb ai/A ( 2218

- 2333 g ai/ha). All applications were made at retreatment intervals (RTIs) of 9

- 11 day s using ground equipment in spray volumes of 430

- 568 gal/A ( 4024

- 5315 L/ha); no adjuvant s w ere used

. At all trials

, pears were harvested at a 7

- day preharvest interval (PHI).

Tea

Sy ngenta Crop Protection, LLC has submitted residue data for azoxystrobin on tea. Four tea

field trials for were conducted in Japan during the 1998 growing season. Each trial consisted of one untreated plot and one treated plot divided into three subplots ( 2, 3, and 4) to establish separate preharvest intervals (PHIs). Each treated plot received three foliar spray applications of a 20% suspension concentrate (SC) formulation of azoxystrobin (Amistar® 20 SC) at 0.196 lb ai/A/application (220 g ai/ha/applica tion), for a total rate of 0.589 lb ai/A ( 660 g ai/ha). Note

that this is about 5 0 % of the proposed label application rate, both per application and per season. All applications were made at retreatment interval s (RTI s ) of 7 days using ground equipment i n spray volumes of 214 gal/A ( 2000 L/ha); no adjuvant s were used. Single samples of green tea

leaves were harvested at PHI s of 7, 14, and 21 days from subplots 2, 3, and 4, respectively, and

were dried.

Coffee

Syngenta Crop Protection, LLC has submit ted residue data for azoxystrobin on coffee from field

trials conducted in Central and South America. Four coffee field trials were conducted during the 2011 and 2012 growing seasons in Colombia (1 trial), Guatemala (1 trial), and Brazil (2 trials). HED has determined that two trials conducted in Colombia are replicate trials; the trial

count reflects this conclusion.Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 16 of 25 Each trial consisted of one untreated plot and one treated plot. At all trial locations, the treated plot received three foliar spray applications of a 1.67 lb ai/gal (200 g ai/L) suspension concentrate (SC) formulation of azoxystrobin (A12910C). The product is a multiple acti ve ingredient (MAI) formulation that also contains cyproconazole at 0.67 lb ai/gal (80 g ai/L). Each treated plot received three applications of azoxystrobin at 0.131

- 0.137 lb ai/A/application (146.7

- 154.0 g ai/ha/application) for total rates of 0.394

- 0.4 10 lb ai/A (441.7

- 459.3 g ai/ha). All applications were made at retreatment intervals (RTIs) of 42

- 49 days using ground equipment in spray volumes of 21.38

- 42.58 gal/A (200.0

- 398.3 L/ha). A nonionic surfactant (NIS) alone or in conjunction with a crop oi l was added to the spray mixtures for all applications. Samples of
coffee bean “cherries” were harvested from all trials at a 14

- to 15

- day preharvest interval (PHI).

Ti

IR

- 4 has petitioned to establish tolerance s for ti palm leaves and ti palm roots . No field trial data were submitted in support of the request. It is proposed to translate the root vegetable subgroup 1A tolerance to ti root and the leaves of root and tuber vegetables group 2 tolerance to ti leaves. ChemSAC (ChemSAC Minutes, 06/11/2 013) approved the proposal based on the following

rationale:

Ti palm parts consumed are roots and tops (leaves). Ti palm is being considered for inclusion into Root and tuber vegetable group 1, and crop subgroups 1A Root vegetable and 1B Root vegetable, except sugar beet subgroup, as well as crop group 2 leaves of root and tuber group. Ti palm is a very minor crop with low dietary intake and its roots are consumed in human die ts and the leaves are used to wrap food items

... .


### The proposed use patterns o n ti palm are identical to the existing use pattern, both foliar and soil application, for carrot, potato, and other root crops. ChemSAC noted that a similar request was approved previously for propiconazole.

Table 5.3.1 . Summary of Residues from Field Trials with Azoxystrobin

Crop

Matrix Analyte Applic.

Rate (lb ai/acre) [g ai/ha] PHI

(days) n * Residues (ppm)

Min. † Max. † LAFT * HAFT * Median * Mean * SD *

Pear Proposed Use = 2 lb ai/acre total application rate, 7

- day PHI

.

Pear (bagged) Azoxy

strobin

+ Z

isomer 1.978

-

2.081 [2218

- 2333] 7 8 <0.02 <0.05 (0.04 1 ) <0.02 <0.05

(0.04 1 ) 0.02 0.03 0.01

Tea Proposed Use = 1.2 lb ai/acre total application rate, 14

- day PHI

.
Tea, dried Azoxy

strobin 0.589

[660] 14 4 0.69 4.66 0.69 4.66 2.80 2.74 1.67

Coffee Proposed Use = 1.2 lb ai/acre total application rate, 14

- day PHI

Coffee, green bean Azoxy

strobin

+ Z

isomer 0.394

-

0.410 [441.7

- 459.3] 14

- 15 4 <0.02 <0.0259 (0.016 1 ) <0.02 <0.0230 0.0202 0.0209 0.0014

† Values based on total number of samples.

* Values based on per

- trial averages. LAFT = Lowest Average Field Trial, HAFT = Highest Average Field Trial, SD = StandardAzoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 17 of 25 Deviation. For computation of the LAFT, HAFT, median, mean, and standard deviation, values < L OQ are assumed to be at the LOQ, or 0.01 ppm for each of azoxystrobin and its Z

- isomer.

1 Azoxystrobin only.



### Conclusions

.

The coffee and pear field trials reflect the proposed use patterns, and the number of independent field trial meet at the minimum number of trial requirements for import purposes. Brazil is a major exporter of coffee to the US , and 4 trials is 80% of the number of trials recommended for coffee (OSCPP 860.1500). Pear is not a major import from South Korea, and the use (bagged fruit) is unique. All pears exported to the US are treated while bagged, in accordance with South Korea regulation. Eight trials is 100% of the number of trials required for a domestic tolerance.

Japan is not a major exporte r of tea to the US, but the pesticide is not registered for use on tea in major exporting countries such as China and India (S. Hill, PRIA 3 Technical Scree n, 04/24/2014 Email). The number of required trials for US (domestic) tolerance is not specified. Four trials is considered adequate. The tea trials were conducted at about 50% of the proposed label rate for each of the three applications. Proportional ity may be used to adjust the residue

values. The analytical methods are adequate for data collection purposes. However, the tea samples were not analyzed for the Z

- isomer. This component is anticipated to be <10% of the total residue, based on field tr ial results for other commodities. Samples from all studies were stored frozen for intervals of known stability of azoxystrobin and Z

- isomer in/on various

commodities.

No trials were conducted for ti palm, but the root and leaf commodities may be include d under crop subgroup 1A and crop group 2, respectively. The proposed use pattern for ti palm is identical to the existing GAP for potato, carrot, and other root crops.

5.3.2 Field Rotational Crops (860.1900 )

This topic is not applicable to the import t olerance requests for tea, pear, and coffee. The plant back interval of 0 days established for all crops with azoxystrobin registered uses, except buckwheat and millet, applies to the rotation of crops into fields of ti palm treated with azoxystrobin.

5. 3.3 Processed Food and Feed (860.1520)

49227503.der2

A processing study was provided for coffee. A processing study was not provided for tea. Asian

pear does not have recognized processed food or feed items. In coffee one trial conducted in

Guatemala during the 20 11 growing season, a treated plot received three foliar spray applications

of a 1.67 lb ai/gal (200 g ai/L) suspension concentrate (SC) formulation of azoxystrobin (A12910C). The treated plot received three applications of azoxystrobin at an exaggerated rate

of 0. 6651

- 0. 6794 lb ai/A/application ( 745.6

- 761.7 g ai/ha/application) for a total rate of 2.014 lb ai/A ( 2258 g ai/ha). The application rate used in the study was ~5x that used in the corresponding field trials. Samples of coffee bean “ cherries” were harvested at a 14

- day preharvest interval (PHI). C offee cherries were processed into green coffee beans at the fieldAzoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 18 of 25 sites , and t he green coffee bean samples were processed into roasted coffee beans and instant coffee at GLP Technologies (N avasota, TX) using simulated commercial practices

. Adequate descriptions of the processing procedures were provided, including material balance summaries.

Table 5.3.3.1

. Residue Data from the Coffee Processing Study with Azoxystrobin

RAC Processed Commodity Total Rate

lb ai/A (g ai/ha) PHI

(day) Residues (ppm) Processing Factor Azoxy

strobin Z

- isomer

(R230310) Azoxy

strobin Z

- isomer

(R230310)

Coffee RAC

(prior to processing)

2.014

(2258) 14 <0.01 <0.01

- -

Dry roasted

coffee <0.0108 <0.01

~ 1.1x 1 NC 2

Instant Coffee <0.0168 <0.01

~ 1.7x 1 NC 2

1 Azoxystrobin residues were <LOQ on the RAC, and residues were slightly above the LOQ in one of two replicate samples for the processed commodities (0.0115 ppm for dry roasted coffee and 0.0236 ppm for instant coffee).

2 Not calculated. Residues were <LOQ in both the RAC and processed fractions for the Z

- isomer



### A processing study was not conducted for the conversion of the raw agricultural commodity (RAC) tea leaves to instant tea. However, the commercial processing of coffee to instant coffee is very similar to the commercial processing of tea to instant tea. Both consist of water extraction of the RAC and removal of water from the extract by freeze drying or spray drying. The percent solids obtained from dried coffee bean and dried tea leaf are similar, approximately 40% vs 50% (P. Kaleniaa, National Coffee A ssociation USA, Coffee Extract Solids , 2007; US Patent 4668525, Thomas J. Lipton, Inc., 1982). The processing factor for instant coffee may be translated to instant tea for azoxystrobin.

C onclusions

.

The coffee processing data are supported by adequate storage stability, and the analytical method is adequate for data collection purposes. The residue of concern, azoxystrobin plus Z

- isomer, was determined for the RAC and processed fractions. A 5X exaggerated rate trial indicated no

residues at o r above the LOQ. Therefore, a processing study is not required. A processing study was conducted nonetheless on a RAC having no quantifiable residues. Residues of azoxystrobin,

but not the Z

- isomer, concentrated slightly in one of two replicates for eac h of instant coffee and

roasted beans.

As the preparation processes are very similar and the percentages of solids extracted similar , the coffee to instant coffee processing factor results may be translated to the conversion of tea to

instant tea. This applies only to the current situation with azoxystrobin.

5.3.4 Meat, Milk, Poultry and Eggs (860.1480)Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 19 of 25 There are no livestock feed items associated with Asian pear, tea, and coffee beans. Therefore, livestock feeding studies are not relevant.

5.3. 4.1 Dietary Burden

There are no feed items associated with Asian pear, tea, and coffee beans. Ti palm root and leaf are not considered a significant feed item. Therefore, livestock dietary burdens are not changed.

5.3. 4.2 Estimated Secondary Residues in Li vestock

The estimated secondary residues in livestock commodities are not changed by the addition of import tolerances for Asian pear, tea, and coffee beans.

5.3. 5

. Food Handling (860.1460)

There are no food handling uses associated with import tolerance requests for Asian pear, tea,

and coffee beans

.



### 5.3. 6 Water, Fish, and Irrigated Crops (860.1400)

Ther e are no water, fish, and irrigated crop uses/issues associated with import tolerance requests.

6.0 Tolerance Derivation

Recommended tolerance level values were obtained by use of the Organization of Economic Cooperation and Development (OECD) calculation procedure. Field trial residue values for pear ranged from <LOQ (0.02 ppm) to 0.05 ppm (n = 8, with 5 <LOQ).

Field tri al residue values for coffee were at or below LOQ (0.02 ppm), with a maximum value of 0.023 ppm. For both commodities, the LOQ value was used for residues <LOQ. The OECD procedure yielded an estimate of 0.04 ppm. This was lowered to 0.03 ppm in order to harmonize

with Codex.

Tea leaf residue values were all (n = 4) substantially above the respective LOQ (0.4 ppm or 1.6 ppm) and ranged from 0.72 to 4.85 ppm. Values were corrected upward by 4% to account for

the failure to determine the Z

- isomer. The Z

- isomer is typically 2

– 7 % of the azoxystrobin concentration in field trials for other commodities. Additionally, the results were corrected by a factor of 2X to account for the field trials being conducted at 50% of the label application rate.

The exist ing tolerances for group subgroup 1A and crop group 2 are translated to ti palm roots and leaves, respectively.

See Appendix B for details.

The coffee processing study was based on a field trial conduc t ed at 5X the label application rate.

Residues with the coffee beans were <LOQ (<0.02 ppm). Therefore, no processing study isAzoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 20 of 25 required (OCSPP 860.1520), and the RAC tolerance will suffice for instant coffee and roasted

coffee. It is noted that the field trial HAFT for azoxystrobin on green coffee beans ( 0.0 16 ppm) multiplied by the instant coffee processing study factor (1.7X) yields a processed commodity

estimate of 0.03 ppm, equivalent to the recommended green coffee bean tolerance (0.03 ppm). The factor for roasted beans was lower (1.1X) than for insta nt coffee.

The HAFT for tea, after correction for application rate, is 9.7 ppm. Using the instant coffee processing factor (1.7X), a process ed commodity tolerance estimate of 16 ppm is obtained. This

is less than the recommended dry tea leaf tolerance of 20.0 ppm. The tea leaf tolerance will cover the processed commodity instant tea

.Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 21 of 25 Appendix A . International Residue Limits Table



## International Residue Limits

Azoxystrobin (PC Code 128810; 08/21 /1 4 )
Summary of US and International Tolerances and Maximum Residue Limits Residue Definition :
US Canada Mexico 2 

### Codex 3

40 CFR 180.507:

Plant: sum of azoxystrobin, [methyl( E )

- 2

- (2

- (6

- (2

- cyanophenoxy) pyrimidin

- 4

- yloxy)phenyl)

- 3

- methoxyacrylate], and the Z

isomer of azoxystrobin [methyl( Z )

- 2

- (2

- (6

- (2

- cyanophenoxy)pyrimidin

- 4

- yloxy)phenyl)

- 3 methoxyacrylate] (αE)

- methyl 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- methoxymethylene)benzene

acetate, including the isomer (Z)

- methyl 2

- [[6

- (2

- cy anophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)benzen

eacetate Azoxystrobin.

The residue is fat

soluble.



### Commodity 1 

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

US Canada Mexico 2 

### Codex 3

Coffee , green bean 0.0 3 0.06 (pending) 0.0 3

Pear 0.07 0.07 (pending) None

Tea 20 20 (pending) None Completed: M. Negussie; 08/21 /201 4

1 Includes only commodities of interest for this action. Tolerance values should be the HED recommendations and

n o t those proposed by the applicant. *The established tolerance should remain at 420 ppm.

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

3 * = absent at the limit of quantitation; Po = postharvest treatment, such as treatment of stored grains. PoP = processed post harvest treated commodity, such as processing of treated stored wheat. (fat) = to be measured on the fat portion of the sample. MRLs indicated as proposed have not been finalized by the CCPR and the CAC.Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 22 of 25 A ppendix B

. OECD MRL Calculation Procedure Inputs /Outputs

Asian Pear (South Korea)

The OECD calculation provides an estimate of 0.07 ppm. Five of seven residue values were below the LOQ.

Residues (mg/kg) n

< 0.02 5

0.03 2

0.05 1

Azoxystrobin

Asian Pear

S Korea

5 X 0.4, 7 d PHI

Total number of data (n) 8

Percentage of censored data 63%

Number of non

- censored data 3

Lowest residue 0.020

Highest residue 0.050

Median residue 0.020

Mean 0.026

Standard deviation (SD) 0.011
Correction factor for censoring (CF) 0.583

Proposed MRL estimate

- Highest residue 0.050

- Mean + 4 SD 0.069

- CF x 3 Mean 0.046

Unrounded MRL 0.069

Rounded MRL 0.07

High uncertainty of MRL estimate.

[High level of censoring]Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 23 of 25 Coffee Bean (Green)

The OECD procedure provides an estimate of 0.04 ppm. Three of four residue values were below the LOQ. Codex has an MRL of 0.03 ppm It is noted that the highest field trial value in the current submission was 0.023, or slightly above the 0.02 ppm LOQ. For purposes of harmonization, the estimate will be adjusted downward to 0.03 ppm.

Residues (mg/kg) n

< 0.02 3

0.023 1

Azoxystrobin

Coffee Bean

Import

3 X 0.13, 14 d PHI

Total number of data (n) 4
Percentage of censored data 75%

Number of non - censored data 1

Lowest residue 0.020

Highest residue 0.023

Median residue 0.020

Mean 0.021

Standard deviation (SD) 0.002
Correction factor for censoring (CF) 0.500

Proposed MRL estimate

- Highest residue 0.023

- Mean + 4 SD 0.027

- CF x 3 Mean 0.031

Unrounded MRL 0.031

Rounded MRL 0.04

High uncertainty of MRL estimate.

[Small dataset and high level of censoring]Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 24 of 25 Tea, Dried Leaves

Field trial samples were analyzed for azoxystrobin only. All trials (n = 4) had residues much in excess of the LOQs. The Z

- isomer was not determined. It may be estimated from field trials

with other commodities.

Commodity DP Barcode Azoxystrobin Me an (ppm) Z

- Isomer

Mean (ppm) Ratio Z /

Azoxystrobin

Radish top D260134 28.6 0.61 0.021 Spinach D260134 18.9 0.42 0.022

Leaf Lettuce D260134 7.5 0.28 0.037

Mandarin Peel D260134 6.98 0.45 0.064

Field Corn Stover D260134 5.23 0.27 0.052

Dill Seed D312949 15.6 0.83 0.053

Fresh Chives D312949 6.54 0.19 0.029

Dried Chives D312040 38.85 0.83 0.021

AVERAGE 0.037



### A factor of 0.04 was used to account for Z

- isomer in the dried tea field trial results, that it, (measured E

- isomer + measured E

- isomer X 0.04 = total residue).

Residues (mg/kg) n

0.72 1

2.41 1

3.4 1

4.85 1



### However, the total application rate was 0.59 lb ai/acre, whereas the label rate is 1.18 lb ai/acre (50% of proposed). Each of the three applications was conducted at 50% of the proposed rate (0.2 lb ai/acre vs 0.4 lb ai/acre label, and therefore p roportionality may be used to adjust for the lower rate ( 50% of proposed). Each trial result is adjusted by a factor of 2X.

Residues (mg/kg) n

1.44 1

4.82 1

6.8 1

9.7 1

Azoxystrobin

Tea, dried

Japan

3 X 0.4, 14 d PHI

Total number of data (n) 4Azoxystrobin Summary of Analytical Chemistry and Residue Data Barcode D423334; D 423718



### Page 25 of 25 Percentage of censored data 0%

Number of non

- censored data 4

Lowest residue 1.440

Highest residue 9.700

Median residue 5.810

Mean 5.690

Standard deviation (SD) 3.470
Correction factor for censoring (CF) 1.000

Proposed MRL estimate

- Highest residue 9.700

- Mean + 4 SD 19.572

- CF x 3 Mean 17.070

Unrounded MRL 19.572

Rounded MRL 20

High uncertainty of MRL estimate.

[Small dataset]Azoxystrobin [PC Code 12881 OJ / Syngenta Crop Protection, LLC



### B.7.6 Residues Resulting from Supervised Trials 

### (Annex llA 6.3; Annex IHA 8.3)

B.7.6.1 Residues in Target Crops

B.7.6,1.1 Pear (Asian)

Document ID: MRID No. 49227501



### Report: Ellis, C. (2013) Azoxystrobin -R esi due Study on Pears in South Korea in

2012: Final Report. Repo rt/Study Num be r : S 12-03087. Task Number:

TK0047640. Unpublished study prepared by Syngenta Crop Protection,

LLC. 134 p. 

### Guidelines: EPA OCSPP Harmonized Test Guideline 860.1500 Crop Field Trials (August 1996)

PMRA Regulator y Directive DIR98-02- Residue Chemistry Guidelines,

Sec t ion 9

- Crop Field Trials

PMRA Regulatory Directive DIR2010-05

- Revisions to th e Residue Chemistry Crop Field Trial Requirements

OECD Guideline 509 Crop Field Trial (September 2009)



### GLP Compliance : No deviations from regulatory requirements were reported which would

have an impact on the valid i ty of the st udy. 

### Acceptability: The study is considered scien t ifical ly acceptable. The acceptability of this study for regulatory purposes is addressed in**th~** 

### forthcoming U.S. EPA

Residue Chemistry Summary Document, D .p'# 418374.



### Evaluator: Steve Funk, Senior Chemist, RAB III 

## I · ,J, 

## l

,

. \

. I 

## l (**~** J

. I \**\** /

. . .II 1,,.,

, .. /

Note: This Data E valuation Record (DER) was originally prepared under contract bJ

· · versar, \ lnc

. (6850 Versar Center, Springfield, VA 22151 ; submitted 9130 1 14 )

. The DER ha s been reviewed by HED and revised to reflect current Office of

Pe s ticide Programs (OPP) policies.



### EXECUTIVE SUMMARY

Syngenta Crop Protection, LLC has submitted field trial data for azoxystrobin on Asian pears. Eigh t pear field trials were conducted in South Korea dur ing the 2012 growing season. All pears

were contained 

### in paper/wax paper bags according to local practices and regulations for this crop in South Korea. The bags were placed on the pears well in advance of the first application and

remained 

### in place u ntil harvest.

Each tr ial consisted of one untreated plot and one treated plot. At all tria l loca t ions

, the treated plot received five foliar broadcast applications of a 10% wettab le powder (WP) formulation of azoxystrobin (A12913A) at 0.359-0.475 lb ai/A/application (402-532 g ai/ha/application) for

total ra tes of 1.978 -2.08 1 lb ai/A (2218-2333 g ai/ha). All applications were made at re treatment

i n terva ls (RTls) of9-11 days using grou nd equipment in spray volumes of 430-568 gal/A (4024-

5315 L/ha); no adjuvants were used

. At all tr ials, pears were harve sted at a 7-day preharvest

interva l (PHI). Additional sam ples were collected from four trials at 0- a nd 3-day PHis to assess

re sidue decline.

Pa e 1 of8



### EPA MRID #: 49227501Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 4922750 1 Page 2 of 8 

### Samples were analyzed for residues of azoxystrobin and its Z

- isomer ( R23010 ) using a high performance liquid chromatography method with tandem mass spectrometry detection (LC/MS/MS), Method RAM 305/03. A cceptable con current recoveries were reported for pear samples at fortification levels of 0.01 and 0.10 ppm , thus validating the method. The limit of quantitation (LOQ ; deter mined as the lowest level of method validation, LLMV ) was 0.01 ppm for each analyte ; the LOQ for combined residues was 0.02 ppm.

All samples were maintained frozen at the testing facility, during shipping to the laboratory, and

were stored frozen until an alysis. The field residue samples were stored frozen a maximum of 66 days (2.2 months) from harvest to analysis. Extraction and analysis dates were not provided; however, the petitioner reported the beginning and ending dates for reside analysis. In add ition the petitioner reported that sample extracts were stored for a maximum of 7 days prior to analysis. The available freezer storage stability data indicate that residues of azoxystrobin and

R230310 are stable when stored frozen ( <

- 18 °C ) for up to 2 years in various crops including apples ( DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/ 98 ). Adequate storage stability data are therefore available to support the storage conditions and intervals for samples in

the current trials.

Following five foliar broadcast applications of the 10% WP formulation a t total rates of 1 .978

- 2.081 lb ai/A ( 2218

- 2333 g ai/ha)

, i ndividual sample (and per

- trial average) combined residues of azoxystrobin and its Z

- isomer ( R230310 ) were <0.02

- <0.05 ppm ( <0.02

- <0.05 ppm) in/on bagged pears harvested at a 7

- day PHI. Residues of the Z

- isomer were below the LOQ (<0.01 ppm) in/on all samples.

In the residue decline trials, r esidues in pears remained approximately the same through the 7 days of residue decli ne.

I. MATERIALS AND METHOD S

A. MATERIALS

Table B.7.6.1.1

- 1. 

### Nomenclature for Azoxystrobin and Metabolites of Interest

. Common name Azoxystrobin

Identity M ethyl (α E )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS no. 131860

- 33

- 8
Company experimental name ICIA5504 (Zeneca), R215504 (Syngenta)
Other synonyms (if applicable) N/A

Metabolite Azoxystrobin, Z

- isomer
Identity Methyl (α Z )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetateAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 4922750 1 Page 3 of 8 Table B.7.6.1.1

- 1. 

### Nomenclature for Azoxystrobin and Metabolites of Interest

. CAS no. Not available
Company experimental name R230310
Other synonyms (if applicable) N/A



### B. Study Design

1. Test Procedure

E ight residue trials on pears were conducted in South Korea with a 10% WP f ormulation (A12913A) during the 2012 growing season

. All trials, except for those listed in the table below, were separated by >20 miles and are therefore considered independent (568 _Criteria for Independence of Tr ials 04/23/2013 (EPA and PMRA)). The trials separated by <20 miles have been assessed for independence as detailed in the table below.

Independent Trial Determination 1

Trial Nos. Differences Decision

- 03,

- 07, &

- 08 Distance : trials separated by ≤15 miles Same variety

No other differences found Independent. The locations are slightly different, and the growing area in South

Korea is limited.

1 All assessments are based on the replicate trial guidance presented in draft memo 568 _Criteria for Independence of T rials 04/23/2013 (EPA and PMRA).



### Table B.7.6.1.1

- 2. Trial Numbers and Geographical Locations.

Crop No.

Trials NAFTA Growing Zone Total

1 2 3 4 5 6 7 8 9 10 11 12

Pear Sub. Not applicable

Req. 1



### Locations and detailed use patterns for the trials are provided in Table B.7.6.1.1

- 3.

Table B.7.6.1.1

- 3. Study Use Pattern.

Location: Town/Village

, Province

, Country ; Year (Trial ID) End

- use

Product 1 Method of Application/

Timing of Application Volume (gal/A) [L/ha] Rate per Application (lb ai/A) [g ai/ha] Retreatment

Interval (days) Total Rate

(lb ai/A) [g ai/ha] Surfactant/

Adjuvant

Namyangju

- si, Gyeonggi

- do, South Korea; 2012 (S12

- 03087

- 01 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 477 [ 4465 ] 0.399

[ 447 ] -- 1.995 [2237] None

2 . Foliar broadcast to bagged fruit; BBCH 76 483 [ 4519 ] 0.403

[ 452 ] 10

3 . Foliar broadcast to bagged fruit; BBCH 77 506 [ 4738 ] 0.423

[ 474 ] 9Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 4922750 1 Page 4 of 8 

### Table B.7.6.1.1

- 3. Study Use Pattern.

Location: Town/Village

, Province

, Country ; Year (Trial ID) End

- use

Product 1 Method of Application/

Timing of Application Volume (gal/A) [L/ha] Rate per Application (lb ai/A) [g ai/ha] Retreatment

Interval (days) Total Rate

(lb ai/A) [g ai/ha] Surfactant/

Adjuvant

4 . Foliar broadcast to bagged fruit; BBCH 77

- 79 443 [ 4140 ] 0.369

[ 414 ] 11

5 . Foliar broadcast to bagged fruit; BBCH 79 481 [ 4499 ] 0.401

[ 450 ] 9

Whaseong

- si, Gyeonggi

- do, South Korea; 2012 (S12

- 03087

- 02 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 442 [ 4137 ] 0.369

[ 414 ] -- 2.081 [2333] None

2

. Foliar broadcast to bagged fruit; BBCH 76 527 [ 4932 ] 0.440

[ 493 ] 10

3 . Foliar broadcast to bagged fruit; BBCH 77 547 [ 5119 ] 0.457

[ 512 ] 10

4 . Foliar broadcast to bagged fruit; BBCH 78 475 [ 4440 ] 0.396

[ 444 ] 10

5 . Foliar broadcast to bagged fruit; BBCH 79 502 [ 4696 ] 0.419

[ 470 ] 9

Asan

- si, Chungcheong

Nam

- do, South Korea; 2012 (S12

- 03087

- 03 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 478 [ 4474 ] 0.399

[ 447 ] -- 1.978 [2218] None

2 . Foliar broadcast to bagged fruit; BBCH 76 489 [ 4572 ] 0.408

[ 457 ] 10

3 . Foliar broadcast to bagged fruit; BBCH 77 481 [ 4504 ] 0.401

[ 450 ] 10

4 . Foliar broadcast to bagged fruit; BBCH 78 441 [ 4124 ] 0.368

[ 412 ] 10

5 . Foliar broadcast to bagged fruit; BBCH 79 483 [ 4517 ] 0.403

[ 452 ] 9

Palbong

- myeon, Seosan

- si, Chung

Nam

- do, South Korea; 2012 (S12

- 03087

- 04 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 430 [ 4024 ] 0.359

[ 402 ] -- 2.031 [2277] None

2 . Foliar broadcast to bagged fruit; BBCH 76 517 [ 4832 ] 0.431

[ 483 ] 11

3 . Foliar broadcast to bagged fruit; BBCH 77 497 [ 4647 ] 0.41 4

[ 464 ] 10

4 . Foliar broadcast to bagged fruit; BBCH 78 512 [ 4791 ] 0.427

[ 479 ] 10

5 . Foliar broadcast to bagged fruit; BBCH 79 480 [ 4489 ] 0.401

[ 449 ] 9

Daewol

- myeon, Icheon

- si, Gyeonggi

- do, South Korea;

2012 (S12

- 03087

- 05 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 460 [ 4300 ] 0.384

[ 430 ] -- 2.047 [2295] None

2 . Foliar broadcast to bagged fruit; BBCH 76 520 [ 4865 ] 0.434

[ 486 ] 10

3 . Foliar broadcast to bagged fruit; BBCH 77 516 [ 4824 ] 0.430

[ 482 ] 10

4 . Foliar broadcast to bagged fruit; BBCH 78 496 [ 4640 ] 0.414

[ 464 ] 11

5 . Foliar broadcast to bagged fruit; BBCH 79 463 [ 4329 ] 0.386

[ 433 ] 9

Yanseong

- my e on, Anseon

- si

, Gyeonggi

- do,

South Korea;

2012 (S12

- 03087

- 06 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 474 [ 4433 ] 0.395

[ 443 ] -- 2.066 [2316] None

2 . Foliar broadcast to bagged fruit; BBCH 76 484 [ 4527 ] 0.404

[ 453 ] 10

3 . Foliar broadcast to bagged fruit; BBCH 77 501 [ 4689 ] 0.418

[ 469 ] 10Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 4922750 1 Page 5 of 8 

### Table B.7.6.1.1

- 3. Study Use Pattern.

Location: Town/Village

, Province

, Country ; Year (Trial ID) End

- use

Product 1 Method of Application/

Timing of Application Volume (gal/A) [L/ha] Rate per Application (lb ai/A) [g ai/ha] Retreatment

Interval (days) Total Rate

(lb ai/A) [g ai/ha] Surfactant/

Adjuvant

4 . Foliar broadcast to bagged fruit; BBCH 78 521 [ 4878 ] 0.435

[ 488 ] 10

5 . Foliar broadcast to bagged fruit; BBCH 79 495 [ 4626 ] 0.413

[ 463 ] 9

Sungnam

- myeon, Dongnam

- gu, Cheon

- an

- si, Chungcheong

Nam

- do, South Korea; 2012 (S12

- 03087

- 07 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 461 [ 4316 ] 0.385

[ 432 ] -- 2.003 [2246] None

2 . Foliar broadcast to bagged fruit; BBCH 76 513 [ 4795 ] 0.427

[ 479 ] 10

3 . Foliar broadcast to bagged fruit; BBCH 77 506 [ 4731 ] 0.422

[ 473 ] 10

4 . Foliar broadcast to bagged fruit; BBCH 78 441 [ 4125 ] 0.368

[ 413 ] 10

5 . Foliar broadcast to bagged fruit; BBCH 79 480 [ 4493 ] 0.401

[ 449 ] 9

Eumbong

- myeon, Yesan

- gun, Chung Nam

- do, South Korea;

2012 (S12

- 03087

- 08 ) 10% WP 1 . Foliar broadcast to bagged fruit; BBCH 75 455 [ 4253 ] 0.379

[ 425 ] -- 2.054 [2303] None

2 . Foliar broadcast to bagged fruit; BBCH 76 568 [ 5315 ] 0.475

[ 532 ] 11

3 . Foliar broadcast to bagged fruit; BBCH 77 480 [ 4491 ] 0.401

[ 449 ] 10

4 . Foliar broadcast to bagged fruit; BBCH 78 481 [ 4500 ] 0.401

[ 450 ] 10

5 . Foliar broadcast to bagged fruit; BBCH 79 478 [ 4473 ] 0.399

[ 447 ] 9

1 End

- use Product is a 10% wettable powder (WP) formulation (A12913A)

.



### Pears were grown and maintained according to typical agricultural practices

. This included having the pears enclosed in bags throughout the test period. Irrigation was not used. No unusual weather conditions were reported during the study

, except at one trial (

- 04 ) where the second application was delaye d 1 day due to a typhoon. This had no impact on the study.

Sample Handling and Preparation

At all test sites, triplicate control and treated pear samples were harvested at normal commercial

harvest (7

- day PHI). Additional samples were also collected at PHIs of 0 and 3 days from four

trial s to assess residue decline. Fruits were removed from bags and placed in frozen storage at

the field sites within 9 hours of collection . All samples were shipped within 16

- 27 days on dry

ice to E urofins Agrosciences Services Ltd. (Derbyshire, UK) for preparation and analysis . In preparation for analysis, the stems w ere removed

, and the samples were homogenized i n the presence of dry ice. Following preparation, samples were stored frozen (~ ≤

- 18 °C) at the analytical laboratory prior to analysis.

2. Description of Analytical Procedures

Samples were analyzed for residues of azoxystrobin and its Z

- isomer ( R230310 ) using an LC/MS/MS method, Method RAM 305/03. A brief d escription of the method wa s included inAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 4922750 1 Page 6 of 8 

### the submission.

Briefly, samples were extracted twice with acetonitrile (ACN):water (90:10, v:v). After centrifugation, the combined extract s w ere cleaned up on a C18 solid phase extraction column

for analy sis by L C / MS/MS.

The LOQ (determi ned as the LLMV) was 0.01 ppm for each analyte; the LOQ for combined residues was 0.02 ppm. T he limit of detection (LOD) was not reported.

II. RESULTS AND DISCUSSION

Method performance was evaluated by use of concurrent recovery samples. S amples of untreated pear were fortified with azoxystrobin and R230310 each at 0.01 and 0.10 ppm. Recoveries were within the acceptable range of 70%

- 120%; therefore, the method was considered valid for the analysis of residues of azoxystrobin and R230310 i n pear (Table

B.7.6.1.1

- 4)

. The fortification levels bracketed the measured residues. It could not be

determined whether c oncurrent recoveries were corrected for apparent residues in controls.

The detector response was linear (coefficient of determinati on, r 2 

### ≥0.999 8 ) within the range of

0. 00005

- 0.01 μ g/mL. Representative chromatograms of control samples, fortified samples and treated samples were provided. The control chromatograms generally had no peaks of interest above the chromatographic backgroun d. The fortified sample chromatograms contained only the analyte of interest, and peaks were symmetrical and well defined. Apparent residues in controls

were below the LOQ ( <0.01 ppm ) for both analytes . The reported residue values were not

corrected for apparent residues in controls.

Table B.7.6.1.1

- 4. Summary of Procedural/Concurrent Recoveries of Azoxystrobin and

its Z

- isomer (R230310) from Pear.

Matrix Analyte Fortification Level (ppm) Sample

size (n) Recoveries 1
(%) Mean ± RSD (%)

Pear, Asian Azoxystrobin 0.01

- 0.10 4 90

- 112 99 ± 10

R230310 0.01

- 0.10 4 84

- 91 89 ± 3.5

1 It could not be determined whether c oncurrent recoveries wer e corrected for apparent residues in controls.



### The field residue samples were stored frozen a maximum of 66 day s (2.2 months) from harvest to analysis (Table B.7.6.1.1

- 5). Extraction and analysis dates were not provided; however, the petitioner reported the reside analysis period (11/15/12

- 11/28/12). In addition the petitioner reported that sample extract solution s were stored for a maximu m of 7 days prior to analysis. The available freezer storage stability data indicate that residues of azoxystrobin and R230310

are stable when stored frozen ( <

- 18 °C ) for up to 2 years in various crops including apples (DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/ 98 ).

Table B.7.6.1.1

- 5. Summary of Storage Conditions.

Matrix Storage Temperature (°C) Actual Storage Duration 1 Interval of Demonstrated Storage StabilityAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 4922750 1 Page 7 of 8 Pear ≤

- 18 42

- 66 days (1.4

- 2.2 months) Residues of azoxystrobin and R230310 are stable

for up to 2 years in various crops including apples stored frozen (<

- 18 °C).

1 Interval from harvest to analysis. The petitioner indicated s amples were analyzed within 7 days of extraction.

2 DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98



### The results from the submitted field trials are presented in Tables B.7.6.1.1

- 6 and B.7.6.1.1

- 7

. Following five foliar broadcast applications of the 10% WP formulation a t total rates of 1.978

- 2.081 lb ai/A (2 218

- 2333 g ai/ha), i ndividual sample (and per

- trial average) combined residues of azoxystrobin and its Z

- isomer (R230310) were <0.02

- <0.05 ppm (<0.02

- <0.05 ppm) in/on bagged pears harvested at a 7

- day PHI. Residues of the Z

- isomer were below the LOQ (<0.0 1 ppm) in/on all samples.

In the residue decline trials, residues in pears remained approximately the same through the 7 days of residue decline.

Table B.7.6.1.1

- 6. Residue Data from Pear Field Trials with Azoxystrobin

. 1

Location: Town/Village

, Province , Country ; Year (Trial ID) Variety Matrix Rate ( lb ai/A) [g ai/ha] PHI

(days) Residues 2 (ppm ) [Average]

A zoxystrobin R230310 Combined 3

Namyangju

- si, Gyeonggi

- do, South Korea; 2012 (S12

- 03087

- 01 ) Shin

- go Fruit 1.995 [2237] 0 <0.01, <0.01

[< 0.01] <0.01, <0.01

[<0.01] <0.02, <0.02

[<0.02]

3 0.02, <0.01

[<0.02] <0.01, <0.01

[<0.01] <0.03, <0.02

[<0.03]

7 0.02, 0.01

[0.02] <0.01, <0.01

[<0.01] <0.03, <0.02

[<0.03]
Whaseong

- si, Gyeonggi

- do, South Korea; 2012 (S12

- 03087

- 02 ) Shin

- go Fruit 2.081 [2333] 0 0.01, 0.02

[0.02] <0.01, <0.01

[<0.01] <0.02, <0.03

[<0.03]

3 <0.01, 0.02

[<0.02] <0.01, <0.01

[<0.01] <0.02, <0.03

[<0.03]

7 <0.01, 0.02

[<0.02] <0.01, <0.01

[<0.01] <0.02, <0.03

[<0.03]

Asan

- si, Chungcheong Nam

- do,

South Korea; 2012 (S12

- 03087

- 03 ) Shin

- go Fruit 1.978 [2218 ] 7 0.01, <0.01

,

[<0.01] <0.01, <0.01

,

[<0.01] <0.02, <0.02,

[<0.02]

Palbong

- myeon, Seosan

- si, Chung Nam

- do, South Korea;

2012 (S12

- 03087

- 04 ) Shin

- go Fruit 2.031 [2277] 7 <0.01, <0.01

[<0.01] <0.01, < 0.01

[<0.01] <0.02, <0.02

[<0.02]

Daewol

- myeon, Icheon

- si, Gyeonggi

- do, South Korea;

2012 (S12

- 03087

- 05 ) Shin

- go Fruit 2.047 [2295] 0 <0.01, <0.01

[<0.01] <0.01, <0.01

[<0.01] <0.02, <0.02

[<0.02]

3 <0.01, <0.01

[<0.01] <0.01, <0.01

[<0.01] <0.02, < 0.02

[<0.02]

7 <0.01, 0.01

[<0.01] <0.01, <0.01

[<0.01] <0.02, <0.02

[<0.02]
Yanseong

- myeon , Anseon

- si, Gyeonggi

- do, South Korea;

2012 (S12

- 03087

- 06 ) Shin

- go Fruit 2.066 [2316] 0 0.03, 0.05

[0.04] <0.01, <0.01

[<0.01] <0.04, <0.06

[<0.05]

3 0.03, 0.03

[0.03] <0.01, <0.01

[<0.01] <0.04, <0.04

[<0.04]

7 0.04, 0.04

[0.04] <0.01, <0.01

[<0.01] <0.05, <0.05

[<0.05]Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 4922750 1 Page 8 of 8 

### Table B.7.6.1.1

- 6. Residue Data from Pear Field Trials with Azoxystrobin

. 1

Location: Town/Village

, Province , Country ; Year (Trial ID) Variety Matrix Rate ( lb ai/A) [g ai/ha] PHI

(days) Residues 2 (ppm ) [Average]

A zoxystrobin R230310 Combined 3

Sungnam

- myeon, Dongnam

- gu, Cheon

- an

- si, Chungcheong

Nam

- do, South Korea; 2012 (S12

- 03087

- 07 ) Shin

- go Fruit 2.003 [2246] 7 <0.01, 0.01

[<0.01] <0.01, <0.01

[<0.01] <0.02, <0.02

[<0.02]

Eumbong

- myeon, Yesan

- gun, Chung Nam

- do, South Korea;

2012 (S12

- 03087

- 08 ) Shin

- go Fruit 2.054 [2303] 7 <0.01, 0.01

[<0.01] <0.01, <0.01

[<0.01] <0.02, <0.02

[<0.02]

1 End

- use Product is a 10% wettable powder (WP) formulation (A12913A).

2 The LOQ was 0.01 ppm for each analyte

. The LOD was not reported. Combined residues and p er

- trial averages were calculated by the study reviewer using the LOQ for all residues reported as <LOQ.

3 Combined residues of azoxystrobin and its Z

- isomer (R230310)



### Table B.7.6.1.1

- 7. Summary of Residues from Pear Field Trials with Azoxystrobin

. Crop Matrix Total Application Rate

(lb ai/A) [g ai/ha] PHI

(days) n 1 Residues Azoxystrobin 2 (ppm)

Min. 3 Max. 3 LAFT 4 HAFT 4 Median 4 Mean 4 SD 4

Pear (bagged) 1.978

- 2.081 [2218

- 2333] 7 8 <0.02 <0.05 <0.02 <0.05 0.02 0.03 0.01

1 n = number of field trials.

2 Combined residues of azoxystrobin and its Z

- isomer (R230310).

3 Values based on total number of samples.

4 Values based on per

- trial averages. LAFT = lowest average field trial, HAFT = highest average field trial, SD = standard deviation. For computation of the LAFT, HAFT, median, mean, and standard deviation, values <LOQ are assumed to be at the LOQ ( 0.01 ppm).



### III. CONCLUSIONS

The pear field trials are considered scientifically acceptable. Following five foliar broadcast applications of the 10% WP formulation a t total rates of 1.978

- 2.081 lb ai/A (2218

- 2333 g ai/ha),

i ndividual sample (and per

- trial av erage) combined residues of azoxystrobin and its Z

- isomer (R230310) were <0.02

- <0.05 ppm (<0.02

- <0.05 ppm) in/on bagged pears harvested at a 7

- day

PHI. Residues of the Z

- isomer were below the LOQ (<0.01 ppm) in/on all samples. In the residue decline trials, residues in pears remained approximately the same through the 7 days of

residue decline.

An acceptable method was used for residue quantitation, and a dequate storage stability data are to support sample storage durations a nd conditions for all analytes

.

REFERENCES

DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/ 98

### Azoxystrobin [PC Code 1288 l O] / Syngenta Crop Protection, LLC



### B.7.6 Residues Resulting from Supervised Trials 

## (Annex IIA 6.3; Annex IIIA 8.3)

B.7.6.1 Residues in Target Crops

B.7.6.1.3 Tea

Document ID: 

### MRID No. 49227502

Report:

Guidelines: 

### Smith, N. (2013) Azoxystrobin SC (A13364A)

- Compilation of Residue

Data 

### in or on Tea. Summary. Report/Task N umb er: TK018502 4

. Unpublished study prepared by Syngenta Crop Protection, LLC. 110 p. EPA OCSPP Harmon ized Test Guideline 860.1500 Crop Field Trials (August 1996)

PMRA Regulatory Directive DIR98-02

- Residue Chemistry Guidelines,

Section 9

- Crop Field Trial s PMRA Regulatory Directive DIR2010-05

- Re visions to the Resid ue Chemistry Crop Field Tr ial Requirements

OECD Guideline 509 Crop Field Trial (Sep t ember 2009)

GLP Compliance: 

### No deviations from regulatory requirements were reported which would

Acceptability:

Evaluator: 

### have an impact on the validity of the study.

The study is considered scientifically acceptable. The acceptability of this study for regulatory purposes is addressed 

### in the fort!woming U.S. EPA

Residue Chemistry Summary Documen t,

## DP**#~83 ·**  . Steve Funk, Senior Chemist, RAB III 1

### ~**,L.LM.~**

· v Note: This Data Evaluation Record (DER) was originally prepared under contract by Versar, In c. (6850 Versa r Center

, Springfield

, VA 22151; submitted 9 / 30/14). The DER has been reviewed by HED and revised to reflect current Office of

Pesticide Programs (OPP) policies.



### EXECUTIVE SUMMARY



### Syngenta Crop Protection, LLC has submi tte d residue data for azoxystrobin on tea. Four tea
field trials for were conducted in Japan during the 1998 growing season.

E ach trial consisted of one untreated plot and one tr eated plot divided into three subplots (2, 3,

and 4) to establish separate preharvest intervals (PHis). Each treated plot received thr ee foliar

spray applications of a 20% suspension concentrate (SC) formulation of azoxyst robin (Amistar® 20 SC) at 0.196 lb ail A/app lication (220 g ai/ha/application), for a total rate of 0.589

lb ai/A (660 g ai/ha). All applications were made at retreatment intervals (RTis) of 7 days using ground equipment in spray volumes of 214 gal/A (2000 L/ha); no adjuvants were used. Single samples of green tea leaves were harvested at PHis of 7, 14, and 21 days from subplots 2, 3, and
4, r espec tiv e ly, and were processed into dried crude tea (dried leaves).

E PA MRID 

### # : 49227502



### Pagel of 10Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 2 of 10 

### Separate subsamples from each trial were analyzed f or residues of azoxystrobin at two analytical laboratories, Japan Analytical Chemistry Consultants Co., Ltd. (JACC) and Japan Food Research Laboratories (JFRL). The laboratories used different high performance liquid chromatography

method s with UV detection ( HP LC/ UV )

. Acceptable concu rrent recoveries were reported for tea samples fortified with azoxystrobin and its Z

- isomer (R230310) at 0.4 ppm each (JACC) and with azoxystrobin at 1 .6 and 10 ppm (JFRL), thus validating the methods. The fortification levels used at JFRL bracketed the measured residues; however, the fortification level used at JACC was more than an order of magnitude lower than the highest measured residues. The reported limits of quantitation ( LOQ s; calculated from t he minimum detectable residues) w ere 0.02 ppm for the JACC method and 0.04 ppm for the JFRL method.

The petitioner indicated that in Japan the residue of concern is parent azoxystrobin only, and that therefore, r esidues of the Z

- isomer ( R230310 ) were not determined in field trial samples by

either laboratory. Concurrent recovery and storage stability data generated by JACC included analysis for R230310

.

All samples were maintained refrigerated at the testing facilit ies and were stored frozen until

anal ysis at the analytical laboratories

. The field residue samples were stored frozen from harvest to analysis for a maximum of 89 day s (2.9 months) at JACC and 113 days (3.7 months) at JFRL. Extraction dates were not provided. To support sample storage dur ations, each laboratory

conducted a concurrent storage stability study. The data demonstrate that residues of azoxystrobin and R230310 were stable in/on dried leaves stored frozen for up to 67

- 83 days (2.2

- 2.7 months) at JACC and that residues of azoxystrobin were stable in/on dried leaves stored frozen for up to 108

- 122 days (3.6

- 4.0 months) at JFRL ; no 0

- day data were provided. These data are acceptable to support the storage conditions and durations of samples from the submitted field trials; however, storage stability studies should always include a 0

- day sampling interval to establish the residue levels present at the time samples are placed into storage [see OCSPP 860.1380(d)(6)(i)].

F ollowing three foliar spr ay applications of the 20% SC formulation a t a total rate of 0.589 lb ai/A (660 g ai/ha), residues of azoxystrobin

, determined by averaging results from both

laboratories

, were 1.56

- 11.5

, 0.69

- 4.66

, and 0.23

- 1.44 ppm, respectively , in /on samples of dried

t ea leaves harvested at PHIs of 7, 14, and 21 days

. R esidue s of azoxystrobin decreased in dried

leaves with increasing PHIs

.

I. MATERIALS AND METHOD S

A. MATERIALS

Table B.7.6.1. 3

- 1. Nomenclature for Azoxystrobin and Metabolites of Interest.

Common name Azoxystrobin

Identity Methyl (α E )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS no. 131860

- 33

- 8
Company experimental name ICIA5504 (Zeneca), R215504 (Syngenta)Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 3 of 10 

### Table B.7.6.1. 3

- 1. Nomenclature for Azoxystrobin and Metabolites of Interest.

Other synonyms (if applicable) N/A

Metabolite Azoxystrobin, Z

- isomer
Identity Methyl (α Z )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS no. Not available
Company experimental name R230310
Other synonyms (if applicable) N/A



### B. Study Design

1. Test Procedure

F our r esidue trials on t ea were conducted in Japan with a 20% SC formulation (Amistar® 20 SC) during the 1998 growing season

. All trials were separated by >20 miles and are therefore considered independent (568 _Criteria for Independence of Trials 04/23/2013 (EPA and PMRA)).

Table B.7.6.1. 3

- 2. Trial Numbers and Geographical Locations.

Crop No.

Trials NAFTA Growing Zone Total

1 2 3 4 5 6 7 8 9 10 11 12

Tea Sub. Not applicable

Req. 1



### Table B.7.6.1. 3

- 3. Study Use Pattern.

Location: City,

Pr efecture

, Country ; Year End

- use

Product 1 Subp lot Method of Application/

Timing of Application Volume (gal/A) [L/ha] Rate per Application (lb ai/A) [g ai/ha] Retreatment

Interval (days) Total Rate

(lb ai/A) [g ai/ha] Surfactant/

Adjuvant

Kanagawa Agricultural Technology

Center

Tsukui

- gun, Kanagawa

, Japan; 1998 20% SC 2 1. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 7 days

before harvest 214 [2000] 0.196

[220] 7

3 1. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] NoneAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 4 of 10 

### Table B.7.6.1. 3

- 3. Study Use Pattern.

Location: City,

Pr efecture

, Country ; Year End

- use

Product 1 Subp lot Method of Application/

Timing of Application Volume (gal/A) [L/ha] Rate per Application (lb ai/A) [g ai/ha] Retreatment

Interval (days) Total Rate

(lb ai/A) [g ai/ha] Surfactant/

Adjuvant

2. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

4 1. Foliar spray; 35 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7

Mie Plant

Protection

Association

Ichishi

- gun, Mie

, Japan; 1998 20% SC 2 1. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 7 days

before harvest 214 [2000] 0.196

[220] 7

3 1. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

4 1. Foliar spray; 35 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 5 of 10 

### Table B.7.6.1. 3

- 3. Study Use Pattern.

Location: City,

Pr efecture

, Country ; Year End

- use

Product 1 Subp lot Method of Application/

Timing of Application Volume (gal/A) [L/ha] Rate per Application (lb ai/A) [g ai/ha] Retreatment

Interval (days) Total Rate

(lb ai/A) [g ai/ha] Surfactant/

Adjuvant

Nara Agricultural Experiment Station; Tea

Branch

Yatawara

- cho,

Nara

- shi , Japan;

1998 20% SC 2 1. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 7 days

before harvest 214 [2000] 0.196

[220] 7

3 1. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

4 1. Foliar spray; 35 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7

Kochi Agricultural Research Center; Tea Experiment

Station

Takaoka

- gun, Kochi , Japan;

1998 20% SC 2 1. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 7 days

before harvest 214 [2000] 0.196

[220] 7

3 1. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 14 days

before harvest 214 [2000] 0.196

[220] 7

4 1. Foliar spray; 35 days

before harvest 214 [2000] 0.196

[220] -- 0.589 [660] None

2. Foliar spray; 28 days

before harvest 214 [2000] 0.196

[220] 7

3. Foliar spray; 21 days

before harvest 214 [2000] 0.196

[220] 7

1 End

- use Product is a 20% (by weight) suspension concentrate (SC) formulation (Amistar® 20 SC).



### Tea plants were grown and maintained according to typical agricultural practices . Irrigation was not used. No unusual weather conditions were reported during the study.

Sample Handling and Prep aration

Single control and treated samples of green tea leaves ( ≥ 2 kg) were collected 7, 14, and 21 days after the last application of the test substance from separate subplots at each trial site . After collection, samples were processed into dried leaves. Briefly, green tea leaves were steamedAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 6 of 10 

### followed by kneading and then dried. S amples of dried leaves were stored in the refrigerator for

0

- 6 days until shipment to the analytical laboratories

, Japan Analytical Chemistry Consultants Co., Ltd. (JAC C) and Japan Food Research Laboratories (JFRL) , where they were stored frozen (

- 20 °C) until they were ground for analysis.

2. Description of Analytical Procedures

Separate subsamples from each trial were analyzed for residues of azoxystrobin (but not the Z isomer) at two analytical laboratories, JACC and JFRL using different HPLC/UV methods

. Complete descriptions of the methods were included in the submission. The reported LOQs ( calculated from the minimum detectable residues) w ere 0.02 ppm for the JACC method and 0.04 ppm for the JFRL method.

JACC method : Briefly, samples were extracted with acetonitrile (ACN) :water (1:3, v:v), filtered, and concentrated under reduced pressure by rotary evaporation. The extract was partitione d twice with ethyl acetate containing saturated sodium chloride solution, and the combined ethyl acetate layer was filtered through anhydrous sodium sulfate

, reduced to dryness,

and redissolved in acetone . The extract was combined with coagulant solution (ammonium chloride and phosphoric acid in water), concentrated, and partitioned with ethyl acetate/sodium chloride solution and reduced to dryness as above, then dissolved in acetone:hexane (30:70, v:v)

. The resulting extract was further purified by seque ntial solid

- phase extraction (SPE) on two silica gel columns followed by an alumina column; residues were eluted with acetone:hexane (30:70, 5:95, and 20:80 v:v). The final eluate was concentrated, evaporated to dryness, and redissolved in ACN:water (1:1, v:v) for HPLC analysis

.

JFRL method : Briefly, samples were extracted with acetone , filtered, and vacuum concentrated.

Sodium chloride and water were added and the extract was purified using porous diatomaceous earth column chromatography . Residues were eluted with ethyl acetate

, and the eluate was

vacuum concentrated

, evaporated to dryness under nitrogen , and redissolved in water:ACN (8:2, v:v) . The extract was further purified by sequential SPE on a C 18 

### silica column (residues eluted

with water:AC N (1:1, v:v) and redissolved in ethyl acetate), activated carbon column (r esidues eluted with ethyl acetate and redissolved in acetone : hexane (1:19, v:v)), and F lorisil column (r esidues eluted with hexane:acetone (8:2, v:v) and redissolved in ACN:water (1: 1, v:v) ) for analysis by HPLC/UV.

II. RESULTS AND DISCUSSION

Method performance was evaluated at each laboratory by use of concurrent recovery samples fortified with azoxystrobin and its Z

- isomer (R230310) at 0.4 ppm each (JACC) and with azoxystrobin at 1.6 and 10 ppm (JFRL)

. Recoveries at both laboratories were within the acceptable range of 70

- 120%; therefore, the method s w ere considered valid for the analysis of azoxystrobin and R230310 residues in tea matrices (Table B.7.6.1. 3

- 4). The fortification levels used at JFRL bracketed the measured residues; however, the fortification level used at JACC was more than an order of magnitude lower than the highest measured residues. Concurrent

recoveries were not corrected for apparent residu es in controls.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 7 of 10 

### Standard curves were provided indicating that the detector response was linear within the range

of 0.025

- 0.5 ppm (JACC) and 0.025

- 1.0 ppm (JFRL); coefficients of determination were not reported

. Representative chromatograms of control sam ples, fortified samples and treated samples were provided. The control chromatograms generally had no peaks of interest above the chromatographic background. The fortified sample chromatograms contained only the analyte of interest, and peaks were symmet rical and well defined. Apparent r esidues in controls were below the method LOQ (<0.02 ppm for the JACC method and <0.04 ppm for the JFRL method) with the exception of the untreated sample from the Kochi site which bore detectable residues of azoxystrobin at 0.06 ppm (detected by both laboratories)

. The reported residue values were not corrected for apparent r esidues in controls.

Table B.7.6.1. 3

- 4. Summary of Procedural/Concurrent Recoveries of Azoxystrobin and its

Z

- isomer (R230310) from Tea 1



### . Matrix Analyte Fortification

Level (ppm) Sample

size (n) Recoveries 1
(%) Mean ± Std. Dev. (%)

JACC method

Dried leaves Azoxystrobin 0.4 8 89, 86, 86.2, 84.1, 92.3, 88.3, 86.5, 82 86.8 ± 3.1

R230310 8 84.6

, 83.5

, 84.3

, 77.8

, 80.7

, 77.8

, 78.9

, 75.5 80.4 ± 3.4

JFRL method

Dried leaves Azoxystrobin 1.6 8 101, 92, 101, 98, 101, 92, 96, 95 9 7 ± 3. 9

10 4 96, 93, 94, 93 94 ± 1.4

1 Concurrent recoveries were not corr ected for apparent residues in controls.



### The field residue samples were stored frozen from harvest to analysis for a maximum of 89 day s (2.9 months) at JACC and 113 days (3.7 months) at JFRL (Table B.7.6.1. 3

- 5). Extraction dates were not provided. To support sample storage durations, each laboratory conducted a concurrent storage stability stu dy; the results are presented in Table B.7.6.1. 3

- 6 . The data demonstrate that residues of azoxystrobin and R230310 were stable in/on dried leaves stored frozen for up to 67

- 83 days (2.2

- 2.7 months) at JACC and that residues of azoxystrobin were stable in/ on dried leaves stored frozen for up to 108

- 122 days (3.6

- 4.0 months) at JFRL; no 0

- day data were provided. These data are acceptable to support the storage conditions and durations of samples from the submitted field trials; however, storage stability st udies should always include a 0

- day sampling interval to establish the residue levels present at the time samples are placed into storage [see OCSPP 860.1380(d)(6)(i)].

Table B.7.6.1. 3

- 5. Summary of Storage Conditions.

Matrix Storage

Temperature (°C) Actual Storage Duration 1 Interval of Demonstrated Storage Stability

JACC method

Tea, dried leaves

- 20 79

- 89 days (2.6

- 2.9 months) 67

- 83 days (2.2

- 2.7 months) 2

JRFL Method

Tea, dried leaves

- 20 106

- 113 days (3.5

- 3.7 months) JFRL: 108

- 122 days (3.6

- 4.0 months) 2

1 Interval from harvest to analysis

. Extraction dates were not reported.

2 Based on concurrent storage stability stud ies . See Table 7.6.1. 3

- 5b.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 8 of 10 

### Table B.7.6.1. 3

- 6

. Stability of Azoxystrobin Residues in Tea.

Commodity /location Analyte Spike

Level (ppm) Storage

interval (days) Fresh Fortification

Recoveries (%) [Avg.] Stored

Sample

Recoveries (%) Mean

Recovery (%) Corrected %

recovery 1

JACC Method

Dried leaves/ Kanagawa Agricultural Technology Center/ Tea Azoxystrobin 1.0 67 89.0, 86.0 [87.5] 93.3, 92.2 92.8 106

R230310 67 84.6, 83.5 [84.0] 95.8, 95.6 95.7 114

Dried leaves/

Mie Plant Protection

Association/ Tea Azoxystrobin 1.0 83 86.2, 84.1 [85.2] 90.3, 88.6 89.7 105

R230310 83 84.3, 77.8 [81.0] 95.2, 93.6 94.4 116

Dried leaves/

Nara Agricultural Experiment Station/ Tea Azoxystrobin 1.0 76 92.3, 88.3 [90.3] 80.8, 76.3 78.6 87.0

R230310 76 80.7, 77.8 [79.2] 80.7, 79.8 80.2 101

Dried leaves/ Kochi Agricultural

Research Center/ Tea Azoxystrobin 1.0 83 86.5, 82.0 [84.2] 81.7, 81.0 81.4 96.7

R230310 83 78.9, 75.5 [77.2] 74.7, 74.0 74.4 96.4

JFRL Method 2

Dried leaves/ Kanagawa Agricultural Technology Center/Tea Azoxystrobin 2 108 101, 92, 101, 98, 101, 92, 95, 96 [97] 2 89, 88 88 91

Dried leaves/

Mie Plant Protection

Association/Tea Azoxystrobin 2 122 84, 83 84 87

Dried leaves/ Nara Agricultural Experiment Station/Tea Azoxystrobin 2 119 91, 88 90 93

Dried leaves/ Kochi Agricultural

Research Center/Tea Azoxystrobin 2 122 94, 92 93 96

1 Corrected by the petitioner based on the recovery of concurrent recovery samples for the analytical procedure

. 2 Recoveries from the 1.6

- ppm fortification level.



### The results from the submitted field trials are presented in Tables B.7.6.1. 3

- 7 and B.7.6.1. 3

- 8

. F ollowing three foliar spray applications of the 20% SC formulation a t a total rate of 0.589 lb ai/A (660 g ai/ha), residues of azoxystrobin

, determined by averaging results from both laboratories, were 1.56

- 11.5, 0.69

- 4.66, and 0.23

- 1.44 ppm, respectively, in/on samples of dried tea leaves harvested at PHIs of 7, 14, and 21 days. R esidues of azoxystrobin decreased in dried

leaves with increas ing PHIs.

Table B.7.6.1. 3

- 7

. Residue Data from Tea F ield Trials with Azoxystrobin

. 1

Location: City, Pr efecture , Country ; Year Tea Variety Matrix Rate ( lb ai/A) [g ai/ha] PHI

(days) Residues 2 (ppm ) [Average]

JACC

Method JFRL

Method Average results

both methods 3

Kanagawa Agricultural Technology Center Tsukui

- gun, Kanagawa, Japan; 1998 Yabukita Dried

leaves 0.589

[660] 7 10.2 10.5 10.3

14 4.56 4.75 4.66

21 1.38 1.51 1.44

Mie Plant Protection Association

Ichishi

- gun, Mie, Japan; 1998 Yabukita Dried

leaves 0.589

[660] 7 7.44 7.78 7.61

14 2.02 2.62 2.32

21 0.95 1.17 1.06Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 9 of 10 

### Table B.7.6.1. 3

- 7

. Residue Data from Tea F ield Trials with Azoxystrobin

. 1

Location: City, Pr efecture , Country ; Year Tea Variety Matrix Rate ( lb ai/A) [g ai/ha] PHI

(days) Residues 2 (ppm ) [Average]

JACC

Method JFRL

Method Average results

both methods 3

Nara Agricultural Experiment Station; Tea Branch

Yatawara

- cho, Nara

- shi, Japan;

1998 Yabukita Dried

leaves 0.589

[660] 7 1.41 1.71 1.56

14 0.58 0.80 0.69

21 0.20 0.26 0.23

Kochi Agricultural Research Center; Tea Experiment Station

Takaoka

- gun, Kochi, Japan; 1998 Yabukita Dried

leaves 0.589

[660] 7 9.93 13.1 11.5

14 3.09 3.46 3.27

21 0.53 0.66 0.59

1 End

- use Product is a 20% (by weight) SC formulation (Amistar® 20 SC).

2 Residues reported for azoxystrobin per se ; r esidues of R230310 were not determined. All values are the mean of duplicate analyses calculated by the study reviewer from reported values.

3 Average of analytical results from both JACC Method and JRFL Method calculated by the study reviewer

.



### Table B.7.6.1. 3

- 8 . Summary of Residues from Tea Field Trials with Azoxystrobin

. Crop Matrix Analyte Total Application

Rate (lb ai/A) [g ai/ha] PHI

(days) n 1 Residues (ppm)

Min. 2 Max. 2 LAFT 3 HAFT 3 Median 3 Mean 3 SD 3

J ACC Method

Tea, dried

leaves Azoxystrobin 0.589 [660] 7 4 1.41 10.2 1.41 10.2 8.6 8 7.25 4.0 9

14 4 0.58 4.56 0.58 4.56 2.56 2.56 1.68

21 4 0.20 1.38 0.20 1.38 0.74 0.7 6 0.51

JFRL Method

Tea, dried

leaves Azoxystrobin 0.589 [660] 7 4 1.71 13.1 1.71 13.1 9.1 2 8.2 6 4.88

14 4 0.80 4.75 0.80 4.75 3.04 2.9 0 1.66

21 4 0.2 7 1.51 0.26 1.51 0.9 1 0.90 0.55
Average results from both methods

Tea, dried

leaves Azoxystrobin 0.589 [660] 7 4 1.56 11.5 1.56 11.5 8.98 7.76 4.44

14 4 0.69 4.66 0.69 4.66 2.80 2.74 1.67

21 4 0.23 1.44 0.23 1.44 0.83 0.83 0.53

1 n = number of field trials.

2 Values based on total number of samples.

3 Values based on per

- trial averages. LAFT = lowest average field trial, HAFT = highest average field t rial, SD = standard

deviation.



### III. CONCLUSIONS

The tea field trials are considered scientifically acceptable

. F ollowing three foliar spray applicati ons of the 20% SC formulation a t a total rate of 0.589 lb ai/A (660 g ai/ha), residues of azoxystrobin per se, determined by averaging results from both laboratories, were 1.56

- 11.5,

0.69

- 4.66, and 0.23

- 1.44 ppm, respectively, in/on samples of dried tea le aves harvested at PHIs of 7, 14, and 21 days. R esidues of azoxystrobin decreased in dried leaves with increasing PHIs.

Acceptable method s w ere used for residue quantitation, and a dequate storage stability data were submitted to support sample storage durations and conditions.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227502

Page 10 of 10 

### REFERENCES

None

### Azoxysrrobin [PC Code 12881 OJ / Syngenta Crop Pro tection, LLC



### B

. 7

. 6 Residues Resulting from Supervised Trials (Annex IIA 6.3; Annex DIA 8.3)



### B.7.6.1 Residues in 

### Target Crops

B

. 7.6.1.2 Coffee

Document ID: MRID No. 49227503



### Report:

Guidelines:

GLP Compliance:

Acceptability :

Evaluator: Mickelson, K. (2012) Azoxystrobin and Cyproconazole (Al 2910C)- Magnitude of the Residues in or on Coffee: Final Report. Report/OLP

Teclmo lo gies Study/Task Number: TK00469 57. Morse Study Number:

67650

. Unpublished study prepared by Syngenta Crop Protection, LL C

. 381 p.
E PA OCSPP Harmoni zed Test Guideline 860.1500 Crop Field Trials (August 1996)

PMRA Regulatory Directive DIR98-02

- Residue Chemistry Guidelines

, Section 9

- Crop Field Trials

PMRA Regulatory Directive DIR2010

- 05 -Revisions to the Residue Chemistry Crop Field Trial Requirements

OECD Guideline 509 Crop Fie ld Trial (September 2009)

No deviations from regulatory req u irement s were reported which would

have an impact on the validity of the study.

The s tudy is considered scient ifica lly acceptable. The acceptability of this study for regulatory purposes is addressed in the**fo~oming** 

### U.S. EPA

Re sid ue Chemistry Summary Document, DP # 41£37

. Steve Funk

, Senior Chemist, RAB III 

# y{

..,,**)JJ\J~**

Note: This Data Evaluation Record (DER) was originally prepared under cont ract by Versar, In c. (6850 Yersar Center, Springfie ld, VA 22151 ; submitted 9/30114). The DER has been reviewed by HED and revised to reflect current Office of

Pesticide Programs (OPP) policies.



### EXECU T IVE SUMMARY

Syngenta Crop Protecti on, LLC has submitted r esidue da t a for azoxystrobin on coffee from field

trials conducted in Ce ntral and South America. Four coffee field trials were conducted during

the 2011 and 2012 growing seasons in Colombia (l trial)

, Guatemala (1 trial), and Brazil (2 trials). HED has determined that two triaJs conducted in Colombia are replicate trials; the above

tria l coun t reflects this conclusion. The submission also includes data for cyproconazo le and the

triazole metabolites

. ; these data are not addressed herein.

Each tria l consisted of one untreated plot and one treated plot. At all tria l locations, the treated plot received three foliar spray applications of a J 

### .67 lb ai/g al (200 g ai / L) suspension

concentrate (SC) formula tion of azoxystrobin (A 1 291 OC). The product i s a mu l tiple active ingredient (MAI) form ulation that also contains cyproconazole at 0.67 lb ai / gal (80 g ai / L). Each

treated plot received three applications of azoxystrobin at 0

. 13 1-0 .137 lb ai/Napplication ( 146.7

- 154.0 g ai/ha/application) for total rates of 0.394-0.410 lb ai / A (441.7-459.3 g ai/ha). All

Pa e I of8

EPA MRID #: 

### 49227503Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 2 of 8 

### applications were made at retreatment intervals (RTIs) of 42

- 49 days using ground equipment in spray volumes of 21.38

- 42.58 gal/A ( 200.0

- 398.3 L/ha)

. A nonionic surfactant (NIS) alone or in conjunction with a crop oil was added to the spray mixtures for all applications

. Samples of
coffee bean “cherries” were harvested from all trials at a 14

- to 15

- day preharvest inte rval (PHI)

. Additional samples were collected from one trial at a 5

- , 10

- , 20

- , and 25

- day PHIs to assess

residue decline. Coffee cherries were processed into green coffee beans at the field site s

.

Samples were analyzed for residues of azoxystrobin an d its Z

- isomer (R23010) using a high performance liquid chromatography method with tandem mass spectrometry detection (LC/MS/MS), Method RAM 305/03. A cceptable method validation and concurrent recoveries were reported for green coffee bean samples at fort ification levels of 0.01 and 1.0 ppm, thus validating the method. The limit of quantitation (LOQ; determined as the lowest level of method validation, LLMV) was 0.01 ppm for each analyte ; the LOQ for combined residues was 0.02

ppm

.

S amples were maintai ned frozen at the testing facility, during shipping to the laboratory, and were stored frozen until analysis. The field residue samples were stored frozen a maximum of 57 days (1.9 months) from harvest to extraction for analysis. Samples were analyzed wi thin 0

- 3 days of extraction. The available freezer storage stability data indicate that residues of azoxystrobin and R230310 are stable when stored frozen (<

- 18 °C) for up to 2 years in various crops including oil seed rape (DP# 248887, D. Dotson, M. Dohe rty, and Y. Donovan, 10/14/98). Adequate storage stability data are therefore available to support the storage conditions and intervals for samples in the current trials.

Following three foliar spray applications of the 1.67 lb ai/gal SC formulation a t t otal rates of

0.394

- 0.410 lb ai/A (441.7

- 459.3 g ai/ha), i ndividual sample (and per

- trial average) combined residues of azoxystrobin and its Z

- isomer (R230310) were <0.02

- <0.0259 (<0.02

- <0.0230) ppm in/on green coffee beans harvested at a 14

- to 15

- day PHI. Residues of the Z

- isomer were below the LOQ (<0.01 ppm) in/on all samples.

In the residue decline trial, combined residues of azoxystrobin and R230310 declined after the 5

- day PHI to below the LOQ (<0.02 ppm) for all remaining PHIs.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 3 of 8 

### I. MATERIALS AND METHODS

A. MATERIALS

Table B.7.6.1. 2

- 1. Nomenclature for Azoxystrobin and Metabolites of Interest.

Common name Azoxystrobin

Identity Methyl (α E )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS no. 131860

- 33

- 8
Company experimental name ICIA5504 (Zeneca), R215504 (Syngenta)
Other synonyms (if applicable) N/A

Metabolite Azoxystrobin, Z

- isomer
Identity Methyl (α Z )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS no. Not available
Company experimental name R230310
Other synonyms (if applicable) N/A



### B. Study Design

1. Test Procedure

Four residue trials on coffee were conducted in Central and South America with a 1.67 lb ai/gal ( 200 g ai/L) SC f

ormulation (A 12910C ) during the 2011 and 2012 growing seasons in Colombia (1 trial), Guatemala (1 trial), and Brazil (2 trials)

. All trials, except for those listed in the table below, were separated by >20 miles and are therefore considered independent (568 _Criteria for

I ndependence of Trials 04/23/2013 (EPA and PMRA)). The trials separated by <20 miles have been assessed for independence as detailed in the table below.

Independent Trial Determination 1

Crop Trial Nos. Differences Decision

Coffee

- 01 &

- 02 Same location and variety

No other differences found Replicates

1 All assessments are based on the replicate trial guidance presented in draft memo 568 _Criteria for Independence of T rials 04/23/2013 (EPA and PMRA).Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 4 of 8 

### Table B.7.6.1. 2

- 2. Trial Numbers and Geographical Locations.

Crop No.

Trials NAFTA Growing Zone Total

1 2 3 4 5 6 7 8 9 10 11 12

Coffee Sub. Not applicable

Req. 1

1 OCSPP 860.1500 specifies 5 trials but does not suggest a geographic distribution.



### Locations and detailed use patterns for the trials are provided in Table B.7.6.1. 2

- 3.

Table B.7.6.1. 2

- 3. Study Use Pattern.

Location: City, Country ; Year (Trial ID) End

- use

Product 1 Method of Application/

Timing of Application Volume (gal/A) [L/ha] Rate per Application (lb ai/A) [g ai/ha] Retreatment

Interval (days) Total Rate

(lb ai/A) [g ai/ha] Surfactant/

Adjuvant 2

Santa Marta, Magdalena, Colombia; 2011 (TK0046957

- 01) 3 1.67 lb ai/gal

SC 1. Foliar spray; BBCH 75 25.70 [ 240.4 ] 0.131

[ 146.7 ] -- 0.394 [441.7] NIS & crop

oil

2. Foliar spray; BBCH 77 25.83 [ 241.6 ] 0.132

[ 147.7 ] 42

3. Foliar spray; BBCH 81 25.85 [ 241.8 ] 0.131

[ 147.3 ] 42

Santa Marta, Magdalena, Colombia; 2011 (TK0046957

- 02) 3 1.67 lb ai/gal

SC 1. Foliar spray; BBCH 75 25.86 [ 241.9 ] 0.132

[ 147.6 ] -- 0.395 [442.8] NIS & crop

oil

2. Foliar spray; BBCH 77 25.83 [ 241.6 ] 0.131

[ 147.4 ] 42

3. Foliar spray; BBCH 81 25.90 [ 242.3 ] 0.132

[ 147.8 ] 42

Santa Rosa, Guatemala; 2011 (TK0046957

- 03) 1.67 lb ai/gal

SC 1. Foliar spray; BBCH 75 21.38 [200.0] 0.134

[ 150.0 ] -- 0.403 [452.3] NIS

2. Foliar spray; BBCH 81 21.69 [202.9] 0.136

[ 152.2 ] 42

3. Foliar spray; BBCH 85 21.39 [200.1] 0.134

[ 150.1 ] 44

Santo Antonio Do Jardim, Brazil;

2012 (TK0046957

- 04) 1.67 lb ai/gal

SC 1. Foliar spray; BBCH 77 42.58 [ 398.3 ] 0.135

[ 151.9 ] -- 0.403 [451.7] NIS

2. Foliar spray; BBCH 80 42.20 [ 394.8 ] 0.133

[ 149.5 ] 45

3. Foliar spray; BBCH 85 41.84 [ 391.4 ] 0.134

[ 150.3 ] 47

Dois Córregos, Brazil; 2012 (TK0046957

- 05) 1.67 lb ai/gal

SC 1. Foliar spray; BBCH 77 40.69 [ 380.6 ] 0.137

[ 154.0 ] -- 0.410 [459.3] NIS

2. Foliar spray; BBCH 80 40.08 [ 374.9 ] 0.135

[ 151.8 ] 43

3. Foliar spray; BBCH 85 40.54 [ 379.2 ] 0.137

[ 153.5 ] 49

1 A multiple active ingredient (MAI) susp ension concentrate (S C ) formulation ( A12910C ) containing 1. 67 lb ai/gal (200 g ai/L) azoxystrobin and 0.67 lb ai/gal (80 g ai/L) cyproconazole

. 2 NIS = non

- ionic surfactant.

3 Considered one trial (dependent)



### Coffee plants were grown and maintained according to typical agricultural practices

. Irrigation

was not used. No unusual weather conditions were reported during the study.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 5 of 8 

### Sample Handling and Preparation

At all test sites, a single control and duplicate treated samples of coffee cherries were harvested

14

- 15 days after the last applica tion. Additional samples were also collected at PHIs of 5, 10, 20, and 25 days in one trial to assess residue decline. Coffee cherries were processed into green

coffee beans at the field site s prior to shipment to the analytical laboratory. For the Colo mbia and Guatemala trials, the process for producing dry green coffee beans included: (i) removing the skin of the berry and some of the pulp by mechanically pressing the fruit through a screen in a water batch; (ii) removal of the remaining pulp using a fermentation and washing process; (iii) drying using forced air or sun drying; and (iv) hand removal of the thin parchment layer that remains after drying. For the Brazil trials, the process for producing dry green coffee beans included: (i) sun drying t he whole berry immediately after collection; (ii) mechanically peeling the dried outer layer ; and (iii) manual cleaning using a sieve and forced air. The samples were placed in frozen storage (temperature unspecified ) at the field sites after collection ( interval between collection and freezing not reported). All samples were shipped frozen via air courier with dry ice within 8

- 32 days of collection to the analytical laboratory, Morse Laboratories, LLC (Sacramento, CA), where they were maintained frozen ( <

- 20 °C) prior to analysis. In preparation for analysis, samples were homogenized.

2. Description of Analytical Procedures

Samples were analyzed for residues of azoxystrobin and its Z

- isomer ( R230310) using an LC/MS/MS method, Method RAM 305/03. A brief description of the method was included in

the submission.

Briefly, samples were extracted with acetonitrile (ACN):water (90:10, v:v). After centrifugation,

the extract was cleaned up on a C18 solid p hase extraction column for analysis by LC/MS/MS.

The LOQ (determined as the LLMV) was 0.01 ppm for each analyte; the LOQ for combined residues was 0.02 ppm. T he limit of detection (LOD) was not reported.

II. RESULTS AND DISCUSSION

Method performance w as evaluated during method validation and by use of concurrent recovery samples by fortifying green coffee beans at 0.01

- 1.0 ppm. Recoveries were within the acceptable range of 70

- 120%; therefore, the method was considered valid for the analysis of

azoxys trobin and R230310 in green coffee beans (Table B.7.6.1. 2

- 4). The fortification levels

bracketed the measured residues

. Concurrent recoveries were corrected for apparent residues in

controls.

The detector response was linear (coefficient of determination, r 2 

### ≥0.99 62 ) within the range of

0.05

- 5.0 ng/mL. Representative chromatograms of control samples, fortified samples and treated samples were provided. The control chromatograms generally had no peaks of interest above the chromatographic ba ckground. The fortified sample chromatograms contained only the analyte of interest, and peaks were symmetrical and well defined. Apparent residues in controls wereAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 6 of 8 

### below the LOQ (<0.01 ppm) for both analytes. The reported residue values were not correc ted for apparent residues in controls.

Table B.7.6.1. 2

- 4. Summary of Method Validation and Procedural/Concurrent

Recoveries of Azoxystrobin and its Z

- isomer (R230310) from Green Coffee Beans

. Matrix Analyte Fortification

Level (ppm) Sample size

(n) Recoveries 1
(%) Mean ± Std. Dev. (%)

Method Validation

Coffee, green bean Azoxystrobin 0.01

- 1.0 6 96

- 106 102 ± 3.4

R230310 0.01

- 1.0 6 104

- 115 109 ± 4.8
Concurrent Recovery

Coffee, green bean Azoxystrobin 0.01

- 1.0 8 87

- 116 102 ± 8.8

R230310 0.01

- 1.0 8 89

- 118 103 ± 8.3

1 Concurrent recoveries were corrected for apparent residues in controls.



### The field residue samples were stored frozen a maximum of 57 days (1.9 months) from harvest to extraction for analysis (Table B.7.6.1. 2

- 5). Samples were analyzed within 0

- 3 days of

extraction. The available freezer storage stability data indicate that residues of azoxystrobin and R230310 are stable when stored frozen (<

- 18 °C) for up to 2 years in various crops including oil seed rape (DP# 24 8887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98).

Table B.7.6.1. 2

- 5. Summary of Storage Conditions.

Matrix Storage Temperature (°C) Actual Storage Duration 1 Interval of Demonstrated Storage Stability

Coffee, green bean

- 20 31

- 57 days (1.0

- 1.9 months) Residues of azoxystrobin and R230310 are stable for

up to 2 years in various crops including oil seed rape stored frozen (<

- 18 °C). 2

1 Interval from harvest to extraction

. Samples were analyzed within 0

- 3 days of extraction.

2 DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98



### The results from the submitted field trials are presented in Tables B.7.6.1.2

- 6 and B.7.6.1. 2

- 7

. Following three foliar spray applications of the 1.67 lb ai/gal SC formulation a t total rates of

0.394

- 0.410 lb ai/A (441.7

- 459.3 g ai/ha), i ndividual sample (and per

- trial average) combined residues of azoxystrobin and its Z

- isomer (R230310) were <0.02

- <0.0259 (<0.02

- <0.0230) ppm in/on green coffee beans harvested at a 14

- to 15

- day PHI. Residues o f the Z

- isomer were below the LOQ (<0.01 ppm) in/on all samples.

In the residue decline trial, combined residues of azoxystrobin and R230310 declined after the 5

- day PHI to below the LOQ (<0.02 ppm) for all remaining PHIs.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 7 of 8 

### Table B.7.6.1. 2

- 6. Residue Data from Coffee Field Trials with Azoxystrobin

. 1

Location: City, Country ; Year (Trial ID) C offee Variety Matrix Rate

( lb ai/A) [g ai/ha] PHI

(days) Residues 2 (ppm ) [Average]

Azoxystrobin R230310 Combined 3

Santa Marta, Magdalena, Colombia; 2011 (TK0046957

- 01 and

- 02) Castillo Green

coffee

bean 0.394

-

0.395 [441.7

- 442.8] 15 <0.01, <0.01,

<0.01, <0.01 [<0.01] <0.01, ND, ND,

ND [<0.01] <0.02, <0.02,

<0.02, <0.02 [<0.02]

Santa Marta, Magdalena, Colombia; 2011 (TK0046957

- 02) (Decline trial ) Castillo Green

coffee

bean 0.395

[442.8] 5 0.0181, 0.0194

[ 0.0188] <0.01, <0.01

[<0.01] <0.0281,

<0.0294 [ <0.0288]

10 <0.01, <0.01

[<0.01] ND, ND

[<0.01] <0.02, <0.02

[<0.02]

20 <0.01, <0.01

[<0.01] ND, ND

[<0.01] <0.02, <0.02

[<0.02]

25 <0.01, <0.01

[<0.01] ND, ND

[<0.01] <0.02, <0.02

[<0.02]

Santa Rosa, Guatemala;

2011 (TK0046957

- 03) Bourbon Green

coffee

bean 0.403

[452.3] 1 4 <0.01, 0.0159

[ <0.0130] ND, <0.01

[<0.01] <0.02, <0.0259

[ <0.0230]

Santo Antonio Do Jardim, Brazil; 2012 (TK0046957

- 04) Obatã Green

coffee

bean 0.403

[451.7] 1 4 <0.01, 0.0107

[ <0.0104] ND, ND

[<0.01] <0.02, <0.0207

[ <0.0204]

Dois Córregos, Brazil;

2012 (TK0046957

- 05) Tupi Green

coffee

bean 0.410

[459.3] 1 4 <0.01, 0.0102

[ <0.010 1 ] ND, ND

[<0.01] <0.02, <0.0202

[ <0.0201]

1 A multiple active ingredient (MAI) suspension concentrate (SC) formulation (A12910C) containing 1.67 lb ai/gal (200 g ai/L) azoxystrobin and 0.67 lb ai/gal (80 g ai/L) cyproconazole was used

. 2 The LOQ was 0.01 ppm for each analyte. The LOD was not repor ted. ND = none detected as reported by the petitioner ; no observable chromatographic response. Combined residues and per

- trial averages were calculated by the study reviewer using the LOQ for all residues reported as <LOQ.

3 Combined residues of azoxystr obin and its Z

- isomer (R230310)

.



### Table B.7.6.1. 2

- 7. Summary of Residues from Coffee Field Trials with Azoxystrobin

. Crop Matrix Total Application Rate

(lb ai/A) [g ai/ha] PHI

(days) n 1 Residues Azoxystrobin 2 (ppm)

Min. 3 Max. 3 LAFT 4 HAFT 4 Median 4 Mean 4 SD 4

Coffee, green bean 0.394

- 0.410 [441.7

- 459.3] 14

- 15 4 <0.02 <0.0259 <0.02 <0.0230 0.0202 0.0209 0.0014

1 n = number of field trials.

2 Combined residues of azoxystrobin and its Z

- isomer (R230310).

3 Values based on total number of samples.

4 Values based on per

- trial averages. LAFT = lowest average field trial, HAFT = highest average field trial, SD = standard deviation. For computation of the LAFT, HAFT, median, mean, and standard deviation, values <LOQ are assumed to be at the LOQ (0.01 p pm).Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 8 of 8 

### III. CONCLUSIONS

The coffee field trials are considered scientifically acceptable. Following three foliar spray applications of the 1.67 lb ai/gal SC formulation a t total rates of 0.394

- 0.410 lb ai/A (441.7

- 459.3 g ai/ha), i ndividual sample (and p er

- trial average) combined residues of azoxystrobin and

its Z

- isomer (R230310) were <0.02

- <0.0259 (<0.02

- <0.0230) ppm in/on green coffee beans

harvested at a 14

- to 15

- day PHI. Residues of the Z

- isomer were below the LOQ (<0.01 ppm) in/on all samples. In the residue decline trial, combined residues of azoxystrobin and R230310

declined after the 5

- day PHI to below the LOQ (<0.02 ppm) for all remaining PHIs.

An acceptable method was used for residue quantitation, and a dequate storage stability data are available to support sample storage durations and conditions for all analytes

.

REFERENCES

DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98Azoxystrobin [PC Code 1288 1 OJ/Syngenta Crop Protection, LLC



### B.7.7

B.7.7.1

B.7.7.2 Effects of Industrial Processing and/or Household Preparation (Annex HA 6.5; Annex IHA 8.5)

Nature of the Residue (Annex HA 6.5

. 1; Annex IHA 8.5.1)

- Not a data requirement in North America

Distribution of the Residue in Peel/Pulp (Annex HA 6.5.2; Annex IHA 8.5.2)

To be included if available.

B.7.7.3 Magnitude of Residues on Set of Representative Processes (Annex HA 6.5.3; Annex IIIA 8.5.3)

B.7.7.3.1 Coffee

Document ID: MRID No. 49227503

Report: Mickelson, K. (2012) Azoxystrobin and Cyproconazo l e (A 1291 OC)

- Magni tude of the Re s idues in or on Coffee: Final Report. Report/OLP Technologies Study/Task Number: TK0046957. Morse Study Number : 67650. Unpublished study prepared by Syngenta Crop Protection, LLC.

381 p. Guidelines: EPA OCSPP Harmonized Test Guideline 860.1520 Processed Food/Feed (August 1996)

PMRA Regula to ry Directive DIR98-02

- Residue Chemistry Guide line s, Section 10

- Processed Food/Feed

OECD Guideline 508 Magnitude of the Pesticide Residues in Processed
Commodities (October 2008)

GLP Compliance: No deviations from regulatory requirements were reported which would

have an impact on the validity of the study. Acceptability: The study is considered sc ie ntifically acceptable. The acceptabi li ty of this study for regulatory purposes is addressed in the forthcoming U.S. E PA

Residue Chemistry Summary Document,**QP~f,18374.** 

### Evaluator: Steve Funk, Senior Chemist, RAB III 

# ; f C{' 0 .,;)_

Note: This Data E valuation Record (DE R ) was originally prepared under contract by Versar

, lnc. (6850 Versar Center, Springfield

, VA 22151; submitted 9/30/ 14). The DER has been reviewed by HED and revised to reflect cu rrent Office of

Pesticide Programs (OPP) policies.



### EXECUTIVE SUMMARY

Syngenta Crop Protection, LLC has submitted 

## a process i ng study with azoxystrobin on coffee.

In one trial conducted in Guatemala during the 2011 growing season, a treated plot received

three fo li ar spray applicat i ons of a 1.67 lb ai/gal (200 g ai/L) suspension concentrate (SC)


## formulation of azoxystrobin (A 1291 OC). The product is a multiple active ingredient (MAI)

formulation that also contains cyproconazole at 0.67 lb ai/gal (80 g ai/L). Data pertaining to

EPA MRID #: 49227503
Page I of8Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 2 of 8 

### cyproconazole are not addressed herein. The treated plot received three applications of azoxystrobin at an exaggerated rate of 0. 6651

- 0. 6794 lb ai/A/application ( 745.6

- 761.7 g ai/ha/applicati on) for a total rate of 2.014 lb ai/A ( 2258 g ai/ha). The application rate used in the study was ~5x that used in the corresponding field trials. A pplications were made at retreatment intervals (RTIs) of 42

- 4 4 days using ground equipment in spray volumes of 21.25

- 21.71 gal/A ( 198.8

- 203.1 L/ha). A nonionic surfactant (NIS) was added to the spray mixtures for all applications. Samples of coffee bean “cherries” were harvested at a 14

- day preharvest interval (PHI ). C offee cherries were processed into green coffee beans at the field sites , and t he green coffee bean samples were processed into roasted coffee beans and instant coffee at GLP Technologies (Navasota, TX) using simulated commercial practices

. Adequate descriptions of the processing procedures were provided, including material balance summaries.

Samples were analyzed for residues of azoxystrobin and its Z

- isomer (R23010) using a high performance liquid chromatography method with tandem mass spectrometry detection (LC/MS/MS), Method RAM 305/03. A cceptable method validation and concurrent recoveries were reported for samples of green coffee bean , roasted coffee bean, and instant coffee at
fortification levels of 0.01

- 1.0 ppm, thus validating the method. The limit of quantitation (LOQ; determined as the lowest level of method validation, LLMV) was 0.01 ppm for each analyte.

S amples were maintained frozen at the testing facility and remained frozen during shipping and storage prior to processing and anal ysis

. Processing took place within 51 days of collection

. The maximum storage interval s from harvest/processing to extraction were 71 and 28 days ( 2.6 and

0.9 months), respectively, for green coffee bean and the processed commodities of roasted coffee

beans and instant coffee . Samples were analyzed within 3 day s of extraction. The available freezer storage stability data indicate that residues of azoxystrobin and R230310 are stable when stored frozen (<

- 18 °C) for up to 2 years in various crops includ ing oil seed rape (DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98). These data are acceptable to support the storage conditions and durations of the green coffee bean RAC samples from the submitted study

. No storage stability data are requir ed for roasted coffee bean and instant coffee because samples were analyzed within ~30 days of processing.

In samples harvested at a 14

- day PHI following the last of three foliar spray applications of the

1.67 lb ai/gal SC formulation at a n exaggerated total rate of 2 .014 lb ai/A (2258 g ai/ha), average residues of azoxystrobin were below the LOQ (<0. 0 1 ppm) in/on green coffee bean (RAC),

<0.01 0 8 ppm in dry roasted coffee, and <0. 0 168 ppm in instant coffee

. A comparison of the

residues in /on green coffe e bean with those in processed coffee fraction s indicated that residues of azoxystrobin may concentrate in dry roasted coffee (processing factor of 1. 1 x) and instant coffee (1.7x). Corresponding residues of the Z

- isomer (R230310) were below the LOQ (<0.01 ppm) in/on all samples of green coffee bean and processed commodities; therefore, processing

factors could not be calculated.

The observed processing factors do not exceed the theoretical concentration factor s of 1.2x for

roasted coffee bean and 4.4x fo r instant coffee [based on separation into components; OCSPP 860.1520, Table 3].Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 3 of 8 

### I. MATERIALS AND METHOD S

A. MATERIALS

Table B. 7.7. 3 .1

- 1

. Nomenclature for Azoxystrobin and Metabolites of Interest.

Common name Azoxystrobin

Identity Methyl (α E )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS no. 131860

- 33

- 8
Company experimental name ICIA5504 (Zeneca), R215504 (Syngenta)
Other synonyms (if applicable) N/A

Metabolite Azoxystrobin, Z

- isomer
Identity Methyl (α Z )

- 2

- [[6

- (2

- cyanophenoxy)

- 4

- pyrimidinyl]oxy]

- α

- (methoxymethylene)

- benzeneacetate

CAS no. Not available
Company experimental name R230310
Other synonyms (if applicable) N/A



### B. Study Design

1. Test Procedure

Location and detailed use pattern for the trial is provided in T able B. 7.7. 3 .1

- 2

.

T able B.7.7. 3 .1

- 2 . Study Use Pattern.

Location: City, Country; Year (Trial ID) End

- use

Product 1 Method of Application/

Timing of Application Volume ( gal/A ) [L/ha] Rate per Application ( lb ai/A ) [g ai/ha] Retreatment

Interval (days) Total Rate

( lb ai/A ) [g ai/ha] Surfactant/

Adjuvant 2

Santa Rosa, Guatemala; 2011 (TK0046957

- 03) 1.67 lb

ai/gal SC 1. Foliar spray; BBCH

75 21.25 [ 198.8 ] 0.6651

[ 745.6 ] -- 2.014 [2258] NIS

2. Foliar spray; BBCH

81 21.71 [ 203.1 ] 0.6794

[ 761.7 ] 42

3. Foliar spray; BBCH

85 21.39 [ 200.1 ] 0.6695

[ 750.6 ] 44

1 A multiple active ingredient (MAI) suspension concentrate (SC) formulation (A12910C) containing 1.67 lb ai/gal (200 g ai/L) azoxystrobin and 0.67 lb ai/gal (80 g ai/L) cyproconazole.

2 NIS = non

- ionic surfactant.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 4 of 8 

### Sample Handling and Preparation

Single control and treated bulk samples (~ 25 kg ) of coffee bean cherries were collected from each plot. Coffee cherries were processed into green coffee beans at the field site prior to shipment to the processing facilities

. T he process for producing dry green coffee beans included: (i) removing the skin of the berry and some of the pulp by mechanically pr essing the fruit through a screen in a water batch; (ii) removal of the remaining pulp using a fermentation and washing process; (iii) drying using forced air or sun drying; and (iv) hand removal of the thin parchment layer that remains after drying. Bulk green coffee bean samples were shipped frozen on dry ice 8 days after harvest to the processing facility, GLP Technologies (Navasota, TX) for processing into roasted coffee bean and instant coffee. At the processor, samples were stored frozen ( ≤ 10 °F) pr ior to processing. Processing was completed within 51 days of harvest, and the samples were returned to frozen storage for up to 15 days prior to shipment via FedEx on dry

ice to the analytical laboratory, Morse Laboratories, LLC (Sacramento, CA), where t hey were maintained frozen (

- 20 °C) prior to analysis.

Sample Processing

The processing procedures simulated commercial operations of coffee production as closely as possible to generate the required fraction of green coffee bean (RAC) and the processed fractions, with some variations to commercial methods. Adequate descriptio ns of the processing procedures were provided, including material balance summaries. A p rocessing flowchart for coffee p rocessed fractions, copied without alteration from MRID 49 227503

, is presented in Figure B.1

.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 5 of 8 

### FIGURE B.1. Processing Flowchart for Coffee

.

2. Description of Analytical Procedures

Samples were analyzed for residues of azoxystrobin and its Z

- isomer ( R230310) using an LC/MS/MS method, Method RAM 305/03. A brief description of the method was included in

the submission.

Briefly, samples were extracted with acetonitrile (ACN):water (90:10, v:v). After centrifugation, the extract was cleaned up on a C18 solid phase extraction column for analysis by LC/MS/MS.

The LOQ (determined as the LLMV) was 0.01 ppm for each analyte; the limit of detection (LOD) was not reported.Azoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 6 of 8 

### II. RESULTS AND DISCUSSION

Method performance was evaluated during method validation and by use of concurrent recovery samples by fortifying green coffee beans , roasted coffee beans, and instant coffee at 0.01

- 1.0

p pm. Recoveries were within the acceptable range of 70

- 120%; therefore, the method was considered valid for the analysis of azoxystrobin and R230310 in green coffee beans , roasted coffee beans, and instant coffee (Table B.7.7.3.1

- 3 ). The fortification levels bracketed the

measured residues . Concurrent recoveries were corrected for apparent residues in controls.

The detector response was linear (coefficient of determination, r 2 

### ≥0.9962) within the range of

0.05

- 5.0 ng/mL. Representative chromatograms of control samples, fortified samples and treated samples were provided. The control chromatograms generally had no peaks of interest above the chromatographic background. The fortified sample chromatograms contained only the analyte of interest, and pea ks were symmetrical and well defined. Apparent residues in controls were below the LOQ (<0.01 ppm) for both analytes. The reported residue values were not corrected for apparent residues in controls.

Table B.7.7.3.1

- 3. Summary of Method Validation and Procedural/Concurrent Recoveries of Azoxystrobin and its Z

- isomer (R230310) from Coffee Matrices.

Matrix Analyte Fortification Level (ppm) Sample size

(n) Recoveries 1
(%) Mean ± Std. Dev. 2
(%)

Method Validation

Coffee, green bean Azoxystrobin 0.01

- 1.0 6 96

- 106 102 ± 3.4

R230310 0.01

- 1.0 6 104

- 115 109 ± 4.8

Roasted coffee

beans Azoxystrobin 0.01

- 1.0 6 72

- 85 81 ± 5.0

R230310 0.01

- 1.0 6 73

- 86 81 ± 5.8

Instant coffee Azoxystrobin 0.01

- 1.0 6 87

- 98 94 ± 3.9

R230310 0.01

- 1.0 6 77

- 97 87 ± 9.9
Concurrent Recovery

Coffee, green bean Azoxystrobin 0.01

- 1.0 8 87

- 116 102 ± 8.8

R230310 0.01

- 1.0 8 89

- 118 103 ± 8.3

Roasted coffee

beans Azoxystrobin 0.01

- 1.0 2 95

- 107 101

R230310 0.01

- 1.0 2 96

- 110 103

Instant coffee Azoxystrobin 0.01

- 1.0 2 76

- 94 85

R230310 0.01

- 1.0 2 72

- 92 82

1 Concurrent recoveries were corrected for apparent residues in controls.

2 Standard deviation is not calculated for sample sizes < 3.



### The maximum storage interval s for samples were 71 and 28 days ( 2.6 and 0.9 months), respectively, for green coffee bean and the processed commodities of roasted coffee beans and instant coffee from harvest/processing to extraction (Table B.7.7.3.1

- 4 ). Samples were analyzed

within 3 day s of extraction. Processing took place within 51 days of collection

.

The available freezer storage stability data indicate that residues of azoxystrobin and R230310 are stable when stored frozen (<

- 18 °C) for up to 2 years in various crops including oil s eed rape (DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98). These data are acceptable to support the storage conditions and durations of the green coffee bean RAC samples from theAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 7 of 8 

### submitted study

. No storage stability data are required for roasted coffee bean and instant coffee

because these samples were analyzed within ~30 days of processing.

Table B.7.7.3.1

- 4. Summary of Storage Conditions 1



### . Matrix Storage Temperature Actual Storage

Duration Interval of Demonstrated Storage Stability

Coffee, green bean (RAC) Frozen at field site;
≤10 °F at processor;

- 2 0 °C at analytical laboratory 71 days (2.6 months) Residues of azoxystrobin and R230310 are stable for up to 2 years in various crops including oil seed rape stored frozen (<

- 18 °C). 2

Dry roasted coffee bean 28 days (0.9 months) Storage stability data are not required for processed coffee commodities as these samples were analyzed within ~30 days of processing. Instant coffee 21 days (0.7 months)

1 Interval from harvest

/processing to extraction. Samples were analyzed within 1

- 3 days of extraction.

2 DP# 248887, D. Dotson, M. Doherty, and Y. Donovan, 10/14/98



### Residues found in samples and processing factors are given in Table B.7.7. 3 .1

- 5

. In samples

harvested at a 14

- day PHI following the last of three foliar spray applications of the 1.67 lb ai/gal

SC formulation at a 5X exaggerated total rate of 2.014 lb ai/A (2258 g ai/ha), average residues of azoxystrobin were below the LOQ (<0.01 ppm) in/on green coffee bean (RAC), <0.010 8 ppm in dry roasted coffee, and <0. 0 168 ppm in instant coffee. A comparison of the residues in/on green coffee bean with those in processed coffee fractions indicated that residues of azoxystrobin may concentrate in dry roasted coffee (processing factor of 1.1x) and instant coffee (1.7x). Corresponding residues of the Z

- isomer (R230310) were below the LOQ (<0.01 ppm) in/on all samples of green coffee bean and processed commodities; therefore, processing factors could not

be calculated.

The observed pro cessing factors do not exceed the theoretical concentration factors of 1.2x for roasted coffee bean and 4.4x for instant coffee [based on separation into components; OCSPP 860.1520, Table 3].

Table B.7.7. 3 .1

- 5 . Residue Data from Coffee Processing Study with Azoxystrobin

. Commodity Analyte Residues 1 (ppm) [Average] Processing Factor 2 Median Processing

Factor

Coffee bean (prior to processing) Azoxystrobin <0.01, <0.01, <0.01 [<0.01] -- Not applicable

R230310 ND, ND, ND [ < 0.01] --

Dry roasted coffee Azoxystrobin 0.01 1 5, <0.01 [<0.01 08 ] > 1. 1 x

R230310 ND, ND [ < 0.01] NC 3

Instant coffee Azoxystrobin <0.01, 0.0236 [<0.0168] > 1.7x

R230310 ND, ND [ < 0.01] NC

1 The LOQ was 0.01 ppm for each analyte. The LOD was not reported. ND = none detected as reported by the petitioner; no observable chromatographic response.

2 Processing Factor = [Measured residue for analyte in the processed fraction] / [Measured residue for analyte in the RAC]

3 NC = Not calculated; residues were below the LOQ in both the RAC and processed fractionAzoxystrobin [PC Code 128810]/Syngenta Crop Protection, LLC

EPA MRID #: 49227503 Page 8 of 8 

### III. CONCLUSIONS

The coffee processing study is considered scientifically acceptable

. In samples harvested at a

14

- day PHI following the last of three foliar spray applications of the 1.67 lb ai/gal SC formulation at an exaggerated total rate of 2.014 lb ai/A (2258 g ai/ha), average residues of azoxystrobin were below the LOQ (<0.01 ppm) in/on green coffee bean (RAC ), <0.0108 ppm in dry roasted coffee, and <0. 0 168 ppm in instant coffee. A comparison of the residues in/on green coffee bean with those in processed coffee fractions indicated that residues of azoxystrobin may concentrate in dry roasted coffee (processin g factor of 1.1x) and instant coffee (1.7x). Corresponding residues of the Z

- isomer (R230310) were below the LOQ (<0.01 ppm) in/on all samples of green coffee bean and processed commodities; therefore, processing factors could not

be calculated.

The obs erved processing factors do not exceed the theoretical concentration factors of 1.2x for roasted coffee bean and 4.4x for instant coffee [based on separation into components; OCSPP 860.1520, Table 3].

An acceptable method was used for residue quantitation, and adequate storage stability data are to support sample storage durations and conditions for all analytes.

REFERENCES

DP# 248887, D. Dotson, M. D oherty, and Y. Donovan, 10/14/98