UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 

WASHINGTON, D.C. 20460 

OFFICE OF 

CHEMICAL SAFETY AND 

POLLUTION PREVENTION 

MEMORANDUM 

Date: 

Subject: 

22-SEP-2015 

Pyrimethanil. Petition for the Establishment of Permanent Tolerances for 

Residues in/on, Cucumbers, Tomato Subgroup 8-1 OA, Lemon Subgroup 10-1 OB, 

Orange Subgroup 10-1 OA, Grapefruit Subgroup 10-1 OC, Pome Fruit Group 11-

10, Stone Fruit Group 12-12 Caneberry Subgroup 13-07A, and Bushberry 

Subgroup 13-07B. Summary of Analytical Chemistry and Residue Data. 

PC Code: 28820 I DP Nos.: 0421844 & 0422294 

Registration Nos.: 264-788 & 43813-32 

Regulatory Action: Section 3 

Decision Nos.: 492391 & 493505 

Petition Nos.: 4F8291 & 4E8302 

Risk Assessment Type: NA 

TXR No.: NA 

Case No.: 7059 

CAS No.: 53112-28-0 

MRID No.: 4931250 I 40 CFR: §180.518 

From: 

Through: 

To: 

1 ?¢'~~ <--- George F. Kramer, Ph.D., Senior Chemist,..oiti 

Risk Assessment Branch 1 (RAB 1) 

Health Effects Division (HED, 7509P) 

Meheret 

Michael A. 

Negussie, 

Doherty

Chemist 

, Ph.D., Senior 

N eJ.evd 

Chemist ~V ~'r:. 

Science Advisory Council for Chemistry (ChemSAC) 

HED (7509P) 

And 

Thurston G. Morton, Acting Branch Chief 

RABl/HED (7509P) 

Andrew Ertman/Barbara Madden, RM 05 

Marcel Howard/Hope Johnson, RM 21 

Registration Division (RD, 7505P) 

Executive Summary 

The Interregional Research Project No. 4 (IR-4) and Bayer CropScience have submitted petitions 

for the use of Scala® SC Fungicide (EPA Reg. No. 264-788), an aqueous suspension-concentrate 

(SC) formulation containing 5.0 lbs/gal of pyrimethanil. The petitioners request that the 

following tolerances for residues of pyrimethanil (4,6-dimethyl-N-phenyl-2-pyrimidinamine) be 

established as a result of the proposed uses: 

Cucumber .......................................................................................... 1.5 ppm 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 42 I 844 

Orange subgroup 10-1 OA ................................................................... 10 ppm 

Lemon subgroup 10-1 OB ................................................................... 11 ppm 

Grapefruit subgroup 10-1 OC .............................................................. 10 ppm 

Fruit, pome, group 11-10 ................................................................... 14 ppm 

Fruit, stone, group 12-12 .................................................................... 10 ppm 

Tomato subgroup 8-lOA .................................................................. 0.50 ppm 

Caneberries subgroup 13-07 A ........................................................ 15.0 ppm 

Bushberries subgroup 13-078 ........................................................... 8.0 ppm 

No new data were submitted to support tolerances on tomato subgroup 8-1 OA, lemon subgroup 

l 0-1 OB, pome fruit group 11-10, orange subgroup I 0-1 OA, grapefruit subgroup l 0-1 OC, and 

stone fruit group 12-1 2. The petitioner has requested that existing tolerances be expanded to 

their respective crop groups or crop subgroups. The residue data for caneberries and bushberri es 

were previously submitted and reviewed under PP#8F7468 (Memo, W. Cutchin, 02-FEB-20 IO; 

D372647). This memorandum was reviewed by two peer reviewers of the ChemSAC, per 

ChemSAC Standard Operating Procedures (SOPs). 

Pyrimethanil tolerances are currently established in 40 CFR § 180.518 and are expressed in tenns 

of: (i) parent only for plant commodities; (ii) parent + Metabolite AEC6 14276 ( 4-[ 4,6-dimethyl2-pyrimidinyl)amino ]phenol) for ruminant tissues; and (iii) parent + Metabolite AEC614277 

( 4,6-dimethyl-2-(phenylamino )-5-pyrimidinol) for milk. 

The propo·seq new use.on greenhouse:grown cucumbers is as a foliar application three times at 

0.70 lbs ai/A with a maximum of2.l lbs ai/A/season and a preharvest interval (PHI) of l day. 

The proposed new use to caneberries and bushberries is as a foliar application 2-4 times at 0.35-

0.70 lbs ill/A with a maximum of 1.4 lbs ai/A/season and a PHI of 1 day. 

The qualitative nature of the pyrimethanil residue in the relevant plant commodities is adequately 

understood based on acceptable metabolism studies in lettuce, grapes. and tomatoes. The HED 

Metabolism Assessment Review Committee (MARC) has determined that for risk assessment 

and tolerance expression, parent only is the residue of concern for plant commodities. 

The data-collection method used to generate the cucumber residue data was a high-performance 

liquid chromatography (HPLC) with tandem mass spectroscopy (MS/MS) Method 140/01 /0 12. 

The lowest level of method validation (LLMV) was 0.05 ppm. This method was adequate for 

data collection. There are also adequate methods available to enforce pyrimethanil tolerances on 

the subject crops. 

The cucumber samples analyzed in this study were held in frozen storage for a maximum of 139 

days prior to analysis of pyrimethanil residues. There are adequate concurrent storage stability 

data to indicate that pyrimethanil residues are stable in/on cucumber for the duration of this 

study. 

The submitted field trial residue data for greenhouse-grown cucumbers are adequate. The field 

trial data reflect the proposed use pattern, an adequate number of trials were conducted, and 

samples were analyzed for the residue of concern using validated data-collection methods. Pertrial-average-residues of pyrimethanil ranged 0.07 ppm to 0.82 ppm in/on five cucumber trials 

with samples harvested at a 1-day PHI (highest individual residue of 0.83 ppm) from the five 

trials. Using the Organi zation for Economic Co-operation and Development (OECD) tolerancecalculation procedures for the residue data set indicates that the requested tolerance of 1.5 ppm 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

for residues of pyrimethanil in/on cucumber is appropriate. 

There are no new uses proposed for crops with associated livestock food/feed items of regulatory 

concern; therefore, a discussion of livestock residues is not germane to these petitions. 

Analytical standards for pyrimethanil, with an expiration date 13-JUL-2018, are currently 

available in the EPA National Pesticide Standards Repository. 

Adequate confined and limited field rotational crop trials are available and support the labelspecified 30-day plant-back interval (PBI) for crops without uses on the Scala® label. The 

available data indicate that tolerances are not currently required for rotational crops. 

For plant commodities, the U.S., Canadian, and Codex residue definitions are harmonized. The 

proposed tolerances for residues in/on caneberry, crop subgroup 13-07 A and bushberry, crop 

subgroup 13-078 are harmonized with the established Canadian maximum residue limits 

(MRLs). The U.S. tolerance for residues in/on tomato (0.50 ppm for the tomato subgroup 8-

1 OA) is harmonized with the Canadian MRL, while the Codex MRL is established at a higher 

level (0.7 ppm). However, Bayer CropScience has requested that EPA not harmonize with 

Codex in order to prevent the creation of a trade barrier with Canada. The U.S. and Codex 

tolerances/MRLs for residues of pyrimethanil in/on citrus are not harmonized. Residues in the 

U.S. residue trials (maximum of 8.43 ppm) were higher than the Codex MRL of 7 ppm, 

precluding harmonization. The U.S. and Canadian tolerances/MRLs for residues of pyrimethanil 

in/on citrus are harmonized, except for the lemon subgroup 10-1 OB. In order to harmonize with 

Canada, HED recommends that the U.S. tolerance for the lemon subgroup 10-lOB be reduced 

from 11 to I 0 ppm. As this value is the same as that recommended for the other citrus 

subgroups, a single tolerance of 10 ppm is appropriate for fruit, citrus, group 10-10. The U.S. 

and Codex tolerances/MRLs for residues of pyrimethanil in/on stone fruit are not harmonized. 

Residues were higher in the U.S. residue trials (maximum of 6.5 ppm) than the Codex MRLs of 

2-4 ppm, precluding harmonization. The U.S. and Canadian tolerances/MRLs for residues of 

pyrimethanil in/on stone fruit are harmonized at 10 ppm. The U.S. and Codex tolerances/MRLs 

for residues of pyrimethanil in/on the pome fruit group are not harmonized. As the difference in 

values is minimal, HED recommends that the U.S. tolerance be increased from 14 to 15 ppm in 

order to harmonize with Codex. There are currently no established Codex, Canadian, or 

Mexican MRLs for pyrimethanil in/on cucumber. 

Regulatory Recommendations and Residue Chemistry Deficiencies 

Pending submission of a revised Section F (see requirements under Proposed Tolerances), there 

are no residue chemistry issues that would preclude granting a registration for the requested uses 

of Scala® SC Fungicide and the following pem1anent tolerances under 40CFR§180.518 (a)(l): 

Cucumber ................................................... .................. 1.5 ppm 

Fruit, citrus, group 10-10 ............................................... 10 ppm 

Fruit, pome, group 11-10 ............................................... 15 ppm 

Fruit, stone, group 12-12 .... ........................................... 10 ppm 

Tomato, subgroup 8-1 OA ........................................... 0.50 ppm 

Caneberry, subgroup 13-07 A ........................................ 15 ppm 

Bushberry, subgroup 13-078 ....................................... 8.0 ppm 

Note to RD: With the establishment of these tolerances, the following tolerances should be 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

removed from 40 CFR § 180.518 (a)(l ): "Fruit, citrus, group 10, except lemon, postharvest," 

"Lemon, preharvest and postharvest," "Fruit, pome, group 11 (pre-harvest and post-harvest)," 

"Fruit, stone, group 12," and "Tomato." Also, the tolerance in 40CFR§180.5 I 8(a)(1) for 

residues of pyrimethanil in/on onion, bulb, subgroup 3-07 A (2.0 ppm) does not match the 

recommended tolerance from a previous assessment (Memo, Tyler et al. , 22-MA Y-2013; 

D389923). HED recommended for a tolerance of 0.20 ppm for residues of pyrimethanil in/on 

onion, bulb, subgroup 3-07 A. 

860 .15 50 Proposed Tolerances 

A summary of the recommended tolerances along with recommendations for commodity 

definitions are presented in Table 7. The petitioner is requested to submit a revised Section F to 

reflect the recommendations in Table 7. 

A human health risk assessment will be prepared as a separate document (DP# 428262). 

Background 

Pyrimethanil is an anilinopyridine (AP) fungicide that inhibits the secretion of fungal enzymes 

which are required during the infection process. Pyrimethanil blocks the ability of the fungus to 

degrade and digest the plant tissues, thus stopping penetration and development of the disease. 

The precise mechanism of inhibition of enzyme secretion has not been fully established. Protein 

synthesis is not inhibited, and evidence suggests that extracellular enzymes accumulate inside the 

fungus, their release being blocked in the presence of the fungicide. Pyrimethanil penetrates 

rapidly into the plant tissues, where it stops the development of the disease, providing a 

significant curative action. 

Pyrimethanil does not exhibit cross-resistance to sterol-inhibitors, dicarboximides, 

benzimidazoles, quinone outside inhibitors, or phenylarnides, but may exhibit cross-resistance in 

certain plant pathogenic fungi including AP compounds such as cyprodinil and mepanipyrim. 

The nomenclature of pyrimethanil is summarized in Table I. The physicochemical properties of 

pyrimethanil are summarized in Table 2. 

Table 1. Test Compound Nomenclature. 

Compound H ()NYrlCH, 

N ~ 

CH, 

Common name Pyrimethanil 

Company experimental names Janssen: R2 I 5559: PH0666 

Aventis: SN 100309; ZK 100309; AE 8100309 

IUPAC name 2-anilino-4,6-dimethylpyrimidine 

CAS name 4,6-dimcthyl-N-phcnyl-2-pyrimidinamine 

CAS registry number 53 112-28-0 

End-use product (EP) Scala® SC Fungicide (EPA Reg. No. 264-788), an SC formulation containing 5.0 lbs/gal 

pyrimethanil 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

Table 2. Physicochemical Properties of Pyrimethanil. 

Parameter Value Reference 

Melling point - 95°C 43301601 

pH Data unavailable 

Density Bulk density = 650-700 Kg/m3 43301601 

Water solubility (25°C) 0. 12 1 glL (pl I 6. I) 44908503 

olvent solubility (g!L at 200C) Dichloromethane: 1000.2 44908503 

Ethyl acetate: 6 16.9 

Acetone: 388.8 

n-Hexane: 23.7 

Vapor pressure at 25°C 2.2 x 10·3 Pa 44908503 

Dissociation constant (pK.) pKa = 3.52 ± 0.02 43301601 

Octanol/water partition coefficient Log(Kow) 2.48 hllp://www.hb-p.com/pyrimethanil.htm 

UV/visible absorption spectrum Data unavailable 

860.1200 Directions for Use 

Table 3. Summary of Directions for Use of Pyrimethanil. 

Applic. Timing, Formulation Applic. Max. No. Max. Seasonal 

Type, and (EPA Reg. Rate Applic. per Applic. Rate PHI Use Directions and 

Equip. No.) (lbs ai/A) Season (lbs ai/A) (days) Limitations 

Cucumber 

Scalatt> SC 

Greenhouse fungicide 0.70 3 2. 1 I Retreatment interval: 7-14 

only (EPA Reg. No. days. 

264-788) 

Small Berries (caneberries and bushberries) 

Sca sc 

Ground or air Fungicide 0.35-0.70 4 1.4 0 Retreatment interval: 7-14 

(EPA Reg. No. days. 

264-788) 

Conclusion: The submitted label is adequate to allow evaluation of the cucumber, caneberry, 

and bushberry residue data relative to the new proposed uses. Pyrimethanil is currently 

registered for use on tomato; citrus fruit, group 10, except lemon (postharvest); lemon 

(preharvest and postharvest); pome fruit group 11 (preharvest and postharvest); and stone fruit 

group 12 (preharvest and postharvest). The petitioner has requested that the existing uses be 

expanded to tomato subgroup 8-1 OA, lemon subgroup I 0-1 OB, pome fruit group I 1-10, orange 

subgroup l 0-1 OA, grapefruit subgroup 10-1 OC, and stone fruit group 12-12. The existing 

directions for use for these crops are unchanged, other than the additional crops covered by the 

updated groups/subgroups. Detailed reviews of the directions for use for these crops can be 

found in previous HED reviews (D361363, 08-APR-2009, G. Kramer; D347247, l 7-JUL-2008, 

G. Kramer; D369788, 08-DEC-2009, G. Kramer; and 0284001 , 12-JAN-2004, J. Morales and G. 

Kramer). 

860.1300 Nature of the Residue - Plants & Livestock 

PP#s 2F06439 and 2F06480, DP#s 28400 1 & 284870, J. Morales and G. Kramer, 12-JAN-2004 

PP# 8F7250, DP# 361363, G. Kramer, 08-APR-2009 

The qualitative nature of the pyrimethanil residue in the relevant plant commodities is adequately 

understood based on acceptable metabolism studies in lettuce, grapes, and tomatoes. The HED 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

MARC has determined that for risk assessment and tolerance expression, parent only is the 

residue of concern. Future new uses on root crops whose tops are significant food/feed items 

will require the analysis of metabolite AEC614278. 

There are no new uses proposed for crops with associated livestock food/feed items of regulatory 

concern; therefore, a discussion of the nature of the pyrimethanil residue in livestock 

commodities is not germane to these petitions. 

860.1340 Residue Analytical Methods 

PP#s 2F6439 and 2F6480, DP#s 284001 & 284870, J. Morales and G. Kramer, 12-JAN-2004 

Enforcement methods 

A residue analytical method titled "Analytical Method for the Determination of Residues of ZK 

100309 in Vines, Strawberries, and Apples by HPLC" was submitted in conjunction with an 

earlier pyrimethanil petition, PP#4E4384, for the establishment of a tolerance on imported wine 

grapes. The method has been subjected to a successful petition method validation (PMV) by 

Analytical Chemistry Branch (ACB)/Biological and Economics Analysis Division (BEAD) (DP# 

288256, E. Kolbe, 07-JUL-2004). ln addition, the QuEChERS method has been shown to 

adequately quantify residues of pyrimethanil 

(http://www.crl-pesticides.eu/library/docs/fv/CRLFV Multiresidue methods.pd!). 

Data-collection method 

The cucumber samples were analyzed at the IR-4 Western Region Laboratory, Department of 

Environmental Toxicology, One Shields Ave., University of California, Davis, Davis, CA 

95616-8588. The method used for the analysis was "Fruit and Vegetables: Analytical Method 

for the Determination of Residues (Improved Version), Pyrimethanil, Active Substance" M.H. 

Peatman, 15 FEB 1999, AgrEvo UK Limited, Saffron Walden, Essex CBlO IXL, England; 

140/01/012. Minor modifications were made to the reference method. These modifications are 

listed on page 98 of the Analytical Summary Report. The samples were analyzed for 

pyrimethanil only. 

Briefly, residues were extracted from cucumber trial samples by homogenizing with acetone. An 

aliquot of the extract was then cleaned up on a polymeric solid-phase extraction (SPE) column 

eluted with acetonitrile:water (80:20, v/v). Residues were then determined by HPLC-MS/MS. 

Method performance was evaluated prior to sample analysis by fortifying control cucumber 

samples with 0.05, 0.5, and 5.0 ppm of pyrimethanil. With the exception of one recovery of 68% 

in a sample fortified with 0.05 ppm of pyrimethanil, all method validation recoveries were within 

the acceptable range of 70-120%. Accuracy of the method was also confirmed by fortifying 

control cucumber samples with 0.05 and 0.5 ppm of pyrimethanil, and determining recoveries 

concurrently with trial sample analysis. All concurrent recoveries were within the acceptable 

range of70-120%. Given that the majority ofrecoveries were within the acceptable range, the 

working method was considered valid for the analysis of pyrimethanil residues in cucumber 

matrices. The fortification levels bracketed the measured residues in trial samples. 

Conclusion: There are adequate methods available to enforce pyrimethanil tolerances on the 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

subject crops. The method used for data collection is adequate. 

860.1360 Multiresidue Methods 

PP#s 2F6439 and 2F6480, DP#s 284001 & 284870, J. Morales and G. Kramer, 12-JAN-2004 

Pyrimethanil was tested through Protocols C, D, and E of the standard Food and Drug 

Administration (FDA) Multiresidue Protocols. Pyrimethanil was found to be nondetectable by 

the electron-capture (EC) detector. The use of a nitrogen-specific detector is recommended. 

Recovery was complete(> 100%) using the Luke procedure for grapes (non-fatty food) fortified 

at 0.05 and 5.0 ppm. No recovery was obtained from cottonseed oil (fatty food) fortified at 0.05 

ppm. For cottonseed oil fortified at 0.5 ppm, average recoveries of28% (range 16-40%) and 

78% (range 75-82%) were obtained when using the ether and the methylene chloride system, 

respectively. Pyrimethanil eluted from the standardized Florisil column. Recovery ranged from 

86 to 98% using two different systems. As noted previously, the QuEChERS multiresidue 

method has been shown to adequately quantify residues of pyrimethanil 

(http://www.crl-pesticides.eu/library/docs/fv/CRLFV Multiresidue methods.pd.!). 

860.1380 Storage Stability 

PP#s 2F06439 and 2F06480, DP#s 284001 & 284870, J. Morales and G. Kramer 12-JAN-2004 

The cucumber trial samples were stored frozen (:S-20 °C) for a maximum of 139 days prior to 

analysis of pyrimethanil residues. Previously submitted freezer storage stability data indicated 

that residues of pyrimethanil were stable for 12 months in lettuce, grape, carrot, and tomato and 

for 22 months in apple. Freezer storage stability data were generated concurrently with the 

analytical portion of the greenhouse cucumber trials. Freezer storage recoveries in cucumbers 

fortified with 5.0 ppm of pyrimethanil and stored frozen for 140 days were all within the 

acceptable 70-120% range. These data are adequate to validate the storage intervals and 

conditions employed in the current study. 

Conclusion: There are adequate storage stability data to indicate that pyrimethanil residues are 

stable in cucumbers for the duration of this study. 

860.1480 Meat, Milk, Poultry, and Eggs 

There are no new uses proposed for crops with associated livestock food/feed items ofregulatory 

concern; therefore, a discussion of livestock residues is not germane to these petitions. 

860.1500 Crop Field Trials 

Cucumber 

DER Reference List 49312501.der.doc 

Five greenhouse trials were conducted on cucumbers in Canada and the United States during 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

20 IO and 2011. As the trials were conducted in commercial greenhouses with controlled 

environmental conditions. the zones in which the trials were conducted are not relevant. 

At each trial location, pyrimethanil, formulated as a suspension concentrate (Scala® SC 

Fungicide; PCP # 2801 1 ), was applied to cucumbers in three fol iar applications at rates of 0.69-

0. 76 lbs ai/A. The re-treatment interval (RTT) was 7-14 days, and the total application rate was 

2. 12-2.22 lbs ai/A. An adjuvant was not included in any of the spray mixtures. Greenhouse 

cucumbers were harvested at a I-day PHI at all trial sites. Additional samples were harvested at 

one trial site at PHis of 0, 5, 11 , and 14 days to determine residue-decline behavior. 

Individual sample (and per-trial average) residues in greenhouse-grown cucumbers ranged from 

0.07 ppm to 0.83 ppm (0.07 ppm to 0.82 ppm) when samples were treated at total rates of 2.1 2-

2.22 lbs ai/A, and harvested at a 1-day PHI. Residue decline data showed that pyrimethanil 

residues decreased in greenhouse cucumbers with increasing PHis when samples were harvested 

at PHis ofO, 1, 5, 11, and 14 days. 

Table 4. Summary of Residues from Greenhouse Cucumber Trials with Pvrimethanil. 

Total App. Rate PHI Pyrimethanil Residues (ppm) 

Crop Matrix (lbs ai/A) (days) n Min.

1 I Max.1 I LAFT2 I HAFT2 I Median2 I Mean2 I SD2 

Cucumber Fruit 2. 12-2.22 I 5 0.07 I o.83 I 0.07 I 0.82 I 0.45 I 0.44 I 0.12 

1 Values based on total number of samples. 

2 Values based on per-trial averages. LAFT =lowest average fie ld trial, HAFT = highest average field trial, SD = 

standard deviation. 

n = number of field trials. 

Conclusions: The submitted residue data are adequate to fulfill data requirements for 

greenhouse-grown cucumbers. The available data will support the proposed use pattern. 

Table 5. Trial Numbers and Geographical Locations. 

e~ on 

Crop I 2 .., 

.) 4 5 6 7 8 9 10 11 12 13 14 Total 

Greenhouse 2 I 1 1 51 

Cucumbers 1 As trials were conducted in enclosed, commercial greenhouses with controlled environmental conditions, the zones 

in which the trials were conducted are not relevant. The HED Science Advisory Council for Chemistry (ChemSAC) 

has recommended that four trials be conducted for greenhouse-grown cucumbers in situations where no 

corresponding field use is proposed/established (Minutes of24-SEP-2008 ChemSAC meeting). 

The residue data for cucumbers were evaluated using the OECD tolerance calculation 

procedures. The recommended tolerance for residues of pyrimethanil is 1.5 ppm for cucumber 

(see Attachment 2). 

Caneberry subgroup 13-07 A 

The residue data for caneben-ies were previously submitted under PP#8F7468; the locations and 

application rates employed in these trials are adequate to support the proposed use. The Agency 

reviewed these data (summarized in Table 6) and determined that they supported a tolerance for 

residues of pyrimethanil in/on caneberry, crop subgroup 13-07A at a level of 12 ppm (using the 

North American Free Trade Agreement (NAFT A) tolerance calculator; Memo, W. Cutchin, 02-

FEB-2010; 0372647). Subsequently, Canada used the same residue data to establish a MRL for 

residues of pyrimethanil in/on caneberries at a level of 15 ppm (using the OECD tolerance 

calculator). HED thus concludes that a tolerance of 15 ppm for residues of pyrimethanil in/on 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

cane berry, crop subgroup 13-07 A is appropriate. 

Bushberry subgroup l 3-07B 

The residue data for bushberries were previously submitted under PP#8F7468; the locations and 

application rates employed in these trials are adequate to support the proposed use. The Agency 

reviewed these data (summarized in Table 6) and determined that they supported a tolerance for 

residues of pyrimethanil in/on bushberry, crop subgroup 13-07 A at a level of 6.0 ppm (using the 

NAFTA tolerance calculator; Memo, W. Cutchin, 02-FEB-2010; D372647). Subsequently, 

Canada used the same residue data to establish a MRL for residues of pyrimethanil inion 

bushberries at a level of 8 ppm (using the OECD tolerance calculator). HED thus concludes that 

a tolerance of 8.0 ppm for residues of pyrimethanil in/on bushberry, crop subgroup 13-07B is 

appropriate. 

Table 6. Summary of Residues from Small Berry Trials with Pvrimethanil. 

Total Applic. PHI Residue Levels ( 00111) 

Commodity Rate (lbs ai/A) (days) n Min. Max. HAFT" Median Mean Std. Dev. 

Cane berry 1.413-1.450 0 10 1.50 8.46 8.38 2.30 3.34 2.69 

Blueberry 1.419-1.441 0 16 1.05 5.76 5.13 2.00 2.25 1.22 1 HAFT = highest-average field lnal. 

Tomato subgroup 8-1 OA 

No tomato crop field trial data were submitted. A tolerance for residues of pyrimethanil inion 

tomato has been established at 0.50 ppm [40 CFR §180.518(a)]. IR-4 has proposed to convert 

this individual tolerance to a crop subgroup 8-1 OA tolerance at the same level. The 

representative commodity of the tomato subgroup 8-1 OA is tomato. 

As the proposed use on the tomato subgroup 8-1 OA is identical to the existing use on tomato on 

the product label for Scala® SC Fungicide (EPA Reg. No. 264-788), the existing tomato 

tolerance can be translated to the tomato subgroup 8-1 OA. 

Orange subgroup 10-1 OA 

No new orange crop field trial data were submitted. A tolerance for residues of pyrimethanil 

in/on orange has been established at 10 ppm [40 CFR §180.518(a)]. IR-4 has proposed to 

convert this individual tolerance to a crop subgroup 10-1 OA tolerance at the same level. The 

representative commodity of the orange subgroup 10-lOA is orange or tangerine/mandarin. 

As the proposed use on the orange subgroup 10-1 OA is identical to the existing use on orange on 

the product label for Penbotec® 400 SC (EPA Reg. No. 43813-32), the existing orange tolerance 

can be translated to the orange subgroup 10-1 OA. However, as this value is the same as that 

recommended for the other citrus subgroups, a single tolerance of l 0 ppm is appropriate for fruit, 

citrus, group I 0-10. 

Lemon subgroup l 0-1 OB 

No new lemon crop field trial data were submitted. A tolerance for residues of pyrimethanil 

in/on lemon has been established at 11 ppm [40 CFR §180.518(a)]. IR-4 has proposed to convert 

this individual tolerance to a crop subgroup 10-1 OB tolerance at the same level. The 

representative commodity of the lemon subgroup 10-1 OB is lemon or lime. 

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Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

As the proposed use on the lemon subgroup 10-1 OB is identical to the existing use on lemons on 

the product labels for Scala® SC Fungicide (EPA Reg. No. 264-788) and Penbotec® 400 SC 

(EPA Reg. No. 43813-32), the existing lemon tolerance can be translated to the lemon subgroup 

10-1 OB. However, in order to harmonize with Canada, HED recommends that the U.S. tolerance 

be reduced from 11 to 10 ppm. As thjs value is the same as that recommended for the other 

citrus subgroups, a single tolerance of 10 ppm is appropriate for fruit, citrus, group 10-10. 

Grapefruit subgroup I 0-1 OC 

No new grapefruit crop field trial data were submitted. A tolerance for residues of pyrimethanil 

in/on grapefruit has been established at 10 ppm [40 CFR §180.518(a)]. IR-4 has proposed to 

convert this individual tolerance to a crop subgroup 10-1 OC tolerance at the same level. The 

representative commodity of the grapefruit subgroup 10-lOC is grapefruit. 

As the proposed use on the grapefruit subgroup 10-1 OC is identical to the existing use on 

grapefruit on the product label for Penbotec® 400 SC (EPA Reg. No. 43813-32), the existing 

grapefruit subgroup tolerance can be translated to the grapefruit subgroup l 0-1 OC. However, as 

this value is the same as that recommended for the other citrus subgroups. a single tolerance of 

l 0 ppm is appropriate for fruit, citrus, group 10-10. 

Pome fruit group 11-10 

No new pome fruit crop field trial data were submitted. A tolerance for residues of pyrimethanil 

in/on pome fruit group 11 has been established at 14 ppm [ 40 CFR § 180.5 18(a)]. IR-4 has 

proposed to convert the c rop group 1 1 tolerance to a crop group 11-10 tolerance at the same 

level. The representative commodities of the pome fruit group 11 and 1 1-10 are the same (apple 

and pear). 

As the proposed use on the pome fruit group 11-10 is identical to the existing use on pome fruit 

on the product labels for Scala® SC Fungicide (EPA Reg. No. 264-788) and Penbotec® 400 SC 

(EPA Reg. No. 43813-32) and since the representative crops are identical, the existing pome fruit 

group tolerance can be translated to fruit, pome, group 1 1-10. However, in order to harmonize 

with Canada, HED recommends that the U.S. tolerance be increased from 14 to 15 ppm. 

Stone fruit group 12-12 

No new stone fruit crop field trial data were submitted. A tolerance for residues of pyrimethanil 

in/on stone fruit group 12 has been established at 10 ppm [40 CFR § l 80.5 l 8(a)]. IR-4 has 

proposed to convert the crop group 12 tolerance to a stone fruit group 12-12 tolerance at the 

san1e level. The representative commodities of the stone fruit group 12 and 12-12 are the same 

(sweet cherry or tart cherry, peach, and plum or prune plum). 

As the proposed use on the stone fruit group 12-12 is identical to the existing use on stone fruit 

on the product labels for Scala® SC Fungicide (EPA Reg. No. 264-788) and Penbotec® 400 SC 

(EPA Reg. No. 43813-32)) and since the representative crops are identical, the existing stone 

fruit group tolerance can be translated to fruit, stone, group 12-12. 

Page 10of15 
Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

860.1520 Processed Food and Feed 

There are no processed food items of regulatory interest for cucumber. Therefore, residue data 

pertaining to processed conunodities are not germane to this tolerance petition. The previously 

submitted tomato and citrus processing data indicate that tolerances in/on the relevant processed 

commodities are unnecessary. 

860.1650 Submittal of Analytical Reference Standards 

Analytical standards for pyrimethanil, AEC614276, and AEC614277 with an expiration dates of 

13-JUL-2018, l 7-NOV-2020, and 06-0CT-2015, respectively, are currently available in the EPA 

National Pesticide Standards Repository (personal communication with Theresa Cole, ACB, 09-

DEC-20 11 ). 

860.1850 and 1900 Confined and Field Accumulation in Rotational Crops 

Adequate confined and limited field rotational crop trials are available and support the labelspecified 30-day plant-back interval (PBI) for crops without uses on the Scala® label. The 

available data indicate that tolerances are not currently required for rotational crops. 

860.1550 Proposed Tolerances 

The petitioner has submitted adequate magnitude of the residue data to support the proposed 

application scenarios. No additional residue data are required. The Agency has determined that 

the residue of concern for the purpose of tolerance expression in plants is parent only. Based on 

the available data and the OECD tolerance-calculation procedure (see Attachment 2), HED 

concludes that the tolerances listed in Table 7 for residues of pyrimethanil are appropriate. 

For plant commodities, the U.S., Canadian, and Codex residue definitions are harmonized. The 

proposed tolerances for residues in/on caneberry, crop subgroup 13-07 A and bushberry, crop 

subgroup 13-078 are harmonized with the established Canadian MRLs. 

The U.S. tolerance for residues in/on tomato (tomato subgroup 8-1 OA) is harmonized with the 

Canadian MRL, while the Codex MRL is established at a higher level (0.7 ppm). However, 

Bayer CropScience has requested that EPA not harmonize with Codex in order to prevent the 

creation of a trade barrier with Canada. 

The U.S. and Codex tolerances/MRLs for residues of pyrimethanil in/on citrus are not 

harmonized. Residues in the U.S. residue trials (maximum of 8.43 ppm) were higher than the 

Codex MRL of 7 ppm, precluding harmonization. The U.S. and Canadian tolerances/MRLs for 

residues of pyrimethanil in/on citrus are harmonized, except for the lemon subgroup I 0-1 OB. In 

order to harmonize with Canada, HED reconunends that the U.S. tolerance for the lemon 

subgroup I 0-1 OB be reduced from 11 to 10 ppm. As this value is the same as that reconunended 

for the other citrus subgroups, a single tolerance of I 0 ppm is appropriate for fruit, citrus, group 

10-10. 

The U.S. and Codex tolerances/MRLs for residues of pyrimcthanil in/on stone fruit are not 

Page 11 of 15 
Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

harmonized. Residues in the U.S. residue trials (maximum of 6.5 ppm) were higher than the 

Codex MRLs of2-4 ppm, precluding harmonization. The U.S. and Canadian tolerances/MRLs 

for residues of pyrimethanil inion stone fruit are harmonized at I 0 ppm. 

The U.S. and Codex tolerances/MRLs for residues of pyrimethanil in/on the pome fruit group are 

not harmonized. As the difference in values is minimal, HED recommends that the U.S. 

tolerance be increased from 14 to 15 ppm in order to harmonize with Codex. 

There are currently no established Codex, Canadian, or Mexican MRLs for pyrimethanil in/on 

cucumber. 

Table 7. Tolerance Summary for Pyrimethanil. 

Proposed Tolerance Recommended 

Commodity (ppm) Tolerance (ppm) 

40 CFR §180.518 (a)(l) 

Cucumber 1.5 1.5 

Orange subgroup I 0- 1 OA 10 10 

Lemon subgroup I 0-1 OB 11 

Grapefruit subgroup 10-1 OC 10 

Fruit, pome, group I 1-10 14 15 

Fruit, stone, group 12-12 10 10 

Tomato, subgroup 8- 1 OA 0.50 0.50 

Caneberries subgroup 13-07 A 15.0 15 

Bushberries subgroup 13-078 8.0 8.0 

Attachment l: International Residue Limit Status Sheet 

Attachment I: MRL Spreadsheet 

ROI: RAB I Chemists (07-JAN-2015), HED ChemSAC (28-JAN-20 15) 

cc: G. Kramer 

G.F. Kramer:S I 0957:PY-S:(703)305-5079:7509P:RAB I 

Page 12of 15 

Comments; Correct Commodity 

Definition 

Harmonization with Canada. 

Fruit, citrus, group 10-10 

Harmonization with Codex. 

Caneberry, subgroup 13-07 A 

811shbenJ1. subgroup 13-07 B 
Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

Attachment 1: International Residue Limits 

Pyrimethanil (288201; 12/8/2014) 

Summary of US and International Tolerances and Maximum Residue Limits 

Residue Definition: 

us Canada Mexico2 Codex3 

40 CFR I 80.5 I 8: Plants: 4,6-dimethyl-N-phenyl-2- Pyrimethanil 

Plant: (a) General. (I) pyrimidinamine The residue is 

Tolerances are established Livestock (except milk): 4,6-dimethyl-N- not fat-soluble. 

for residues of the fungicide phenyl-2-pyridinamine, including the 

pyrimethanil, including its rnetabol ite phenol, 4-(( 4,6-dimethyl-2-

metabolites and degradates, pyrim id i ny l)am ino] 

in or on the commodities in Mille 4,6-dimethyl-N-phenyl-2-

the following table pyridinamine, including the metabolite 5-

Compliance with the pyrimidinol, 4,6-dimethyl-2-

tolerance levels specified in (phenylamino) 

the following table is to be 

determined by measuring 

only pyrimethanil (4,6-

dimethyl-N-phenyl-2-

pyrimidinamine). 

Commodity' Tolerance (pom)/Maximum Residue Limit (mCI/kf.!) 

us Canada Mexico2 Codex3 

Cucwnber 1.5 

Orange subgroup 10-I OA 10 10 calamondins, citrus citrons, 7 citrus fruits 

citrus hybrids, oranges, satsuma Po 

mandarins, tangerines 

150 citrus oil 

Lemon subgroup 10-1 OB 11 IO kumquats, lemons, limes 

Grapefruit subgroup I 0-1 OC IO I 0 grapefruits, pummelos 

Fruit, pome, group 11-10 14 14 apples, Asian pears, 15 porne fruits 

Po crabapples, loquats, mayhaws, 40 apple pears, quinces pomace, drv 

I 0 American plums, apricots, 3 apricot 

beach plums, black cherries, 4 cherries Po 

Canada plums, capulins, cherry 4 nectarine, 

plums, chicksaw plums, damson peach 

Fruit, stone, group I 2- 12 10 plums, fresh prune plums, 2 plums 

Japanese apricots, Japanese (including 

plums, klamath plums, nanking prunes) 

cherries, nectarines, peaches, 

plumcots, plums, sloes, sweet 

cherries, tart cherries 

Tomato subgroup 8- 1 OA 0.50 0.5 tomato 0.7 

Caneberry subgroup 13-07 A 15.0 15 blackberries, loganberries, 

raspberries, wild raspberries 

Bushberry subgroup 13-078 8.0 8 aronia berries, buffalo currants, 

Chilean guavas, currants 

elderberries, European barberries, 

highbush (blueberries, 

cranberries), honeysuckle, 

huckleberries, jostaberries, 

lingonberries, native currants, 

salal berries, Saskatoon berries 

(Juneberries), sea buckthom 

3 lowbush blueberries 

5 gooseberries 

Page 13of15 
Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 

Summary of US and International Tolerances and Maximum Residue Limits 

Residue Definition: 

us I Canada l Mexico2 l Codex3 

Completed: M. Negussie; 12/ 10/ 14 .. 1 Includes only commod1t1es of interest for this action. Tolerance values should be the H ED recommendations and 

not those proposed by the applicant. 2 Mexico adopts US tolerances and/or Codex MRLs for its export purposes. 3 * = absent at the limit of quantitation; Po= postharvest treatment, such as treatment of stored grains. PoP = 

processed postharvest treated commodity, such as processing of treated stored wheat. (fat) = to be measured on the 

fat portion of the sample. MR Ls indicated as proposed have not been fmalized by the CCPR and the CAC. 

Page 14of15 
Pyrimethanil Summary of Analytical Chemistry and Residue Data 

Attachment 2: MRL Spreadsheet 

Pyrimethanil 

Greenhouse Cucumbers 

US/Canada 

2.12-2.22 lbs ai/A; I-day PHI 

Total number of da ta (n) 

Percentage of censored data 

Number of non-censored data 

Lowest r esidue 

Highest residue 

Median residue 

Mean 

Standard deviation (SD) 

Correction factor for censoring (CF) 

Proposed MRL estimate 

- Highest r esidue 

- Mean + 4 SD 

- CF x 3 Mea n 

Unrounded MRL 

Rounded MRL 

High uncertainty of MRL estimate. 

[Small dataset) 

Residues (mg/kg) n 

0.07 I 

0.38 I 

0.45 1 

0.47 I 

0.82 I 

Page 15of 15 

5 

0% 

5 

0.070 

0.820 

0.450 

0.438 

0.267 

1.000 

0.820 

1.507 

1.314 

1.507 

DP# 42 1844 
Pyrimethanil [PYI]/ Bayer CropScience Inc. [BCZ] 

B.7.6 

B.7.6.1 

B.7.6.1.1 

Document ID: 

Report: 

Guidelines: 

Residues Resulting from Supervised Trials 

(Annex llA 6.3; Annex IHA 8.3) 

Residues in Target Crops 

Greenhouse Cucumber 

MRID No. 49312501 

PMRA No. 2443911 

Ballantine, J. (2014) "Pyrimethanil: Magnitude of the Residue on 

Cucumber, Greenhouse." Study Number AAFC 10-056R. Laboratory 

Identification Number AAFC 10-056R-2 1 l. UI?published study prepared 

by Pest Management Centre, Agriculture and Agri-Food Canada, Ottawa, 

ON, Canada. 204 pages. 

EPA OCSPP Harmonized 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 Field Trial (September 2009) 

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 scientifically acceptable. 

Evaluator: 

Peer Reviewer: 

Melissa Watchorn, Pest Management Regulatory Agency, Health Canada 

George F. Kramer, Ph.D., OCSPP, U.S. EP

~ 

A ~ ,s 4, 5 

EXECUTIVE SUMMARY 

Five greenhouse trials were conducted on cucumbers in Canada and the United States during 

2010 and 2011. As the trials were conducted in commercial greenhouses with controlled 

environmental conditions, the zones in which the trials were conducted are not relevant. 

At each trial location, pyrimethanil, formulated as a suspension concentrate (Scala® SC 

Fungicide; PCP # 2801 1), was applied to cucumbers in three foliar applications at rates of 777-

848 g ai/ha (0.69-0.76 lbs ai/A). The re-treatment interval (RTI) was 7-14 days, and the total 

application rate was 2372-2483 g ai/ha (2.12-2.22 lbs ai/A). An adjuvant was not included in 

any of the spray mixtures. Greenhouse cucumbers were harvested at a I -day preharvest interval 

(PHI) at all trial sites. Additional samples were harvested at one trial site at PHls of 0, 5, 11 , and 

14 days to determine residue-decline behavior. 

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

were stored frozen until analysis. The maximum storage interval for samples between harvest 

and analysis was 139 days. Residues ofpyrimethanil were shown to be stable in cucumbers for 

up to 140 days under frozen conditions in a storage stability study conducted concurrently with 

EPA MRID#: 49312501 

PMRA# of document: 247 1398 

Page I of7 
Pyrimethanil [PYI)/ Bayer CropScience Inc. [BCZ] 

the analytical portion of the current residue study. Adequate storage stability data are therefore 

available to support the storage conditions and intervals for samples in the current trials. 

Residues of pyrimethanil in trial samples were determined using a working method based on the 

reference method "Frnits and Vegetables: Analytical Method for the Determination of Residues 

(Improved Version)" Study identification: 140/01/012, Report No. DGM C05/98-0. The 

reference method has been reviewed previously and deemed acceptable for data gathering and 

enforcement purposes in plants. Acceptable method validation and concurrent recoveries were 

reported for cucumber samples at fortification levels of 0.05-5.0 ppm, thus validating the 

method. The validated limit of quantitation (LOQ; determined as the lowest level of method 

validation, LLMV) and the estimated limit of detection (LOD) were 0.05 ppm and 0.0225 ppm, 

respectively, for residues of pyrimethanil in cucumbers in this study. 

Individual sample (and per-trial average) residues in greenhouse cucumbers ranged from 0.07 

ppm to 0.83 ppm (0.07 ppm to 0.82 ppm) when samples were treated at total rates of2372-2483 

g ai/ha (2. 12-2.22 lbs ail A), and harvested at a 1-day PHI. Residue decline data showed that 

pyrimethanil residues decreased in greenhouse cucumbers with increasing PHis when samples 

were harvested at PHis of 0, 1, 5, 11 , and 14 days. 

I. MATERIALS AND METHODS 

A. MATERIALS 

Table B.7.6.1.1-1. Nomenclature for Pvrimethanil. 

Common name Pvrimethanil 

CAS Name· 4,6-dimethyl-N-phenvl-2-ovrimidinamine 

CAS no. 531 12-28-0 

Company experimenta l name AE 8100309 

B. Study Design 

1. Test Procedure 

A total of five greenhouse residue trials in/on cucumbers were conducted with pyrimethanil, 

formulated as a suspension concentrate, during 2010 and 2011 (Table B.7.6.1.1-2). 

Table B.7.6.1.1-2. Trial Numbers a nd Geographical Locations. 

Crop 

Region Total 

I 2 3 4 5 6 7 8 9 IO 11 12 13 14 

Greenhouse 2 I I I 51 

Cucumbers 

1 As trials were conducted in enclosed, commercial greenhouses with controlled environmental conditions, the zones 

in which the trials were conducted are not relevant. 

Locations and detailed use patterns for the trials are provided in Table B.7.6.1.1-3. 

EPA MRID#: 49312501 

PMRA# of document: 247 1398 

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Pyrimethanil [PYJ]/ Bayer CropScience Inc. [BCZ] 

Table B.7.6.1.1-3. Study Use Pattern. 

Location: City, End-use Volume Rate per Retreatment Total Rate State/Province; Product/ Method of Application/ (L/ha) Application Interval (g ai/ha) Surfactant/ 

Year Formulation Timing of Application [gal/A] (g ai/ha) (days) [lbs ai/A] Adjuvant 

(Trial LD) 1 (% ai) [lbs ai/A] 

Salisbury, MD/ Scala® SC I. Foliar/ 11 32 797 -- 239 1 None 

2010 Fungicide First fruits nearly mature [121] [0.71 1] [2.1 3] 

(Trial # ID 206) 2. Foliar/ l 132 797 7 

Fruiting [121] [0.711] 

3. Foliar/ 1132 797 7 

Fruiting r 12 n [0.711] 

Raleigh, NC/ Scala® SC I. Foliar/ 10 10 795 -- 2372 None 

2010 Fungicide Flowering and fruiting [108] [0.709] [2. 12] 

(Trial lD # 207) 2. Foliar/ 988 777 7 

Flowering and fruiting [106] [0.693] 

3. Foliar/ 1016 800 7 

Fruiting [109] [0.714] 

Citra, FL/ Scala® SC I. Foliar/ 926 79 1 -- 2405 None 

2011 Fungicide Bloom, fruiting [991 [0.706] [2. 15) 

(Trial ID # 208) 2. Foliar/ 948 810 14 

Bloom, fruiting [IO I] [0.723] 

3. Foliar/ 942 804 13 

Bloom, fruiting [I 0 I] [0.717] 

Parlier, CN Scala® SC I. Foliar/ 1162 828 -- 2483 None 

20 10 Fungicide Fruiting [124) [0.739] [2.22) 

(Trial ID # 209) 2. Foliar/ 1191 848 7 

Fruiting [ 127] [0.757] 

3. Foliar/ 11 33 807 7 

Fruiting r 12 11 ro.1201 

Harrow, ON/ Scala® SC I. Foliar/ 2008 802 -- 2395 None 

2010 Fungicide Mature fruit [2151 f0.7161 [2.1 4] 

(Trial ID # 210) 2. Foliar/ 2004 801 8 

Mature fruit [2 141 f0.7151 

3. Foliar/ 1982 792 7 

Mature fruit [2 121 f0.7071 1 All Trial ID #s have the prefix AAFC I 0-056R-. 

Cucumbers were grown and maintained according to typical agricultural practices for 

greenhouse operations. Irrigation was applied as a drip to soil media, with a microsprinkler, or 

with a hydroponic system. 

Sample Handling and Preparation 

Mature, marketable cucumbers were harvested randomly, avoiding row ends, first from the 

untreated plot, and then the treated plot. Either 12 or 24 cucumbers were harvested from each 

plot, and the minimum sample size was 2359 g (5.2 pounds). Cucumbers were halved or 

quartered to reduce sample weight when necessary, and any adhering stems or debris were 

removed by hand. The trial samples were placed in labeled sample bags, and were then either 

placed directly in freezers, or in coolers with ice for transport to freezers. All samples were 

placed in frozen storage within 33 minutes of harvest. The samples were shipped frozen to the 

analytical facility at the University of California, Davis, where they arrived frozen and in good 

condition. The samples were placed in frozen storage (S-20 °C), where they remained, except 

EPA MRID#: 49312501 

PMRA# of document: 24 71398 

Page 3 of? 
Pyrimethanil [PYI]/ Bayer CropScience Inc. [BCZ] 

during sample preparation. The samples were prepared by chopping with dry ice in a Hobart 

Food Chopper. 

2. Description of Analytical Procedures 

Cucumber samples were analyzed for pyrimethanil residues using a working method based on 

the reference method entitled "Fruits and Vegetables: Analytical Method for the Determination 

of Residues (Improved Version)" Study identification: 140/01/012, Report No. DGM C05/98-0 

(PMRA# 1095293; EPA MRID# 44908503). The reference method has been reviewed 

previously by PMRA and EPA and deemed acceptable for data gathering and enforcement 

purposes in plants (S2001-2137; PMRA# 895867; EPA DP# D389985). Briefly, residues were 

extracted from cucumber trial samples by homogenizing with acetone. An aliquot of the extract 

was then cleaned up on a polymeric solid-phase extraction (SPE) column eluted with 

acetonitrile:water (80:20, v/v). Residues were then determined by high-performance liquid 

chromatography (HPLC) with tandem mass spectroscopy (MS/MS). The following steps in the 

reference method were modified: 

• The hexane and basified liquid-liquid partition steps were eliminated because they were 

not needed when using LC-MS/MS for detection which allows for a simplified cleanup 

procedure. 

• The silica SPE column cleanup was changed to an Evolute® ABN SPE, which is better 

suited for the cleanup of aqueous extracts. 

• The gas chromatography/mass-selective detector (GC/MSD) detector was replaced by 

LC-MS/MS which provides better sample throughput, reduced solvent requirements, and 

does not require an internal standard to correct for enhancement effects. 

The validated LOQ determined as the LLMV was 0.05 ppm, and the LOD was estimated to be 

0.0225 ppm in cucumbers in this study. 

II. RESULTS AND DISCUSSION 

Method performance was evaluated prior to sample analysis by fortifying control cucumber 

samples with 0.05, 0.5, and 5.0 ppm of pyrimethanil. With the exception of one recovery of 68% 

in a sample fortified with 0.05 ppm of pyrimethanil, all method validation recoveries were within 

the acceptable range of 70-120%. Accuracy of the method was also confirmed by fortifying 

control cucumber samples with 0.05 and 0.5 ppm of pyrimethanil, and determining recoveries 

concurrently with trial sample analysis. All concurrent recoveries were within the acceptable 

range of 70-120%. Given that the majority of recoveries were within the acceptable range, the 

working method was considered valid for the analysis of pyrimethanil residues in cucumber 

matrices (Table B.7.6.1.1 -4). The fortification levels bracketed the measured residues in trial 

samples. 

The detector response was linear (coefficient of determination, r2 ::'.'.: 0.999569) within the range of 

0.5-10 pg/μL. Representative chromatograms of control samples, fortified samples and treated 

samples were provided. The fortified sample chromatograms contained only the analyte of 

EPA MRlD#: 49312501 

PMRA# of document: 2471398 

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Pyrimethanil [PYI)/ Bayer CropScience Inc. [BCZ] 

interest, and peaks were symmetrical and well defined. There were residues observed at levels 

- 25% of the treated samples in the untreated control samples collected from the greenhouse 

located in Ontario (Trial ID # 210). Although residues in concurrent recovery samples were 

corrected for the residues in controls, the reported residue values in the treated samples were not 

corrected. The study report indicated that the control samples may have been contaminated due 

to inadequate plot separation as the plastic sheeting used to separate the plots did not reach the 

greenhouse ceiling. 

Table B. 7.6. 1. 1-4. Summary of Method Validation, Concurrent Recoveries, and Freezer Storage Stability 

Recoveries of Pvrimethanil from Greenhouse Cucumbers. 

Matrix Fortification Level (oom) Recoveries(%) Mean ± Std. Dev.(%) 

Method Validation 

Greenhouse cucumber 0.05 84, 73,68 75 ± 8 

0.5 78, 83, 81 81 ± 3 

5.0 73,84, 84 80 ± 6 

Concurrent Recovery 

Greenhouse cucumber 0.05 93, 891

, 106 1, 102 98± 8 

0.5 92, 931

, 731, 94 88 ± 10 

Freezer Stora2c Recoveries Following 31 days of Frozen Storage 

Concurrent recoveries 0.05 90 --

5.0 96, 85,82 88 ± 7 

Freezer storage 5.0 83,92, 78 84 ± 7 

recoveries 

Corrected freezer storage stability recovery2 95 

Freezer Storage Recoveries Following 140 days of Frozen Storage 

Concurrent recoveries 5.0 88,89 89 

Freezer storage 5.0 90, 91 , 90 90 ± I 

recoveries 

Corrected freezer storage stabilitv recoverv2 IOI 1 Corrected for residues observed in control samples. 

2 Mean recovery was corrected for average concurrent recovery <I 00% from concurrent recovery samples spiked 

with 5.0 ppm ofpyrimethanil. 

The cucumber trial samples were stored frozen (::S-20 °C) for a maximum of 139 days from 

harvest to ana lysis (Table B.7.6.1.1-5). Residues were determined on the same day as they were 

extracted from cucumber samples. Freezer storage stability data were generated concurrently 

with the analytical portion of the greenhouse cucumber trials (Table B.7.6.1.1-4). Freezer 

storage recoveries in cucumbers fortified with 5.0 ppm of pyrimethanil and stored frozen for 140 

days were all within the acceptable 70-120% range. These data show that pyrimethartil residues 

are stable for the same duration the trial samples were stored frozen. Therefore, there are no 

concerns regarding the stability of pyrimethanil residues in cucumbers in this study. 

EPA MRID#: 49312501 

PMRA# of document: 247 1398 

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Pyrimethanil [PY!)/ Bayer CropScience Inc. [BCZ] 

Table B.7.6.1.1-5. Summa ry of Storage Conditions. 

Matrix Storage Actual Storage Interval of Demonstrated Storage Stability (RAC or Extract) Temperature (0C) Duration (days)' 

Greenhouse Cucumbers -20 139 A freezer storage stability study was 

conducted concurrently with the analytical 

portion of the residue fie ld trial study 

(Table B. 7 .6.1.1-4 ). The data indicated 

that pyrimethanil residues are stable when 

stored frozen in cucumbers for up to 140 

days. This covers the period that trial 

samples were stored frozen. 

1 From harvest to residue extraction and analysis. Residues were determined on the same day as residues were 

extracted from samples. 

The results from these trials showed that when harvested 1 day after the last of 3 foliar 

applications at a total rate of2372-2483 g ai/ha (2. 12-2.22 lbs ai/A), pyrimethanil residues in 

greenhouse cucumbers ranged from 0.07-0.83 ppm (Tables B.7.6.1.1-6 and B.7.6.1.1 -7). 

In the residue decline trials, mean residue levels decreased from 0.46 ppm to 0. 14 ppm in 

greenhouse cucumber samples harvested between PHls of 0 and 14 days. 

Table B.7.6.1.1-6. Residue Data from Greenhouse Cucumber Tria ls with Pyrimet hanil. 

Location: City, Crop/ End-Use Total Rate PHJ Residues (ppm) 

State!Province; Region Variety 

Matrix Product (g ai/ha) (days) Pyrimethan il Per-trial 

Year (Trial ID) 1 [lbs ai/A] average 

Salisbury, MD/ Cucumber/ Scala® SC 2391 0.07 

2010 NIA Samir Fruit Fungicide [2.13] I 0.07 0.07 

(Trial # ID 206) 

Raleigh, NC/ Cucumber/ Scala® SC 2372 0.38 

2010 NIA Jawell Fl Fruit Fungicide [2. 12) I 0.38 0.38 

(Trial ID # 207) 

Citra, FL/ Cucumber/ Scala® SC 2405 0.44 

201 1 NIA Fruit I 0.47 

(Trial ID # 208) Jawell Fl Fungicide [2.15) 0.49 

Parlier, CA/ Cucumber/ Scala® SC 2483 0.83 

20 10 NIA Cumlaude Fruit Fungicide [2.22) I 0.80 0.82 

(Trial ID # 209) 

0 0.50 0.46 0.42 

I 0.48 0.45 0.42 

Harrow, ON/ Cucumber/ Scala® SC 2395 0.33 20 10 NIA Camaro Fruit Fungicide [2. 14) 5 0.33 0.33 

(Trial ID # 2 10)2 

0.16 11 0.17 0.17 

14 0.14 0.14 0.14 1 All Trial ID #s have the prefo: AAFC I 0-056R-. 

2 Residues of 0. 10 and 0.1 1 ppm were observed in the control samples at this trial site due to possible contamination 

in the greenhouse. Residues in the treated samples were not adjusted for residues in the control samples. 

EPA MRJD#: 49312501 

PMRA# of document: 24 7 1398 

Page 6 of7 
Pyrimethanil [PYI)/ Bayer CropScience Inc. [BCZ] 

Table B.7.6.1.1-7. Summary of Residues from Greenhouse Cucumber Trials with Pyrimethanil. 

Total Pyrimethanil Residues (oom) 

Application PHI Crop Matrix Rate (days) 11 

Min.

1 Max.1 LAFT2 HAFT2 Median2 Mean2 so2 

(g ai/ha) 

[lbsai/Al 

Cucumber Fruit 2372-2483 I 5 0.07 0.83 0.07 0.82 0.45 0.44 0.12 

f2. I 2-2.22] 1 Values based on total number of samples. 2 Values based on per-trial averages. LAFT = lowest average field trial, HAFT = highest average field trial, SD = 

standard deviation. 

n = number of fi eld trials. 

III. CONCLUSIONS 

The greenhouse cucumber trials are considered scientifically acceptable. The results of the study 

showed that following a total application of 23 72-2483 g ai/ha (2. 12-2.22 lbs ail A), pyrimethanil 

residues ranged from 0.07-0.83 ppm in samples collected at a I-day PHI. A decline study 

indicated that pyrimethanil residues in greenhouse cucumbers decreased with time when samples 

were harvested at PHis of 0, 1, 5, I 1, and 14 days. Adequate concurrent storage stability data are 

available to support sample storage durations and conditions. 

REFERENCES 

PMRA# 1095293; EPA MRID# 44908503. Peatman, M.H. (1999) " Fruit and Vegetables: 

Analytical Method for the Determination of Residues (Improved Version).'. Report No. DGM 

C05/98-0. Study Number 140/011012, Report Number C000292. Unpublished study prepared 

by AgrEvo USA Company, Wilmington, DE, USA. 39 pages. 

DOCUMENT TRACKJNG 

RDI: RABI Chemists ( 12/ l0/ I4) 

Petition Number: 4E8302 

DP Barcode: 422294 

PC Code: 28820 I 

EPA MRJD#: 4931 250 I 

PMRA# of document: 247 1398 

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