### UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D .C

. 20460

OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVE N TION 

### MEMORANDUM Date: Subject: 22 -S EP

- 2015 

### Pyrim ethanil

. Petition for the Estab li shment of Permanent Tolerances for Residues in/on, Cucumbers, Tomato Subgroup 8-1 OA, Lemon S ub gro up 10-1 OB, Orange Subgroup 10-1 OA , Grapefruit Subgroup 10-1 OC, Pome Fruit Group 11- 10 , Stone Fruit Group 12-12 Caneberry Subg roup 13-07A, and Bu shberry 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 : Sect i on 3 Deci s ion Nos.: 492391 & 493505 Peti t ion Nos.: 4F8291 & 4E8302 Risk Assessment Type : NA TXR No.: NA Case No.: 7059 CAS No.: 53112-28-0 40 CFR: §180.518 MRID No. : 4931250 I 

### From:
Through:

To: 1

### ?¢'~~ 

# <--- George F. Kramer, Ph.D., Senior Chemis t,..oiti Risk Assessment Branch 1 (RAB 1) Health Effects Division (HED, 7509P) Michael A. 

### Doherty , Ph.D. , Senior Chemist

# ~V Meheret Negussie, Chemist 

## N eJ.evd**~'r:.** Science Advisory Council fo r 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 2 1 Registration Division (RD , 7505P) 

### Exec utive Summary The Interregional Research Project No. 4 (IR-4) and Bayer CropScience have subm itted petitions for the use of Scala® SC Fungicide (EPA Reg. No
. 264-788) , an aqueous s uspen sion -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 estab li shed as a result of the proposed uses: Cucumber

. .. . .. .. .. . .. .. .. . ........................................................................ 1.5 ppm Page I of 15Pyrimethanil Summary ofAnalytical Chemistry and R esidue Data DP # 42 I 844 Oran ge subgroup 10 -1 OA
.............................. ......... ............................ 10 ppm Lemo n s ub gro up 10

- 1 OB
.............................. .......... ................... .. ...... 11 ppm Gr a p e fruit s ub gro up 10-1 OC
.............................................................. 10 ppm Fruit , p o me , gro up 11-10
...................... .. .. ................... ...................... 14 ppm Fruit , s tone , gro up 12-12
...... ........ ........................................ . ............. 10 ppm Tomato s ub g roup 8

- lOA

........................................................... . .. .... 0.50 ppm Canebe rri es s ubgroup 13-07 A
.. .. ... ........... ................ . . .......... .. ..... .. . 15.0 ppm Bu s hb er ri es subgroup 1 3 -078
............................... . ........................... 8.0 ppm No new data we re submitted to support tolerances o n tomato subgroup 8-1 OA , le m o n subgroup l 0-1 OB , pome fruit group 11-10 , orange s ub group I 0-1 OA , grapefruit s ub group l 0-1 OC , and s ton e fruit group 12 -1 2. The petitioner ha s req ues ted that existing tol erances be expanded to their respecti ve crop gro up s or crop subgroups. The re si due data for caneberries and bushb e rri es were previously submitted and reviewed under PP # 8F7468 (Me mo , W. Cutc hin , 02-FEB- 2 0 IO ; D 3 72647). T hi s m e m o randum was reviewed b y two peer reviewers of th e C he mSAC , per ChemSAC Standard Operating Procedure s (SO P s). Py rimethanil tolerance s are c u rre ntl y estab li shed in 40 CFR 

### § 180.518 and are expressed in te nn s of: ( i) parent o nl y for pl ant co mmoditie s; ( ii ) parent + Metabolite AEC6 14 276 (4-[ 4 , 6-dimethyl2 -p yrimidiny l )am in o]phenol) fo r ruminant tissues ; and (iii) parent + Metabolite AEC614277 ( 4 , 6-dimethyl-2-(phenylamino) -5-pyrimidin o l) for milk. Th e propo · seq new use . on gree nhou se:grown c ucumbers is as a foliar appl ication three t im es at 0.70 lbs ai/A with a maximum of2.l lb s a i/A/seaso n and a preharvest inte r val (PHI) of l da y . T he proposed new use to caneberries and bu s hb e rrie s is as a foliar applicat io n 2 -4 times at 0.35- 0.70 lb s ill/ A with a max imum of 1.4 lb s ai/A/season and a PHI of 1 day. T h e qualitative nature of the pyrimethanil residue in the r e lev ant pl ant co mm od iti es i s adequately und erstood based o n accep tab le metabolism stud ies in l ettuc e , grapes. and tomatoe s . The HED Metabo li sm Assessment Review Committee (M AR C) has determin e d th at for risk assessment and tolerance ex press io n , pare nt only is the resid ue of concern for plant co mmoditi es . The data-collection me thod u se d to generate th e cucumber residue dat a wa s a high-performanc e liquid chromatography ( HP LC) with tand e m m ass sp ec tro s copy (MS/ M S) M e th o d 140 / 01 / 0 12. The lo west le ve l of method va lidation ( LLM V) was 0.05 ppm. T hi s met hod was adequate for data collection. Th ere are a lso adequate method s ava il ab le to e nforc e pyri m e thani l to lerance s on t h e s ubj ect crops. The c ucumb e r sam pl es a nal yzed in this study were he ld in frozen s tora ge for a maximum of 139 day s prior to anal ys is of py rimethanil re s idu es. There are adequate concurrent sto rage s tability data to indicate that pyrimethanil residues are s tab l e in/on cucumber for th e duration of this st

ud y . The s ubmitte d field tria l residue data for greenho u se-grown cucumbers are adeq u ate
. Th e field trial data refle c t the proposed use pattern , an adequat e number of tri a ls were co nducted, and samp le s we re an a l yzed for the residue of concern using validated data-collection methods. Pertrial-average -r es idu es of pyrimethanil ran ged 0.07 ppm to 0.82 ppm in/on five cucumber trial s w ith s ample s harv es t e d at a 1-day PHI (hi g hest individual residue of 0.83 ppm) from the fi ve tri als. Us ing the Orga ni zation for Econom i c Co

- operation and Developm e nt (OECD) tol e ranc e calculation procedures fo r the residue data se t indicate s that the reque s te d tolerance of 1
. 5 ppm P

age 2o f15Pyrimethanil 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 labelspec ified 30-day plant-back interval (PBI) for crops without us es 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 harmoni zed 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) i s 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 high er 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 l e mon subgroup 10

- lOB b e reduced from 11 to I 0 ppm. As this value is the same as that recommended for the other citrus s ub groups, 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 high er 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 value s 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. Regu l atory Recommendations and Residue Chemistry Deficiencies Pending submission of a revised Section F (see requirements und er Proposed Toleranc es), 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, s ub g roup 13-07 A
. ........................... . ... . ... . ... 15 ppm Bushberry , subgroup 13-078
.... . ... . ... . .......................... 8.0 ppm Note to RD: With the establishment of these to lerances, the following tolerances should b e Page3ofl5Pyrimethanil Summary of Analytical Chem istry 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 , subg r oup 3

- 07A (2 .0 ppm) does not match the recommended tolerance from a previous assessment (Memo , Tyler 

### et al. , 22

- MAY-2013; D389923). HED recommended for a tolerance of 0.20 ppm for residues of pyrimethan il in/on onion, bulb , subgroup 3-07A. 

### 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 whic h 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 secretio n has not been fully estab li shed. Protein synthesis is not inhibited, and evidence suggests that extracellular enzym e s 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 do e s not exhibit cross-resistance to stero l

- inhibi tors , dicarboximides , benzimidazoles , quinone outside inhibitors , or phenylarnides , but may exhibit cross -resis t ance 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 summari z ed in Table 2.

Table 1. Test Compound Nomenclature. C omp o und H 

# ()NYrl C H

, N**~** C H, Co mm o n n ame Py rim e th anil Co mpany ex p e rim e nta l names Jan ss en: R2 I 5559: PH0666 Ave nti s : S N 10 03 09 ; ZK 100309 ; AE 8100309 IU PAC nam e 2

- a nilin o -4 , 6

-dim e th y lpy rimidin e CAS n ame 4 , 6-dim c th y l- N-ph c ny l- 2 -py rimidin a min e C A S reg i s t ry numb e r 5 3 112-28- 0 End-u se produ c t (E P) S c a la® SC Fun g icid e (E PA R eg. No . 264-788 ), a n SC fo rmul a tion containin g 5.0 lb s / ga l p y rim e th anil
Page 4of15Py rimethanil Summary of Analytical Chemistry and Re s idue Data DP # 421844 T ab le 2. Ph ysicoc hemi ca l Properties of P y rim et hanil. Parameter Value R efere n ce Melling point

- 95 ° C 43301601 pH D a t a unavailable Den s it y Bulk density = 650-700 K g/

m

3 43301601 Water solubility (25 ° C) 0. 1 2 1 glL (p l I 6. I) 44 908503

olvent s olubility (g!L at 200C) Dichloromethane: 1000.2 44908503 E

th yl acet at

e: 6 1 6.9 Acetone: 388.8 n-H exane: 23.7 Vapor pr ess ure at 25 ° C 2.2 x 10· 3 P a 44 908503 Dissociation constant (pK. ) pKa = 3.52 ± 0.02 4330160 1 Oc t ano l / water partition coefficient Log( K ow) 2.48 hllp: // www.hb-p.com / pyrimethanil.htm UV/ visible absorption spec trum Data unavailabl e 

### 860.1200 Directions for Use

T ab l e 3. S umm a r y of Dir ec ti o n s for Use of P y rimethanil. Appli c. Tim in g , Formulation Applic. Max. No. Max. Seasonal Type , a nd (E PA Reg. Rate Applic. per Applic. Rate PH I Use Directions and Eq uip

. No.) (lbs a i/ A) Season (lbs ai / A) ( days) Limitations Cucumber Scalatt> SC Greenho use fungicide 0
. 70 3 2. 1 I R etreatment interval: 7-14 only (E P A R eg. No. days . 264-788) Small Berries (caneberries and bu s hb erri es)**Sca sc**  Ground o r a ir Fungicide 0.35-0.70 4 1.4 0 R etreatment interval: 7 -14 (E P A R eg. No. days. 264-788) 

### Co nclus ion : The s ubmitted label is adequate to a ll ow evalu at ion of the cuc umb er , caneberry, and bu s hberry res idue data re lative to the new propo se d u ses . Pyrimethanil is currently registered for u se on tomato; citrus fruit , group 1 0 , except lemon (postharvest); le mon (preharvest and postharvest); pome fruit gro up 11 (preharvest and postharvest) ; and stone fruit g roup 12 (preharvest and postharvest). The petitioner has requested that the ex isting uses be expanded to tomato s ubgroup 8

- 1 OA , lemon subgroup I 0-1 OB , pome fruit group I 1-10 , orange s ubgroup l 0-1 OA , grapefruit subgroup 10-1 OC, and sto ne fruit gro up 12-12. The existing direction s for u se for th ese crops are unchange d , other than the additional crops covered by the updated g roup s/ s ubgroups. Detailed re v iews of the direction s for u s e for these crops can be found in pre v ious HED reviews (D361363 , 08-APR-2009 , G. Kram e r ; D347247 , l 7 -J UL

- 2008 , G. Kramer ; D 369 788 , 08-DEC-2009 , G. Kram e r ; and 0284001 , 12-JAN-2004 , J. Morales and G. Kram er ).


### 860.1300 Nature of the Residue

- P l ants & 

### Lives t ock
PP#s 2F06439 and 2F06480, DP #s 28400 1 & 284870 , J
. Morale s and G. Kramer, 1 2 -JAN-2004 PP# 8F 7250, DP # 3 61363 , G. Kramer, 08-APR-2009 The qualitativ e nature of the pyrimethanil res idu e in th e re leva nt plant co mm od i ties is ade qu ately und er stoo d ba se d on acceptab l e metabolism studies in le ttuce , grapes, and tomatoes. The HED Page 5of15Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 MARC has determined that for risk assessment and to l erance 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 res idue in livestock commodities is not germane to these petitions.


### 86 0 .1340 Resid u e A na lyti ca l 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 earl ier 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) b y Analytical Chemistry Branch (ACB)/ Biological and Economics Anal ysis 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 Vegetab l es: 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 samp les 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). Res i dues were then determined by HPLC

- MS / MS. Method performance was eva luated prior to samp le analysis by fort i fying control cucumber samples with 0
. 05 , 0.5 , and 5.0 ppm of pyrimethanil. With the exception of one recovery of 68% in a samp l e fortified with 0.05 ppm of pyrimethanil, all method validation recoveries were within the acceptabl e range of 70

- 120 %
. Accuracy of the method was also confirmed by fortifying contro l cucumber samples wi th 0.05 and 0.5 ppm of pyrimethanil , and determining recoveries concurrently with trial samp le analysis. All concurrent recoveries were within the acceptab le range of70-120%. Given that the majority ofrecoveries w ere within the acceptable range , the working method was cons idered valid for the analysis of pyrimethani l residues in cucumber matrices. The fortification levels bracketed the measured residues in trial samp l es. 

### Conclus ion: There are adequate methods available to enforce pyrimethanil tolerances on the Page 6of15Py rimethanil 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. Morale s and G
. Kramer, 12-JAN-2004 

### Pyrimethanil was tested through Protocol s 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 th e meth y lene chloride system , respectively. Pyrimethanil eluted from the standardized Flor i sil column. Recovery ranged from 86 to 98% using two differe nt systems
. As noted previously , the QuEChERS multiresidue method has been shown to adequately quantify residues of pyrimethanil (http: //www . crl-pestic id es.eu/library/ docs/ fv/ CRLFV Multiresidue methods.pd.!).


### 860.1380 Storage Stability
PP#s 2F06439 and 2F06480, DP #s 284001 & 284870 , J. Morale s 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 subm itted freezer storage stability data indicated that residues of pyrimethanil were stable for 12 months in lettuce , grape , carrot , and tomato and fo r 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 emp lo yed in the current study. 

### Conclusion: There are adequate storage stabi lity 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 assoc i ated livestock food/feed items ofregulatory concern; therefore , a discussion of liv estock residues is not germane to these petitions.


### 860.1500 Crop Field Trials Cucumber
DER R efe re nce Li st 49312501.der.doc 

### Five g reenhouse trials were conducted on cucumbers 

### in Canada and the United States during Page 7of15Pyrimethanil Summary of Analytical Chemistry and R esidue Data DP # 421844 20 IO and 20 11. As the trials were conducted in co mm e rc ial greenhouses with controlled enviro nm e ntal cond iti ons. th e zo ne s in which the trials we re conduc t ed are not re le vant. A t eac h tri al l ocat ion , pyrimethanil, formulated as a s u s pe nsion concentrate (Scala ® SC Fun gicide; PCP # 2 801 1 ), was applied to cucumbers in three fol iar app l icati o n s at rates of 0
. 69- 0. 76 lbs ai/ A. The re-trea tment interva l (RTT) was 7-14 days, and the total application rate was 2. 12

- 2.22 lb s ai / A. An ad ju van t was not includ ed in any of the spray mi xtures. Greenhouse c u cumbers were h arvested at a I

- day PHI at a ll tria l si t es. Ad dition a l samp les were harvested at one t ri a l s ite at PHi s of 0, 5, 11 , and 14 days to determine residue-decline behavior. Indi v idual sampl e (and per-trial average) residues in g reenho u se - grown c u cumbers ranged from 0.07 ppm to 0.83 ppm (0.07 ppm to 0.82 ppm ) when samp les were treate d at total rates of 2 .1 2- 2.22 lbs ai/A , and harveste d at a 1-day PHI. Resid ue d ecl in e data s howed that pyrimethanil re s idues decr ease d in g ree nhouse cucumb e rs with increasing PHis when sample s were harv ested a t PH i s ofO , 1 , 5 , 1 1 , and 14 days

. Table 4. S umm a r y o f Res id u es fr o m G r ee n ho use C u c um be r T r ia ls w it h Pvrim et h an il

. To tal App. Rate PHI Pyrimethanil R esidues (ppm) Crop Matrix (lbs ai/A) (days) n Mi n . 1 

### I Max. 1 

### I LAFT2 

### I HAFT2 

### I Median 2 

### I Mean 2 

### I SD 2 Cucumbe r Fruit 2. 1 2-2.22 I 5 0.07 

### I o.83 

### I 0.07 

### I 0.82 

### I 0.45 

### I 0.44 

### I 0.12 1 Va lu es based on total number of samp les. 2 Va lu es based on per-trial averages. LAFT =lowes t average fie ld trial , HAFT = highe s t average field trial , SD = s tandard deviation. n = numb er of field tria ls. 

### Conclusions: The s ubmitte d residue data are ad eq uat e to fulfill data requirements for gree nhous e-g rown c uc umb ers . The ava il ab le d ata will s upport th e proposed u se pattern. Ta b le 5. Tri a l Numb er s an d Geo g r ap hica l Locatio n s.**e~ on**  Crop I 2 .., .) 4 5 6 7 8 9 10 11 12 13 1 4 Total Gree nhou se 2 I 1 1 51 C uc umb e r s 1 As trials were conducted in e nclo sed , commercial g r ee nhou ses with controlled environm e ntal co ndition s, th e zo nes in which th e tri als were conducted are not relevant. The H ED Scie nce Advisory Cou n c il fo r Che mi stry (Che mSAC) ha s recommended that four trial s be conducted for greenhouse-grown cu cumbers in s ituation s where no corresponding field use is proposed/established ( Minute s of24-SE P- 2008 ChemSAC meeting). T he residue data for cucumbers were evaluat ed u s in g the OECD tolerance calc ul ation procedures. The recommended tol erance fo r residues of pyrimethanil is 1 .5 ppm for cucumber (see Attachment 2)
. C aneberry subgroup 1 3- 07 A T h e residue d ata fo r caneben-ies were previously s ubmitte d under PP#8F7468; the locations and ap pli catio n rates e mpl oyed in these trials are adequate to su pport the proposed use. The Age ncy reviewed these data (summarized in T ab le 6) and dete rmined that they su pported a to l erance for residues of py rim ethani l in/on caneberry, crop s ubgroup 1 3

- 07A at a leve l of 12 ppm (u s in g the North American Free T rad e Agreemen t (NAFTA) t oleranc e calculator ; M emo, W. Cutchin , 02

- FE B- 20 10 ; 0372647). Subseque ntl y, Canada u sed th e same res idu e d ata to es tabli s h a 

### MRL for res idues of pyrim e than i l in/o n caneberries at a leve l of 15 ppm (us i ng th e O EC D toleranc e cal cu l ator). H ED thu s concludes that a to l e ranc e of 1 5 ppm for re s idue s of pyrimethanil in/on P

age 8of15P y rimethanil Summary of Analytical Chemistry and Residue Data DP # 421844 

### caneberry , crop subgroup 13-07A i s 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 u se. The Agency reviewed these data (summarized in Table 6) and determined that they s upported a tolerance for residues of pyrimethanil in/on bushberry, crop s ub gro up 13-07A at a l evel of 6.0 ppm (using the NAFTA to l erance calculator ; Memo , W. Cutchin, 02

- FEB-2010 ; D 372647). Subsequently , Canada used the same residue data to establish a MRL for residues of pyrimethanil inion bu sh berries at a level of 8 ppm (u sing the OECD tolerance calcu lator). HED thus concludes that a to l erance of 8.0 ppm for residues of pyrimethanil in/on bushberry , crop subgroup 13 -07B i s appropriate.
Table 6. S umm ary of Residues from Sma ll Berry Trials with Pvrimethanil. Total App lic. PHI Re s idue Levels ( 00111) Commodity Rate (l b s ai/A) (days) n Min. Max. H A F T " 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 establ i shed at 0.50 ppm [40 CFR §180
. 518(a)]. IR-4 has proposed to convert this individual to l erance to a crop subgroup 8

- 1 OA tolerance at the same level. The representative commodity of the tomato subgroup 8-1 OA i s tomato. As the proposed use on the tomato subgroup 8-1 OA is identical to the existing use on tomato on the product lab el for Scala ® SC Fungicide (EPA Reg. No. 264- 788) , the ex i sting 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 estab li shed at 10 ppm [40 CFR §180.518(a)]. IR-4 has proposed to convert this indi vidual tolerance to a crop subgroup 10-1 OA tolerance at the same level. The representative commodi ty 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 existi ng orange to lerance can be translated to the orange subgroup 10-1 OA. However , as this valu e i s the same as that recommended for the other citrus subgroups, a single tolerance of l 0 ppm i s 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 thi s individual tolerance to a crop subgroup 10-1 OB tolerance at the same level. Th e represe ntati ve commodity of the l emon subgroup 10-1 OB is lemon or lime. Page 9of15Pyrimethanil Summary of Analytical Chemistry and Residue Data DP# 421844 As the p roposed use on the lemon subgroup 10-1 OB is identical to th e 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. Howev e r, in order to harmonize with Canada , HED recomme nd s that th e U.S
. tolerance be reduced from 11 to 10 ppm. As thj s va lu e is the same as that reco mm ended for the other citrus s ubgroup s, a s in g le tolerance of 10 ppm is appropriate for fruit , citru s, gro up 10-10. Grapefruit subgroup I 0-1 OC No new grapefru it crop field trial data were submitted. A tolerance for re s idues of pyrimethanil in/on grapefruit has been established at 10 ppm [40 CFR § 180. 518(a)]. IR-4 has proposed to convert this individu al tolerance to a crop subgro up 10-1 OC tol erance at the same level. The representative commodity of the grapefruit s ub gro up 10-lOC i s grapefruit. As the proposed use on th e grapefru it subgroup 10-1 OC is identical to the ex i sting use on grapefruit on the product label for Penb otec® 400 SC (EPA Reg . No. 43813-32) , the existing grapefruit subgroup to lerance can be translated to th e grapefru it subgroup l 0-1 OC. However, as thi s value is the s am e a s that recommended for the other citrus s ubgroups. a s in gle toleranc e 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 subm itted

. A tolerance for r esid ue s of pyrimethanil i n/o n pome fruit gro up 11 has been established at 14 ppm [ 40 CFR 

### § 180 .5 18 (a)]. IR-4 has proposed to convert the c rop gro up 1 1 toleranc e to a crop group 11-10 tol e rance at the same leve l. The repre se ntative commodities of the pome fruit group 1 1 and 1 1-10 are the same (a pple and pear). As the proposed u se on the pome fruit group 11-10 is identical to the existing u se on pome fruit on the product labels fo r Scala ® SC Fun gic id e (E PA Re g. No. 264- 788) and Penbotec® 400 SC (EPA Reg. No. 43813-32) and s ince the rep rese ntative crops are identical , the existing pom e fruit group to l erance can be translated to fruit , pome , g roup 1 1-10. However, in order to harmonize w ith 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 s ubmitted. A tolerance for residues of pyrimethanil in/on sto ne 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 gro up 12 tolerance to a sto ne fruit group 12- 1 2 tolerance at the san1e level. The rep resentat iv e commodities of the stone fruit group 1 2 and 12-12 are the same (sweet cherry or tart c h erry, peach , and plum or prune plum). As the propo se d u se on the stone fruit group 12-12 i s identical to the ex is tin g u se on stone fru i t on the product lab e ls for Scala® SC Fungicid e (E PA Reg. No. 264- 788) and Penbotec® 400 SC (E PA Reg. No. 43813-32)) and since the repr esentative crops are identical , the existing stone fruit group toleranc e can be translated to fruit , sto ne , group 12-12.

Page 10of15Pyrimethanil Summary of Analytical Chem istry and Residue Data DP # 421844 

### 860.1520 Processed Food and Feed There are no processed food items of regulatory interest fo r cucumber. Therefore, residue data pertaining to processed conunodities are not germane to this tolerance petition. The previous ly submitted tomato and citrus processing data indicate that tolerances in/on the relevant processed commodities are unnecessary.


### 860.1650 Submitta l of Analytical Reference Standards Analyt ical s tandard s for pyrimethanil, AEC614276 , and AEC614277 with an expiration dates of 1 3-JUL-20 1 8 , l 7

-NOV

- 2020, and 06 -0 CT-2015, respective l y, a re currently available in the EPA Nat io nal Pestic ide Standards Repository (personal communication w i th T heresa Cole, ACB, 09- D EC-20 11 ).


### 860.1850 and 1900 Co nfined and Field Accumu l ation in Rotat i onal Crops Adequate confined and limited field rotational crop trial s are available and s upport the labelspecified 30-day plant-back interval ( PBI) for crops w ith out use s on the Scala® label. Th e available data indicate that tolerances are not curre ntl y requ i red for rotational crops.


### 860.1550 Propo se d To l erances The petitioner has submitted adequate magnitude of the residue data to support the proposed application sce narios. No additional residue data are required. The Age n cy has determined that the re s idu e of concern for the purpose of tolerance exp ress ion in plants is parent only. Based on the availab le data and the OECD tolerance-calculation procedure (see A tt achment 2), H E D concludes that the tolerances li sted in Table 7 for res idu es of py r imethanil are appropriate

. Fo r p lant co mmoditi es, the U.S., Canadian, and Codex re s idue defin it ions are h armoni zed. The proposed to leranc es for res i dues in/o n caneberry, c r op s ub gro u p 1 3-07 A and bushberry , crop subgroup 13-078 are harmonize d with the estab li s hed Canadian MRL s. The U.S. tolerance for residues in/on tomato (tomato s ub group 8-1 OA) is harmonized with the Canadian MRL , while the Codex MRL is established at a higher l eve l (0.7 ppm). Howe ver, Bayer CropSc ience has requested that EPA not harmoni ze w ith Codex in order to prevent the creation of a trade barrier with Canada. The U.S
. and Codex tolerances/MRLs for residues of py rimethanil in/on citrus are not harmonized. Residues in the U.S. residue trials (maximum of 8.43 ppm) were higher than the Co dex MRL of 7 ppm , precluding harm onization. The U .S. and Canadian tolerances/MRLs for re s idue s of pyrimethanil in/on citrus are harmonized , except for the lemo n subgroup I 0-1 OB. In order to harmoni ze with Canada, HED reconunends that th e U.S. tolerance for the lemon subgroup I 0-1 OB be reduced from 11 to 10 ppm. As thi s 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 pyr imcthanil in/on s tone fruit are not Page 11 of 15Pyrimethanil Su mmary of Analytical Ch e mi s try and R e s idue Data DP # 421844 harmo ni zed

. Residues in the U
. S. residue trials (max imum of 6.5 ppm) were higher than the Co d ex MRL s of2 -4 ppm, precluding harmoni zatio n. T h e U.S. and Canadia n tolerances/ MRLs for residues of pyrimethanil i nio n stone frui t are harm onized at I 0 ppm. T he U.S. and Codex tol erances/MRLs for res idu es of pyrimethanil in/on the pome fruit group are not harmonized. As the difference in values is minimal , H ED recommends th at the U .S. to leran ce be in c reased from 14 to 15 ppm in order to harmoni z e with Codex. There are cu rr e ntl y no estab li shed Codex, Canadian , o r Mexican MRLs for pyrimethanil in/o n cucu mb er.

Tab le 7. To le r a nce S umm a r y for P y rim eth a nil. Proposed Tolerance R eco mm end ed Co mm od ity (ppm) Tolerance (ppm) 40 C FR § 1 8 0 .5 1 8 (a)( l ) Cucu mb e r 1.5 1. 5 O range subgroup I 0- 1 OA 1 0 10 Lemo n subgroup I 0-1 OB 11 Grapefrui t s ubg roup 10-1 OC 1 0 Fruit , pome, g roup I 1-10 14 15 Frui t, s tone , g roup 12-12 10 10 Tomato , s ub g roup 8- 1 OA 0.50 0.50 Caneberrie s s ubg roup 13-07 A 15.0 15 Bu shberrie s subgroup 13-078 8.0 8.0

Attachm e nt l: In ternatio nal Res idu e Lim it Status S heet Attachment I : MRL Spreadsheet

RO I : RAB I Ch e mi st s (07- JAN- 2015) , HED ChemSAC (28-JAN- 2 0 15) cc: G. Kr ame r G.F. Kram e r :S I 0957 :PY- S:(703)3 05-5079: 7509 P : RAB I Pa ge 1 2of 15 Co mm e nt s ; Co rr ect Comm odity D e

fini t ion

Harmonization with Canada. Fruit , c itrus, g r o up 10-10
Harmonization with Codex.

Can e b e rry , s ubgroup 13
- 0 7 A 811 sh be nJ 1
. s u bg r o up 13
- 0 7 BPyrimethanil Summary of Ana l ytica l Che mi stry and Residue Data DP# 421844 

### Attachment 1: International Residue Limits Py rimethanil 

### (28820 1 ; 12/ 8/ 2014) Summary ofUS and International To l erances and Maximum Res idu e Limits Residue Definition: 

# us Ca n ada Mex ico 2 Codex 3 40 CF R I 80.5 I 8: Plants: 4,6-dimethy l- N

-phenyl

-2

- Pyrim etha nil Pl a nt: (a) General. ( I ) pyrimid in amin e The residue is Tolerances are established Livestock (except mi lk): 4,6-d imethyl-N- not fat-soluble. for residues of the fungicide pheny l- 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-d imethyl-N-phenyl

- 2

- the following table pyridinamine, including the metabol ite 5- Compliance with the pyrimidinol , 4,6 -dim ethy l-2- tolerance levels specified in (phenylamino) the follow in g table is to be determined by measuring only pyrim etha nil (4,6- dimeth y l-N-phenyl-2

- pyrimidinamine). Comm od ity ' Tolerance (pom)/Maximum Residue Limit (mCI / kf.!) 

## us Canada Mexico 2 Codex 3 Cucwnber 1.5 Orange subgroup 10- I OA 10 10 calamondins , citrus c itrons , 7 citrus fruits citrus hybrids , oranges , satsuma Po mandar in s, tangerines 150 citrus o il Lemon s ubgroup 10-1 OB 11 IO kumquats, lemons, l imes Grapefru it subgroup I 0-1 OC IO I0 g rap efruits, pummelos Fru it , pome, group 11-10 14 14 apples, Asian pears , 15 porne fru i ts Po crabapples , loquats, mayhaws , 40 apple pears , quinces pomace, drv I 0 Americ an plums , apricots , 3 apricot beach plums, black cherries, 4 cherries Po Canada plums , capu l ins , cherry 4 nectarine , p lums , chicksaw plums , damson peach Fruit, stone, gro up I 2

- 12 10 p lums , fresh prune p lums , 2 plums Japan ese apricots , Japan ese ( in cl udin g plums , klamath plums , nanking prun es) cherries , nectarines , peaches , plumcots , plums, sloes, sweet cherries , tart cherries Tomato subgroup 8- 1 OA 0.50 0.5 tomato 0.7 Can e b e rry subgroup 1 3-07 A 15.0 15 blackberries, loganberries, raspberries , w i ld raspberries Bushberry subgroup 13-078 8.0 8 aro ni a berries , buffalo currants , Chi lean guavas, currants e lderberries , European barberries , highbush (b lueberrie s, cranberries) , hon eysuckle, huckleberries , jo staberrie s, l ingonberries, nativ e currants , salal berries, Saskatoon berries (J uneb e rri es) , sea buckthom 3 lowbush blueberries 5 goosebe rri es Page 13of15Pyrimethanil Summary of Analytical Chemistry and Re sidue Data DP # 421844 S umm ary of US and Internationa l Tolerances and Max imum Residue Limits Residue Definition: 

# us I Canada 

## l Mexico 2 

## l Codex 3 Comp leted: M. Negussie ; 1 2 / 10/ 14

.. 1 Includes only commod1t 1 es of intere s t for this action. To lerance values s hou ld be th e HED recommendation s and not those proposed by the applicant. 2 Mexico adopts US tolerances and/or Codex MRLs for it s export purpo ses. 3 

### * = absent at the limit of quantitation ; Po= postharves t treatment , s uch as treatment of sto red gra ins. PoP = processed postharvest treat ed commod ity , such as proces s ing o f treated stored wheat. (fa t ) = to be measured on th e fat portion ofthe sample. MR Ls indicated as proposed have not been fmalized by the CC PR and the CAC.

Pa ge 14of15Pyrimethan il Sum m

ary ofAnalytical Chem istry and R es idue Data 

### Attachment 2: MRL Spreadsheet
Py rim etha nil Greenhou s e C ucumb e r s US / Canada 2. 1 2 -2 .22 lb s ai/A; I-d ay PH I
T o tal num be r o f d a ta ( n ) Percenta ge o f ce n s ored data N umb er of n o n -ce n so red data Low es t r e s idue Hi g h es t re s idue M e dian re s idu e M ea n Sta ndard d ev iation (S D) Co rrection factor for ce n s orin g (CF)
P roposed MRL estimat e

- Hi g h e s t r es idue

- M ea n + 4 S D

- CF x 3 Mea n U nro un ded MRL Rounded MRL Hi g h uncertaint y of MRL estimate. [Small data se t)
R e s idue s ( m g/kg ) n 0.07 I 0.38 I 0.45 1 0.47 I 0
. 8 2 I

P age 1 5of 15 5 0 % 5 0.070 0.820 0.450 0.438 0. 2 67 1.000

0.820 1.507 1.314 1.507 DP # 42 1844Pyrimethanil [PYI] / B aye r CropScie nce In c. [BCZ] B.7.6
B.7.6.1 B.7.6 .1.1 Document ID : Report:

G uid e lin es: Residues R es ultin g from S up erv ised Tri al s (Annex llA 

### 6.3; Ann ex IHA 8.3) Residues in Targe t Cro ps Greenho use C u cumb er MRID No. 49312501 PMRA No
. 2 443911 Ballantine, 

### J. (2 014 ) " Pyrimethanil: Ma g nitud e of the Residue on Cucumber, Greenhouse. " Study Number AAFC 10-056R. Laboratory Id e ntificati on Number AAFC 10-056R-2 1 l. UI?published study prepar e d by Pest Management Centre, Ag ri c ul ture and Agri-Food Canada, Ottawa, ON, Canada. 204 pages. E PA OCSPP Harmonized T es t Guid e lin e 860. 1 500 Crop Field Trials (A ug u s t 1996) PMRA Regulato ry Directi ve DIR98-0 2

- Res idu e C he mistry Guidelin es, Section 9

- Crop Field Trials PMRA Regu lato ry Directi ve DIR2010-05

- Revisions to the Residu e Chemistry Crop Fi e ld Trial Requirements OECD Guide li ne 509 Crop F ield Trial (Sep te mb er 2009) GLP Co mpliance: No deviations from r egu latory requirements were rep orted w hich would have an impact on th e va lidi ty of the study. Acceptab ili ty : The study is considered scientifica ll y acceptable. Eval u ator: Peer Reviewer: Melissa Watchorn, Pest Man agement Regu latory Agency, H ealth Canada George F. Kramer, Ph.D., OCSPP , U.S. EPA**~** 

### ,s 4,**~** 

# 5 EXECUTIVE SUMMARY Five g ree nh o u se trials were co nducted on cucumbers in Canad a and the Unite d S tates durin g 2010 a nd 20 11. As th e trials were conducted in commerc ia l g r ee nh ouses with controlled e n v iro nm e nt a l co nditi o n s, th e zones in wh i c h th e tri a l s were co nducted are not relevant. At eac h trial locatio n , p yrimethanil , formulated as a s u spe n s io n co nce ntrate (Scala ® SC Fungic id e ; P CP # 2801 1) , was applied to c ucumb ers in thr ee fo li ar app lic ations at rates of 777- 848 g ai/ha (0.69-0.76 lbs ai/A). The re-treatment interval (RT I ) was 7-14 days, and the tota l application rate was 2372

- 2483 g ai/ha (2.12

- 2.22 lbs ai/A). A n ad ju vant was no t includ e d in any of the spray mixtures. Greenhouse cucumbers were harvested at a I -day preharvest interval (PHI) at a ll trial s i tes. Add itional sam ple s we re harvested a t one trial si te at PH l s of 0, 5 , 11 , and 14 days to determi ne residue -de cline behavior. All samp les we re maintaine d fro zen at the testi ng facil ity , during s hipping to th e laboratory , and were stored frozen until anal ys i s. The maximum s to r age interval for sampl es between harv es t and anal ysis was 139 days. Res idue s ofp y rim etha nil we re s hown to be s table in cucumbers for up to 140 days und er frozen conditions in a s torage stab ili ty stu d y co nducted concurrent ly with
EPA MRID # : 49312501 PMRA # of document: 247 1398 Page I of7Pyrimethanil [ PY I )/ Bayer CropScience Inc. [BCZ] 

### th e analytical port ion of the current residue study. Ade quate storage stability data are therefore available to s upp ort the storage conditions and intervals for samples 

### in the current trials. Residues of pyrimethanil in tri al samples were determined using a working m eth od based on the reference method "Frnit s and Vegetab les : A na lytica l Method fo r the D etermi nation of R esidues (Improved Version)" Study ide nti fication: 140/01/0 12, Report No. DGM C05/98

- 0. The reference method has been reviewed previously and deemed acceptable for data gathering and enfo rcement purposes in plants. Acceptable method validation and concurrent recoveri es w ere reported for cucum ber samp les at fort i ficat io n levels of 0.05

- 5.0 ppm, thu s validat in g the me thod. T he valid ated limit of quantitation (L OQ ; determined as th e l owest l eve l of method val id ation , LLMV) and the estimate d limit of detection (LO D) we re 0.05 ppm and 0.0225 ppm, respectively, for r es idu es of pyrimethanil in cuc umb ers in t hi s study. Indi vidual samp le (an d per-tr i a l average) residues 

### in greenhouse cucumbers ranged from 0.07 ppm to 0
. 83 ppm (0.07 ppm to 0.82 ppm) w hen samp l es were treated at total rates of2372

- 2483 g a i /ha (2. 12-2
. 22 lb s ail A), and harvested at a 1

- day PHI. R esidue decline data sho wed th at pyri meth anil residues decreased in greenhouse cucumbers wi th incre asing PHis w h en samp l es were harvested at PHi s of 0 , 1, 5 , 11 , and 14 day s . 

### I. MATERIALS AND METHODS A. MATERIALS
T ab le B .7. 6
. 1.1-1. Nome n clatu re for P v ri m ethani l

. Common n ame P vrimethan il CAS Name · 4,6-dimethy l-N-phenvl-2-ovrimid in am in e CAS no. 531 12 -28-0 Company experime n ta l na m e AE 8100309 

### B. Study Design 1. Test Proced u re A tota l of five g reenho u se residue trials in/on cucumbers were conduc ted with pyrimethanil , formulated as a s u spens io n co nc e ntrate, durin g 2010 and 2011 (Tab le B.7 .6 .1.1

- 2).
Table B
. 7
. 6.1.1-2
. Tria l N u mbe r s a n d Geograp hi ca l Locatio n s. Cro p Re gion Tota l I 2 3 4 5 6 7 8 9 IO 11 12 13 14 Greenhouse 2 I I I 51 Cucumbers 1 A s trials were conducted in enclosed , co mm e rc ia l green ho u ses w ith controlled e nviro nm e ntal cond itions , the zones in which the trial s were conducted are not re levant. 

### Locations and d etailed us e patterns for the trial s are provid e d in T ab l e B.7.6.1.1-3.

EPA MRID # : 49312501 PMRA# of document: 247 1 398 P age 2 of7Pyrimethan il [ PY J] / Ba ye r Cro p Science In c . [ B CZ] Tab le B.7.6.1.1-3. Stud y Use Patte rn .

Location: City , E nd-u se Volume R ate per Retreatment Total Rate State/Provi nc e; Product/ Method of Application / (L/ha) Application Int erval (g ai/ ha) Surfactan t/ Year Formulation T im ing of Application [ga l / A] (g ai/ha) (days) [ lbs ai /A] Adjuvant ( Trial LD ) 1 (% ai) [ lb s ai/A] Salisbury , MD/ Sca la® SC I. Fo l iar / 11 32 797 

### -- 239 1 None 2010 Fungicide First fruits nearly mature [121] [0.71 1] [2 .1 3] ( Trial # ID 2 06) 2. Foliar / l 1 32 797 7 Fruiting [121] [0.711] 3. Foliar / 1 132 797 7 Fruiting 

## r 12 

## n [0.711] Ralei g h , NC/ Scala® SC I. Fol iar / 10 1 0 795 

## - - 2372 None 2010 Fun g icid e Flowe rin g and fruiting [108] [0.709] [2. 1 2] (Trial lD # 207) 2. Fol iar / 988 777 7 Flowering and fru it ing [ 10 6] [0.693] 3. Fo li ar / 1016 800 7 Fru iting [109 ] [0.714] C itra , F L/ Sca la® SC I
. Foliar / 926 79 1 

### -- 2405 None 2 011 Fungicide Bloom , fruit in g [991 [0.706] [2. 1 5 ) ( Trial ID # 208 ) 2. Foliar / 948 810 14 Bloom , fru iting [ IO I ] [0.723] 3. Foliar / 942 804 13 Bl oom , fruit in g [I 0 I] [0.717] Parlier , CN Scala® SC I. Fo liar / 1 162 828 

### -- 2483 None 2 0 1 0 Fu ngic id e Fruiting [124) [0.739] [2.22) (Tria l ID # 209) 2. Fol iar / 1 191 848 7 F rui t in g [ 127] [0
. 757 ] 3. Fol iar / 11 33 807 7 Fruiting r 12 1 1 ro.1201 H arrow , ON/ Sca la® SC I. Fo l iar / 2008 802 

## -- 2395 None 2010 Fungicide Mature fruit [2151 f0.7161 [2 .1 4] ( Trial ID # 210) 2
. Fo li a r / 2004 801 8 Matu re fruit [2 141 f0

. 7151 3. Foliar / 1982 792 7 Mature fruit [2 12 1 f0.7071 1 All Trial ID # s have the prefix AAFC I 0

-056R-. 

### Cucumbers were grown and m ai ntained accord in g to typical ag ricu ltura l practices for gree nhou se operations. Irri gation wa s app lie d as a drip to so il med ia , with a microsprinkler, o r with a hydroponic system. 

### Samp le Ha n d li ng an d Preparatio n Mature, marketable cucumbers were harvested randomly , avoi din g row ends , first from the untreated p lot, and then the treate d plot. E ither 1 2 or 24 cucumbers we r e harv ested from each p lot , and the minimum sampl e size was 2359 g (5.2 pounds). C ucumb er s were halved or quartered to red uce samp le we ig ht w hen n ecessary , and an y adh er in g ste m s or deb ri s were re moved by hand. Th e trial samp l es were placed in l abe led sampl e bags, and we re then either p laced directly in freezers , o r in coole rs with ice for transport to freezers. All samp le s were placed in frozen storage within 33 minutes of harvest. The sampl es were shipp ed frozen to the analytical fac il ity at the U ni vers ity of Cal i fornia , Dav i s, where th ey arrived froze n and in goo d cond it io n. T he sampl es were placed in froze n sto rage ( S -20 ° C) , w here the y remaine d , exc ep t
E PA M RID # : 49312501 PMRA# of document: 2471398 Page 3 of?Pyrimethanil [PYI] / Bayer CropScience Inc. [BC Z ] 

### during sample preparation

. Th e samples were prepared by chopping with dry ice in a Hobart Food Chopper. 2. De sc ription of Analytical Pro ced ure s 

### Cucumber samples were analyzed for pyrimethani l residues using a working method based on the reference method entitled "Frui ts and Vegetab l es: Analytical Method for the Determination of Re s idues ( Improved Version) " Study identification: 140/01/012 , Report No. DGM C05 / 98

- 0 (PMRA# 1095 293; EPA MRID # 44908503). The reference method has been reviewed previously by PMRA and EPA and d ee med acceptable for da ta gathering and enforcement purposes in plants (S2001-2 1 37; PMRA# 895867 ; EPA DP# D389985). Briefly , res idues were extracted from cucumber trial samp les by homogenizing with acetone. An aliquot of the extract was then cleaned up on a polymeric so lid- phase extraction (S PE) column e lu ted w i th acetonitril e : water (80:20, v / v). Res idues were then determined by hi gh-pe rformance liquid chromatography (HPLC) w ith tandem mass spectroscopy (MS/MS). The following steps in the reference m ethod were modified:

• The hexane and basified liquid- li quid partition steps we re e li minated because they were not n ee ded when using LC -M S/MS for detection whi ch allows for a simp li fied c l eanup procedure. • The si lica S P E column cleanup was changed to an Evo lute ® ABN SPE , which is better suited for the cleanup of aqueous extracts. • The gas chromatography/ mass- se lecti ve detector (GC/MSD) detector was replaced by LC-MS/MS which prov id es better sample throughput , reduced solvent requirement s, and does not req uir e an internal standard to correct for enhanceme n t effec ts . 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 DISC USSI ON 

### Method performance was evaluated prior to sample analys i s by fort i fy ing contro l cucumber samp le s with 0.05 , 0.5 , and 5.0 ppm of pyrimethani l. With the exception of one recovery of 68% in a sample fortified with 0
. 05 ppm of pyrimethanil , all m ethod validation recoveries we re within the acceptab l e range of 70-120 %. Accuracy of th e meth od was also confirmed by fortifying contro l cucumber samp les w i th 0.05 and 0.5 ppm of pyrimethani l , and determi nin g recoveries concurrently with trial samp l e analysis. All concurrent recoveries were within the acceptable ran ge of 70-120 %. Given that the majority of recoveries were within the acceptab l e range, the wo rking method was considered valid for the analysis of pyrimethani l re s idue s in cucumber matrices (Table B
. 7.6.1.1

- 4). The fortification leve ls bracketed the measure d residues in trial sample s. The detector response was lin ear (coefficient of determination , 

### r2 ::'.'.: 0.999569 ) within the ran ge of 0
. 5-10 p g / μL. Representative chromatograms of control samp les , fortified samp les and treated samp le s were provided

. The fortified sample chromatograms contained on ly the ana lyte of
EPA MRlD # : 49312501 PMRA # of doc ume nt: 2471398 Page 4 of7Pyrimethanil [PY I )/ Bayer CropSc ience Inc. [BCZ] interest , and peaks were symmetrical and well defined. Th e re we re res idue s observed at l evels

- 25% of the tre a ted samp le s 

### in the untreated control samp les co ll ec t e d from the greenhouse located in O ntari o ( Tri al ID 

### # 210). Althoug h r es idu es i n co nc urre nt r ecove ry s amples w ere corrected fo r the res idu es in controls , t h e report ed resid ue va lu es i n the tr eated sam ples were not correc ted. Th e s tud y rep o rt indicated that th e c o ntro l samp les may have been contaminated due to inadequate plot separation as the plas ti c s he eting u sed to separate the plots did not reach th e g reenho u se ce ilin g.

Table B. 7.6. 1. 1

- 4. S ummary of Method Validation , Concu rr e nt R ecoverie s, and F r eeze r Sto r age Sta bilit y Recoveries of Pvrimeth a nil from G r eenho u se Cucumbers. M atrix Fortification Leve l (oom) R ecove ri es(%) Mean ± Std. Dev.( %) Method Va l idation Greenhouse c uc umb er 0
. 05 84, 73,68 75 ± 8 0.5 78 , 83 , 81 81 ± 3 5.0 73,84, 84 80 ± 6 Co ncurr e nt Recovery Green house cucumber 0.05 93, 89 1
, 10 6 1
, 10 2 98± 8 0.5 92 , 93 1
, 731, 94 88 ± 10 Freezer Sto ra2 c R ecoveri es Fo ll ow in g 31 da ys of Fro ze n S torag e Co ncurren t recove ri es 0.05 90


### -- 5
. 0 96 , 85,82 88 ± 7 Freezer s t o rage 5.0 8 3,92, 78 84 ± 7 recoverie s Correc ted freezer storage s tabi l ity recovery2 95 Freezer Sto r age Rec ove ri es Fo ll owing 140 days of Frozen S t o rag e Conc urrent recoveries 5.0 88,89 89 Freezer s tora ge 5.0 90 , 91 , 90 90 ± I recoverie s Co rrected freezer storage s tabili tv recoverv 2 IOI 1 Correc te d fo r res idues observed in control samples. 2 M ean recovery was co rrec ted for ave rage concurrent recov ery < I 00% fro m concurrent recovery s ample s spiked w ith 5.0 ppm o fp y rim e thanil. Th e c ucumber trial samples were stored frozen ( ::S-20 ° C) for a m aximum of 139 days from har vest to a n a lys i s (Tab le B.7.6.1.1

- 5). Residues were determined o n the same day as they were ex trac ted from cucumber s amples. Freezer storage s tability data were ge n erated concurrentl y with the an a l y ti ca l portion of the g reenh ouse cuc um be r tri a l s (Tab le B.7.6.1.1-4)
. Freezer sto rage recoveries in c uc umb ers fortified with 5.0 ppm of p yr im et h anil and s tore d frozen for 140 days were all within the acceptable 70-120 % ran ge. T hese d ata s ho w that pyrimethartil re s idues are s table fo r the same duration the trial samples we re s tored froze n . Therefore , there are no concerns r ega rding the stabili ty of pyrime th anil residues in cucumbers in this s tud y.

E PA MRID # : 49312501 PMRA # of docume nt : 247 1 398 Page 5 of7Pyrimethanil [PY!) / Bayer CropScience Inc. [BCZ] Tabl e B
. 7
. 6 .1.1-5. S u mm a r y of St ora g e C ond i ti o n s. Matrix Storage Actual S t orage In t e rval of Demonstrated Storage Stability (RAC or Extract) Temperature ( 0 C) Duration (days)' Greenhouse Cucumbers**-20** 139 A freezer storage stabi li ty study was conducted concurrently with the analytical portion of the res idue fie ld tr ia l study (Table B. 7 .6
. 1.1-4). The data indicated that py r imethan il residues are stable when sto r ed froze n in cucumbers for up to 140 days. This cove r s the period that tr ial samples were s t ored frozen. 1 From harvest to residue extraction and analysis. Residues were determined on the same day as residues were extracted from samples. 

### T he res ul ts from th ese tri al s showed that when harvested 1 day afte r the last of 3 fol i ar app lications at a total rate of2372-24 8 3 g a i /h a (2. 12-2.22 lbs a i / A) , pyrimethanil residues in g reen ho u se c uc umbe rs ran ged fro m 0.07

- 0.83 ppm (Ta bl es B.7.6. 1. 1

- 6 and B. 7 .6.1.1 -7 ). In th e resid ue decl i ne trial s, mean r esidue leve l s dec reased from 0.46 ppm to 0. 14 ppm in gree nh o u se cucumber samp l es harveste d betwee n PHl s of 0 an d 14 days

. Ta b le B .7. 6
. 1.1

- 6. R es i d u e D at a fr o m Gree nhou se C u c umb e r Tri a ls w i th P y r i m e t hanil. Location: City , Crop/ End-Use Total Rate PHJ Residues (ppm) State!Province; Region Variety Matrix Product (g ai/ha) (days) Pyrimethan il Per

-tria l Year (Trial ID ) 1 [ lbs a i / A] average Sal isbury, MD / Cucumbe r / Scala ® SC 2391 0
. 07 20 1 0 N I A Samir Fruit Fungicide [2
. 13] I 0.07 0.07 (T ri a l # ID 206)

Ra leigh , NC/ Cucumber / Sca la® SC 2372 0.38 2010 N I A J awe ll Fl Fru it Fun g icide [2. 12) I 0.38 0.38 (Trial ID # 207) Citra, FL/ Cucumber / Sca la® SC 2405 0.44 201 1 N I A Fru it I 0
.47 (Trial ID # 208) Jawell Fl Fu ng icide [2.15) 0.49

Parl ier , CA/ Cucumber / Scala® SC 2483 0.83 20 10 N I A Cumlaude Fruit Fung ic ide [2.22) I 0.80 0.82 (Tria l ID # 209) 0 0.50 0.46 0.42 I 0.48 0.45 0.42 Harrow , ON/ Cuc umber / Scala® SC 2395 0
. 33 20 1 0 N I A Camaro Fru it Fungicide [2. 14) 5 0.33 0 .33 (T r ia l ID # 2 1 0) 2 0.16 11 0.17 0.17 14 0
. 14 0.14 0.14 1 All Trial ID #s have the prefo: AAFC I0-056R-. 2 Res idues of 0. 10 and 0.1 1 ppm were observed in the control samples at th is trial site due to possible contamination in the greenhouse. Residues in t h e treated samples were not adjusted for residues in the contro l samp les.

EPA MRJD # : 49312501 PMRA # of document: 24 7 1 398 Page 6 of7Pyrimethanil [PYI) / B ayer CropScience Inc. [BCZ] Tabl e B .7.6. 1. 1-7. S umm a r y o f Res idu es from G ree nh o use C u cumb e r T r ia ls wit h P yrim et h a nil. Total Pyrimethanil R es idu es ( oom ) App licati o n PH I Crop Matrix R ate ( d ays) 11 Min . 1 Ma x . 1 LA F T 2 HAFT 2 M edian 2 Mean 2 

### so 2 (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 f 2. I2-2.22] 1 Values based on total number of sample s . 2 Values based on per-trial averages. LAFT = lowest ave r age field trial , HAFT = highe s t ave rage field trial , SD = s tandard deviation. n = number of fi e ld tri als.


### III. C ON C LUS I ON S Th e g reenhouse cucumber trials are consid ered sc ie nti fically acceptab l e . The resu l ts of the study s howed that following a to tal appl ication of 23 72-2483 g ai/ha (2. 12-2.22 lb s 

### ailA) , pyrimethanil res idue s ranged from 0.07-0.83 ppm in s ampl es collected at a I

- da y PH I. A de c line study indicated that p y rim e thanil residues in greenhou se cucumbers decreased with time when samples were harvested at PHi s of 0, 1 , 5, I 1 , and 14 da ys. Adequate conc urrent s torage stabi lity data are available to suppo rt s ample storage duration s and co nditio n s.


### RE FERE NCES PMRA# 1095 293; EPA MR ID # 4490850 3. Peatman , M.H. (1999) " Fruit and Ve ge tab les : Ana lyt ical Method fo r th e Determination of R es idu es ( Impro ve d Version) .'
. Rep ort No
. D GM C05 / 98 -0
. Study Number 140 / 011012 , Report N umb er C000292. Unpubli shed s tud y prepared by AgrEvo USA Co mpany , Wi lmington , DE , USA. 39 pages.


### DO CUMENT TRA C KJNG RD I : RABI Chemists ( 12/ l0/ I4) Pe titi o n N umber: 4E8302 DP Barcode: 422294 PC Code: 28820 I

EPA MRJD # : 4931 25 0 I PMRA # of docum e nt : 247 1 39 8 Page 7 of7