### UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, 

### D.C. 20460

MEMORANDUM

Date: 22-July-2015 OFFICE OF CHEMICAL SAFETY AND POLLUTION PREVENTION



### SUBJECT: Fludioxonil; Petitions for Tolerances for Residues in/on Carrot, Stone Fruit, Group 12-12, and Rapeseed, Subgroup 20A. 

### Summary of Analytical Chemistry and Residue Data.

PC Code: Decision Nos.: Petition Nos.: 071503 491305, 491195 4E8272 (Carrot) & 4F8277 (Rapeseed) DP Barcodes: Registration Nos. Regulatory Action:

Risk Assessment Type: NA Case No.: TXR No.: NA CAS No.:

MRID No.: 49347001 /:1 /) tH..**~~**
From:

# 'W**illiam** D. Wassell, Chemist 

# fj;p 'rt-XI
Risk Assessment Branch 1 (RAB 1) Health Effects Division (HED, 7509P) 0421064, 0421602 100-1242

, 100-758 Section 3 Registration

7017 131341-86-1 §180.516

Through: George 

### F. Kramer, Ph.D., Branch Senior

### Chem**~** 

### tt 

### ;::ISE 

# 2 

# 's-z

RAB 1/HED (7509P) ;::::::::;--

To: Barbara Madden/ A. Willis Ertman, RM 05 Registration Division (7505P}



### Executive Summary

Fludioxonil, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)-lH-pyrrole-3-carbonitrile, is a phenyl-pyrrole fungicide registered for use on a variety of field and vegetable crops, fruit trees, berries, herbs, and grasses. It can be applied as a seed treatment, an at-planting soil application, broadcast foliar applications, and/or post-harvest uses. A total of 26 end-use products (EPs) containing fludioxonil are currently registered to Syngenta Crop Protection for use on food/feed crops, with the majority of these EPs being registered for seed treatment uses. These EPs contain 0.13 to 50% fludioxonil as the active ingredient (ai) and are formulated as wettable-powders (WP), water-dispersible granules (WDG), flowable-concentrates (FlC), flowable suspension
concentrates (SC), and dusts. /

Permanent tolerances have been established for residues of fludioxonil 

### per se in/on a variety of plant commodities, ranging from 0.01 ppm on numerous commodities to 500 ppm on citrus oil [40 CFR §180.516(a)(l)]. Specifically, tolerances for residues of fludioxonil are established

Page 1 of 14Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 2 of 14 

### in/on rapeseed, crambe, and lesquerella at 0.01 ppm, and stone fruit group 12 at 5.0 ppm. Additionally, permanent tolerances have been established for residues of fludioxonil and its metabolites converted to 2,2-difluoro-l,3-benz odioxole-4-carboxylic acid in/on a livestock commodities ranging from 0.01 ppm to 0.05 ppm [40 CFR §180.516(a)(2)].

The Interregional Research Project No. 4 (IR-4) has proposed the use of Scholar ® 

### SC Fungicide (EPA Reg. No. 100-1242) on carrots as a post-harvest treatment for the control of white mold. Scholar ® 

### is an SC formulation which contains 1.9 2 lbs of fludioxonil per gallon. The proposed use on carrots is for a single dip or drench a pplication at 16 fl. oz. product per 100 gallons (0.23 lbs ai/100 gallon). Additionally, IR-4 has propos ed the fludioxonil tolerance and use for stone fruit, group 12 be extended to the redefined stone fruit, group 12-12. The tr eatment of stone fruit is for the control of brown rot, gray mold, rhizop us rot, and gilbertella ro t. In conjunction with the proposed use, IR-4 has proposed the follo wing tolerances for fludioxonil residues in/on:

Carrot ...................................................................................7.0 ppm Fruit, stone, group 12-12 ......................................................5.0 ppm

In conjunction with this proposal , the tolerance for residues in/ on vegetable, root, except sugar beet, subgroup 1B should be changed to root, except sugar beet and carrot, subgroup 1B. Additionally, tolerances for resi dues of fludioxonil in/on crambe, lesquerella, and flax seed should be deleted as the tolerance for resi dues on rapeseed subgroup 20A covers these commodities.

Syngenta has proposed the use of fludioxonil on rapeseed subgroup 20A, except flax seed. Fludioxonil is registered for use as a seed treatment on rapeseed which is the representative commodity for subgroup 20A. The formulation registered for use on rapeseed is Maxim ® 

### 4FS (EPA Reg. No. 100-758) which contai ns 4 lbs ai per gallon. Maxim ® 

### 4FS is also registered for use on flax, crambe, and lesquerella which are also members of subgroup 20A. The tolerance level for residues of fludioxonil in/on rapeseed, crambe, and le squerella is 0.01 ppm while the tolerance level for residues in/on flax is 0.05 pp m. The registered use on rapeseed, crambe, lesquerella, and flax is for the app lication of 0.08 to 0.16 fl oz of Maxim ® 

### 4FS per 100 lbs of seed (0.0025 to 0.0050 lbs ai/100 lbs seed) for protection against seed -borne and soil-borne fungi which cause decay, damping off, and seedling bl ight. In conjunction with the proposed use, Syngenta has proposed the following to lerance for fludioxonil residues in/on:

Rapeseed, subgroup 20A, except Flax Seed .......................0.01 ppm

Syngenta makes note that this re quests reflects the establishe d Canadian maximum residue limit (MRL) for residues at 0.01 ppm in/on rape seed, but not the C odex MRL of 0.02 ppm.

The nature of the fludioxonil residues in plants is adequately understood based on adequate metabolism studies on peaches, grapes, onions, and h ead lettuce and seed treatment applications to rice, wheat, cotton and soybeans. Based on the results from these studies, HED has determined that the residue of concern in plan ts following foliar applications is fludioxonil per

se.
The nature of the residues in livestock is also understood based on the adequate goat and hen metabolism studies. For purposes of tolerance en forcement and risk assessment, the residues ofFludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 3 of 14 

### concern in ruminants are fludioxonil and Metabolit e B-1, and the residues of concern in poultry are fludioxonil, CGA-344623, and Metabolite I-1.

Adequate high-performance liquid chromatogr aphy/ultraviolet light detector (HPLC/UV) methods (Syngenta Methods AG-597 and AG-597B) ar e available for enforc ing tolerances of fludioxonil in plant commodities. In the current post-harvest trials, residues of fludioxonil in/on carrots were determined using a liquid chroma tography and tandem mass-spectrometry detection (LC-MS/MS) method, which is a modified version of Method AG- 597B. The LC-MS/MS method was adequately validated in conjunction with the analysis of samples from the postharvest trial. The validated limit of quant itation (LOQ) for fludioxonil was 0.01 ppm in each canola matrix, and the limit of detection (LOD) was 0.003 ppm.

Based on the potential dietary exposure of livestock to fludioxonil residues from the current and proposed uses in the U.S., quantif iable residues of fludioxonil are not likely to occur in livestock commodities [40 CFR §180.6(a)(3)]. Therefore, HED has concluded that cattle and poultry feeding studies and tolerances for livestock commodities are not required at this time.

The submitted carrot post-harvest data are adequate and support the proposed use on carrots. An adequate number of field trials were conducted at ~1x the maximum proposed application rate. Samples were collected after the treatment solu tion dried and analyzed using an adequate LCMS/MS method. The residue data would support a 7.0 ppm tolerance for residues of fludioxonil in/on carrots.

Adequate confined and limited field rotational crop trials are available and support the labelspecified 30-day plant-back inte rval (PBI) for crops without us es on the fludioxonil label. The available data indicate that tolerances ar e not currently required for rotational crops.

Regulatory Recommendations and Residue Chemistry Deficiencies

There are no residue chemistry issues that woul d preclude establishing a permanent tolerance for fludioxonil residues in/on carrots, stone fruit, group 12-12, and rapeseed, subgroup 20A, except flax seed. A human-health risk asse ssment for these uses is required.

Background

Fludioxonil is a contact, phenyl-py rrole fungicide which inhibits protein kinase (Group 12), leading to reduced fungal growth and developmen t. In the U.S., fludioxonil is registered to Syngenta for use on a wide variety of field and ve getable crops, fruit trees, berries, herbs, and grasses. Fludioxonil is applie d to food/feed crops as a seed treatment, at-planting soil application, broadcast foliar applications and/or post-h arvest applications.

In support for a purposed use on carrots as a pos t-harvest treatment, IR-4 has submitted data generated by The Pest Manage ment Centre (PMC) of Agri culture and Agri-Food Canada (AAFC) for fludioxonil to support the proposed use on carrots. No new data have been submitted to support the expansion of the stone fruit and rapeseed uses. The chemical structure, nomenclature, and physicochemical properties of fludioxonil are presented in Tables 1 and 2.Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 4 of 14 Table 1. Fludio xonil Nomenclature. Compound

Common name Fludioxonil Company experimental name CGA-173506 IUPAC name 4-(2,2-difluoro-1,3-benzodioxol-4-yl) )- 1H -pyrrole-3-carbonitrile CAS name 4-(2,2-difluoro-1,3-benzodioxol-4-yl)- 1H- pyrrole-3-carbonitrile CAS registry number 131341-86-1 End-use products (EPs) Scholar ® SC Fungicide (EPA Reg. No. 100-1242) Maxim ® 4FS Fungicide (EPA Reg. No. 100-758)

Table 2. Physicochemical Properties of Fludioxonil. Parameter Valu e Reference Melting point 199.8°C DP# 325160, G. Kramer, 11/16/2006 pH 8-9 @ 25°C (1% aqueous dispersion) Density 1.54 g/cm 3 typical at 23°C Water solubility (25°C) 1.8 mg/L Solvent solubility (mg/L @ 25°C) Ethanol 44,000 Acetone 190,000 Toluene 2,700 n-Octanol 20,000 n-Hexane 7.8 Vapor pressure (25°C) 2.9 x 10 -9 mm Hg Dissociation constant, pK a pK a1 <0 pK a2 ~ 14.1 Octanol/water partition coefficient, Log(K OW ) 4.12 @ 25°C UV/visible absorption spectrum 12,384 L/mo l x cm @266 nm (neutral solution) 12,327 L/mol x cm @ 265 nm (acidic solution) 11,790 L/mol x cm @ 271 nm (basic solution)



### 860.1200 Directions for Use

IR-4 is proposing the use of Scholar ® 

### SC Fungicide (EPA Reg. No. 100-1242) for the control of white mold on carrots. Appli cations are proposed as post-ha rvest in-line dip or drench applications at 16 fl oz (0.23 lbs ai) per 100 ga llons. The application solution may be made using water, wax/emulsion, or aqueous dilution of wax/oil emulsion. The fruit should be dipped for approximately 30 seconds and allowed to drain. The following restricti on is included: do not make more than one post-harves t application to carrots.

The currently registered use for Scholar ® 

### SC on stone fruits (except cherries) is for in-line dip or drench application at 16 fl oz (0.23 lbs ai) per 100 gallons or in-line a queous or fruit coating spray at 16 to 32 fl oz (0.23 to 0.46 lbs ai) per 200,000 lbs of fruit for th e control of brown rot, gray mold, rhizopus rot, and gilbertella rot. The application may be made using water, wax/emulsion, or aqueous dilution of wax/oil em ulsion. When performing the dip application, fruit should be dipped for approximately 30 seconds and allowed to drain. Use T-Jet, CDA, or similar application system for in-line aqueous or fruit coating applications. The following restrictions are included: do not make more than one post-harvest application to the fruit; for maximum efficacy, use low volume concentrate applic ation systems for treatment of plums. The currently registered use for use for Scholar ® 

### SC on cherries is for in-line aqueous or flooderFludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 5 of 14 

### application at 16 to 32 fl oz (0.23 to 0.46 lbs ai) per 50,000 lbs of fruit. The application solution may be made using water, wax/emulsion, or aque ous dilution of wax/oil emulsion. Use flooders, T-Jet, or similar application system. The following restrictions are includ ed: do not make more than one post-harvest applic ation to the fruit.

The currently registered use for Maxim ® 

### 4FS (EPA Reg. No. 100-758) on rapeseed, flax, crambe, and lesquerella is for protection against seed-borne and soil-bo rne fungi which cause decay, damping-off, and seedling blight. Applic ations are made at 0.08 to 0.16 fl oz (0.0025 to 0.0050 lbs ai) of formulated produc t per 100 pounds of seed.

The proposed and registered use patte rns are summarized in Table 3.

Table 3. Summary of Directions for Use of Fludioxonil.

Applic. Timing, Type, and Equip. 1 Formulation [EPA Reg. No.] Applic. Rate Max. No. Applic.

per Season Max. Seasonal Applic. Rate PHI (days) Use Directions and Limitations

Carrots

Post-harvest dip or drench Suspension
concentrate [100-1242] 16 fl oz per 100 gallons (0.23 lbs ai) 1 16 fl oz per 100 gallons (0.23 lbs ai) NA The fruit should be dipped for 30 seconds and allowed to drain. Do not make more than one post-harvest application. Stone Fruit except Cherry

Post-harvest dip, drench, in-line aqueous or fruit coating spray Suspension
concentrate [100-1242] 16 to 32 fl oz per 100 gallons (dip, drench) or

per 200,000 lbs fruit (aqueous or fruit coating spray) (0.23 to 0.46 lbs ai) 1 32 fl oz (0.46 lbs ai) NA When performing the dip application, fru it should be dipped for approximately 30 seconds and allowed to drain. Use T-Jet, CDA, or similar application system for in-line aqueous or fruit coating applications. Do not make more than one post-harvest application to the fruit; for maximum efficacy, use low volume concentrate application systems for treatment of plums. Cherry

Post-harvest inline aqueous or flooder application Suspension
concentrate [100-1242] 16 to 32 fl oz per 50,000 lbs fruit (0.23 to 0.46 lbs ai) 1 32 fl oz (0.46 lbs ai) NA Use flooders, T-Jet or similar application system. Do notmake more than one postharvest application to the fruit. Rapeseed Subgroup 20A

Seed treatment Water-based slurry [100-758] 0.08 to 0.16 fl oz per 100 lbs seed (0.0025 to 0.0050 lbs ai) 1 0.16 fl oz (0.0050 lbs ai) NA Seeds that are treated and bagged for later use must be labelled to say this seed has been treated with fludioxonil seed treatment. Do not use treated seed for feed, food, or oil purposes.



### Conclusions: The proposed use directions for carrots , stone fruit, and rapeseed subgroup 20A are adequate to allow for evaluation of the uses. The available field tria l data for fludioxonil on carrots support the prop osed use directions.Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 6 of 14 

### 860.1300 Nature of the Residue - Plants

Memo, 10/27/97, S. Willett, D206301 Memo, 08/31/98, W. Wassell, D246235 Memo, 12/14/99, W. Donovan, D261603 Memo, 02/12/2003, T. Bloem, D287808 MARC Decision Memo, 1/18/2000, W. Donovan, D262022



### The nature of fludioxonil in plan ts is understood based on adequate metabolism studies utilizing foliar applications to peaches, gr apes, onions, and head lettuce and seed treatment applications to rice, wheat, cotton, and soybeans. Based on the results of these studies, HED has determined that the residues of concer n in plants is fludioxonil per se

.

860.1300 Nature of the Residue - Livestock

Memo, 12/18/95, S. Willett, D210762 MARC Decision Memo, 01/18/2000, W. Donovan, D262022



### Adequate poultry and ruminant metabolism studies are available. The metabolism of fludioxonil in ruminants involves hydroxylation of the pyrrole ring followed by formation of glucuronide or sulfate conjugates. In poultry, fludioxonil is metabolized by oxidation, ring hydroxylation, degradation of the pyrrole moiety, and formation of glucuronide or sulfat e conjugates. Based on the results of these studies, HE D has concluded that the residues of concern in ruminants, for purposes of tolerance expression and risk as sessment, are fludioxonil and Metabolite B-1 [4- (2',2'-difluoro-1',3'-benzdioxol-4'-yl)-1 H -pyrrole-3-carbonitrile, 2- O -glucuronide]. The residues of concern in poultry, for purposes of tolerance expression and risk asse ssment, are fludioxonil, CGA-344623 [2-cyano-3-(2,2-difluor o-1,3-benzdioxol-4-yl)succinami c acid], and Metabolite I-1 [4-(2',2'-difluoro-1',3'-benzdioxol -4'-yl)-pyrrole-3-carbonitrile, 1- O -sulfate ester].

860.1340 Residue Analytical Methods

Enforcement methods: Adequate HPLC/UV methods (Methods AG-597 and AG-597B) are available for enforcing tolerances for fludioxon il on plant commodities. The LOQs for these methods range from 0.008 to 0.05 ppm depending on the plant commodity.

Data collection methods: In the submitted carrot field trials, residues of fludioxonil were determined using Method AG-597B which determin es residues by analysis using LC-MS/MS.

Residues were extracted by blending the sample in the presence of acetonitrile (ACN):water (90:10, v/v) twice. The extracts were centrifuged, combined, and adjusted to a total volume of 200 mL. The ACN extract was concentrated on a ro tary evaporator and a saturated solution of NaCl was added to the extract. The extract is then partitioned with dichloromethane and then evaporated to dryness. The extract is recons tituted in ACN containing 0.1 % acetic acid. Residues were analyzed by LC-MS/MS using the m/z 247 → 180 and m/z 247 → 125 ion transitions for quantification and confirmation of fludioxonil, respectively. Residues were quantified using external standards. The va lidated LOQ is 0.01 ppm and the LOD was reported as 0.003 ppm.Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 7 of 14 

### The above method was adequately validated usin g control samples of carrot fortified with fludioxonil at levels of 0.01 to 4.0 ppm.

Conclusions: Adequate methods are available for en forcing the proposed tolerance for residues on carrots and the residue data fr om carrot post-harvest trials were determined using an adequate LC-MS/MS method.

860.1360 Multiresidue Methods

DP# 206301, S. Willett, 3/01/1995


### Multiresidue method testing data are available for fludioxonil. Fludioxonil was tested according to Protocols C, D, and E using sorghum, corn, and potatoes. R ecoveries were inadequate using corn and sorghum; however, fludioxonil was recove red from potatoes, a representative nonfatty crop. Testing was not conducted according to pr otocols A and B as fludioxonil does not have an N

-methylcarbamate structure (protocol A) nor is it an acid or phenol (protocol B). Recoveries from potatoes (using multiresidue protocol D) we re 49 to 121% at the 0.05 ppm fortification level, and 78 to 87% at the 0.5 ppm fortificati on level. Additionally, fludioxonil is recoverable by the multiresidue method QuEChERS us ing HPLC-MS/MS for analysis.

860.1380 Storage Stability

DP# 216233, S. Willett, 8/17/1995 DP# 258870, W. Donovan, 12/20/1999 DP# 258861, W. Donovan, 11/29/1999 DP# 280799, W. Donovan, 2/28/2002 DP# 287808, T. Bloem, 2/12/2003



### Adequate storage stability data are available indicating that fludi oxonil is completely stable at -20°C for at least 24 months in corn grain and forage, sweet corn ears, sorghum hay, and potatoes; 28.5 months in grapes ; 12 months in carrots, broccoli, cabbage, and mustard greens; 6 months in corn meal, sorghum flour, and potat o flakes; and 4 months in stone fruits and raspberries. To date, no decline of fludioxonil during frozen storage has been observed in any plant commodities tested.

The storage durations and conditi ons of samples from the canol a field trials and processing studies submitted to support this petit ion are presented in Table 4.

Table 4. Summary of Storage Conditions and Dura tions of Samples from Canola Field Trial and Processing Studies.
Matrix Storage Temperature (°C) Actual Storage Duration (days) Interval of Demonstrated Storage Stability (days)

Carrots ≤ -15.6 162 365



### Conclusions: Adequate storage stability data are available for fludioxonil in/on carrots to validate the storage interval for samples in the crop field trials.Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 8 of 14 

### 860.1480 Meat, Milk, Poultry, and Eggs

DP# 287808, T. Bloem, 2/12/2003



### There are no livestock feeding st udies available for fludioxonil. Based on the available goat and poultry metabolism data and the previously calc ulated dietary exposures of livestock to fludioxonil residues, HED previously concluded that quantifiabl e residues of fludioxonil were unlikely to occur in livestock commodities [ 40 CFR §180.6(a)(3)]. Therefore, cattle and poultry feeding studies and tolerances for livestock commodities were not required.

The maximum dietary burdens of livestock to flud ioxonil residues were prev iously calculated to be 0.13 ppm for beef cattle, 0.11 ppm for dair y cattle, 0.03 ppm for poultry, and 0.02 ppm for swine (DP# 287808, T. Bloem, 2/12/2003). The maximum dietary burdens of livestock to fludioxonil residues has been recalculated to be 0.047 ppm for beef cattle, 0.033 ppm for dairy, 0.026 ppm for poultry, and 0.023 ppm for swine (Table 5).

As the recalculated dietary burden does not alte r HED’s previous conclusi ons regarding the need for livestock feeding studies and tolerances for livestock commodities.

Table 5. Calculation of Dietary Burdens of Fludioxonil Residues for Livestock.

Feedstuff Dietary Component % Dry Matter 1 % Diet 1 Residues (ppm) 2 Dietary Contribution (ppm) 3

Beef Cattle Alfalfa, hay R 89 15 0.01 0.002 Corn, grain CC 88 25 0.02 0.006 Sorghum, grain CC 86 25 0.02 0.006 Potato, culls CC 20 30 0.02 4 0.030 Flax, meal PC 88 5 0.05 0.0028
TOTAL BURDEN 100 0.047 Dairy Cattle 5 Alfalfa, forage R 35 20 0.01 0.006 Grass, hay R 88 25 0.01 0.003 Sorghum, grain CC 86 35 0.02 0.008 Potato, culls CC 20 10 0.02 4 0.010 Flax, meal PC 88 10 0.05 0.0057
TOTAL BURDEN 100 0.033 Poultry Sorghum, grain CC NA 75 0.02 0.015 Canola, meal PC NA 5 0.01 6 0.001 Flax, meal PC NA 20 0.05 0.01
TOTAL BURDEN 100 0.026

Swine Sorghum, grain CC NA 80 0.02 0.016 Corn, grain CC NA 5 0.02 0.001 Canola, meal PC NA 5 0.01 6 0.001 Flax, meal PC NA 10 0.05 0.005
TOTAL BURDEN 100 0.023Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 9 of 14 1 Potential dietary burden s for livestock were determined usin g recent Agency guidance on calculating reasonably balanced diets for livestock (memo, 6/30/2008).

2 The tolerance level for the RAC was used for any associated processed fractions unless otherwise indicated.

3 Contribution = ([tolerance /% DM] X % diet) for beef an d dairy cattle; contribution = ([tolerance] X % diet) for poultry and swine.

4 Based on 0.02-ppm tolerance on root and tuber vegetables (group 1).

5 Although there is a 30 ppm tolerance for leaves of root and tuber vegetables, turnips tops were not included in the diet for dairy cattle as the label prohibits the feeding of leaves of root and tuber vegetables to livestock.

6 Based on 0.01 ppm tolerance for rapeseed seed.



### 860.1500 Crop Field Trials

Carrot :

49347001.der.docx (Carrots - Canadian post-harvest trials)


### IR-4 has submitted residue data for fludioxonil on carrots to support the proposed use expansion to this crop. Two post-harvest tr ials were conducted in Canada, w ith one trial in Zone 1A (Nova Scotia) and one trial in Zone 12 (British Columbia). The carrots were grown during the 2009 growing season. Samples of carrot roots were ha rvested from both trials, and stored for ~1-2 months. The carrots were then treated with a mixture containing 0.3 g ai/L (0.0025 lbs ai/gal) fludioxonil SC formulation. At each trial site, two treatment regime ns were used. For the first treatment, the test mixture was applied via a dren ch application (TRT 03), where the carrots were placed in a plastic mesh bag in a single layer a nd sprayed with test mixture for 10 seconds, then flipped over and sprayed for another 10 seconds; the spray rate was not indicated. For the second treatment, the test mixture was applied vi a a dip application (TRT 02), where the carrots were placed in plastic mesh boxes and submerge d in the test mixture for ~30 seconds. An adjuvant was not added to the spray mixture for a ny of the applications. Samples of carrots were collected after the test mixture had dried on the day of application [0 DAA (days after application)] and placed in frozen storage.

When carrots were treated with 1 applicati on of fludioxonil at 0.3 g ai/L (0.0025 lbs ai/gal), fludioxonil residues ranged from 1.91 to 3.49 ppm for the dip application (TRT 02) and 1.63 to 2.35 ppm for the drench applica tion (TRT 03). The results of the post-harvest trials are summarized in Table 6.

TABLE 6. Summary of Residue Data from Crop Field Trials with Fludioxonil. Commodity Total Applic. Rate g ai/L (lbs ai/gal) DAA (days) Residue Levels (ppm) n Min. Max. HAFT 1 LAFT 2 Median (STMdR) Mean (STMR) Std. Dev.

TRT 02 (Dip) Carrot roots 0.3 (0.0025) 0 8 1.91 3.49 -- -- 2.43 2.51 0.53 2 -- -- 2.59 2.43 2.51 2.51 -- TRT 03 (Drench) Carrot roots 0.3 (0.0025) 0 8 1.63 2.35 -- -- 1.94 1.95 0.22 2 -- -- 2.01 1.88 1.95 1.95 --

1 HAFT = Highest Average Field Trial.

2 LAFT = Lowest Average Field Trial.Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 10 of 14 

### Stone Fruit, Crop Group 12-12:

Memo, 11/16/2006, G. Kramer, D325160



### Tolerances are currently established for residue s of fludioxonil in/on ston e fruit, crop group 12 at 5.0 ppm in conjunction with a post-harvest use of Scholar ® 

### SC. IR-4 has proposed to extend the tolerance and registered use for fludioxonil in/on crop group 12 to the newly defined crop group 12-12 which includes additional commodities.

Conclusions: HED has no objection to extending the tolerance and regist ered use for fludioxonil in/on crop group 12 to crop group 12-12.

Rapeseed, Subgroup 20A:

Memo, 08/31/1998, W. Wassell, D246235



### Tolerances are currently established for resi dues of fludioxonil in/on rapeseed and forage, crambe, and lesquerella at 0.01 ppm in conjunc tion with a seed treatment use of Maxim ® 

### 4FS. Additionally, a tolerance is currently established for resi dues of fludioxonil in/on flax at 0.05 ppm in conjunction with a s eed treatment use of Maxim ® 

### 4FS. Syngenta has proposed to extend the tolerance and registered use for fludioxonil in /on rapeseed to the rapeseed subgroup 20A. Rapeseed, canola varieties only, is the represen tative commodity for th e rapeseed crop subgroup 20A. Crambe, lesquerella, and flax ar e members of the rapeseed subgroup.

Conclusions: HED has no objection to extending the tolerance and regist ered use for fludioxonil in/on rapeseed to the rapeseed subgroup 20A, except flax seed.

860.1520 Processed Food and Feed

Memo, 11/04/2009, W. Wassell, D362488 47644301.de4.doc (canola)



### Syngenta has previously submitted processing da ta for fludioxonil in/on rapeseed. Following a single broadcast foliar application of fludioxonil to canola at rates of ~750 g ai/ha (0.669 lbs ai/A), residues were <LOD (<0.003 ppm) in sample s of canola seed, meal, and refined oil from both field trials. Therefore, processing fact ors could not be calculated. The theoretical processing factors for canola are 1.9x for meal and 3.0x for refined oil.

Conclusions: The data indicate that quantifiable resi dues of fludioxonil are unlikely to occur in canola meal and refined oil following an appli cation at 1x the maximum use rate; therefore, separate tolerances are not required for canola meal and refined oil.

860.1650 Submittal of Analytic al Reference Standards

Analytical reference standards for fludioxonil and its metabolite B-1 are cu rrently available at the EPA National Pesticide Standards Repository (personal communication with Theresa Cole, ACB, 11/03/2014). Availability of analytical grade st andards are not an issue for these petitions.Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 11 of 14 

### 860.1850/1900 Confined and Field Accumulation in Rotational Crops

DP# 258865, W. Donovan, 12/17/1999 MARC Decision Memo, DP# 262022, W. Donovan, 1/18/2000



### An adequate confined rotational crop study is av ailable reflecting the application of [phenyl14 

### C]fludioxonil to soil at ~1.0 lb ai/A. Based on the results from this st udy, HED has concluded that the residue of concern in rotational crops is fludioxonil per se

. An adequate limited field rotational crop study is also available. At two test sites in CA and NY, fludioxonil (50% WP) was applied to bare soil as four broadcast a pplications at 0.25 lb ai/A/application at 7-day RTIs, for a total rate of 1.0 lb ai/A (1.1x maximum seasonal rate). Rotational crops of lettuce, turnips, and wheat were planted at each site at PBIs of 27 to 30 days. Single control and duplicate treated samples of le ttuce, turnip roots and tops, and wheat forage, hay, grain, and straw were harvested from each tr ial at the appropriate stage for maturity, and samples were analyzed for residues of fludioxonil using an adequate HPLC/UV method (Method AG-597B). Residues of fludioxonil were <L OQ (<0.01 ppm) in/on all samples of each rotational crop matrix.

These data support the 30-day PBI on the curren t fludioxonil labels and indicate that rotational crop tolerances are not currently required.

860.1550 Proposed Tolerances

The Agency has determined that the residues of concern in plant commodities are fludioxonil. Permanent tolerances have been established fo r residues of fludioxonil. Permanent tolerances have been established [40 CFR §180.516(a)(1)] for residues of the fungicide fludioxonil, including its metabolites and degradates, in or on the various co mmodities ranging from 0.01 ppm to 500 ppm. Compliance with the tolerance leve ls specified in the following table is to be determined by measuring only fludioxonil.

Recommended Tolerances: Table 7 is a summary of the proposed and HED-recommended tolerances for residues of fludioxonil. A revised Section F specifying the ne w tolerance expression and the HED-recommended tolerances should be submitted.

Table 7. Tolerance Summary for Fludioxonil.
Commodity Proposed Tolerance (ppm) Recommended Tolerance (ppm) Correct Commodity Definition/Comments To be established under 40 CFR §180.516 (a) General. (1) Carrots 7.0 Fruit, stone, group 12-12 5.0 Rapeseed subgroup 20A, except Flax Seed 0.01



### The U.S. tolerance and Codex and Canadian MRLs for fludioxonil in/on fruit, stone are harmonized. The U.S. tolerance and Canadian MRL for residues in/on carrots are harmonized; however the Codex MRL is significantly lower. The U.S. tolerance and Canadian MRL for residues in carrots are based on a post-harvest use whereas the Codex MRL is based on a foliar use. The U.S. tolerance and Canadian MRL for fludioxonil in/on rapeseeds are harmonized; however, the Codex MRL is not harmonized. Ca nadian MRLs for fludioxonil in/on flax seed,Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 12 of 14 

### mustard seed, and poppy seed are not harmonized as these commodities are included in subgroup 20A.

Attachments: Appendix I. International Residue Limit Status Sheet. Appendix II. Tolerance- Assessment Calculations.

Petition Numbers: 4E8272, 4F8277 DP#s: 421064, D421602 PC Code: 071503Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 13 of 14 

### Appendix I. International Tolerances 

### International Re sidue Limits

Fludioxonil (071503; 10/30/2014) Summary of US and International Tolerances and Maximum Residue Limits Residue Definition : US Canada Mexico 2 Codex 3 40 CFR 180.490: Plant: 4-(2,2-difluoro-1,3- benzodioxol-4-yl)-1- H-pyrrole3-carbonitrile Livestock: N/A 4-(2,2-difluoro-1,3- benzodioxol-4-yl) 1H-pyrrole-3- carbonitrile Plants: Fludioxonil Livestock: fludioxonil and its benzopyrrole metabolites, determined as 2,2-difluoro-1,3- benzodioxole-4- caboxylic acid and expressed as fludioxonil. The residue is fat soluble.
Commodity 1 Tolerance (ppm) /Maximum Residue Limit (mg/kg) US Canada Mexico 2 Codex

Carrots 7.0 7 carrot roots 0.7

Fruit, stone, group 12- 12

5.0 5.0 apricots, fresh prune plums, nectarines, peaches, plumcots, plums, prune plums, sweet cherries, tart cherries 5 Po

Rapeseed, subgroup 20A

0.01 0.05 flaxseeds

0.02 mustard seeds, poppy seeds

0.01 rapeseeds (canola) 0.02 rape seed (*)

Completed: M. Negussie; 11/03/14

1 Includes only commodities of interest for this action. Tolerance values should be the HED 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 co mmodity, such as processing of treated stored wheat. (fat ) = to be measured on the fat portion of the sample. MRLs indicated as proposed have not been finalized by the CCPR and the CAC.Fludioxonil Summary of Analytical Chemistry and Residue Data DP#: 421064

Page 14 of 14 

### Appendix II. Tolerance-Assessment Calculations.

**Fludioxonil**

**Carrot**
**Post-harvest 1**  **6 fl oz per 100 gallons (0.23 lbs ai)** 

**Total number of data (n)** 4

**Percentage of censored data** 0% **Number of non-censored data** 4

**Lowest residue (LR)** 1.880 **Highest residue (HR)** 2.590 **Median residue (STMR)** 2.220

**Mean** 2.228 **Standard deviation (SD)** 0.337

**Correction factor for censoring (CF)** 1.000

**Proposed MRL estimate**

**Unrounde d**  6.683 **Rounded to the next MRL class 7** 

High uncertainty of MRL estimate due to small dataset.

Fludioxonil
Carrot Post-harvest "16 fl oz per 100 gallons(0.23 lbs ai)"

Residues (mg/kg)

2.590 1.880 2.430 2.010Fludioxonil/FLD/ Syngenta Canada Inc

. /SYZ DACO 7

. 4

. 117.4

. 2/0PPTS 860.1500/0ECD IIA 6

. 3.l

, 6

. 3

. 2, 6

. 3

. 3 and IIIA 8.3

. 1, 8

. 3

. 2, 8.3

. 3

- Crop Field Trial/ Re s idue Decline

- Carrot roots

Primary Evaluato

Approved by W lliam D. Wassell, Chemist Risk Assessment Branch 1 (RABI); Heath Effects Division (HED) (7509P)

George F

. Kramer, Ph.D., Senior Chemist RABI, HED (7509P) Date: 22-July-20I5

Note : This DER was originally prepared by the Canadian Pest Management Regulatory Agency (PMRA)

. The DER ha s been reviewed by HED and revised to reflect current Office of Pesticide Program s (OPP) policies

.



### STUDY REPORTS:

PMRA No. 2309994. MRID No. 49347001. Subedi, K. (20I2) "Fludioxonil: Magnitude of the Residue on Carrots." Study Number AAFC08-013R. Laboratory Identification Number AAFC08-013R-556. Unpublished study prepared by Agriculture and Agri-Food Canada, Pest Management Centre

. 302 pages.



### EXECUTIVE SUMMARY:

The Pest Management Centre (PMC) of Agriculture and Agri-Food Canada (AAFC) has submitted residue data for fludioxonil on carrots to support the proposed use expansion to this
crop.

Two post-harvest trials were conducted in Canada, with one trial in Zone IA (Nova Scotia) and

one trial in Zone I2 (British Columbia). The carrots were grown during the 2009 growing

season

. Samples of carrot roots were harvested from both trials, and stored for -I-2 months

. The carrots were then treated with a mixture containing 0.3 g ai/L (0.0025 lbs ai/gal) fludioxonil

s oluble-concentrate (SC) formulation

. At each trial site, two treatment regimens were used. For the first treatment, the test mixture was applied via a drench application (TRT 03), where the
carrots were placed in a plastic mesh bag in a single layer and sprayed with test mixture for IO

se conds

, then flipped over and sprayed for another 10 seconds; the spray rate was not indicated. For the second treatment, the test mixture was applied via a dip application (TRT 02)

, where the
carrots were placed in plastic mesh boxes and submerged in the test mixture for -30 seconds. An adjuvant was not added to the spray mixture for any of the applications. Samples of carrots

were collected after the test mixture had dried on the day of application [O DAA (Days After Application)] and placed in frozen storage.

Carrot s amples were analyzed for fludioxonil residues using a modified version of the reference method " Analytical Method for Determination of CGA-I 73506 in Crops by High Performance Liquid Chromatography Including Validation Data ," Analytical Method No. AG-597B (PMRA # 2044023, MRID No. 43960411). The reference method has been reviewed and deemed acceptable for data gathering and enforcement purposes (REG 2006-08; Memo, 8/I4/95, S

. Willett, D20630I). Modifications to the method include analysis using liquid chromatography with tandem mass spectroscopy (LC/MS/MS) instead of high-performance liquid chromatography with ultraviolet detection (HPLC/UV), using a reverse phase Phenomenex Polar-RP column with acetic acid water/methanol phase instead of a normal column with

MRID No

. 49347001 Pagel of 8Fludioxonil/FLD/ Syngenta Canada Inc. /SYZ DACO 7.4.1/7.4.2/OPPTS 860.1500/OECD IIA 6.3.1, 6.3.2, 6.3.3 and IIIA 8.3.1, 8.3.2, 8.3.3 Crop Field Trial/ Residue Decline – Carrot roots

MRID No. 49347001 Page 2 of 8 

### hexane/methanol/isopropanol phase, usi ng dichloromethane instead of methyl tert -butyl ether (MTBE) for the liquid/liquid partition, and omitting the solid-phase extraction (SPE) clean-up steps. The limit of quantitation (LOQ) was set at 0.01 ppm, and the limit of detection (LOD) was set at 0.003 ppm. The method was validated prior to sample analysis by spiking untreated control samples with 0.01, 0.5, 1.0, 2.0, and 4.0 ppm fludioxonil. All method validation recoveries were within the acceptable 70-120% ra nge. Adequacy of the method was confirmed by spiking control samples with 0.01 and 1.0 ppm fludioxonil, and determining recoveries concurrently with analysis of treated sample sets. All concurrent recoveries were also within the acceptable range. Given that all method validation and concurrent recoveries were within the acceptable range, Analytical Me thod No. AG-597B, as modified for the current study, is adequate for the determination of fludioxonil residues in this study.

Carrot samples were stored frozen ( ≤ -15.6 o 

### C) from sampling to extr action for a maximum of 162 days. Samples were analyzed for residues with in 27 days of extraction. A storage stability study was not conducted concurrently with the analyt ical portion of the residue trial study. Data on file indicates that residues of fludioxonil are stable when stored frozen for up to 24 months in corn, sorghum, and potato (PMRA # 1189618; Re viewed with S1998-1449; Memo, 8/17/95, S. Willett, D216233, MRID No. 43690403). Given that th e storage stability ha s been demonstrated in another root crop, the potato, the assumption can be made that fludioxonil residues are stable in all root and tuber vegetables for up to 24 mont hs (DIR98-02; Section 5.3.2). Therefore, there are no concerns regarding the stab ility of fludioxonil in this study.

When carrots were treated with 1 application of fludioxonil at 0.3 g ai/L (0.0025 lbs ai/gal), fludioxonil residues ranged from 1.91 to 3.49 ppm for the dip application (TRT 02) and 1.63 to 2.35 ppm for the drench application (TRT 03).

STUDY/WAIVER ACCEPTABILITY/ DEFICIENCIES/CLARIFICATIONS :

Under the conditions and parameters used in the study, the field trial residue data are classified as scientifically acceptable.

The acceptability of this study for regulatory pur poses is addressed in Canada’s forthcoming Evaluation Report and in EPA’s summary memo.

COMPLIANCE:

Signed and dated Good Laboratory Practice (GLP), Quality Assurance and Data Confidentiality statements were provided. The study was conduc ted in compliance with the Organization for Economic Co-operation and Development (OECD) Principles for Good Laboratory Practice (GLP) (revision 1997), with the exception of the following:

 Information on weather records, irrigati on records, soil characterization, pH measurement, test site history and cultural practices for carrots production, maintenance fertilizers and pesticides data, and sample weight measurement were not collected according to GLP.Fludioxonil/FLD/ Syngenta Canada Inc. /SYZ DACO 7.4.1/7.4.2/OPPTS 860.1500/OECD IIA 6.3.1, 6.3.2, 6.3.3 and IIIA 8.3.1, 8.3.2, 8.3.3 Crop Field Trial/ Residue Decline – Carrot roots

MRID No. 49347001 Page 3 of 8 

### It is the opinion of the Study Director and the Evaluators that the cited deviations did not affect the scientific integrity of the study.

A. BACKGROUND INFORMATION

Fludioxonil is a contact fungicide, which is active through inhibition of protein kinase leading to reduced growth and development.

TABLE A.1. Test Compound Nomenclature. Compound

Common name Fludioxonil Company experimental name A9859E IUPAC name 4-(2,2-difluoro-1,3-benzodio xol-4-yl)pyrrole-3-carbonitrile CAS name 4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1 H -pyrrole-3-carbonitrile CAS # 131341-86-1 End-use product/(EP) Fludioxonil (Scholar 230 SC)

TABLE A.2. Physicochemica l Properties of Fludioxonil Parameter Valu e Reference Melting point 199.8 o C e-Pesticide Manual, Thirteenth Edition, Version 3.1 pH Not indicated Density (20 o C) 1.54 g/cm 3 Water solubility ( 25°C) 1.8 mg/L Solvent solubility (g/L at 25°C) Solvent Solubility (g/L) Acetone Ethanol Toluene n-octanol Hexane 190 44 2.7 20 0.01 Vapour pressure at 25°C 3.9 x 10 -4 mPa Dissociation constant (pK a ) pKa 1 <0; pK 2 c. 14.1 Octanol/water partit ion coefficient Log(K OW ) 4.12 (25 o C) UV/visible absorption spectrum Not indicated



### B. EXPERIMENTAL DESIGN

B.1. Study Site Information

TABLE B.1.1. Tria l Site Conditions. Trial Identification (City, P rov./Year) Soil characteristics Type %OM* pH* CEC* meq/g Trial ID # AAFC08-013R-554 Berwick 1 , NS/2009 Sandy Loam 2.3 6.3 10.7

Trial ID # AAFC08-013R-555 Abbotsford 2 , BC/2009 Sandy Loam 2.2 6.0 5.8

*These parameters are optional except in cases where their value affects the use pattern for the chemical.

1 Because this study was conducted as a post-harvest trial, the pesticide was applied in Kentiville, NS although the carrots were grown in Berwick, NS. O O F F N H CNFludioxonil/FLD/ Syngenta Canada Inc. /SYZ DACO 7.4.1/7.4.2/OPPTS 860.1500/OECD IIA 6.3.1, 6.3.2, 6.3.3 and IIIA 8.3.1, 8.3.2, 8.3.3 Crop Field Trial/ Residue Decline – Carrot roots

MRID No. 49347001 Page 4 of 8 2 Because this study was conducted as a post-harvest trial, the pesticide was applied in Summerland, BC although the carrots were grown in Abbotsford, BC.



### No weather data was provided for these trials because the trials were conducted indoors with post-harvest applications under ambient te mperatures and controlled conditions.

TABLE B.1.2. Study Use Pattern. Location (City, Prov./Year) Trial ID EP 1 Application Tank Mix/ Adjuvants Treatment No. Method/ Timing Total Treatment Volume (L) Rate g ai/L (lbs ai/gal) RTI 2 (days) Total Rate g ai/L (lbs ai/gal)

Trial ID # AAFC08- 013R-554 Kentiville, NS/2009 Fludioxonil (Scholar 230 SC) 02 Dip/ Postharvest 30 0.3 (0.0025) n/a 3 0.3 (0.0025) None

03 Drench/Postharvest 5 0.3 (0.0025) n/a

Trial ID # AAFC08- 013R-555 Summerland, BC/2009 Fludioxonil (Scholar 230 SC) 02 Dip/ Postharvest 12 0.3 (0.0025) n/a 0.3 (0.0025) None

03 Drench/Postharvest 6 0.3 (0.0025) n/a

1 EP = End-use Product

2 Retreatment Interval

3 n/a = not applicable

TABLE B.1.3. Trial Numbers and Geographical Locations

. NAFTA Growing Zones Carrots Submitted Requested*

1A 1 -- 5 -- -- 5B -- -- 12 1 -- Total 2 2

* Given that the post-harvest trials are conducted indoors under controlled conditions, the trials can be conducted in any zone (DIR98-02 section 9.4, point 13).



### B.2. Sample Handling and Preparation

At all test sites, four carrot samples were coll ected from each treated lot (TRT 02 and TRT 03), while two carrot samples were collected from each untreated lot (TRT 01). All samples were placed in frozen storage ~4 to 4.5 hours after treatment. Each sample weighed at least 2.0 kg (maximum of 3.0 kg) and consisted of 20 carrots.

The samples were shipped frozen to ALS La boratory Group (Edmonton, AB) via Fed-Ex for residue analysis, where they arrived frozen a nd in good condition. The samples were stored frozen at ≤ -15.6 o 

### C until sample preparation. Samples were prepared by grinding with dry ice in a Hobart food grinder while frozen. The macerated samples were then placed in frozen storage until extraction.Fludioxonil/FLD/ Syngenta Canada Inc. /SYZ DACO 7.4.1/7.4.2/OPPTS 860.1500/OECD IIA 6.3.1, 6.3.2, 6.3.3 and IIIA 8.3.1, 8.3.2, 8.3.3 Crop Field Trial/ Residue Decline – Carrot roots

MRID No. 49347001 Page 5 of 8 

### B.3. Analytical Methodology

Residues of fludioxonil were determined in carro t samples using a modified version of the reference method “Analytical Method for De termination of CGA-173506 in Crops by High Performance Liquid Chromatography Including Validation Data,” Analytical Method No. AG597B (PMRA # 2044023, MRID No. 43960411). The reference method has been reviewed and deemed acceptable for data gathering and enforc ement purposes (REG 2006-08). Modifications to the method include analysis using LC/MS/MS instead of HPLC/UV, using a reverse phase Phenomenex Polar-RP column w ith acetic acid water/methanol phase instead of a normal column with hexane/methanol/isopropanol phase , using dichloromethane instead of methyl tert

butyl ether for the liquid/liquid partition, and omitting the SPE clean-up steps.

Briefly, residues were extracted by blending a 10g carrot sample with a 150 mL solution of acetonitrile (ACN): water (90:10, v/v). The extract was centrifuged, and the supernatant was extracted again with 40 mL ACN: water (90:10, v/v). The extracts were combined, adjusted to a total volume of 200 mL with ACN: water (90:10, v/v), and concentr ated on a rotary evaporator. A saturated NaCl solution was added, and the so lution was partitioned with dichloromethane. The solution was then evaporated to dryness, and the extract was reconstituted in 10 mL ACN with 0.1% acetic acid. Residues were then de termined using LC/MS/MS. The LOQ was set at 0.01 ppm, and the LOD was set at 0.003 ppm.

The method was validated prior to sample analys is by spiking untreated control samples with 0.01, 0.5, 1.0, 2.0, and 4.0 ppm fludioxonil. A ll method validation recoveries were within the acceptable 70-120% range. Mean method valida tion recoveries were 98 ± 4%, 86 ± 7%, 84 ± 6%, 96 ± 6%, and 74 ± 1% in samples spiked with 0.01, 0.5, 1.0, 2.0, and 4.0 ppm fludioxonil, respectively. Adequacy of the method was confirmed by spiking control samples with 0.01 and 1.0 ppm fludioxonil, and determinin g recoveries concurrently with analysis of treated sample sets. All concurrent recoveries were also w ithin the acceptable range. Mean concurrent recoveries were 89 ± 15% and 98 ± 10% in samp les spiked with 0.01 and 1.0 ppm fludioxonil, respectively. Given that all method validation and concurrent recoveri es were within the acceptable range, Analytical Me thod No. AG-597B, as modified for the current study, is adequate for the determination of fludi oxonil residues on carrots in this study.

C. RESULTS AND DISCUSSION

Two post-harvest trials were c onducted on carrots in Canada in the 2009 growing season. The trials were conducted in Zone 1A (Nova Scotia), and 12 (British Columbia). Fludioxonil, formulated as a suspension concentrate, was applie d once to the carrots post -harvest at a rate of 0.3 g ai/L (0.0025 lbs ai/gal). Adjuvants were no t added to the solution. Samples were collected on the day of application after the treatment solu tion dried. Two treatment regimens were used at each test site. The first was a dip applic ation (TRT 02), and the second was a drench application (TRT 03).

Residues of fludioxonil were determined in carro t samples using a modified version of the reference method “Analytical Method for De termination of CGA-173506 in Crops by HighFludioxonil/FLD/ Syngenta Canada Inc. /SYZ DACO 7.4.1/7.4.2/OPPTS 860.1500/OECD IIA 6.3.1, 6.3.2, 6.3.3 and IIIA 8.3.1, 8.3.2, 8.3.3 Crop Field Trial/ Residue Decline – Carrot roots

MRID No. 49347001 Page 6 of 8 

### Performance Liquid Chromatography Including Validation Data,” Analytical Method No. AG597B (PMRA # 2044023). The reference method has been reviewed and deemed acceptable for data gathering and enforcement purposes (REG 2006-08; Memo, 8/14/95, S. Willett, D206301). Modifications to the method include analysis using LC/MS/MS instead of HPLC/UV, using a reverse phase Phenomenex Polar-RP column with acetic acid water/metha nol phase instead of a normal column with hexane/methanol/isopropanol phase, using dichloromethane instead of methyl tert -butyl ether for the liquid/liquid partition, and omitting the SPE clean-up steps. The LOQ was set at 0.01 ppm, and the LOD was set at 0.003 ppm. The method was validated prior to sample analysis by spiking untreated control samples with 0.01, 0.5, 1.0, 2.0, and 4.0 ppm fludioxonil. All method validation recoveries were within the acceptable 70-120% range (Table C.1). Adequacy of the method was confirmed by spiking control samples with 0.01 and 1.0 ppm fludioxonil, and determining recoveries concurrently with analysis of trea ted sample sets. All concurrent recoveries were also within the a cceptable range. Given that all method validation and concurrent recoveries were within the acceptable range, Analytical Method No. AG-597B, as modified for the current study, is adequate for the determination of fludioxonil residues in carrots in this study. Sample chromatograms were provided for standards, solvent blanks, untreated control samples, fortified controls, and treated samples. Overall, the peaks were well defined and symmetrical, and untreated cont rols were free from interference above the chromatographic background. In the submitted calibration curves, detector linearity was demonstrated over a 6-point range of 1.00-40.0 ng/mL (R 2 

### ≥ 0.9970).

Carrot samples were stored frozen ( ≤ -15.6 o 

### C) from sample collection to extraction for a maximum of 162 days (Table C.2). Samples were analyzed for residues within 9 to 27 days of extraction. A storage stability study was not co nducted concurrently with the analytical portion of the residue trial study. Data on file indicate that residues of fludioxonil are stable when stored frozen for up to 24 months in corn, sorghum, and potato (PMRA # 1189618; Reviewed with S1998-1449; Memo, 8/17/95, S. Willett, D21623 3, MRID No. 43690403). Given that the storage stability has been demonstrated in anot her root crop, the potato, the assumption can be made that fludioxonil residues are stable in all root and tuber vegetables for up to 24 months (DIR98-02; Section 5.3.2). Theref ore, there are no concerns rega rding the storage stability of fludioxonil in this study.

When carrots were treated with 1 application of fludioxonil at 0.3 g ai/L (0.0025 lbs ai/gal), fludioxonil residues ranged from 1.91 to 3.49 ppm for the dip application (TRT 02) and 1.63 to 2.35 ppm for the drench applicati on (TRT 03) (Table C.3 and C.4).Fludioxonil/FLD/ Syngenta Canada Inc. /SYZ DACO 7.4.1/7.4.2/OPPTS 860.1500/OECD IIA 6.3.1, 6.3.2, 6.3.3 and IIIA 8.3.1, 8.3.2, 8.3.3 Crop Field Trial/ Residue Decline – Carrot roots

MRID No. 49347001 Page 7 of 8 TABLE C.1. Summary of Method Validation and Concurrent Recoveri es of Fludioxonil from Carrots. Matrix Recovery Type Spike level (ppm) Sample size (n) Recoveries (%) Mean ± std dev (%)

Fludioxonil Carrots Method Validation 0.01 3 102, 98.4, 94.8 98 ± 4 0.5 3 78.3, 86.3, 93.2 86 ± 7 1.0 3 78.0, 88.8, 86.2 84 ± 6 2.0 3 88.8, 99.3, 100 96 ± 6 4.0 3 72.8, 74.5, 73.8 74 ± 1 Concurrent Recovery 0.01 9 95.9, 81.8, 86.9, 126*, 82.7*, 86.1, 76.2, 79.3, 81.6* 89 ± 15

1.0 3 110*, 94.0, 91.0 98 ± 10 * Average of duplicate analysis

TABLE C.2. Summary of Storage Conditions

. Matrix (RAC) Storage Temperature (°C) Actual Storage Duration (days) Interval of Demonstrated Storage Stability (months)
Carrots -31 to -15.6 162 days* A storage stab ility study was not conducted with the analytical portion of the residue trial. Data on file indicates residues of fludioxonil are stable when stored frozen for up to 24 months in corn, sorghum, and potato (PMRA # 1189618; Reviewed with S1998-1449; Memo, 8/17/95, S. Willett, D216233, MRID No. 43690403). Given that storage stability data has been demonstrated in a root crop, the potato, the assumption can be made that residues are stable in all root and tuber vegetables for up to 24 months (DIR98-02; Section 5.3.2). * Longest storage duration of any sample from time of sampling to ex traction. Samples were analyz ed within 9 and 27 days of extraction.

TABLE C.3. Residue Data from Cr op Field Trials with Fludioxonil.

Trial ID

(City, Prov./Year) Zone Crop/ Variety Commodity Total Rate g ai/L (lbs ai/gal) DAA 1 (days) Application Method Residues (ppm) [Average]

Trial ID # AAFC08- 013R-554 Kentiville, NS/2009 1A Carrot/ Pronto Carrot (roots) 0.3 (0.0025) 0 Dip [TRT 02] 3.49 2.61 2.30 1.94 [2.59]
0.3 (0.0025) 0 Drench [TRT 03] 2.07 2.04 1.79 1.63 [1.88]
Trial ID # AAFC08- 013R-555 Summerland

BC/2009 12 Carrot/ Bolero Carrot (roots) 0.3 (0.0025) 0 Dip [TRT 02] 2.96 2.55 2.31 1.91 [2.43]
0.3 (0.0025) 0 Drench [TRT 03] 2.01 1.81 2.35 1.87 [2.01]Fludioxonil/FLD/ Syngenta Canada Inc. /SYZ DACO 7.4.1/7.4.2/OPPTS 860.1500/OECD IIA 6.3.1, 6.3.2, 6.3.3 and IIIA 8.3.1, 8.3.2, 8.3.3 Crop Field Trial/ Residue Decline – Carrot roots

MRID No. 49347001 Page 8 of 8 1 DAA = Days After Application.

TABLE C.4. Summary of Residue Data fr om Crop Field Tria ls with Fludioxonil. Commodity Total Applic. Rate g ai/L (lbs ai/gal) DAA (days) Residue Levels (ppm) n Min. Max. HAFT 1 LAFT 2 Median (STMdR) Mean (STMR) Std. Dev.

TRT 02 (Dip) Carrot roots 0.3 (0.0025) 0 8 1.91 3.49 -- -- 2.43 2.51 0.53 2 -- -- 2.59 2.43 2.51 2.51 -- TRT 03 (Drench) Carrot roots 0.3 (0.0025) 0 8 1.63 2.35 -- -- 1.94 1.95 0.22 2 -- -- 2.01 1.88 1.95 1.95 --

1 HAFT = Highest Average Field Trial.

2 LAFT = Lowest Average Field Trial.



### D. CONCLUSION

The supervised crop field trials for fludioxonil on carrots are considered scientifically valid.

Two post-harvest trials were c onducted on carrots in Zone 1A and 12. Fludioxonil was applied once to the carrots post-harvest at a rate of 0.3 g ai/L (0.0025 lbs ai/gal). Residues of fludioxonil ranged from 1.91 to 3.49 ppm for the dip application (TRT 02) and 1.63 to 2.35 ppm for the drench application (TRT 03).

E. REFERENCES

PMRA # 1189618. MRID No. 43690403. Eudy, L.W. (1997) “Stability of CGA-173506 Fortified into Corn, Sorghum, and Potato Subs trates under Freezer Storage Conditions.” Report No. ABR-97108. Study No. 115-93. Unpublished st udy prepared by Novartis Crop Production Inc., Greensboro, USA. 78 pages.

PMRA # 2044023. MRID No. 43960411. Campbell, D.D. (1996) “Analytical Method for the determination of CGA-173506 in Crops by High Pe rformance Liquid Chromatography Including Validation Data.” Analytical Method No. AG-5 97B. Protocol No. 56-92. Project No. 426982. Unpublished study prepared by Ciba-Geigy Corporation, Greensboro, USA. 112 pages.

F. DOCUMENT TRACKING

Not Applicable.

Template Version June 2005.