Page 1 of 10 **UNITED STA TES ENVIRONMENTA**  **L PROTECTION A GENCY** 

**WA SHINGTON, D.C**  **. 20460**  **OFFICE OF CHEMICA** **L SA FETY**  **AND POLLUTION PREVENTION**  **MEMORANDUM Date**  **:** 4 June 2015 **SUBJECT:** Fluensulfone

– Revised Tolerance Recommendation for Tomato Paste .

PC Code: 050410 DP Barcode: D 427654 Decision No.: 505068 Registration No. : 66222 - 243 Petition No.: 5F8365 Regulatory Action: Section 3 Risk Assessment T ype: Single Chemical Aggregate Case No.: None T XR No.: NA CAS No.: 318290 - 98 - 1 MRID No.: 49556801 40 CFR: 180.680 **FROM:** Michael A. Doherty, Ph.D., Senior Chemist

Risk Assessment Branch II (RAB II) Health Effects Division ( HED; 7509P) **THROUGH:** Christina Swartz, Chief

RAB II H ED (7509P) **TO:** Rita Kumar/Mark Suarez/Meredith Laws Invertebrate and Vertebrate Branch 3 Registration Division ( 7505P ) The new nematicide fluensulfone was recentl y evaluated under a global joint review project , with Canada and Australia , for use on cucurbit and fruiting vegetables (crop groups 9 and 8 - 10, respectivel y). In the human health risk assessment (D403767, 18 June 2014; D422674, 4 September 2014) , HED concluded that a tolerance for residues of fluensulfone in/on both crop groups was supported at 0.5 ppm , and tolerance s were established in September 2014 (40 CFR 180.680) . The tolerance expression specifies that for compliance, the anal yt e of interest is 3,4,4 - trifluoro but - 3 - ene - 1 - sulfonic acid (a.k.a. BSA , a metabolite and degradate found in crops treated with fluensulfone ). Based on the information available to the Agency at that time, which showed no concentration of fluensulfone or the BSA metabolite , separate tolerances for residues in processed tomato products were not estab lished . Recently , the Agency

received a new tomato processing study which demonstrates concentration of BSA to a degree that warrants a separate tolerance for residues in tomato paste. The study,Fluensulfone D427654

Page 2 of 10 Magnitude of the Residue of Fluensulfone in Tomato Process ed Commodities ( Study No. AA120702 ; MRID 49556801), was reviewed b y Health Canada’s Pest Management Regulatory Agency (PMRA) and was found to be acceptable. EPA has not conducted additional review of the study . The PMRA evaluation is included as Attachment 1. **HED Conclusions**  The processing study indicates that residues of BSA may concentrate in tomato puree (1.4X) , tomato paste (3.5X) , and dried tomato (6.6X) . Based on these concentration factors and the highest average field trial (HAFT) residue (0.29 pp m) 1 in tomato fruits , the tolerance for res idues in tomato is sufficient to cover residues in puree. The registrant has not requested a tolerance for residues in dried tomato , dried tomato is not a significantly traded food commodity, and a tolerance is not necessary for harmonization purposes; therefore, a tolerance for residues in dried tomato is not necessary , per HED policy . For tomato paste, the product of the concentration factor and the HAFT residue supports a tolerance of 1.0 ppm.

1 Expressed as parent compound and adjusted to reflect a mitigated application rate; see D422659, 4 September 2014Fluensulfone D427654

Page 3 of 10 **Attachment 1 –**  **PMRA Evaluation of MRID 49556801 ( Magnitude of the Residue of**  **Fluensulfone in Tomato Processed Commodities, Study No. AA120702 )** 

**B.7.7 Effects of Industrial Processing and/or Household Preparation** 

**(Annex IIA 6.5; Annex IIIA 8.5) B.7.7.3**  **Magnitude of Re sidues on Set of Representative Processes** 

**(Annex IIA 6.5.3; Annex IIIA 8.5.3) B.7.7.3.1**  **TOMATO Document ID:**  MRID No. 49556801

PMRA No. 2402078 **Report:** Magnitude of the Residue of Fluensulfone in Tomato Processed

Commodities , Study

No. AA120702 **Guidelines:** EPA OCSPP Harmonized Test Guideline 860.1520 Processed Food/Feed

(August 1996) PMRA Regulatory

Directive DIR98 - 02

– Residue Chemistry Guidelines, Section 10

– Processed Food/Feed OECD Guideline 508 Magnitude of the Pesticide Residues in Proces sed Commodities (October 2008) **GL P Compliance:**  No deviations from regulatory requirements were reported which would have an impact on the validity of the study . **Acceptability:** The study is considered scientificall y acceptable. **Evaluator:** Anne - Marie Boulanger, Ph.D., Scientific Evaluator III, EXP - 1, HED **EXECUTIVE SUMMARY** Tomato field trial s for fluensulfone w ere conducted in the United States during the 2012 growing season . Fluensulfone, formulated as an emulsifiable concentrate (EC) of 480 g/L, was applied 7 days before transplanting of tomatoes as one pre -plant incorporated (PPI) application at rates of ca. 12 kg ai/ha (TRT #1) and ca. 20 kg ai/ha (TRT #2). Tomatoes were harvested only from one test plot of one trial (TRT #2 of T - CA) at commercial maturity (PHIs of 118 - 133 days) . The tomato fruits were processed into juice, purée, paste, wet pomace and dry pomace using simulated commercial practices . All RAC samples were frozen at the testing facility and remained frozen during shipping and storag e prior to anal ys is. All RAC samples harvested for processing were kept cool at the testing facility until shipping to the processing facility and remained frozen during storage after to processing and prior to analysis. The maximum storage interval for samples was 83 days (i.e. from harvest to processing to analysis ) . Storage conditions and durations are supported by studies showing that residues of fluensulfone are stable for up to 469 days in tomato RAC, and 181 days for tomato paste and purée under froz en conditions.Fluensulfone D427654

Page 4 of 10 Samples were anal yz ed using Method 1977W , a HPL C - MS/MS method to determine residues of fluensulfone and M - 3627 in tomato matrices . Acceptable concurrent recoveries were reported for tomato samples at various fortification levels, thus validating the method. The limit of quantitation (LOQ) was 0.01 ppm per anal yt e for tomato RAC, juice and purée, and 0.10 ppm per anal yt e for tomato paste, wet pomace and dry pomace . A comparison of the residues in the raw agricultural commodity tomato fruit with those in each processed fraction resulted in processing factors of 1 - fold for residues of fluensulfone in all tomato processed fractions, and processing factors of 0.66 - to 6.57 - fold for residues of M - 3627 in tomato proc essed fractions. These processing factors were less than the th eoretical concentration factors for tomato juice, purée, paste and dry pomace. **I. MATERIALS AND METHOD**  **S A.**  **MATERIALS Table 7.7.3.1**  **- 1. Nomenclature for**  **Fluensulfone .**  **Common name** Fluensulfone **Identity** 5 - chloro - 2 - [(3,4,4 -trifluoro - 3 -buten - 1 - yl)sulfonyl]thiazole **CAS no.** 318290 - 98 - 1 **Company experimental name** MCW - 2 **B. Study Design 1. Test Procedure**  Location and detailed use pattern for the trial are provided in Table B.7.7.3.1 - 2. At each trial location, two treated plots were established at ca. 12 kg ai/ha (TRT #1; 4.2 - fold maximum US registered GAP) and ca. 20 kg ai/ha (TRT #2; 7.1 - fold maximum US registered GAP). The trials using the lower application rate were conducted due to concerns with phy totoxicity at 7.1 - fold max GAP. However, tomato fruit samples were only collected from the 7.1 - fold Californian trial (TRT#2) as the tomatoes matured first in California and no phytotoxicity was observed. **Ta ble B.7.7.3.1**  **- 2. Study Use Pattern.**  Location: City, State/Province; Year (Trial ID) End -use

Product/ Formulation Method and

Timing of Application Volume

[L/ha] Rate per Application [kg ai/ha] Retreatment

Interval (days) Total

Rate [kg ai/ha] Surfactant/ Adjuvant Porterville, CA; 2012; (T CA) Fluensulfone

480 g/L EC TRT #1: one pre plant incorporated application using backpack sprayer, 7 days before transplanting 336.15 11.84 N/A 11.84 NoneFluensulfone D427654

Page 5 of 10 **Ta ble B.7.7.3.1**  **- 2. Study Use Pattern.**  Location: City, State/Province; Year (Trial ID) End -use

Product/ Formulation Method and

Timing of Application Volume

[L/ha] Rate per Application [kg ai/ha] Retreatment

Interval (days) Total

Rate [kg ai/ha] Surfactant/ Adjuvant TRT #2: one pre plant incorporated application using backpack sprayer, 7 days before transplanting 339.04 19.92 N/A 19.92 None

Dover, FL; 2012; (T - FL) Fluensulfone

480 g/L EC TRT #1: one pre plant incorporated application using backpack sprayer, 7 days before transplanting 276.59 11.72 N/A 11.72 None TRT #2: one pre plant incorporated application using backpack sprayer, 7 days before transplanting 284.50 20.13 N/A 20.13 None Duplicate tomato fruit samples (minimum of 12 fruits; ca. 2 kg per sample) were harvested, for anal ys is of tomato RAC, at normal commercial harvest. In addition, single bulk tomato fruit samples (ca. 40 kg per sample) were also harvested at normal commerci al harvest and transferred to the processing facility

for preparation of tomato juice, purée, paste and pomace (wet and dry). **Sample Handling and Preparation** Tomato RAC samples were frozen after harvest and shipped frozen to the laboratory . Tomato sample s harvested for processing were kept cool following harvest and shipped unfrozen to the processing facility . **Sample Processing** Untreated tomato samples were processed before the treated tomato samples. Tomatoes were processed according to simulated indus trial practice as closel y as possible. Tomato fruits were first sorted for any fruits unsuitable for processing. Whole tomatoes were then placed in warm water at 52 - 57°C for 3 - 5 minutes to loosen extraneous material, rinsed with water, and defects or off - c olor areas were trimmed off the tomato fruits prior to processing. Cleaned tomatoes were chopped to a fine consistency and fed into a pulper/finisher with a 6/64 ′′ screen. The material that passed through the screen was collected and heated rapidly to 91 - 97°C by pumping through a heat exchanger. The pulp material that did not pass through the screen was set aside. The hot break material was fed through another pulper/finisher with a 0.033 ′′ screen;Fluensulfone D427654

Page 6 of 10 the material that did not passed through the screen was pulp. The resulting juice was checked for acidity and percent solids. If necessary , the acidity was adjusted to pH 4.5 or less with citric acid. The pulp material was combined and a portion was taken for the wet pomace fraction. The remaining pulp was dri ed in an oven at 54 - 71°C for 20 - 24 hours. The resulting dry pomace was collected. Fractions of tomato wet and dry pomace were then stored frozen. A portion of tomato juice was heated to 85 - 91°C for ca. 3 minutes, placed in a can and sealed. The sealed can was pressure cooked for 40 - 45 seconds at 121 - 124°C; cooled in a water bath at 16 - 27°C for 28 - 32 minutes. Fractions of tomato juice were then stored frozen. The remaining tomato juice was used to produce tomato paste and purée. Both paste and purée were p roduced b y vacuum evaporation of water at the lowest possible temperature and highest possible vacuum. The juice was concentrated to percent solids of 8 - 24% for purée and 24 - 30% for paste. Purée and paste were then heated to 85 - 91°C, placed in metal cans, sealed and cooled in water bath at 16 - 27°C for 28 - 32 minutes. Fractions of tomato purée and paste were then stored frozen. **2. Description of Analytical Procedures** Samples of tomato were anal yz ed for residues of fluensulfone and metabolites M - 3625, M - 362 6 and M - 3627 using the Analy tical Method 1977W (PMRA # 2181331; 2181930 (ILV)) . The method was fully

validated in the Annex B.5.2 (OECD). **Note:** Metabolite M - 3626 (i.e. methyl sulfone) is a soil metabolite and not a plant metabolite. Metabolite M - 3625 (i.e. thiazole sulfonic acid) is a plant metabolite. However, these two metabolites are not included in the residue definitions in plant commodities for enforcement and risk assessment purposes. As such, they will not be discussed in this document. Briefl y, samples were extracted once with acetonitrile:water (ACN:H 2 O). For determination of fluensulfone (i.e. MCW - 2), an aliquot of the extract was subjected to HPLC - MS/MS using atmospheric pressure chemical ionization in positive polarity mode (APCI(+)) with multiple reaction monitoring (MRM). For determination of metabolite M - 3627, an aliquot of the extract w as cleaned up by

SPE (i.e. Bond Elut) and the resulting extract was anal yz ed HPL C - MS/MS using electrospray

ionization in negative polarity mode (ESI( - )) with MRM . The LOQ for each anal yt e in tomato RAC, juice and purée was 0.01 ppm. The LOQ for all analy tes in tomato paste, wet pomace and dry

pomace was 0.10 ppm. The LODs were determined to be the lowest calibrant for each anal yt e resulting in values of 0.003 ppm (MCW - 2) and 0.004 ppm (M3627). **II. RESULTS AND DISCUSSION** Method performance was evaluated b y use of concurrent recovery samples by

fortifying tomato RAC and processed commodities (i.e. juice, purée, paste, pomace (wet and dry)) with fluensulfone at 0.01 ppm and 0.10 ppm (n = 1 - 4 per fortification level); M - 3627 at 0.01 ppm, 0.10 ppm, 2.5 ppm, 5.0 ppm, 10 ppm and/or 20 ppm (n = 1 - 6 per fortification level) (Table B.7.7.3.1 - 3) . The fortification levels bracket ed the measured residues.Fluensulfone D427654

Page 7 of 10 In tomato RAC and processed commodities, the majority of individual recoveries for residues of fluensulfone were within the acceptable range of recoveries with a few exceptions in tomato paste and dry

pomace at 0.01 ppm. For metabolite M - 3627, very few individual recoveries were outside the acceptable range of recoveries. The standard deviations were also less than ± 20%. Concurrent recoveries for each anal yt e were measured using both the quantitation and confirmation ion transitions . The data are reported in Table B.7. 7.3.1 - 3 . The confirmatory data are in agreement with the quantitation data but are not reported herein. The detector response was linear (coefficient of determination, r2 > 0.99 ) for each anal yt e within the range of 0.0005 - 0.100 μg/mL . Representative chro matograms of control samples, fortified samples and treated samples were provided. The control chromatograms generall y had no peaks of interest above the chromatographic background at the retention time of the anal yt es of interest . P eaks were usually sy mmetrical and well defined. **Table B.7.7.3.1 -** **3. Summary of Procedural/Concurrent Recoveries** ***** **of Fluensulfone**  **and**

**Metabolite M -** **3627 from**  **Tomato RAC and Processed Commodities .**  Matrix Fortification

Level (ppm) Quantitation Ion Transition Recoveries (%) Mean ± SD (RSD) (%) **Fluensulfone (MCW -**  **2)** Tomato RAC 0.01 80 0.10 87 Tomato juice 0.01 90, 120 105 0.10 99, 93 96 Tomato purée 0.01 100, 100 100 0.10 100, 100 100 Tomato paste 0.01 **130** , 100 115 0.10 97, 89 93 Tomato wet pomace 0.01 90, 80 85 0.10 90, 92 91 Tomato dry pomace 0.01 **150** , **170** , **140** , 98 **140** ± 30 ( **22** ) 0.10 111, 115 113

**M -** **3627** Tomato RAC 0.01 **130** 0.10 100 2.5 80, 83 82 Tomato juice 0.01 110, 80 95 0.10 98, 97, 70, 83 87 ± 13 (15) 5.0 90, 73 82 Tomato purée 0.01 100, 100 100 0.10 105, 104, 91, 102 101 ± 6.5 (6.4) 5.0 100, 92 96 Tomato paste 0.01 100, 100 100 0.10 92, 118, 92, 86, 98, 91 96 ± 14 (15) 10 98, 84, **111** , 87 95 ± 12 ( **13** )Fluensulfone D427654

Page 8 of 10 **Table B.7.7.3.1 -** **3. Summary of Procedural/Concurrent Recoveries** ***** **of Fluensulfone**  **and**

**Metabolite M -** **3627 from**  **Tomato RAC and Processed Commodities .**  Matrix Fortification

Level (ppm) Quantitation Ion Transition Recoveries (%) Mean ± SD (RSD) (%) Tomato wet pomace 0.01 120, 90 105 0.10 100, 77, 79, 93 87 ± 11 (13) 5.0 85, 87 86 Tomato dry pomace 0.01 80, 100 90 0.10 76, 85, 79, 75 79 ± 4.5 (5.7) 20 99, 100 100 * Recoveries in **bold and red** are outside the acceptable ranges of (1) 60 - 120% for fortification levels of ≤ 0.01 ppm; (2) 70 - 120% for > 0.01 ppm to ≤ 0.10 ppm; (3) 70 - 110% for > 0.1 ppm. Relative standard deviations in **bold and red** are greater than the acceptable value of (1) 30% for fortification levels of ≤ 0.01 ppm; (2) 20% for > 0.01 ppm to ≤ 0.10 ppm; (3) 15% for > 0.1 ppm ≤ 1.0 ppm; (4) 10% > 1 ppm, as per OECD Guidance Document on Pesticide Residue Anal ytical Methods [ENV/JM/MONO(2007)17]. All the processed samples except tomato dry pomace were stored frozen 30 days or less from harvest to processing to analysis while tomato dry pomace was stored for a maximum of 83 days from harvest to processing to analysis (Table B.7.7.3.1 - 4) . The available freezer storage stability data indicate that residues of fluensulfo ne (MCW - 2) and metabolite M - 3627 were stable when stored frozen between - 12°C and - 20 °C in tomato RAC for up to 469 days, and in tomato paste and purée for up to 181 days. Thus, the storage intervals of the tomato RAC and processed commodities are covered by the demonstrated storage intervals. **Table B.7.7.3.1 -**  **4. Summary of Storage Conditions.** Matrix (RAC or Extract) Storage

Temperature (°C) Actual Storage

Duration (days) Interval of Demonstrated

Storage Stability

(days) Tomato RAC

- 20 2 469 Tomato juice 27 - 28 181 (paste, purée ) Tomato purée 22 - 26 Tomato paste 25 - 30 Tomato wet pomace 25 - 26 Tomato dry pomace 82 - 83 Residues of fluensulfone (MCW - 2) and metabolite M - 3627, found in the various tomato samples , and their respective processing factors are given in Table s B.7.7.3.1 - 5 .1 and B.7.7.3.1 - 5 .2 . The residue levels were reported using both the quantitation and confirmation ion transitions. The data are in agreement. However, onl y the data obtained using the quantitation ion transitions f or fluensulfone and M - 3627 are reported herein.Fluensulfone D427654

Page 9 of 10 The experimental processing factors of fluensulfone and M - 3627 are less than the theoretical concentration factors (based on water loss or separation into components) for tomato juice and purée (1.4 - fold) and tomato paste (5.5 - fold), and the maximum observed (experimental) concentration factor for tomato dry pomace (80 - fold) (DIR98 - 02; Section 10

– Processed Food/Feed; Appendix A; Tables 2 - 4). **Table B.7.7.3.1 -**  **5. Residue Data from Tomato Processing Study w ith Fluensulfone.**  **Commod ity**  **Residues 1**  **(ppm) Processing Factors**  **MCW -**  **2 M**  **- 3627**  **MCW -**  **2 M**  **- 3627**  Tomato (RAC) <0.01; <0.01 2.196; 2.145

--- ---

Mean <0.01 2.17 Tomato Juice <0.01 1.56; 2.06 1 0.83

Mean --- 1.81 Tomato Purée <0.01 3.296; 2.71 1 1.38

Mean --- 3.00 Tomato Paste <0.10 8.765; 7.374; 6.917 1 2 3.54 Media n --- 7.69 Tomato Wet Pomace <0.10 1.54; 1.309 1 2 0.66

Mean

--- 1.42 Tomato Dry Pomace <0.10 15.51; 13.013 1 2 6.57

Mean

--- 14.3 1 If residues were < LOQ, they were accounted a s 0.01 ppm (tomato RAC, juice, purée) or 0.10 ppm (tomato paste, wet and dry pomace) in the calculations. 2 The LOQs for fluensulfone in tomato RAC, and tomato paste, dry and wet pomace differ due to the nature of the matrix (0.0 1 ppm vs 0.10 ppm). However, as residues of fluensulfone were not quantifiable in any tomato matrix, a processing factor of 1 was assigned to tomato paste, wet and dry pomace.Fluensulfone D427654

Page 10 of 10 **III. CONCLUSIONS** The tomato processing study is considered scientifically acceptable . A comparison of the residues in tomato fruit with those in each processed tomato fraction indicated that residues of fluensulfone do not concentrate in any of the other processed commodities of tom ato. Residues of M - 3627 concentrate in tomato purée, tomato paste and tomato dry pomace but do not concentrate in any other tomato processed commodities. Adequate storage stability data are available to support sample storage duration s and conditions. **REFERENCES PMRA # 2448366**  , Annex B.5.2 (OECD), Anal ytical methods (residue) for plants, plant products, foodstuffs of plant and animal origin, feedingstuffs, 26 pages. **PMRA # 2448367** , Annex B.7 (OECD), Residue Data, 115 pages.