Page 1 of 37 UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. 20460

OFFICE OF PREVENTION, PESTICIDES AND TOXIC SUBSTANCES

MEMORANDUM

Date: 4/24/2007

Subject: Metiram. Petition for the Establishment of Import Tolerances on Grape and Banana. Summary of Analytical Chemistr y and Residue Data. PP# 9E6006

DP No: D311550, D321530, D322230, D323877 Decision No.: TBD

PC Code: 014601 MRID(s): 46501200, 45100601, 45100603, 46501201, 46501202, 46501203, 46501204, 46501205, 46501206, 46501207, 46501208, 46501209, 46501210, 46562000, 46547701, 46655000, and 46655001

40 CFR 180 217 Chemical Class: EBDC Fungicide

From: Christine Olinger, Chemist Reregistration Branch 1 Health Effects Division (7509P)

Through: Toiya Goodlow, Chemist Reregistration Branch 1 Health Effects Division (7509P)

And

Michael S. Metzger, Chief Reregistration Branch 1 Health Effects Division (7509P)

To: Cynthia Giles-Parker, Chief Fungicide-Herbicide Branch Registration Division (7505P)

This document was originally prepared under contract by Dynamac Corporation (2275 Research Boul evard, Suite 300, Rockville, MD 20850; submitted 1/25/2006). The document ha s been reviewed by the Health Effects Division (HED) and revised to reflect current Office of Pesticide Programs (OPP) policies.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 2 of 37 Executive Summary

The petitioner, BASF Corporation, has proposed to establish import tolerances for residues of the fungicide metiram in/on the raw agricultural commodities (RACs) listed below; the proposed tolerance expression is in terms of the parent compound (metiram per se ):

Banana ..................................................................................................... 4.0 ppm Banana, Pulp ....................................................................... 0.5 ppm Grapes .............................................................................. 8.5 ppm

Metiram belongs to the EBDC (et hylene bisdithiocarbamates) group of fungicides. It is registered for the prevention of downy mildews, anthracnose, rusts, leaf spots, and seedling damping off on food/feed crops as well as on ornamental plants. Revised Metiram Product and Residue Chemistry Chapters for the Reregistration Eligibility Deci sion (RED) Document were issued 10/13/2004. According to the Residue Chemistry Chapter, appl es and potatoes are the only food/feed crops with registered uses in the U.S.

In support of the requested import tolerances, BASF has submitted several volumes of residue chemistry studies. These studies were eval uated according to the draft NAFTA Guidance Document on Data Requirements for Tolerances on Imported Commodities jointly issued on April 2003 by the U.S. Environmental Protection Agen cy, Canada’s Pest Management Regulatory Agency (PMRA), and Mexico’s Comision Intersecret arial para el Control del Proceso y Uso de Plaguicidas y Sustancias Toxicas (CICOPLAFEST).

For bananas grown in Central and South America, the Polyram® 80 WG formulation is proposed for multiple spray applications; HED could not determine from the specimen label if the application rates were in terms of product or active ingredient. The proposed preharvest interval (PHI) is 7 days. The submitted label for bananas is inadequate to allow evaluation of the residue data relative to the proposed foreign use patter n because the label does not specify the maximum number of applications (or tota l application rate) that may be made on banana crops grown in Central and South America per growing season. In addition ̧ the la bel does not provide information pertaining to the t ype of equipment which may be used for applications. The petitioner may rely on the submitted field trial data for bananas provided the product label is revised for consistency with the re sults of the field trial data; deta ils of suggested label revisions are presented in the “Regulatory Recommendations and Residue Chemistry Deficiencies” section of this document.

For grapes grown in Europe, the Polyram® DF Fungicide and Polyram® WG formulations are proposed for multiple spray applications; HED could not determine from the specimen labels if the application rates were in terms of product or active ingredient. The proposed PHIs are 28 days in Italy, 35 days in France, and 56 days in Germany. The submitted labels for grapes are inadequate to allow evaluation of the residue data relative to the proposed foreign use pattern because not all labels specify the maximum single and seasonal rate s as well as the preharve st intervals for each European country where uses are proposed. Howe ver, the petitioner has i ndicated that during the past few years, the European Union (EU) is at tempting to harmonize label uses of metiram for grapes grown all over Europe. The proposed harmoni zed grape use pattern in EU specifies: aSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 3 of 37 maximum single application rate of 1.8 kg ai/ha ( 1.6 lb ai/A), a maximum of 3 applications per growing season for an implied seasonal rate of 5.4 kg ai/ha (4.8 lb ai/A), and a 56-day PHI.

When EU has completed the harmonization of all metiram labels intended for use on grapes, EPA requires the submission of revised labels to veri fy whether the available residue data can support the harmonized use patterns. In the interim, the Agency will assess the adequacy of the submitted residue data for grape data relative to the maximu m use patterns for each European country (where labels are provided) as well as the proposed harmonized use pattern.

The nature of the residues in plants and anim als is adequately understood. The Agency has determined that the terminal residues of concer n in plants and livestock are metiram and its metabolite ethylenethiourea (ETU).

Metiram tolerances are established under 40 CFR §180.217 and are currently expressed in terms of residues of a fungicide that is a mixture of 5.2 parts by weight of ammoniates of [ethylenebis(dithiocarbamato)]zinc with 1 part by weight ethylenebis [dithiocarbamic acid] bimolecular and trimolecular cyclic anhydrosul fides and disulfides, calculated as zinc ethylenebisdithiocarbamate. The HED Metabolis m Assessment Review Committee (MARC) has recommended a change in the tolerance expre ssion for metiram and the other EBDCs such as mancozeb and maneb with registered uses (see the 10/13/2004 Residue Chemistry Chapter). The EBDC tolerance expressions will be revised to include residues of the parent EBDC only, calculated as CS 2 , rather than as zineb. Dietary exposure and risk assessments will continue to include residues of ETU, a metabolite common to all EBDCs. This change will serve to update the CFR to include only those EBDCs with registered uses, and will also allow the Agency to harmonize its EBDC tolerance definitions with Codex.

The available analytical methodol ogy is considered adequate for tolerance enforcement. The Pesticide Analytical Manual (PAM) Vol. II lists Methods I, II, III, IV, and A for the determination of dithiocarbamate residues in/on plant co mmodities. These methods are based on the decomposition of dithiocarbamates with release of carbon disulfide (CS 2 ). Using these methods, the CS 2 is swept through a trap to remove any H 2 S and into a reaction tube containing a solution of copper acetate and an amine. A colored copper dithiocarbamate complex is formed, and its absorbance is read as a measure of the original dithiocarbamate. The stated limit of detection (LOD) for Method I is 0.5-4.0 ppm.

Although enforcement methods which are specific to metiram and ETU are not available, no additional analytical methodologi es are required. It was c oncluded in the 10/13/2004 Residue Chemistry Chapter that analytical methods conver ting all EBDCs and some metabolites to carbon disulfide will be considered adequate for enfor cement, along with a specific method for ETU. The colorimetric method of Keppel (Method III in PAM Vo l. II) is currently the preferred enforcement method for residues of metiram per se . For determination of ETU residues, the Agency recommends the GC method of Onley ( AOAC 14th Edition 29.119:554) which provides acceptable results when properly validated with rec overy and control data. In conjunction with the reregistration of other EBDCs (maneb and manc ozeb), the Agency has recommended use of the Onley method as the official, final action me thod for determination of ETU residues in/on potatoes, spinach, apple sauce, and milk.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 4 of 37 The data-collection methods used for the analysis of samples, taken from field and processing studies, are adequate based on acceptable method recoveries which were, overall, within the acceptable range of 70-120%. Samples of grapes a nd its processed commodities were analyzed for residues of metiram, determined as CS 2 , using a spectrophotometry method (BASF Methods 135, 135/4, or Institut Fresenius Method No. IF-95/22962- 00); the reported limits of quantitation (LOQ) for CS 2 ranged from 0.03 to 0.05 ppm. Grapes and its processed commodities were analyzed for ETU using an HPLC method (B ASF Method 373/2, 373/1, or 373/0) with pulsed amperometric detection or an HPLC/UV method (Institut Fresenius No. IF-95/24090-00) based on BASF Method No. 373; the reported LOQ for ETU ra nged from 0.01 to 0.05 ppm. The ETU method (BASF Method 373/2) was subjected to successful independent laboratory validation (ILV). The EBDC and ETU methods need not be further va lidated by Agency chemists at ACB/BEAD since there are adequate enforcemen t methodology for metiram and ETU. Samples of banana were analyzed for residues of metiram, determined as CS 2 , using a GC/MSD method (LAARL SOP PA.0244) and for ETU using an LC/UV method (LAARL SOP PA.0247); the validated LOQ was 0.05 ppm for metiram and ETU in whole banana, pulp, and peel (0.03 ppm for CS 2 ).

Adequate storage stability data for metiram ar e available to support th e storage conditions and intervals of RAC samples collected from the grape and banana fiel d studies as well as samples from the grape processing studies. The 10/13/04 Residue Chemistry Chapter of the Metiram RED reported that metiram is relatively stable in/on di verse crop matrices such as apple, peanut, potato, sugar beet, and tomato and in apple processed co mmodities when stored frozen for up to one year; these data for metiram may be translated to bananas, grapes, and grape processed commodities. There are also adequate storage stability data for ETU on grapes. Weathered residues of ETU were found to be reasonably stable for up to 8.5 months in/on grapes under frozen storage conditions. The maximum freezer storage intervals of grape samples, from harvest to analysis,

were ≤ 8.3 months for metiram and ≤ 7.9 months for ETU. The ma ximum storage interval of whole banana samples, from harvest to analys is, was 4.0 months for metiram and ETU; maximum storage interval for banana pulp and peel was 4.5 months.

There are, however, inadequate storage stabil ity data for ETU in/on bananas and in grape processed commodities (raisins and juice); these data are required for risk assessment. Because of the instability of ETU in some plant commodities, the Agency has taken the approach that storage stability data for metiram residues of concern (including ETU) are not translatable to data collected by other laboratories. Therefore, HED request s the petitioner to use the same analytical laboratories, which performed the analysis of samples collected from the submitted banana field study and grape processing study, in the generation of the requested storage stability data for ETU.

The magnitude of the residue data for bananas we re generated from a total of 12 field trials conducted between the 2004 and 2005 growing seasons in Costa Rica (2 trials), Colombia (2 trials), Ecuador (2 trials), Honduras (2 trials), Ma rtinique (2 trials), and Mexico (2 trials). The number and locations of field trials are ade quate for the purpose of establishing an import tolerance on bananas. The maximum residues of metiram, determined as CS 2 , in/on samples harvested 0 days following the last of 10 or 11 broadcast foliar applications of the 70% WG formulation for a total seasonal rate of 12.5-13.9 lb ai/A were: (i) 0.13 ppm in/on bagged whole bananas, (ii) 2.8 ppm in/on unbagged whole bana nas, (iii) below the method LOQ (<0.03 ppm)Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 5 of 37 in/on pulp from bagged bananas, (iv) 0.11 ppm in/on pulp from unbagged bananas; (v) 0.16 ppm in/on peel from bagged bananas and; (vi) 1.5 ppm in /on peel from unbagged bananas. Residues of ETU were: (i) below the method LOQ (<0.05 ppm) in/on all treated bagged/unbagged samples of whole bananas and banana pulp; (ii) below the method LOQ (< 0.05 ppm) in/on peel from bagged bananas and; (iii) at or below the method LOQ ( ≤ 0.05 ppm) in/on peel from unbagged bananas.

Because quantifiable residues of metiram were observed in/on all samples of bananas, the tolerance spreadsheet was used to determine the appropriate tolerance leve l; residues were first converted from metiram equivalents to CS 2 equivalents. Based on the ca lculations in the tolerance spreadsheet, the appropriate tolerance level for bananas is 3.0 ppm. The pe titioner is required to submit a revised Section F to delete the toleran ce proposal for banana pulp since the Agency does not set tolerances on banana pulp and peel; however, data for banana pulp and peel are useful for dietary risk assessment.

The magnitude of the residue data for grapes were generated from a total of 34 field trials conducted between the 1999 and 2003 growing seasons in France (13 trials), Germany (9 trials), Italy (2 trials), and Spain (10 trials). The number and locations of field trials are adequate for the purpose of establishing an import tolerance on grap es. Varieties tested included wine and table varieties of grapes.

Data bracketing a 27/28/29-day PHI indicate that the maximum residues of metiram, determined as CS 2 , in/on mature grapes were: (i) 1.5 ppm fo llowing eight applications of the 55% WG formulation for a total rate of 7.4-7.7 lb ai/A; (ii) 2.6 ppm following eight applications of the 70% WG formulation for a total rate of 9.5-9.8 lb ai/A; (iii) 2.05 ppm fo llowing six applications of the 70% WG formulation for a tota l rate of 8.2-8.5 lb ai/A; a nd (iv) 1.96 ppm following three applications of the 55% WG formulation for a tota l rate of 2.9 lb ai/A. Residues of ETU in/on the respective treated samples ranged from belo w the method LOQ (<0.01 or <0.05 ppm) to 0.032 ppm. These data may be used to support the la bel PHI of 28 days in It aly pending submission of additional use pattern information. The residue data summarized a bove reflect a total application rate range of 2.9-9.8 lb ai/A.

Data bracketing a 35/36-day PHI indicate that th e maximum residues of metiram, determined as CS 2 , in/on mature grapes were: (i) 1.7 ppm fo llowing eight applications of the 55% WG formulation for a total rate of 7.4-7.7 lb ai/A; (ii) 2.2 ppm following eight applications of the 70% WG formulation for a total rate of 9.5-9.8 lb a i/A; (iii) 1.49 ppm following three applications of the 55% WG formulation for a total rate of 2.9 lb ai/A; and (iv) 2.3 ppm following three applications of the 70% WG formulation for a tota l rate of 2.9-3.0 lb ai/A. Residues of ETU in/on the respective treated samples ranged from below the method LOQ (<0.01 or <0.05 ppm) to 0.015 ppm. These data may be used to support the la bel use pattern in France which specifies a 35-day PHI and an implied maximum seasonal rate of 2.9 lb ai/A. The residue data summarized above reflect a total application rate range of 2.9-9.8 lb ai/A (1.0-3.4x th e maximum seasonal label rate in France).

Data bracketing a 54/55/56-day PHI indicate that the maximum residues of metiram, determined as CS 2 , in/on mature grapes were: (i) 1.2 ppm fo llowing eight applications of the 55% WG formulation for a total rate of 7.4-7.7 lb ai/A; (ii) 1.8 ppm following eight applications of the 70%Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 6 of 37 WG formulation for a total rate of 9.5-9.8 lb ai/A; (iii) 1.81 ppm fo llowing six applications of the 70% WG formulation for a total ra te of 8.2-8.5 lb ai/A; (iv) 1.69 ppm following three applications of the 70% WG formulation for a total rate of 2.9-3.0 lb ai/A . Residues of ETU in/on the respective treated samples ranged from belo w the method LOQ (<0.01 or <0.05 ppm) to 0.012 ppm. These data may be used to support th e proposed harmonized use pattern in EU which specifies a 56-day PHI and an implied maximum s easonal rate of 4.8 lb ai /A. The residue data summarized above reflect a total application rate range of 2.9-9.8 lb ai/A (0.6-2.0x the maximum harmonized seasonal rate in EU).

Quantifiable residues of metiram were observed in/on all samples of grapes. Current product labels vary considerably among the regions of Europe , but the registrant has stated that it is their intention to develop a harmonized label. HED has concluded that a tolerance level of 5 ppm would be appropriate considering the current use patterns and the re gistrant’s proposal, and would harmonize with the Codex Maximum Residue Limit for grapes. The petitioner is required to submit a revised Section F reflect ing a tolerance of 5 ppm.

The submitted grape processing studies are incomplete to satisfy guideline requirements because these studies did not include re sidue data for grape juice. According to Table 1 of OPPTS 860.1000, the regulated processed commodities of grapes are juice and raisins. Although incomplete, the grape processing data indicate that residues of metir am (determined as CS 2 ) and ETU concentrated by average processing fact ors of 3.3x and 1.7x, respec tively, in raisins following processing of the RAC (grapes) with detectable residues and using procedures simulating commercial practices. The maximum expected residues of metiram in imported raisins can be calculated by multiplying the processing factor (3.3x) by the highe st RAC residue value expressed as CS 2 (2.6 ppm) obtained from a trial reflecting 28-day PHI which may have been conducted at an exaggerated rate pending use cl arification. The product of 8.58 ppm is greater than the recommended tolerance of 5 ppm. Th e registrant should submit a revised Section F proposing a tolerance in/on raisins of 10 ppm.

HED will make a definitive determination rega rding the need for import tolerances on grape processed commodities when the requested bridging data for grape juice become available.

The submitted grape processing studies included re sidue data for various matrices following processing of wine varieties of grapes using pr ocedures for commercial wine production. Average processing factors were reported for metiram (determined as CS 2 ) in: Rosé pomace (1.0x and 2.9x), Rosé must (0.1x and 0.6x), Rosé young wine (<0.02x), Rosé mature wine (<0.02x and <0.1x), Red pomace (1.1x and 1.5x), Red must (0.1x and 0.5x), Red young wine (<0.02x), and Red mature wine (<0.03x and <0.1x). Average pro cessing factors were reported for ETU in: Rosé pomace (0.6x and 0.9x), Rosé must (<0.3x and 0.8x) , Rosé young wine (>3.0x), Rosé mature wine (0.6x and >2.9x), Red pomace (>1.3x and 5.4x), Red must (>2.5x and 10.4x), Red young wine (>3.7x), and Red mature wine (>3.5x and 10.7x). The Agency does not set pesticide tolerances in wine because wine is under the purview of the Bureau of Alcohol, Tobacco, and Firearms.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 7 of 37 Regulatory Recommendations and Residue Chemistry Deficiencies

HED has examined the residue chemistry database for metiram and reviewed the residue chemistry studies submitted by BASF in support of the request ed tolerances. Although several deficiencies were identified, HED does not obj ect to granting temporary import tolerances for bananas at 3.0 ppm, pending resolutions of defici encies regarding directions for use, storage stability, and the submission of a revised Section F. A full resoluti on of these deficiencies is required before HED can recommend the establishment of permanent import tolerances.

Although several deficiencies were identifie d, HED does not object to establishing import tolerances for grapes at 5 ppm and raisins at 10 ppm, provided a revi sed Section F and product labels are submitted. Confirmatory storage stability and processing data are required as described below.

A human health risk assessment is forthcoming.

860.1200 Directions for Use

• Copies of labels, translated to English, mu st include, but are not limited to, the maximum single application rate, the maxi mum annual application rate, app lication timing (as it relates to plant growth stage), re-treatment interval, application tank-mix preparation, volume of spray mix per unit area, application equipment, and the pre- harvest interval (PHI). The application rates should be expressed in units of pounds active ingr edient per acre (or kilograms per hectare).

• The submitted label for bananas is inadequate to allow evaluation of the residue data relative to the proposed foreign use pattern b ecause the label does not specify the maximum number of applications (or tota l application rate) that may be made on banana crops grown in Central and South America per growing season. In addition ̧ the la bel does not provide information pertaining to the type of equipment which may be used for applications. The available data will, however, support a minimum retreatment in terval of 5 days and th e use of a surfactant. If the registrant wishes to rely on the available field trial data fo r bananas, then label amendments are required to specify: (1) a maximum of ten br oadcast foliar applications at 1.25 lb ai/A per application for a seasonal rate of 12.5 lb ai/A; and (2) a spray vol ume of 3 gallons per acre using ground equipment. If the petitione r wishes to include higher sp ray volumes on the label, then additional residue data will be required.

• The submitted labels for grapes are also inadequate to allow evaluation of the residue data relative to the proposed foreign use pattern becau se not all labels clearly specify the maximum single and seasonal rates as well as the preharvest intervals for each European country where uses are proposed. However, the petitioner has indi cated that during the past few years, EU is attempting to harmonize label uses of metiram on grapes grown all over Europe. When EU has completed the harmonization of all metiram labe ls intended for use on grapes, EPA requires the submission of revised labels to determine whet her the available residue data can support the harmonized use patterns. If there are any devi ations from the harmonized use pattern due to localized pest infestation or good agricultural practices, information pertaining to these deviations should be reported.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 8 of 37 860.1380 Storage Stability

• There are inadequate storage stability data for ETU in/on ba nanas and in grape processed commodities; these data are required for risk assessment. Because of the instability of ETU in some plant commodities, the Agency has taken the a pproach that storage stability data for metiram residues of concern (including ETU) are not translatable to data co llected by other laboratories. Therefore, HED requests the petitioner to use the same analytical labora tories, which performed the analysis of samples collected from the s ubmitted banana field st udy and grape processing (raisin and juice only) study, in the generation of the requested storage stability data for ETU.

860.1520 Processing Data

• The petitioner is required to conduct a brid ging grape processing st udy to investigate the potential for concentration of me tiram and ETU residues in grape ju ice. In the requested study, the RAC should be processed in a manner simulatin g typical commercial pract ice. The RAC should have detectable residues so a con centration factor may be calculated. It is noted th at juice studies conducted for other commodities generally have not demonstrated concentration in juice.

860.1550 Proposed Tolerances

• Based on HED MARC’s determination regardin g the appropriate tole rance expression for EBDCs, the petitioner is required to submit a revi sed Section F to include residues of the parent EBDC only, calculated as CS 2 , rather than as zineb. The peti tioner should modify the value for grapes to 5 ppm and propose a tole rance in/on raisins at 10 ppm.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 9 of 37 Background

Metiram is the common name of a pesticide wh ich is a mixture of 5.2 parts by weight of ammoniates of [ethylenebis(dithiocarbamato )]zinc with 1 part by weight ethylenebis [dithiocarbamic acid] bimolecular and trimolecular cyclic anhydrosulfi des and disulfides. It is a broad spectrum contact fungicide registered on ap ples, potatoes, and ornamental plants (mainly roses) for the prevention of downy mildews, anthrac nose, rusts, leaf spots, and seedling damping off. Table 1 lists the test compound nomenclatu re for metiram. The physicochemical properties of the technical grade of metiram are presented in Table 2.

Table 1. Test Compound Nomenclature. Compound

N H S

N H Zn

S

S S

N H S

N H S

S S

3

x Common name Metiram Company experimental name BAS 222 F
IUPAC name zinc ammoniate et hylenebis(dithiocarbamate)-pol y(ethylenethiuram disulfide CAS name mixture of 5.2 parts by weight of ammoni ates of [ethylenebis(dithiocarbamato)]zinc with 1 part by weight ethylenebis [dithiocarbamic acid] bimolecular and trimolecular cyclic anhydrosulfides and disulfides CAS registry number 9006-42-2 End-use products (EPs) used in residue field studies 70% WG (BAS 222 28 F; Polyram DF Fungicide) 55% WG (BAS 518 00 F)

Table 2. Physicochemical Properties of the Technical Grade of Metiram.

Parameter Valu e Reference Melting point/range decomposes at ~ 140 oC Product Chemistry Chapter of the Metiram Update, 8/11/1992 pH Not applicable because of low water solubility; titrations with acid/base will not yield reliable pH values. Density 0.33 (loose), 0.49 (packed) kg/L Water solubility practically in soluble (2 mg L at 20 oC) Solvent solubility 8 x 10 -3 g/100g ethanol at 20 oC; insoluble in acetone, benzene, and ethyl alcohol Vapor pressure <1 x 10 -7 mbar at 20 °C Dissociation constant, pK a Not applicable; titrations with acid/base will not yield reliable pKa values. Octanol/water partition coefficient, Log(K OW ) 1.76-2.48 at pH 7 and 21 oC UV/visible absorption spectrum Not availableSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 10 of 37 860.1200 Directions for Use

Labels from Section B of Petition; MRID 46547701

In support of the proposed import tolerances, the petitioner has submitted specimen labels with English translation. For bananas , a specimen label was submitted for Polyram® 80 WG for the preventative control of Black Sigatoka on banana crops grown in Central and South America. For
grapes , labels for Polyram® DF and Polyram® WG were submitted for control and prevention of excoriosis, black-rot, rot Brenner, and mildew on grape orchards in Europe. The BASF designation for Polyram® DF is BAS 222 28 F. A summary of the propos ed use patterns was extracted from the various labels included in the petition’s Section B, and is reported in Table 3.

Table 3. Summary of Use Directions for Metiram on Bananas and Grapes. Application Timing; Equipment Type 1 Formulation Applic. Rate 2 Max. No. Applic/ Season Max. Seasonal Applic. Rate

(lb ai/A) PHI (days) Use Directions and Limitations

Bananas (For Use in Ce ntral and South America)

Broadcast spray to established banana crops Polyram® 80 WG 2.0-2.5 kg/ha Not specified

(NS) NS 7 Spray mix is to be prepared by adding 0.4 L/ha of Nu Film (surfactant) to water (spray volume not specified) and Polyram® 80 WG. Initial application may be made when disease symptoms first appear and repeated at 8-15 day intervals. Grapes (For Use in Italy)

Broadcast spray to established grape orchards Polyram® DF Fungicide 150-400 g/100 L
water NS NS 28 When mixed with other formulations, the longest waiting period must be observed. The following varieties may be sensitive to Polyram® DF: Butirra d’Estate, Conference, Coscia, Gentil Bianca, S. Maria, and Spadona. Grapes (For Use in France) Broadcast spray to established grape orchards Polyram® DF Fungicide 2.0-3.5 kg/ha NS NS NS

Grapes (For Use in Germany)

Broadcast spray to established grape orchards Polyram® WG 0.8-3.2 kg/ha 8 NS 56 Do not apply more than 8 applications in producing plantings, of which maximally 4 with decaying flowers until start of maturing (vine stages 68- 81, BBCH Code)

1 Type of application equipment is not specified on the labels.

2 It could not be determined if the application rates were in terms of product or the active ingredient.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 11 of 37 According to the petitioner (p. 5 of MRID 46547701) , the label directions for the most important metiram-containing formulations in grapes are in the process of bei ng harmonized all over Europe during the past few years. On national levels , up to six applications and maximum single application rates of 2.24 kg ai/ha (equ ivalent to 2.0 lb ai/A ) are currently regist ered. The petitioner has compiled the use pattern information for Po lyram® DF and Cabrio Top (BAS 518 00 F; 55% WG), and the use pattern information from this compilation is presented in Table 4.

Table 4. Label Directions for the Use of Metiram on Grapes Grown in Europe.

Country Product Name Growth Stage & Season BBCH No. Applic.

per Season 1 Single Applic. Rate Implied Max. Seasonal Rate PHI (days)

Germany 2 Polyram® DF 15-79 6 2.24 kg ai/ha (2.0 lb ai/A) 13.44 kg ai/ha (12.0 lb ai/A) 56

EU (N+S-EU) 3 Polyram® DF 15-79 3 1.1 kg ai/ha (1.0 lb ai/A) 3.3 kg ai/ha (2.9 lb ai/A) 56

EU (N+ S-EU) 4 Polyram® DF 15-79 3 1.8 kg ai/ha (1.6 lb ai/A) 5.4 kg ai/ha (4.8 lb ai/A) 56

France (N + S-EU) 518 01F 60-80 3 1.1 kg ai/ha (1.0 lb ai/A) 3.3 kg ai/ha (2.9 lb ai/A) 35

1 Minimum retreatment interval is 12 days

2 Exemplarily listed for a national label direction.
3 Minimum use rate for metiram in grapes (supports also use of mix formulations)

4 Future EU harmonized GAP.

Conclusions: The submitted label for bananas is inadequa te to allow evaluation of the residue data relative to the proposed foreign use pattern b ecause the label does not specify the maximum number of applications (or tota l application rate) that may be made on banana crops grown in Central and South America per growing season. In addition ̧ the la bel does not provide information pertaining to the type of equipment which may be used for applications. The available data will, however, support a minimum retreatment in terval of 5 days and th e use of a surfactant. If the registrant wishes to rely on the available field trial data fo r bananas, then label amendments are required to specify: (1) a maximum of ten br oadcast foliar applications at 1.25 lb ai/A per application for a seasonal rate of 12.5 lb ai/A; and (2) a spray vol ume of 3 gallons per acre using ground equipment. If the petitione r wishes to include higher sp ray volumes on the label, then additional residue data will be required.

The submitted labels for grapes are also inadequate to allow evaluation of the residue data relative to the proposed foreign use pattern because not a ll labels clearly specify the maximum single and seasonal rates as well as the preharvest interv als for each European country where uses are proposed. However, the petitioner has indicated that during the past few years, EU is attempting to harmonize label uses of metiram on grapes grown all over Europe. When EU has completed the harmonization of all metiram labels intended fo r use on grapes, EPA requires the submission of revised labels to determine whether the availa ble residue data can support the harmonized use patterns. If there are any deviations from th e harmonized use pattern due to localized pestSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 12 of 37 infestation or good agricultural practices, informa tion pertaining to these deviations should be reported.

860.1300 Nature of the Residue – Plants and Animals

Memo (DP Barcode D200791, 9/16/94, R. Perfetti) MARC Memorandum, C. Swartz, 12/02/02 Revised Metiram Residue Chemistry Chapter for RED Document (DP Barcode D305910, 10/13/2004, F. Fort)

The nature of metiram residues in plants is adequately understood based on acceptable studies conducted on apples and potatoes; these studies indicate that the bulk of total radioactive residues represent the incorporation of carbon fragments into natural products. The nature of metiram residues in livestock is also adequately understood based on acceptable goat and poultry metabolism studies.

The Agency has determined (DP Barcode D200791, 9/ 16/94, R. Perfetti) that the terminal residues of concern in plants and livestock are metir am and ETU. Subsequently, the HED Metabolism Assessment Review Committee (MARC) has recommended a change in the tolerance expression for metiram and the other EBDCs such as manco zeb and maneb with registered uses (see the 10/13/2004 Residue Chemistry Chapter). Pending i nput from registrants, the EBDC tolerance expressions will be revised to include residues of the parent EBDC only, calculated as CS 2 , rather than as zineb. Dietary exposure a nd risk assessments will continue to include residues of ETU, a metabolite common to all EBDCs. This change w ill serve to update the CFR to include only those EBDCs with registered uses, and will also allo w the Agency to harmonize its EBDC tolerance definitions with Codex.

There are no livestock feed items associated w ith the proposed import tolerances on banana and grape. Therefore, the conditions described in 40 CFR 180.6(a)(3) are applicable for the purpose of this import tolerance petition, i.e ., there is no reasonable expectati on of residues being transferred to livestock commodities via consumption of feed items derived from crops treated with metiram according to the propose use directions.

860.1340 Residue Analytical Methods

46501207.der.doc (EBDC Method for Crop Commodities) 46501208.der.doc (Includes MRID 46501209; ETU Method for Crop Commodities) Revised Metiram Residue Chemistry Chapter for RED Document (DP Barcode D305910, 10/13/2004, F. Fort)

The available analytical methodol ogy is considered adequate for tolerance enforcement. The Pesticide Analytical Manual (PAM) Vol. II lists Methods I, II, III, IV, and A for the determination of dithiocarbamate residues in/on plant co mmodities. These methods are based on the decomposition of dithiocarbamates with release of carbon disulfide (CS 2 ). Using these methods, the CS 2 is swept through a trap to remove any H 2 S and into a reaction tube containing a solution of copper acetate and an amine. A colored copper dithiocarbamate complex is formed, and its absorbance is read as a measure of the original dithiocarbamate. The stated limit of detection (LOD) for Method I is 0.5-4.0 ppm.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 13 of 37 Although enforcement methods which are specific to metiram and ETU are not available, no additional analytical methodologi es are required. It was c oncluded in the 10/13/2004 Residue Chemistry Chapter that analytical methods conver ting all EBDCs and some metabolites to carbon disulfide will be considered adequate for enfor cement, along with a specific method for ETU. The colorimetric method of Keppel (Method III in PAM Vo l. II) is currently the preferred enforcement method for residues of metiram per se . For determination of ETU residues, the Agency recommends the GC method of Onley ( AOAC 14th Edition 29.119:554) which provides acceptable results when properly validated with rec overy and control data. In conjunction with the reregistration of other EBDCs (maneb and manc ozeb), the Agency has recommended use of the Onley method as the official, final action me thod for determination of ETU residues in/on potatoes, spinach, apple sauce, and milk.

The data-collection methods used for the analysis of samples, taken from field and processing studies, are adequate based on acceptable method recoveries which were, overall, within the acceptable range of 70-120%. Samples of grapes a nd its processed commodities were analyzed for residues of metiram, determined as CS 2 , using a spectrophotometry method (BASF Methods 135, 135/4, or Institut Fresenius Method No. IF-95/22962- 00); the reported limits of quantitation (LOQ) for CS 2 ranged from 0.03 to 0.05 ppm. Grapes and its processed commodities were analyzed for ETU using an HPLC method (B ASF Method 373/2, 373/1, or 373/0) with pulsed amperometric detection or an HPLC/UV method (Institut Fresenius No. IF-95/24090-00) based on BASF Method No. 373; the reported LOQ for ETU ra nged from 0.01 to 0.05 ppm. The ETU method (BASF Method 373/2) was subjected to successful independent laboratory validation (ILV). The EBDC and ETU methods need not be further va lidated by Agency chemists at ACB/BEAD since there are adequate enforcemen t methodology for metiram and ETU. Samples of banana were analyzed for residues of metiram, determined as CS 2 , using a GC/MSD method (LAARL SOP PA.0244) and for ETU using an LC/UV method (LAARL SOP PA.0247); the validated LOQ was 0.05 ppm for metiram and ETU in whole banana, pulp, and peel (0.03 ppm for CS 2 ).

The Executive Summary DERs from analytical method submissions are reproduced below.

MRID 46501207

BASF Corporation has submitted validation data for a photometry method (Method 135/4) for the determination of ethylene bisdithiocarbamate (EBDC) residues in/on plant commodities. This method is similar to the colorimetric method of Keppel, which is listed as Method III in the Pesticide Analytical Method Volu me II as the enforcement method for dithiocarbamates. Method 135/4 or earlier versions of the method were used for analysis of grape samples from the field trials and the 2001 processing study submitted in conjunction with DP Barcode D267866.

Briefly, EBDC residues are decom posed to carbon disulfide (CS 2 ) by boiling the crop sample with hydrochloric acid under reducing conditions. The CS 2 is distilled and absorbed in alkaline methanol. Residues are quantit ated by photometric measurement of the xanthogenate at 302 nm. The LOQ is matrix dependent and is reported as the lowest concentr ation level validated.

Crop samples obtained commercia lly were fortified with CS 2 equivalents of metiram or mancozeb at 0.02-6.7 ppm. Adequate recoveries were obtai ned for residues of metiram or mancozeb, as CS 2,Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 14 of 37 from apple, grape, and tomato matrices; tobacco was also validated for metiram. The range of percent recoveries [± coefficien t of variation] for metiram were 77-93% [0.5-3.1] for apple juice and puree fortified at 0.020 pp m (LOQ) and 2.00 ppm; 87-115% [2.1-12.1] for grape vine and juice fortified at 0.056 ppm (LOQ) and 1.120 ppm ; 76-94% [0.7-9.1] for tomato, mark, ketchup, and juice fortified at 0.067 ppm (LOQ) and 6.700 ppm; 81-98% [1.0-7.4] for tomato pomace fortified at 0.05 ppm (LOQ) and 5.000 ppm; a nd 87-111% [12.1] for tobacco fortified at 0.826
ppm.

The range of percent recoveries [± coefficient of variation] for mancozeb were 93-107% [0.8-3.7] for apple, juice, and puree fortified at 0.020 ppm (LOQ) and 2.00 ppm; 104-121% [0.7-6.1] for grape, vine, and juice fortified at 0.028 ppm (LOQ) and 2.810 ppm; 74-114% [1.8-20.8] for tomato, mark, and ketchup fortified at 0.050 pp m (LOQ) and 5.00 ppm; a nd 63-79% [5.8-7.4] for tomato juice fortified at 0.050 ppm (LOQ) and 5.00 pp m. We note that slightly low recoveries (average = 66.8%) were obtained for residues of mancozeb in/on tomato juice fortified at 0.050
ppm.

In addition, adequate concurrent method validat ion data for the photometry method (or earlier versions) were submitted in conjunction with the gr ape field trials and 2001 grape processing study for metiram using grapes fortif ied at 0.05-20 ppm, raisins, rosé and red pomace, and red stalks fortified at 0.5-20 ppm, rosé must fortified at 0.5 ppm, red must fortified at 0.05-5.0 ppm, and rosé and red wine fortified at 0.05-0.5 ppm. Refer to DERs for MRIDs 45100601, 46501201, 46501202, 46501203, 46501204, 46501205, 46501206, and 46501210.

ILV data are not required for the CS 2 photometry method because it is similar to the PAM Vol. II method for EBDC residues in plants . The petitioner stated that if UV determination is not possible due to blanks or unspecific absorption, GC can be used for quantitation. GC confirmatory methods were referenced as Methods 135 (plants) and 135/2 (animals); no additional data were submitted.

MRIDs 46501208 and 46501209

BASF Corporation has submitted validation data for an HPLC method (Method 373/2) which may be used for the determination of ethyle nethiourea (ETU), a me tabolite of ethylene bisdithiocarbamates (EBDCs) such as metiram, in /on plant commodities. This same method (or earlier versions) was used for the analysis of samples collected from the grape field trials submitted in conjunction with DP Barcode D267866; it is also similar to the data-collection method (Morse Laboratories SOP# Method 17, Re vision #2, 8/92) discussed in the 10/13/04 Residue Chemistry Chapter of the Metiram RED.

Briefly, ETU residues are extracted from plant ma trices with a mixture of sodium ascorbate, ethyleneurea, ammonium chloride, and methanol/water. The extract pH is adjusted to 8, and the methanol is evaporated. The remaining water ex tract is cleaned up by liqui d/liquid partitioning on an aluminum-oxide column. Residues are qu antitated by HPLC with pulsed amperometric detection (PAD). The reported LOQ is 0.01 ppm in plant matrices.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 15 of 37 Crop samples were fortified with ETU at the L OQ (0.01 ppm) and 10-100x the LOQ. The plant matrices chosen for the validation study represen t an oil-containing matrix (rape seed), watercontaining matrix (grape), acid-containing matrix (tomato), starch-containi ng matrix (potato), and processed product (wine); apple, lettuce, and cher ry were also included as matrices. Adequate method recoveries were obtained fr om grape, lettuce, oilseed rape seed, potato, tomato, and wine. Although a few slightly low recoveries were obtained from apple and cherry at fortification levels of 0.01 or 0.1 ppm, the overall recoveries were within the 70-120% acceptabl e range. In addition, adequate concurrent method validation data for ETU were submitted in conjunction with the grape field trials and 2001 grape processing study for grap es, raisins, rosé and red pomace, and red stalks fortified at 0.01-0.2 ppm, rosé and red must for tified at 0.01-0.1 ppm, and rosé and red wine fortified at 0.01-1.0 ppm. Refer to DERs for MRIDs 45100601, 46501201, 46501202, 46501203, 46501204, 46501205, 46501206, and 46501210.

A successful ILV trial was conducted using sample s of apple, grape, lettuce, melon (fruit and pale), potato, tomato, and wine fortified with ETU at 0.05 ppm and 0.5 or 2.0 ppm. Due to low recoveries and problems with the chromatography using the specified Dionex column, the following modifications to the method were made: (i) a smaller aliquot was applied to the cleanup column; (ii) an additional Al 2 O 3 layer was added to the bottom of the cleanup column; (iii) a smaller sample size was injected onto the HPLC system; (iv) an Aqua C18 column was used instead of the specified Dionex column; and (v) di chloromethane was purified prior to use. These changes have been incorporated into the method version 373/2.

860.1360 Multiresidue Methods

Revised Metiram Residue Chemistry Chapter for RED Document (DP Barcode D305910, 10/13/2004, F. Fort)

Metiram and ETU are not recovered using any of FDA Multiresidue Protocols. The Residue Chemistry Chapter to the Metiram Update repor ted that metiram is not recovered using FDA Multiresidue Protocol A-E and 232.3. The 10/99 FDA PESTDATA database (PAM Volume I, Appendix I) indicates that ETU is not recovered using method Sections 303 (Mills, Onley, and Gaither method; Protocol E), and 304 (Mills me thod for fatty food); there is a small recovery (<50%) of ETU using multiresidue method Section 302 (Luke method; Protocol D).

860.1380 Storage Stability

Revised Metiram Residue Chemistry Chapter for RED Document (DP Barcode D305910, 10/13/2004, F. Fort) 46501201.der.doc

Adequate storage stability data for metiram ar e available to support th e storage conditions and intervals of RAC samples collected from the grape and banana fiel d studies as well as samples from the grape processing studies. The 10/13/04 Residue Chemistry Chapter of the Metiram RED reported that metiram is relatively stable in/on di verse crop matrices such as apple, peanut, potato, sugar beet, and tomato and in apple processed co mmodities when stored frozen for up to one year; these data for metiram may be translated to bananas, grapes, and grape processed commodities. There are also adequate storage stability data for ETU on grapes. Weathered residues of ETU were found to be reasonably stable for up to 8.5 months in/on grapes under frozen storage conditions. The maximum freezer storage intervals of grape samples, from harvest to analysis,Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 16 of 37 were ≤ 8.3 months for metiram and ≤ 7.9 months for ETU. The ma ximum storage interval of whole banana samples, from harvest to analys is, was 4.0 months for metiram and ETU; maximum storage interval for banana pulp and peel was 4.5 months.

There are, however, inadequate storage stabil ity data for ETU in/on bananas and in grape processed commodities (raisins and juice); these data are required for risk assessment. Because of the instability of ETU in some plant commodities, the Agency has taken the approach that storage stability data for metiram residues of concern (including ETU) are not translatable to data collected by other laboratories. Therefore, HED request s the petitioner to use the same analytical laboratories, which performed the analysis of samples collected from the submitted banana field study and grape processing study, in the generation of the requested storage stability data for ETU.

860.1400 Water, Fish, and Irrigated Crops

There are no proposed uses that are relevant to this guideline topic.

860.1460 Food Handling

There are no proposed uses that are relevant to this guideline topic.

860.1480 Meat, Milk, Poultry, and Eggs

There are no livestock feed items associated w ith the proposed import tolerances on banana and grape. Therefore, the situation described in 40 CF R 180.6(a)(3) is applicable for the purpose of this import tolerance petition, i.e., there is no reasonab le expectation of residu es being transferred to livestock commodities via consumption of feed items derived from crops treated with metiram according to the propose use directions.

860.1500 Crop Field Trials

BASF has proposed to establish import tolerances for residues of metiram per se in/on banana at 4.0 ppm, banana pulp at 0.5 ppm, and grapes at 8.5 ppm. The studies submitted to support these tolerance proposals have been reviewed by HED. The Executive Summaries of study DERs are reproduced below followe d by a crop conclusion.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 17 of 37 Bananas

46655001.der.doc

BASF Corporation has submitted residue data for metiram on bananas from field trials conducted in Central and South America. A total of twel ve banana field tests we re conducted between the 2004 and 2005 growing season in Costa Rica (2 trials), Colombia (2 trials), Ecuador (2 trials), Honduras (2 trials), Martinique (2 trials), and Mexico (2 trials). The test formulation used in all trials was BAS 222 28 F (Polyram® DF), a wetta ble granule (WG) formulation containing 70% metiram. Each field test consisted of one untreated plot and one treated plot . In the treated plot, bananas received ten broadcast foliar applications of the test formulation at 1.4 kg ai/ha/application (1.25 lb ai/A/application) for a tota l rate of ~14 kg ai/ha (12.5 lb ai /A). At the two Mexico trials, an eleventh application was made because the sa mples collected after the tenth application were lost; total application rate at th ese trials was ~15.6 kg ai/ha (13.9 lb ai/A). All applications were made with a 5- to 8-day retreatment interval , using ground equipment from above the canopy to simulate aerial application in ~3 gal/A (29-32 L/ha) spray volumes; an adjuvant was added to the spray mixture (spray oil at 3 L/ha, plus emulsi fier). Bagged and unbagged bananas were harvested 0 days after the last application (DALA).

The maximum storage interval of whole banana samples from harvest to analysis was 122 days (4.0 months) for metiram and ETU; maximum storage interval for pulp and peel was 137 days (4.5 months). No supporting storage stability data we re included in the current study submission. The 10/13/04 Residue Chemistry Chapter of the Metira m RED reported that metiram is relatively stable in diverse crop matrices such as apple, peanut, potato, sugar beet, and tomato when stored frozen for up to one year; these storage stability da ta for metiram may be translated to bananas. However, storage stability data for ETU on ba nanas are required to validate sample storage conditions and intervals and to verify whether the lack of ETU residues in/on bananas is not because of storage instability. Because of the instability of ETU in some plant commodities, the Agency has taken the approach that storage st ability data for metiram residues of concern (including ETU) are not translatab le to data collected by other laboratories (see Residue Chemistry Chapter of the Metiram RED). Therefore, HED re quests the petitioner to us e the same analytical laboratory (BASF S.A., Rese nde, Rio de Janeiro, Brazil), which performed the analysis of samples collected from the submitted banana field trials, in the generation of the requested storage stability data for ETU.

Banana samples were analyzed for re sidues of metiram, determined as CS 2 , using a GC/MSD method (LAARL SOP PA.0244) and for ETU us ing an LC/UV method (LAARL SOP PA.0247). The methods are adequate for data collection based on acceptable concurrent method recovery data. The validated LOQ was 0.05 ppm for metira m and ETU in whole banana, pulp, and peel (0.03 ppm for CS 2 ). The reported LOD was 0.01 ppm for each analyte.

The maximum residues of metiram, determined as CS 2 , in/on samples harvested 0 days following the last of 10 or 11 broadcast foli ar applications of the 70% WG formulation for a total seasonal rate of 12.5-13.9 lb ai/A were: (i) 0.13 ppm in /on bagged whole bananas, (ii) 2.8 ppm in/on unbagged whole bananas, (iii) below the me thod LOQ (<0.03 ppm) in/on pulp from bagged bananas, and (iv) 0.11 ppm in/on pulp from unbagge d bananas. Residues of ETU were below theSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 18 of 37 method LOQ (<0.05 ppm) in/on all treated bagged/ unbagged samples of whole bananas well as in banana pulp. Residues are pr esented below in Table 5.

Table 5. Summary of Residue Data from Banana Field Trials with Metiram. Commodity Total Applic. Rate (lb ai/A) [kg ai/ha] 1 PHI (days) Analyte Residue Levels (ppm) 2

n Min. Max. HAFT 3 Median (STMdR) Mean (STMR) Std. Dev.

Whole banana, bagged 12.5-13.9 [14.0-15.5] 0 Metiram 12 <0.05 0.23 0.23 0.025 0.069 0.067
CS 2 12 <0.03 0.13 0.13 0.015 0.040 0.037
ETU 12 <0.05 <0.05 <0.05 0.025 0.025 0 Whole banana, unbagged 12.5-13.9 [14.0-15.5] 0 Metiram 12 <0.05 5.0 5.0 0.66 1.01 1.33

CS 2 12 <0.03 2.8 2.8 0.37 0.56 0.75
ETU 12 <0.05 <0.05 <0.05 0.025 0.025 0 Pulp, bagged 12.5-13.9 [14.0-15.5] 0 Metiram 12 <0.05 <0.05 <0.05 0.025 0.025 0
CS 2 12 <0.03 <0.03 <0.03 0.015 0.015 0
ETU 12 <0.05 <0.05 <0.05 0.025 0.025 0 Pulp, unbagged 12.5-13.9 [14.0-15.5] 0 Metiram 12 <0.05 0.20 0.20 0.048 0.070 0.057

CS 2 12 <0.03 0.11 0.11 0.028 0.040 0.031
ETU 12 <0.05 <0.05 <0.05 0.025 0.025 0

1 All trials received 10 applications except the Mexico trials which received 11 applications; the samples from the Mexico trial s did not bear the highest residues and therefore are included in the summarization of the data.
2 The LOQ was 0.05 ppm for metiram and ETU, and 0.03 ppm for CS 2 . The LOD is 0.01 ppm for each analyte. The minimum, maximum, and HAFT values are based on the L OQ. For calculating the median, mean, a nd standard deviation, half the LOQ was used for residues reported below the LOQ.
3 HAFT = Highest Average Field Trial.
Although not considered a significant food/feed item of banana, th e study included data for banana peel. Residues of metiram, determined as CS 2, were <0.03-0.16 ppm in/on peel from bagged banana and 0.05-1.5 ppm in/on peel from unbagged banana. Residues of ETU were below the method LOQ (<0.05 ppm) in/on peel from bagged banana and at or below the method LOQ ( ≤ 0.05 ppm) in/on peel fr om unbagged banana.

Banana field trial data conclusions : The number and locations of fi eld trials are adequate for the purpose of establishing an import tolerance on bananas. The maximum residues of metiram, determined as CS 2 , in/on samples harvested 0 days following the last of 10 or 11 broadcast foliar applications of the 70% WG formulation for a tota l seasonal rate of 12.5-1 3.9 lb ai/A were: (i) 0.13 ppm in/on bagged whole bananas, (ii) 2.8 ppm in/on unbagged whole bananas, (iii) below the method LOQ (<0.03 ppm) in/on pulp from bagged bananas, (iv) 0.11 ppm in/on pulp from unbagged bananas; (v) 0.16 ppm in/on peel from ba gged bananas and; (vi) 1.5 ppm in/on peel from unbagged bananas. Residues of ETU were: (i ) below the method LOQ (<0.05 ppm) in/on all treated bagged/unbagged samples of whole banana s and banana pulp; (ii) below the method LOQ (<0.05 ppm) in/on peel from bagged bananas an d; (iii) at or below the method LOQ ( ≤ 0.05 ppm) in/on peel from unbagged bananas. Although the proposed foreign use pattern of metiram on bananas has not been fully elucidated and residu e data reflecting the label 7-day PHI were not provided, the available data will conditionally support a tolerance of 3.0 ppm for whole banana fruit pending label revisions. The petitioner is required to submit a revised Section F to delete the tolerance proposal for banana pulp since the Agen cy does not set tolerances on banana pulp and peel; however, data for these commodities are useful for dietary risk assessment.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 19 of 37 Grapes

1999 Trials

45100601.der.doc

BASF Corporation has submitted field trial data for metiram on wine varieties of grapes grown in Europe. A total of 5 grape field tests were c onducted during the 1999 growing season in Spain (2 trials), Germany (1 trial), and France (2 trials). Each field test consisted of one untreated plot and three treated plots. The treatment plots received spray applications of the following formulations: (i) BAS 518 00F, a wettable granule (WG) formul ation containing multiple active ingredients of metiram (55% ai) and pyraclostrob in (5% ai); (ii) BAS 222 28 F, a WG formulation containing a nominal concentration of 70% metiram as the sing le active ingredient; or (iii) BAS 500 00 F, an emulsifiable concentrate (EC) formulation cont aining 250 g ai/L of pyracl ostrobin. For purpose of brevity, data from the plot treated with pyraclost robin (BAS 500 00 F) are not further discussed or reviewed herein.

For the 55% WG formulation (BAS 518 00F), a total of eight broa dcast foliar applications were made to grape vines for a total rate of ~8,580 g ai/h a (7.7 lb ai/A). The first 4 applications were made at 660 g ai/ha, the fifth at 1,100 g ai/ha, the sixth at 1,320 g ai/h a, and the last two (7 & 8) at 1,760 g ai/ha. For the 70% WG formulation (BAS 222 28 F), a total of eight broadcast foliar applications were made to grape vines for a total rate of ~10,920 g ai/ha (9.7 lb ai/A). The first 4 applications were made at 840 g ai/ha, the fifth at 1,400 g ai/ha, the sixth at 1,680 g ai/ha, and the last two (7 & 8) at 2,240 g ai/ha. All applications were made with a 7- to 14-day retreatment interval, using ground equipment (knapsack motorsprayer) in 29.6-89.4 gal/A (279-843 L/ha) spray volumes. The spray volumes increased with the later applications; an adjuvant was not added to the spray mixture. Grapes were coll ected at preharvest in tervals of 0, 27/28, 35, 41/42, 48, and/or 55/56 days following the last treatment.

Storage stability has been demonstrated for the samples in the study. The 10/13/04 Residue Chemistry Chapter of the Metiram RED reported th at residues of metiram are relatively stable in/on plant matrices such as apple and tomato stored frozen for up to one year . It was also reported from a 2000 grape field study (MRID 46501201) that weathered residues of ETU are relatively stable for up to 8.5 months in/on grapes under frozen storage conditions. The maximum storage interval of grape samples from harvest to anal ysis was 105 days (3.5 months) for metiram and 127 days (4.2 months) for ETU.

Grape samples were analyzed for residues of metiram, determined as CS 2 , using a spectrophotometry method (BASF Me thod 135). The stated limit of quantitation (LOQ) was 0.05 ppm for CS 2 which corresponds to approximately 0.1 ppm of metiram in all sample materials. Grape samples were also analyzed for residue s of ETU using an HPLC method (BASF Method 373/0) with pulsed amperometric detection. The reported LOQ was 0.05 ppm for ETU. Both methods are adequate for data collection base d on acceptable concurrent method recovery data.

Following applications of the 55% WG formulati on (BAS 518 00F) for a total seasonal rate of 7.4- 7.7 lb ai/A, the maximum residues of metiram, determined as CS 2 , were 1.7 and 1.2 ppm,Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 20 of 37 respectively in/on mature samples of grapes colle cted at PHIs of 35 and 55/56 days, respectively; see Table 6. Following applica tions of the 70% WG formulation (BAS 222 28 F) for a total seasonal rate of 9.5-9.8 lb ai /A, the maximum residues of metiram, determined as CS 2 , were 2.2 and 1.8 ppm, respectively in/on mature samples of grapes collected at PHIs of 35 and 55/56 days, respectively . Residues of ETU were below the method LOQ of 0.05 ppm in/on all treated samples except for one sample treated with th e 70% WG formulation which bore residues of 0.055 ppm; however, this sample was harvested at the 0- day PHI. The residue d ecline data indicate that residues were generally highe st at the 0-day PHI and d ecreased with longer PHIs.

TABLE 6. Summary of Residue Data from Grape Field Trials with Metiram. Commodity Total Applic. Rate (lb ai/A) [g ai/ha] PHI (days) Analyte Residue Levels (ppm) 1

N Min. Max. HAFT 2 Median (STMdR) Mean (STMR) Std. Dev.

Eight broadcast foliar applications of the 55% WG formulation Grape, fruit 7.402-7.647 [8,297-8,571] 27-28 Metiram 4 0.8 2.6 2.6 2.3 2.0 0.8
CS 2 4 0.5 1.5 1.5 1.3 1.2 0.5
ETU 4 <0.05 <0.05 <0.05 0.025 0.025 0.0 Grape, fruit 7.402-7.647 [8,297-8,571] 35 3 Metiram 5 0.7 3.0 3.0 1.9 1.9 0.8

CS 2 5 0.4 1.7 1.7 1.1 1.1 0.5
ETU 5 <0.05 <0.05 <0.05 0.025 0.025 0.0 Grape, fruit 7.402-7.647 [8,297-8,571] 55-56 4 Metiram 5 0.6 2.0 2.0 1.8 1.5 0.6
CS 2 5 0.3 1.2 1.2 1.0 0.8 0.4
ETU 5 <0.05 <0.05 <0.05 0.025 0.025 0.0 Eight broadcast foliar applications of the 70% WG formulation Grape, fruit 9.533-9.804 [10,685-10,989] 27-28 Metiram 4 1.1 4.5 4.5 2.9 2.9 1.4
CS 2 4 0.6 2.6 2.6 1.7 1.6 0.8
ETU 4 <0.05 <0.05 <0.05 0.025 0.025 0.0 Grape, fruit 9.533-9.804 [10,685-10,989] 35 3 Metiram 5 1.4 3.8 3.8 3.0 2.8 1.0

CS 2 5 0.8 2.2 2.2 1.7 1.6 0.6
ETU 5 <0.05 <0.05 <0.05 0.025 0.025 0.0 Grape, fruit 9.533-9.804 [10,685-10,989] 55-56 4 Metiram 5 0.6 3.1 3.1 2.4 2.2 0.9
CS 2 5 0.3 1.8 1.8 1.4 1.2 0.6
ETU 5 <0.05 <0.05 <0.05 0.025 0.025 0.0

1 The LOQ was 0.1 ppm for metiram, 0.05 ppm for CS 2 , and 0.05 ppm for ETU; for calculat ing the median, mean, and standard deviation, half the LOQ was used for residues reported be low the LOQ.
2 HAFT = Highest Average Field Trial.
3 It was stated that this PHI reflects the beginning of commercial harvest.
4 The PHI summarized reflects the propos ed PHI for grapes using the 70% WG.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 21 of 37 2000-2001 Trials

46501201.der.doc (Includes MRIDs 46501202 and 46547701)

BASF Corporation has submitted field trial data fo r metiram on grapes grown in Europe. During the 2000 growing season, eight grape field tests we re conducted in France (2 trials), Germany (2 trials) and Spain (4 trials). During the 2001 grow ing season, four grape field tests were conducted in France (1 trial), Germany (2 trials ), and Spain (1 trial). Most of the varieties used in these trials were described as market types of grapes.

Each field test consisted of one untreated plot and one treated plot. Grape vines received six broadcast foliar applications of a 70% wettabl e granule (WG) formul ation (BAS 222 28 F; Polyram DF) for a total rate of ~9,240 g ai/ha (8.2 lb ai/A). The first two applications were made at 840 g ai/ha/application, the third at 1,400 g ai/ha, the fourth at 1,680 g ai/ha, and the last two (5 & 6) at 2,240 g ai/ha/application. All applications were made w ith a 3- to 12-day retreatment interval, using ground equipment in ~31-88 ga l/A (~294-833 L/ha) spray volumes; higher spray volumes were used for the later applications. An adjuvant was not added to the spray mixture. Grapes were harvested 54-56 days after the last application (DALA); the submission stated that the intended PHI for grapes in Europe is 56 days. To generate residue decline data, additional grape samples were collected from the treated plot at 0, 27-29, 40- 43, and 61-63 DALA.

The maximum storage interval of grape sample s from harvest to analysis was 253 days (8.3 months) for metiram and 85 days (2.8 months ) for ETU analyzed by the BASF laboratory (2001 trials) or 183 days (6.0 months) for ETU analyzed by Labor Dr. Mölle rfeld GmbH (2000 trials). It was reported in the 10/13/04 Resi due Chemistry Chapter of the Metiram RED that residues of metiram are relatively stable in/on fruit matrices su ch as apple and tomato stored frozen for up to one year. Concurrent storage stability data for ETU were submitted in support of the 2000 field trials; these data demonstrated that residues of ETU are relative ly stable in/on grapes bearing weathered residues under frozen stor age conditions for up to 8.5 months.

Grape samples were analyzed for residues of metiram, as CS 2 , using a spectrophotometry method (BASF Method 135/4) with HPLC/UV detection. The stated limit of quantitation (LOQ) was 0.03 ppm for CS 2 which corresponds to approximately 0.05 ppm of metiram in all materials. Grape samples were also analyzed for residues of ETU using an HPLC method (BASF Method 373/1) with pulsed amperometric detection. The reported LOQ was 0.05 ppm for ETU for the 2000 samples; however changes to the method were made to reduce the LOQ to 0.01 ppm for the 2001 samples. The changes have been incorporated into the method version 373/2. These methods are adequate for data collection based on accep table concurrent method recovery data.

Maximum residues of metiram, determined as CS 2, in/on grapes harvested 54-56 days following the last of six broadcast foliar applications of the 70% WG form ulation for a total seasonal rate of 8.2-8.5 lb ai/A were 1.81 ppm; see Table 7. Maxi mum residues of ETU were 0.05 ppm in/on the respective treated grape samples. The residue decline data indicat e that residues of metiram, as CS 2, generally decreased with longer PHIs; however, the results from a few decline trials were inconclusive as residues increased at variable PHIs, including at the longest PHI (63 days). TheSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 22 of 37 highest residues typically occu rred in/on samples from the 0-day PHI, and the lowest residues occurred in/on samples from the 56- or 63-day PHI.

TABLE 7. Summary of Residue Data from Grape Field Trials with Metiram. Commodity Total Applic. Rate (lb ai/A) [g ai/ha] PHI (days) Analyte Residue Levels (ppm) 1

n Min. Max. HAFT 2 Median (STMdR) Mean (STMR) Std. Dev.

Grape, fruit 8.242-8.483 [9,238-9,508] 27-29 Metiram 12 1.02 3.66 3.66 2.39 2.26 0.88
CS 2 12 0.57 2.05 2.05 1.34 1.27 0.49
ETU 12 <0.05 0.032 0.032 0.025 0.026 0.013 Grape, fruit 8.242-8.483 [9,238-9,508] 54-56 3 Metiram 12 0.75 3.23 3.23 1.60 1.74 0.81

CS 2 12 0.42 1.81 1.81 0.90 0.97 0.46
ETU 12 <0.01 0.05 0.05 0.025 0.023 0.011

1 The LOQ was 0.05 ppm for metiram, 0.03 ppm for CS 2 , and 0.01 ppm (2001 trials) or 0.05 ppm (2000 trials) for ETU; for calculating the median, mean, and standard deviation, half the LOQ was used for residues reported below the LOQ.
2 HAFT = Highest Average Field Trial.
3 The PHI summarized reflects the proposed PHI for grapes in Europe.

2001 and 2002 Trials

46501203.der.doc (Includes MRIDs 46501204 and 46547701)
BASF Corporation has submitted field trial data fo r metiram on grapes grown in Europe. A total of three grape field trials were conducted during the 2001 growing s eason in France (1 trial) and Spain (2 trials), and a total of four grape field tests were conducted during the 2002 growing season in France (1 trial), Germany (2 trials), and It aly (1 trial). Each fiel d test consisted of one untreated plot and one treated plot . Grape vines received three br oadcast foliar applications of a 70% wettable granule (WG) formulation (BAS 222 28 F; Polyram DF) at ~1,120 g ai/ha/application for a total rate of ~3,360 g ai/ha (3.0 lb ai/A). A ll applications were made with a 10- to 14-day retreatment interval, using gr ound equipment in ~106 gal/A (~1000 L/ha) spray volumes; an adjuvant was not added to the spray mi xture. Grapes were harvested 56 days after the last application (DALA). To generate residue decline data, additional grape samples were collected from the treated plot at 0, 35-36, and/or 62-63 DALA.

The maximum storage interval of grape samples fro m harvest to analysis was 84 days (2.8 months) for metiram and 85 days (2.8 months) for ETU. No st orage stability data on grapes were included in the grape residue study. However, it was repo rted in the 10/13/04 Residue Chemistry Chapter of the Metiram RED that residues of metiram are relatively stable in/on fruit matrices such as apple and tomato stored frozen for up to one year. Concurrent storage stab ility data for ETU were submitted in support of the 2000 field tria ls (see DER for MRID 46501201); these data demonstrated that residues of ETU are relatively stable in/on grapes be aring weathered residues under frozen storage conditions for up to 8.5 months.

Grape samples were analyzed for residues of metiram, determined as CS 2 , using a spectrophotometry method (BASF Method 135/4); HPLC/UV detection was used for the 2002 samples. The stated limit of quantitation (LOQ) was 0.03 ppm for CS 2 which corresponds to approximately 0.05 ppm of metiram in all material s. Grape samples were also analyzed for residues of ETU using an HPLC method (BA SF Method 373/2) with pu lsed amperometricSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 23 of 37 detection. The reported LOQ was 0.01 ppm for ETU. Both methods are adequate for data collection based on acceptable conc urrent method recovery data.

Maximum residues of metiram, as CS 2 , in/on grapes harvested 56 days following the last of three broadcast foliar applications of the 70% WG fo rmulation for a total seasonal rate of 2.96-3.00 lb ai/A were 1.69 ppm; see Table 8. Maximum resi dues of ETU were 0.012 pp m in/on the respective treated grape samples. The residue dec line data indicate that residues of CS 2 generally decreased with longer PHIs; however, the results from a few decline tria ls were inconclusive as residues increased at variable PHIs, includ ing at the longest PHI (62 days) in one trial. The lowest residues typically occurred in/on samp les from the 56-day PHI.

TABLE 8. Summary of Residue Data from Grape Field Trials with Metiram. Commodity Total Applic. Rate (lb ai/A) [g ai/ha] PHI (days) Analyte Residue Levels (ppm) 1

n Min. Max. HAFT 2 Median (STMdR) Mean (STMR) Std. Dev.

Grape, fruit 2.96-3.00 [3,313-3,360] 35-36 Metiram 7 0.67 4.11 4.11 1.13 1.56 1.23
CS 2 7 0.37 2.30 2.30 0.63 0.87 0.69
ETU 7 <0.01 0.02 0.02 0.005 0.010 0.007 Grape, fruit 2.96-3.00 [3,313-3,360] 56 3 Metiram 7 0.36 3.02 3.02 0.77 1.21 0.97
CS 2 7 0.20 1.69 1.69 0.43 0.67 0.54
ETU 7 <0.01 0.012 0.012 0.005 0.006 <0.01

1 The LOQ was 0.05 ppm for metiram, 0.03 ppm for CS 2 , and 0.01 ppm for ETU; for calculating the median, mean, and standard deviation, half the LOQ was used for residues reported be low the LOQ.
2 HAFT = Highest Average Field Trial.
3 The PHI summarized reflects the proposed PHI for grapes in Europe.

2002- 2003 Trials

46501206.der.doc (Includes MRIDs 46501210 and 46547701)

BASF Corporation has submitted field trial data fo r metiram on grapes grown in Europe. During the 2002 growing season, seven field tests were conducted in France (4 trials), Germany (2 trials), and Italy (1 trial) on table vari eties of grapes. During the 2003 growing season, three grape field tests were conducted on wine varietie s of grapes in France (2 trials) and Spain (1 trial). Each field test consisted of one untreated plot and one treated plot. The test formulation used in all trials was BAS 518 01 F, a wettable granule (WG) formulati on containing multiple active ingredients of 55% metiram and 5% pyraclostrobin.

Grape vines received three broadcast foliar applications of the test formulation for a total metiram rate of 3,300 g ai/ha (2.9 lb ai/A ). The data for the pyraclostr obin active ingredient are not reviewed herein. All applications were made w ith a 10- to 14-day retreatment interval, using ground equipment in ~106 gal/A (~ 1000 L/ha) spray volumes; an adjuvant was not added to the spray mixture. Grapes were harvested 35 days af ter the last application (DALA), which was stated as the intended PHI for this formulation in Fran ce. To generate residue decline data, additional grape samples were collected from the tr eated plot at 0, 27-29, and 41-42 DALA.

The maximum storage interval of grape samples fro m harvest to analysis was 72 days (2.4 months) for metiram and 66 days (2.2 months) for ETU. No supporting storage stability data were includedSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 24 of 37 in the current study submissions. However, it was reported in the 10/13 /04 Residue Chemistry Chapter of the Metiram RED that residues of metir am are relatively stable in/on plant matrices such as apple and tomato stored frozen for up to one year. It was also reported from a 2000 grape field study (MRID 46501201) that weat hered residues of ETU are relatively stable for up to 8.5 months in/on grapes under frozen storage conditions.

Grape samples were analyzed for residues of metiram, as CS 2 , using a spectrophotometry method (BASF Method 135/4) with HPLC/UV. The stated limit of quantitati on (LOQ) was 0.03 ppm for CS 2 which corresponds to approximately 0.05 ppm of metiram in all materials. Grape samples were also analyzed for residues of ETU using an HPLC method (BASF Me thod 373/2) with pulsed amperometric detection. The reported LOQ was 0.01 ppm for ETU. These methods are adequate for data collection based on acceptable concurrent method recovery data.

Maximum residues of metiram, determined as CS 2, in/on grapes harvested 35 days following the last of three broadcast foliar applications of the 55% WG form ulation for a total seasonal rate of ~2.9 lb ai/A (3,300 g ai/ha) were 1.49 ppm; see Table 9. Maximum residues of ETU were 0.015 ppm in/on the respective treated grape samples.

TABLE 9. Summary of Residue Data from Grape Field Trials with Metiram. Commodity Total Applic. Rate (lb ai/A) [g ai/ha] PHI (days) Analyte Residue Levels (ppm) 1

n Min. Max. HAFT 2 Median (STMdR) Mean (STMR) Std. Dev.

Grape, fruit 2.944 [3,300] 27-29 Metiram 7 0.98 3.50 3.50 2.24 2.24 0.82

CS 2 7 0.55 1.96 1.96 1.25 1.25 0.46
ETU 7 <0.01 0.015 0.015 0.011 0.010 0.004 Grape, fruit 2.944 [3,300] 35 3 Metiram 7 0.60 2.67 2.67 1.66 1.67 0.72
CS 2 7 0.34 1.49 1.49 0.93 0.93 0.40
ETU 7 <0.01 0.015 0.015 0.005 0.008 0.004

1 The LOQ was 0.05 ppm for metiram, 0.03 ppm for CS 2 , and 0.01 ppm for ETU; for calculating the median, mean, and standard deviation, half the LOQ was used for residues reported below th e LOQ. Residues from the three 2002 France trials, determined invalid, are not included.
2 HAFT = Highest Average Field Trial.
3 The PHI summarized reflects the stated/propos ed PHI for grapes using this formulation.

We note that in three 2002 trials conducted in France, the control samples bore high residues of CS 2 (0.12-0.61 ppm); the petitioner stat ed that the higher residues in these control samples likely resulted from applications of me tiram or mancozeb products (EBDCs ) made to the test plots just prior to the start of the study (prior to flowering); therefore, these trials were considered invalid and are not included in the data summary.

The residue decline data i ndicate that residues of CS 2 generally decreased from the 0-day PHI to the 28/29-day PHI. Residues were variable with longer PHIs; in some samples residues continued to decrease, while in others residues fluctuate d. The lowest residues typically occurred in/on samples from the 35- or 41/42-day PHIs.

Grape field trial data conclusions : The magnitude of the residue data for grapes were generated from a total of 34 field trials conducted betw een the 1999 and 2003 growing seasons in France,Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 25 of 37 Germany, Italy, and Spain. The number and location of field trials are adequate for this petition request. Varieties tested included wi ne and table varieties of grapes.

Data bracketing a 27/28/29-day PHI indicate that the maximum residues of metiram, determined as CS 2 , in/on mature grapes were: (i) 1.5 ppm fo llowing eight applications of the 55% WG formulation for a total rate of 7.4-7.7 lb ai/A; (ii) 2.6 ppm following eight applications of the 70% WG formulation for a total rate of 9.5-9.8 lb ai/A; (iii) 2.05 ppm fo llowing six applications of the 70% WG formulation for a tota l rate of 8.2-8.5 lb ai/A; a nd (iv) 1.96 ppm following three applications of the 55% WG formulation for a tota l rate of 2.9 lb ai/A. Residues of ETU in/on the respective treated samples ranged from belo w the method LOQ (<0.01 or <0.05 ppm) to 0.032 ppm. These data may be used to support the la bel PHI of 28 days in It aly pending submission of additional use pattern information. The residue data summarized a bove reflect a total application rate range of 2.9-9.8 lb ai/A.

Data bracketing a 35/36-day PHI indicate that th e maximum residues of metiram, determined as CS 2 , in/on mature grapes were: (i) 1.7 ppm fo llowing eight applications of the 55% WG formulation for a total rate of 7.4-7.7 lb ai/A; (ii) 2.2 ppm following eight applications of the 70% WG formulation for a total rate of 9.5-9.8 lb a i/A; (iii) 1.49 ppm following three applications of the 55% WG formulation for a total rate of 2.9 lb ai/A; and (iv) 2.3 ppm following three applications of the 70% WG formulation for a tota l rate of 2.9-3.0 lb ai/A. Residues of ETU in/on the respective treated samples ranged from below the method LOQ (<0.01 or <0.05 ppm) to 0.015 ppm. These data may be used to support the la bel use pattern in France which specifies a 35-day PHI and an implied maximum seasonal rate of 2.9 lb ai/A. The residue data summarized above reflect a total application rate range of 2.9-9.8 lb ai/A (1.0-3.4x th e maximum seasonal label rate in France).

Data bracketing a 54/55/56-day PHI indicate that the maximum residues of metiram, determined as CS 2 , in/on mature grapes were: (i) 1.2 ppm fo llowing eight applications of the 55% WG formulation for a total rate of 7.4-7.7 lb ai/A; (ii) 1.8 ppm following eight applications of the 70% WG formulation for a total rate of 9.5-9.8 lb ai/A; (iii) 1.81 ppm fo llowing six applications of the 70% WG formulation for a total ra te of 8.2-8.5 lb ai/A; (iv) 1.69 ppm following three applications of the 70% WG formulation for a total rate of 2.9-3.0 lb ai/A . Residues of ETU in/on the respective treated samples ranged from belo w the method LOQ (<0.01 or <0.05 ppm) to 0.012 ppm. These data may be used to support th e proposed harmonized use pattern in EU which specifies a 56-day PHI and an implied maximum seasonal rate of 4.8 lb ai/A. The residue data summarized above reflect a total application rate range of 2.9-9.8 lb ai/A (0.6-2.0x the proposed maximum harmonized seasonal rate in EU).

The aggregate of submitted residue data for grapes indicate that residues of metiram, determined as CS 2 , will support a tolerance on imported grapes of 5 ppm.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 26 of 37 860.1520 Processed Food and Feed

BASF has submitted grape processing studies which have been reviewed by HED. The Executive Summaries of study DERs are reproduced below fo llowed by a conclusion regarding the adequacy of the processing data.

Grapes

MRID 45100603

45100603.der.doc

BAS 222 28 F, a 70% wettable granular (WG) form ulation of metiram, was applied ten times as broadcast foliar spray app lications to red wine va rieties of grapes grown in France during the 1997 crop year at a target ra te of ~2.5 kg ai/ha/application (2.2 lb ai/A/application) for a total of 25 kg ai/ha (22.3 lb ai/A/application). Grapes were ha rvested 21 days after the last application. The harvested grape samples were processed into pomace, must, young wine, and mature wine using simulated commercial procedures for rosé and red wines.

Grape and its processed samples were analyzed for residues of metiram, determined as CS 2 , using a spectrophotometry method (Institut Fresenius No. IF-95/22962-00). Samples were also analyzed for residues of ETU using a HPLC/UV method (Institut Fresenius No. IF-95/24090-00) based on BASF Method No. 373. Both methods are adequa te for data collection based on acceptable concurrent method recovery data. The method LOQ was 0.05 ppm for CS 2 which corresponds to approximately 0.1 ppm of metiram in all sample materials. The method LOQ for ETU was 0.05
ppm.

The maximum storage intervals of grape (RAC) sa mples from harvest to analysis were 147 days (4.8 months) for metiram and 239 days (7.9 months ) for ETU. The maximum storage intervals of processed grape commodities for metiram anal ysis were 146-156 days (~5 months) for rosé pomace, must, young rosé wine, and red pomace; 231-241 days (~8 months) for red must and young red wine; and 365 days (12.0 months) for matu re rosé and red wine. The maximum storage intervals of processed grape commodities for ETU analysis were 330-333 days (~11.0 months) for rosé and red pomace; 287 days (9.4 months) for rosé must; 297-309 days (~10 months) for young rosé and red wine, and red must; and 316-322 days (~10.5 months) for mature rosé and red wine. Storage stability has not been ad equately demonstrated for all samples in the study. However, these data are not required because the study did not generate data for raisin and grape juice, which are the recognized processed commodities of grapes as per Table 1 of OPPTS 860.1000.

A comparison of the residues in the RAC with th ose in each processed fraction resulted in processing factors listed below; average processing factors are pr esented in parentheses. The maximum theoretical concentration factor for grapes is 5x (OPPTS GLN 860.1520, Table 1).Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 27 of 37

Processed Grape Matrix Pro cessing Factors for Metiram, Determined as CS 2 Processing Factors for ETU

Rosé pomace 0.6x, 0.8x, 1.2x , 1.4x (1.0x) 0.4x, 1.0x, 1.0x , 1.2x (0.9x) Rosé must 0.3x, 0.5x, 0.6x, 0.9x (0.6x) 0.4x, <0.8x, 1.0x, 1.0x (0.8x) Rosé young wine <0.01x, <0.02x, 0.02x, <0.03x (<0.02x) 1.3x, >3.4x, >3.2x, 4.0x (>3.0x) Rosé mature wine <0.01x, <0.02x, 0.02x, <0.03x (<0.02x) 1.4x, >3.0x, >3.2x, 4.0x (>2.9x) Red pomace 0.7x, 0.8x, 1.3x, 1.6x (1.1x) 0.6x, 1.0x, >1.7 x, >2.0x (>1.3x) Red must 0.3x, 0.5x, 0.6x, 0.6x (0.5x) 1.0x, 2.0x, >3.2, >3.8x (>2.5x) Red young wine <0.01x, <0.02x, <0.03x, 0.03x (<0.02x) 2.1x, 3.2x, >4.8x, >4.8x (>3.7x) Red mature wine <0.01x, <0.02x, <0.03x, 0.04x (<0.03x) 2.0x, 3.1x, >4.4x, >4.4x (>3.5x)

MRID 46501205

46501205.der.doc

BAS 222 28 F, a 70% wettable granular (WG) form ulation of metiram, was applied six times as broadcast foliar spray app lications to wine varieties of gr apes grown in Germany during the 2001 crop year for a total rate of 13.9 kg ai/ha (12.4 lb ai/A). Grapes were harvested 0 and 55-56 days following the last application, and grape sample s from the 55/56-day PHI were processed into must, pomace, and wine using ro sé and red wine commercial pro cedures. A subsample was also processed into raisins.

Grape and its processed samples were analyzed for residues of metiram, determined as CS 2 , using a spectrophotometry method (BASF Method 135/4) and also for resi dues of ETU using a modified version of HPLC Method 373/1 (BASF Method 373/2) with pulsed amperometric detection. Both methods are adequate for data collection based on acceptable concurrent method recovery data. The method LOQ wa s 0.03 ppm for CS 2 which corresponds to approximately 0.05 ppm of metiram in all sample materials. Th e method LOQ was 0.01 ppm for ETU.

The maximum storage interval from harvest (col lection for processed commodities) to analysis was 104 days (3.4 months) for metiram and ETU in/on grape (RAC); 36 days (1.2 months) for metiram and ETU in raisin; 8 days (0.3 months) for metiram and ETU in rosé and red wine; 41 days (1.3 months) for metiram and ETU in rosé and red must; 43 days (1.4 months) for metiram and ETU in red pomace; and 51 days (1.7 months) for metiram and 45 days (1.5 months) for ETU in rosé pomace.

Storage stability has not been demonstrated fo r all samples in the study. The 10/13/04 Residue Chemistry Chapter of the Metiram RED reported that metiram is relatively stable in/on fruits (apple and tomato) and in apple processed commodities stored frozen for up to one year; these data for metiram may be translated to grapes and its processed commodities. However, supporting storage stability data for ETU on grape processe d commodities (raisins) are required to support sample storage conditions and intervals from the cu rrent study. Because of the instability of ETU in some plant commodities, the Agency has taken the approach that storage stability data for metiram residues of concern (including ETU) are not translatable to data collected by other laboratories (see Residue Chemistr y Chapter of the Metiram RED). Therefore, HED requests theSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 28 of 37 petitioner to use the same analytical labor atory (BASF Aktiengesell schaft, Limbergerhof, Germany), which performed the analysis of samples collected from the submitted grape processing study, in the generation of the requested stor age stability data for ETU for raisins.

According to Table 1 of OPPTS 860.1000, the processed commodities of grapes requiring regulation are raisin and juice. In the current study, residue s of metiram (determined as CS 2 ) and ETU showed average processing factors of 3.3x a nd 1.7x, respectively in raisins; no data were generated for grape juice. A comparison of the re sidues in the RAC with t hose in each processed fraction resulted in processing f actors listed below; average processing factors are presented in parentheses. The maximum theoretical concen tration factor for gr apes is 5x (OPPTS GLN 860.1520, Table 1).

Processed Grape Matrix Pro cessing Factors for Metiram, Determined as CS 2 Processing Factors for ETU

Raisin 0.7x, 3.3x, 4.3x, 5.0x (3.3x) 0.8x, 1.2x, 1.3x, 3.3x (1.7x) Rosé must <0.1x, 0.1x, 0.1x, 0.2x (0.1x) <0.2x, 0.2x, 0.3x, <0.4x (<0.3x) Rosé pomace 1.8x, 2.5x, 3.6x , 3.7x (2.9x) 0.4x, 0.4x, 0.8x , 0.9x (0.6x) Rosé wine <0.1x 0.5x, 0.6x, 0.6x, 0.7x (0.6x) Red stalks 2.0x, 2.5x, 2.5x, 3.3x (2.6x) 1.2x, 1.2x, 1.3x, 2.7x (1.6x) Red must 0.1x, 0.1x, 0.1x, 0.2x (0.1x) 7.1x, 8.4x, 12.3x, 13.9x (10.4x) Red pomace 1.3x, 1.4x , 1.5x, 1.9x (1.5 x) 4.0x, 4. 4x, 5.9x, 7. 3x (5.4x) Red wine <0.1x, <0.1x, <0.01x, 0.1x (<0.1x) 7.3x, 8.7x, 13x, 13.8x (10.7x)

Grape processing data conclusions : The submitted grape processing studies are incomplete to satisfy guideline requirements because these studies did not include residue data for grape juice. According to Table 1 of OPPTS 860.1000, the regul ated processed commodities of grapes are juice and raisins. Although incomplete, the grape pr ocessing data indicate th at residues of metiram (determined as CS 2 ) and ETU concentrated by averag e processing factors of 3.3x and 1.7x, respectively, in raisins followi ng processing of the RAC (grapes) with detectable residues and using procedures simulating commer cial practices. The maximum exp ected residues of metiram in imported raisins can be calculated by multiplying the processing factor (3.3x) by the highest RAC residue value (2.6 ppm) obtained from a trial reflecting 28-day PHI which may have been conducted at an exaggerated rate pending use clarification. The product of 8.58 ppm is about equal to the proposed RAC tolerance of 8.5 ppm. Based on this calculation, HED tentatively concludes that an import tolerance for raisin need not be proposed if the RAC tolerance is assessed at 8.5 ppm.

860.1650 Submittal of Analytic al Reference Standards

Analytical standards for metiram and ETU are currently available in the National Pesticide Standards Repository. Analytical reference standards of metiram a nd ETU must be replenished as requested by the Repository. The reference standa rds should be sent to th e Analytical Chemistry Lab, which is located at Fort Meade, to the attent ion of either Theresa Cole or Frederic Siegelman at the following address:Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 29 of 37 USEPA National Pesticide Standards Repository/Analytical Chemistry Branch/OPP 701 Mapes Road Fort George G. Meade, MD 20755-5350

(Note that the mail will be returned if the extended zip code is not used.)

860.1850 Confined Accumulation in Rotational Crops 860.1900 Field Accumulation in Rotational Crops

The requirements for confined/limited rotational crop data on metiram are not needed for the purposes of this petition since bananas and grap es are perennial crops and under normal practices, there are no succeeding crops. In addition, data concerning these guidelines are not required for import tolerances.

860.1550 Proposed Tolerances

BASF Corporation requests that to lerances be established for residues of the fungicide tris[ammine [ethylenebis(dithiocarbamato)]zinc(2+)][tetrahy dro 1,2,4,7-dithiadiazocine- 3,8-dithione], polymer, metiram in/on the raw agricultural commodity as follows:

Banana ..................................................................................................... 4.0 ppm Banana, Pulp ....................................................................... 0.5 ppm Grapes .............................................................................. 8.5 ppm

The HED MARC has recommended a change in th e tolerance expression for metiram and the other EBDCs such as mancozeb and maneb with re gistered uses. Pending i nput from registrants, the EBDC tolerance expressions will be revise d to include residues of the parent EBDC only, calculated as CS 2 , rather than as zineb. Dietary exposure and risk assessments will continue to include residues of ETU, a metabolite common to all EBDCs. This change will serve to update the CFR to include only those EBDCs with registered uses, and will also allow the Agency to harmonize its EBDC tolerance definitions with Codex.

Based on HED MARC’s determination regarding the appropriate tolerance e xpression for EBDCs, the petitioner is required to submit a revised Sect ion F to include residues of the parent EBDC only, calculated as CS 2 , rather than as zineb. In addition, th e petitioner should de lete the tolerance proposal for banana pulp since the Agency does not set tolerances on banana pulp and peel.

HED has examined the residue chemistry database for metiram and reviewed the residue chemistry studies submitted by BASF in support of the request ed tolerances. Becaus e quantifiable residues of metiram were observed in/on a ll samples of bananas, the tolerance spreadsheet was used to determine the appropriate toleran ce level; residues were first converted from metiram equivalents to CS 2 equivalents. Based on the calculations in the tolerance spreadsheet, the appropriate tolerance level for bananas is 3.0 ppm. Although several deficien cies were identified, HED does not object to granting temporary import tolerances for bananas at 3.0 ppm pending resolutions of deficiencies regarding directions for use, storage stability, and th e submission of a revised SectionSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 30 of 37 F. HED does not object to establishing tolerances for grapes at 5 ppm and raisins at 10 ppm provided product labels and a revised Section F ar e submitted and confirmatory storage stability and processing studies for juice are submitted. A full resolution of these deficiencies is required before HED can recommend the establishment of permanent import tolerances. The proposed tolerances should be revised to reflect the correc t commodity definitions as specified in Table 10.

Table 10. Tolerance Summary for Metiram Commodity Proposed Tolerance (ppm) Recommended Import Tolerance (ppm) Comments/ Correct Commodity Definition

Banana 4.0 3.0 Recommendation is contingent on label revisions to make the use pattern consistent with the submitted residue field trial data. Banana Pulp 0.5 Not needed Delete from Section F. Grapes 8.5 8.5 Grape Raisin Not Proposed 10 ppm

CODEX HARMONIZATION

There are no established or proposed Codex MRLs for metiram residues per se ; however, Codex limits for dimethyldithiocarbamate fungicides are grouped under dithiocarbamates. Maximum residue limits (MRLs) for the dithiocarbamates are established for several commodities resulting from the use of mancozeb, maneb, metiram , propineb, thiram, and ziram and are currently expressed as ppm carbon disulfide. The residue definition has been harmonized with Codex. The recommended tolerance for banana, 3 ppm, cannot be harmonized with Codex because residues exceeded the Codex MRL. HED has recommende d harmonizing the proposed grape tolerance with the Codex MRL of 5 ppm. The Codex MRLs for dithiocarbamates (including metiram) are presented in Table 11. An international residue limit status sheet is attached.Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 31 of 37 Table 11. Codex MRLs for dithiocarbamates 1

. Codex Codex Comments Commodity, As Defined MRL 2 (mg/kg)
Almond hulls 20 Source of data: maneb, ziram Almonds 0.1 (*) Source of data: maneb, ziram Asparagus 0.1 Source of data: mancozeb
Banana 2 Source of data: mancozeb Barley 1 Source of data: mancozeb Barley straw and fodder, dry 25 Source of data: mancozeb, maneb Cabbages, head 5 Source of data: mancozeb, maneb
Carrot 1 Source of data: mancozeb
Cherries 1 Source of data: thiram
Cos lettuce 10 Source of data: maneb Cranberry 5 Source of data: mancozeb
Cucumber 2 Source of data: mancozeb, maneb Currants, black, red, white 10 Source of data: mancozeb, metiram 3 Edible offal (mammalian) 0.1 Source of data: mancozeb, metiram 3 Eggs 0.05 (*) Source of data: mancozeb
Garlic 0.5 Source of data: mancozeb Grapes 5 Source of data: mancozeb, metiram 3 , maneb, propineb Hops, dry 30 Source of data: metiram 3
Kale 15 Source of data: mancozeb, maneb
Leek 0.5 Source of data: mancozeb Lettuce, head 10 Source of data: mancozeb, maneb, metiram 3

Maize fodder 2 Source of data: mancozeb
Mandarins 10 Source of data: mancozeb Mango 2 Source of data: mancozeb Meat (from mammals other than marine mammals) 0.05 (*) Source of data: mancozeb, metiram 3

Melons, except watermelon 0.5 Source of data: mancozeb, propineb
Milks 0.05 (*) Source of data: mancozeb, metiram Onion, bulb 0.5 Source of data: mancozeb, propineb Oranges, sweet, sour 2 Source of data: mancozeb Papaya 5 Source of data: mancozeb Peanut 0.1 (*) Source of data: mancozeb
Peanut fodder 5 Source of data: mancozeb Pepper, sweet 1 Source of data: mancozeb, maneb Plums (including prunes) 1 Source of data: thiram

Pome fruits 5 Source of data: mancozeb, metiram 3 , propineb, thiram, ziram

Potato 0.2 Source of data: mancozeb, maneb, metiram 3 Poultry meat 0.1 Source of data: mancozeb Poultry, edible offal of 0.1 Source of data: mancozebSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 32 of 37 Codex Codex Comments Commodity, As Defined MRL 2 (mg/kg)
Pumpkins 0.2 Source of data: mancozeb Spring onion 10 Source of data: maneb Squash, summer 1 Source of data: mancozeb Sugar beet 0.5 Source of data: mancozeb, maneb Sugar beet leaves or tops 20 Source of data: mancozeb, maneb Sweet corn (corn-on-the-cob) 0.1 (*) Source of data: mancozeb

Tomato 5 Source of data: mancozeb, maneb, metiram 3 , propineb Watermelon 1 Source of data: mancozeb, maneb
Wheat 1 Source of data: mancozeb, maneb, metiram 3 Wheat straw and fodder, dry 25 Source of data: mancozeb, maneb, metiram 3 Winter squash 0.1 Source of data: mancozeb

1 Plant and animal commodities, maximum residue limits (MRLs), and source of data for residues of dithiocarbamates and ethylene thiourea (ETU) were obtained from a sear ch conducted on 2/9/00 of the FAO STAT Database, Codex Alimentarius Pesticide Residues in Food (http://apps1.fao.org/servlet/org.fao .waicent.codex.PesticideServlet).

2 All MRLs are at CXL step. An aste risk (*) signifies that the MRL was established at or about the limit of detection.
3 Shaded rows indicate that one of the so urces of data for the Codex MRL was metiram.

List of Agency Memo Citations

DP Barcode: D305910 Subject: Metiram (Chemical ID No. 014601, Case No. 0644) Revised Product and Residue Chemistry Chapters for the Reregistrati on Eligibility Decision (RED) Document. From: F. Fort To: T. Dole Dated: 10/13/04 MRIDs: None

DP Barcode: None Subject: Ethylene bisdithiocarbamates (EBDCs ): Mancozeb, Maneb, and Metiram. Outcome of the Metabolism Asse ssment Review Committee (MARC) Meeting of 1/16/02. (TXR No.0050408) From: Christina Swartz To: Yan Donovan Dated: 12/03/02 MRID(s): NoneSummary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 33 of 37 DP Barcode: D200791 Subject: Response to the Metiram Reregistrati on Standard: Plant and Livestock Metabolism Upgrades. From: R. Perfetti To: E. Saito Dated: 9/16/94 MRID(s): 43064001

Attachment: Appendix I - Tolerance Assessment Calculation International Residue Limit Status Sheet

Template Version September 2003Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 34 of 37 Appendix I. Tolerance Assessment Calculations.

The dataset used to establish a tolerance for me tiram on bananass consisted of field trial data representing an application rate of 14.4 lb ai/A (3 applications at 4.8 lb ai/A/application) with a 136-161-day PHI. As specified by the Guidance for Setting Pesticide Tolerances Based on Field Trial Data SOP, the field trial application rates and PHIs are within 25% of the maximum label application rate and minimum labe l PHI, respectively. The residue s values used to calculate the tolerance are provided in Table I-1. Because the re sidue values were reported in terms of metiram and HED has determined that tolerances fo r EBDCs should be expressed in terms of CS 2 , the residue values for bananas were converted to CS 2 equivalents using a conversion factor of 0.56 (DP Barcode D288607, 2/28/03, C. Swartz).

All 10 field trial sample results were above the L OQ. Since there were no values reported below the LOQ, maximum likelihood estimation procedures were not needed to im pute censored values.

The metiram-banana dataset was entered into the to lerance spreadsheet. Vi sual inspection of the lognormal probability plot (Figure I-1) provided in the spreadsheet indicates that the dataset is reasonably lognormal. The result from the approxima te Shapiro-Francia test statistic (Figure I-2) confirmed that the assumption of l ognormality should not be rejected.

Since the field trial data for metiram on banana s represent a small dataset (i.e., less than 15 samples) and are reasonably lognormal, the uppe r bound estimate of the 95th percentile based on the median residue value was compared to th e minimum of the 95% upper confidence limit (UCL) on the 95th percentile and the point estimate of the 99th percentile, and the minimum value was selected as the tolerance value. Using the rounding procedure as outlined in the Guidance for Setting Pesticide Tolerances Based on Field Trial Data SOP , both the 95% UCL on the 95th percentile and the point estimate of the 99 th percentile round to the va lue 4.0 ppm (Figure I-2). Because this value was the minimum value, 3.0 ppm is the recommended tolerance level for metiram, as CS 2 , on bananas.

Table I-1. Residue data used to calculate tolerance for metiram on bananas Regulator: EPA
Chemical: Metiram Crop: Bananas
PHI: 0 Days App. Rate: 12.5 – 13.9 lb ai/A
Submitter: BASF
MRID Citation: MRID 46655001 ppm CS 2 0.94

0.65

2.8

0.24

0.42Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 35 of 37

Table I-1. Residue data used to calculate tolerance for metiram on bananas Regulator: EPA
Chemical: Metiram Crop: Bananas
PHI: 0 Days App. Rate: 12.5 – 13.9 lb ai/A
Submitter: BASF
MRID Citation: MRID 46655001 ppm CS 2 0.31

0.16

0.13

0.45

0.43

0.21

0.05

0.94

0.65

2.8

**Regulator:** EPA

**Chemical:** Metiram **Crop:** Banana

**PHI:** 0 **App. Rate:** 12.5 - 13.9 **Submitter:**

**n :**  12 **min:** 0.05

**max:** 2.80 **median;** 0.37

**average:** 0.57

**95th Percentile**  **9 9th**  **Percentile 9**  **9.9th Percentile** 
**EU Method I Normal**  1.8 2.5 3.0

(3.0) (3.5) (--) **EU Method I Log Normal**  1.9 **4 .0**  9.0

**(6.0)** (16) (--) **EU Method II Distribution** 
**Free** 1.2

**California Method**  μ + **3** σ **3 .0** Summary of Analytical Chemistry and Residue Data Metiram Barcode D322230

____________________________________________________________________________________________ Page 36 of 37

**UPLMedian95th 3**  **.0**

**Approximate Shapiro-Francia**

**Normality Test Statistic** 0.9652

p-value > 0.05 : Do not reject lognormality assumption

**Lognormal Probability Plot**

99.9 99 98 95 90 80 70 50 30 20 10 5 2 1 0.1 3.0000

1.5000

0.7500

0.3750

0.1875

0.0938

0.0469 y = 1.0653x - 1.0834

R 2 = 0.9652

**Percentiles Concentrations**  **EPA Metiram Banana 0 12.5 - 13.9**Page 37 of 37 

## INTERNATIONAL RESIDUE LIMIT STATUS

CAS Name: A mixture of 5.2 parts by weight of ammoniates of [ethylenebis(dithiocarbam ato)]zinc with 1 part by weight ethylenebis [dithiocarbamic acid] bimolecular and trimolecular cyclic anhydrosulfides and disulfides Common Name: Metiram X Proposed tolerance  Reevaluated tolerance  Other Date: 1/26/2005



### Proposed EU MRLs ( Maximum Residue Limits) 

### U. S. Tolerances

 No Codex proposal step 6 or above X Codex proposal step 6 or above for the crops requested Petition Number: 9E6006 DP Barcodes: D267866 and D322230 Other Identifier: BAS 222 F

Residue definition: Codex limits for dimethyldithiocarbamate fungicides are grouped under dithiocarbamates. Reviewer/Branch: C. Olinger

Residue definition listed in Section F: In terms of the fungicide tris[ammine [ethylenebis(dithiocarbamato )]zinc(2+)][tetra-hydro 1,2,4,7-dithiadiazocine-3,8-dithione], polymer, metiram Crop (s) MRL (mg/kg) Crop(s) Tolerance (ppm)

Banana 2.0 Banana 4.0 Grapes 5.0 Banana, Pulp 0.5 Grapes 8.5



### Limits for Canada Limits for Mexico

 No Limits X No Limits for the crops requested  No Limits X No Limits for the crops requested

Residue definition: NA Residue definition: NA Crop(s) MRL (mg/kg) Crop(s) MRL (mg/kg)

Notes/Special Instructions:

Rev. 1998