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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 Chemistry 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 Boulevard, Suite 300, 

Rockville, MD 20850; submitted 1/25/2006). The document has been reviewed by the Health Effects Division (HED) 

and revised to reflect current Office of Pesticide Programs (OPP) policies. 
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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 (ethylene 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 Decision (RED) Document were issued 10/13/2004. 

According to the Residue Chemistry Chapter, apples 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 evaluated 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 Agency, Canada’s Pest Management Regulatory 

Agency (PMRA), and Mexico’s Comision Intersecretarial 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 pattern because the label does not specify the maximum 

number of applications (or total application rate) that may be made on banana crops grown in 

Central and South America per growing season. In addition ̧ the label does not provide 

information pertaining to the type 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 results of the field trial data; details 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 rates as well as the preharvest intervals for each 

European country where uses are proposed. However, the petitioner has indicated that during the 

past few years, the European Union (EU) is attempting to harmonize label uses of metiram for 

grapes grown all over Europe. The proposed harmonized grape use pattern in EU specifies: a 
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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 verify 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 maximum 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 animals is adequately understood. The Agency has 

determined that the terminal residues of concern 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 anhydrosulfides and disulfides, calculated as zinc 

ethylenebisdithiocarbamate. The HED Metabolism Assessment Review Committee (MARC) has 

recommended a change in the tolerance expression 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 CS2, 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 methodology 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 commodities. These methods are based on the 

decomposition of dithiocarbamates with release of carbon disulfide (CS2). Using these methods, 

the CS2 is swept through a trap to remove any H2S 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 methodologies are required. It was concluded in the 10/13/2004 Residue 

Chemistry Chapter that analytical methods converting all EBDCs and some metabolites to carbon 

disulfide will be considered adequate for enforcement, along with a specific method for ETU. The 

colorimetric method of Keppel (Method III in PAM Vol. 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 recovery and control data. In conjunction with the 

reregistration of other EBDCs (maneb and mancozeb), the Agency has recommended use of the 

Onley method as the official, final action method for determination of ETU residues in/on 

potatoes, spinach, apple sauce, and milk. 
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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 and its processed commodities were analyzed for 

residues of metiram, determined as CS2, 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 CS2 ranged from 0.03 to 0.05 ppm. Grapes and its processed commodities were analyzed for 

ETU using an HPLC method (BASF 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 ranged 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 validated by Agency chemists at ACB/BEAD since 

there are adequate enforcement methodology for metiram and ETU. Samples of banana were 

analyzed for residues of metiram, determined as CS2, 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 CS2). 

Adequate storage stability data for metiram are available to support the storage conditions and 

intervals of RAC samples collected from the grape and banana field 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 diverse crop matrices such as apple, peanut, potato, 

sugar beet, and tomato and in apple processed commodities 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 maximum storage interval of 

whole banana samples, from harvest to analysis, 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 stability 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 requests 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 were 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), Martinique (2 trials), and Mexico (2 trials). The 

number and locations of field trials are adequate for the purpose of establishing an import 

tolerance on bananas. The maximum residues of metiram, determined as CS2, 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 bananas, (iii) below the method LOQ (<0.03 ppm) 
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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 level; residues were first 

converted from metiram equivalents to CS2 equivalents. Based on the calculations in the tolerance 

spreadsheet, the appropriate tolerance level for bananas is 3.0 ppm. The petitioner is required to 

submit a revised Section F to delete the tolerance 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 grapes. 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 

CS2, in/on mature grapes were: (i) 1.5 ppm following 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 following six applications of the 

70% WG formulation for a total rate of 8.2-8.5 lb ai/A; and (iv) 1.96 ppm following three 

applications of the 55% WG formulation for a total rate of 2.9 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 0.032 

ppm. These data may be used to support the label PHI of 28 days in Italy pending submission of 

additional use pattern information. The residue data summarized above reflect a total application 

rate range of 2.9-9.8 lb ai/A. 

Data bracketing a 35/36-day PHI indicate that the maximum residues of metiram, determined as 

CS2, in/on mature grapes were: (i) 1.7 ppm following 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 ai/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 total 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 label 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 the maximum seasonal label rate in 

France). 

Data bracketing a 54/55/56-day PHI indicate that the maximum residues of metiram, determined as 

CS2, in/on mature grapes were: (i) 1.2 ppm following 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% 
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WG formulation for a total rate of 9.5-9.8 lb ai/A; (iii) 1.81 ppm following six applications of the 

70% WG formulation for a total rate 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 below the method LOQ (<0.01 or <0.05 ppm) to 0.012 

ppm. These data may be used to support the 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 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 registrant’s proposal, and would 

harmonize with the Codex Maximum Residue Limit for grapes. The petitioner is required to 

submit a revised Section F reflecting a tolerance of 5 ppm. 

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 regulated processed commodities of grapes are juice and raisins. Although 

incomplete, the grape processing data indicate that residues of metiram (determined as CS2) and 

ETU concentrated by average processing factors of 3.3x and 1.7x, respectively, 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 highest RAC residue value 

expressed as CS2 (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 greater 

than the recommended tolerance of 5 ppm. The registrant should submit a revised Section F 

proposing a tolerance in/on raisins of 10 ppm. 

HED will make a definitive determination regarding 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 residue data for various matrices following 

processing of wine varieties of grapes using procedures for commercial wine production. Average 

processing factors were reported for metiram (determined as CS2) 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 processing 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. 
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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 requested tolerances. Although several deficiencies 

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 the 

submission of a revised Section F. A full resolution of these deficiencies is required before HED 

can recommend the establishment of permanent import tolerances. 

Although several deficiencies were identified, HED does not object to establishing import 

tolerances for grapes at 5 ppm and raisins at 10 ppm, provided a revised 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, must include, but are not limited to, the maximum 

single application rate, the maximum annual application rate, application 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 ingredient 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 because the label does not specify the maximum 

number of applications (or total application rate) that may be made on banana crops grown in 

Central and South America per growing season. In addition ̧ the label 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 interval of 5 days and the use of a surfactant. 

If the registrant wishes to rely on the available field trial data for bananas, then label amendments 

are required to specify: (1) a maximum of ten broadcast foliar applications at 1.25 lb ai/A per 

application for a seasonal rate of 12.5 lb ai/A; and (2) a spray volume of 3 gallons per acre using 

ground equipment. If the petitioner wishes to include higher spray 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 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 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 for use on grapes, EPA requires the 

submission of revised labels to determine whether the available residue data can support the 

harmonized use patterns. If there are any deviations from the harmonized use pattern due to 

localized pest infestation or good agricultural practices, information pertaining to these deviations 

should be reported. 
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860.1380 Storage Stability

• There are inadequate storage stability data for ETU in/on bananas 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 approach that storage stability data for metiram 

residues of concern (including ETU) are not translatable to data collected by other laboratories. 

Therefore, HED requests the petitioner to use the same analytical laboratories, which performed 

the analysis of samples collected from the submitted banana field study 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 bridging grape processing study to investigate the 

potential for concentration of metiram and ETU residues in grape juice. In the requested study, the 

RAC should be processed in a manner simulating typical commercial practice. The RAC should 

have detectable residues so a concentration factor may be calculated. It is noted that juice studies 

conducted for other commodities generally have not demonstrated concentration in juice. 

860.1550 Proposed Tolerances

• Based on HED MARC’s determination regarding the appropriate tolerance expression for 

EBDCs, the petitioner is required to submit a revised Section F to include residues of the parent 

EBDC only, calculated as CS2, rather than as zineb. The petitioner should modify the value for 

grapes to 5 ppm and propose a tolerance in/on raisins at 10 ppm. 
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Background

Metiram is the common name of a pesticide which 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 anhydrosulfides and disulfides. It is a 

broad spectrum contact fungicide registered on apples, potatoes, and ornamental plants (mainly 

roses) for the prevention of downy mildews, anthracnose, rusts, leaf spots, and seedling damping 

off. Table 1 lists the test compound nomenclature for metiram. The physicochemical properties of 

the technical grade of metiram are presented in Table 2. 

Table 1. Test Compound Nomenclature.

Compound 

HN S

HN

Zn

S

S

S

HN S

HN

S

S

S

3 x

Common name Metiram 

Company experimental name BAS 222 F 

IUPAC name zinc ammoniate ethylenebis(dithiocarbamate)-poly(ethylenethiuram disulfide 

CAS name 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 

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 Value 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 insoluble (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, pKa Not applicable; titrations with acid/base will 

not yield reliable pKa values. 

Octanol/water partition coefficient, Log(KOW) 1.76-2.48 at pH 7 and 21 oC 

UV/visible absorption spectrum Not available 
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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 proposed 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 Central 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. 
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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 being 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 (equivalent to 2.0 lb ai/A) are currently registered. The petitioner 

has compiled the use pattern information for Polyram® 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 

Season1 

Single Applic. 

Rate 

Implied Max. 

Seasonal Rate 

PHI 

(days) 

Germany2 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 inadequate to allow evaluation of the residue data 

relative to the proposed foreign use pattern because the label does not specify the maximum 

number of applications (or total application rate) that may be made on banana crops grown in 

Central and South America per growing season. In addition ̧ the label 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 interval of 5 days and the use of a surfactant. 

If the registrant wishes to rely on the available field trial data for bananas, then label amendments 

are required to specify: (1) a maximum of ten broadcast foliar applications at 1.25 lb ai/A per 

application for a seasonal rate of 12.5 lb ai/A; and (2) a spray volume of 3 gallons per acre using 

ground equipment. If the petitioner wishes to include higher spray 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 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 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 for use on grapes, EPA requires the submission of 

revised labels to determine whether the available residue data can support the harmonized use 

patterns. If there are any deviations from the harmonized use pattern due to localized pest 
Summary of Analytical Chemistry and Residue Data

Metiram Barcode D322230 

____________________________________________________________________________________________ 

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infestation or good agricultural practices, information 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 metiram 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 mancozeb and maneb with registered uses (see the 

10/13/2004 Residue Chemistry Chapter). Pending input from registrants, the EBDC tolerance 

expressions will be revised to include residues of the parent EBDC only, calculated as CS2, 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. 

There are no livestock feed items associated with 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 expectation 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 methodology 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 commodities. These methods are based on the 

decomposition of dithiocarbamates with release of carbon disulfide (CS2). Using these methods, 

the CS2 is swept through a trap to remove any H2S 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 methodologies are required. It was concluded in the 10/13/2004 Residue 

Chemistry Chapter that analytical methods converting all EBDCs and some metabolites to carbon 

disulfide will be considered adequate for enforcement, along with a specific method for ETU. The 

colorimetric method of Keppel (Method III in PAM Vol. 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 recovery and control data. In conjunction with the 

reregistration of other EBDCs (maneb and mancozeb), the Agency has recommended use of the 

Onley method as the official, final action method 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 and its processed commodities were analyzed for 

residues of metiram, determined as CS2, 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 CS2 ranged from 0.03 to 0.05 ppm. Grapes and its processed commodities were analyzed for 

ETU using an HPLC method (BASF 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 ranged 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 validated by Agency chemists at ACB/BEAD since 

there are adequate enforcement methodology for metiram and ETU. Samples of banana were 

analyzed for residues of metiram, determined as CS2, 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 CS2). 

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 Volume 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 decomposed to carbon disulfide (CS2) by boiling the crop sample with 

hydrochloric acid under reducing conditions. The CS2 is distilled and absorbed in alkaline 

methanol. Residues are quantitated by photometric measurement of the xanthogenate at 302 nm. 

The LOQ is matrix dependent and is reported as the lowest concentration level validated. 

Crop samples obtained commercially were fortified with CS2 equivalents of metiram or mancozeb 

at 0.02-6.7 ppm. Adequate recoveries were obtained for residues of metiram or mancozeb, as CS2, 
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 [± coefficient of variation] for metiram were 77-93% [0.5-3.1] for apple juice 

and puree fortified at 0.020 ppm (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; and 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 ppm (LOQ) and 5.00 ppm; and 63-79% [5.8-7.4] for 

tomato juice fortified at 0.050 ppm (LOQ) and 5.00 ppm. 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 validation data for the photometry method (or earlier 

versions) were submitted in conjunction with the grape field trials and 2001 grape processing study 

for metiram using grapes fortified 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 CS2 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 ethylenethiourea (ETU), a metabolite 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, Revision #2, 8/92) discussed in the 10/13/04 

Residue Chemistry Chapter of the Metiram RED. 

Briefly, ETU residues are extracted from plant matrices 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 extract is cleaned up by liquid/liquid partitioning on 

an aluminum-oxide column. Residues are quantitated 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 LOQ (0.01 ppm) and 10-100x the LOQ. The plant 

matrices chosen for the validation study represent an oil-containing matrix (rape seed), watercontaining matrix (grape), acid-containing matrix (tomato), starch-containing matrix (potato), and 

processed product (wine); apple, lettuce, and cherry were also included as matrices. Adequate 

method recoveries were obtained from 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% acceptable 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 grapes, raisins, rosé and red pomace, and red stalks 

fortified at 0.01-0.2 ppm, rosé and red must fortified 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 samples 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 Al2O3 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) dichloromethane 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 reported 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 method 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 are available to support the storage conditions and 

intervals of RAC samples collected from the grape and banana field 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 diverse crop matrices such as apple, peanut, potato, 

sugar beet, and tomato and in apple processed commodities 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 maximum storage interval of 

whole banana samples, from harvest to analysis, 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 stability 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 requests 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 with the proposed import tolerances on banana and 

grape. Therefore, the situation described in 40 CFR 180.6(a)(3) is applicable for the purpose of this 

import tolerance petition, i.e., there is no reasonable expectation of residues being transferred to 

livestock commodities via consumption of feed items derived from crops treated with metiram 

according to the propose use directions. 

860.1500 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 followed 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 twelve banana field tests were 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 wettable 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 total rate of ~14 kg ai/ha (12.5 lb ai/A). At the two Mexico trials, 

an eleventh application was made because the samples collected after the tenth application were 

lost; total application rate at these 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 emulsifier). 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 were included in the current study submission. The 

10/13/04 Residue Chemistry Chapter of the Metiram 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 data for metiram may be translated to bananas. 

However, storage stability data for ETU on bananas 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 stability data for metiram residues of concern 

(including ETU) are not translatable to data collected by other laboratories (see Residue Chemistry 

Chapter of the Metiram RED). Therefore, HED requests the petitioner to use the same analytical 

laboratory (BASF S.A., Resende, 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 residues of metiram, determined as CS2, using a GC/MSD 

method (LAARL SOP PA.0244) and for ETU using 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 metiram and ETU in whole banana, pulp, and peel 

(0.03 ppm for CS2). The reported LOD was 0.01 ppm for each analyte. 

The maximum residues of metiram, determined as CS2, 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 bananas, (iii) below the method LOQ (<0.03 ppm) in/on pulp from bagged 

bananas, and (iv) 0.11 ppm in/on pulp from unbagged bananas. Residues of ETU were below the 
Summary of Analytical Chemistry and Residue Data

Metiram Barcode D322230 

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 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 presented 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. HAFT3 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 

CS2 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 

CS2 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 

CS2 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 

CS2 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 trials 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 CS2. The LOD is 0.01 ppm for each analyte. The minimum, 

maximum, and HAFT values are based on the LOQ. For calculating the median, mean, and 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, the study included data for banana 

peel. Residues of metiram, determined as CS2, 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 from unbagged banana. 

Banana field trial data conclusions: The number and locations of field trials are adequate for the 

purpose of establishing an import tolerance on bananas. The maximum residues of metiram, 

determined as CS2, 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 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 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. Although the proposed foreign use pattern of metiram on 

bananas has not been fully elucidated and residue 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 Agency 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

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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 conducted 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) formulation containing multiple active ingredients of 

metiram (55% ai) and pyraclostrobin (5% ai); (ii) BAS 222 28 F, a WG formulation containing a 

nominal concentration of 70% metiram as the single active ingredient; or (iii) BAS 500 00 F, an 

emulsifiable concentrate (EC) formulation containing 250 g ai/L of pyraclostrobin. For purpose of 

brevity, data from the plot treated with pyraclostrobin (BAS 500 00 F) are not further discussed or 

reviewed herein. 

For the 55% WG formulation (BAS 518 00F), a total of eight broadcast foliar applications were 

made to grape vines for a total rate of ~8,580 g ai/ha (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/ha, 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 collected at preharvest intervals 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 that 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 analysis 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 CS2, using a 

spectrophotometry method (BASF Method 135). The stated limit of quantitation (LOQ) was 0.05 

ppm for CS2 which corresponds to approximately 0.1 ppm of metiram in all sample materials. 

Grape samples were also analyzed for residues 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 based on acceptable concurrent method recovery data. 

Following applications of the 55% WG formulation (BAS 518 00F) for a total seasonal rate of 7.4-

7.7 lb ai/A, the maximum residues of metiram, determined as CS2, were 1.7 and 1.2 ppm, 
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respectively in/on mature samples of grapes collected at PHIs of 35 and 55/56 days, respectively; 

see Table 6. Following applications 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 CS2, 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 the 70% WG formulation which bore residues of 0.055 

ppm; however, this sample was harvested at the 0-day PHI. The residue decline data indicate that 

residues were generally highest at the 0-day PHI and decreased 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. HAFT2 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 

CS2 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 

CS2 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 

CS2 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 

CS2 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 

CS2 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 

CS2 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 CS2, and 0.05 ppm 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

 It was stated that this PHI reflects the beginning of commercial harvest. 

4

 The PHI summarized reflects the proposed PHI for grapes using the 70% WG. 
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2000-2001 Trials

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

BASF Corporation has submitted field trial data for metiram on grapes grown in Europe. During 

the 2000 growing season, eight grape field tests were conducted in France (2 trials), Germany (2 

trials) and Spain (4 trials). During the 2001 growing 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% wettable granule (WG) formulation (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 with a 3- to 12-day retreatment 

interval, using ground equipment in ~31-88 gal/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 samples 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. Möllerfeld GmbH (2000 trials). It 

was reported 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 stability data for ETU were submitted in support of the 2000 field 

trials; these data demonstrated that residues of ETU are relatively stable in/on grapes bearing 

weathered residues under frozen storage conditions for up to 8.5 months. 

Grape samples were analyzed for residues of metiram, as CS2, using a spectrophotometry method 

(BASF Method 135/4) with HPLC/UV detection. The stated limit of quantitation (LOQ) was 0.03 

ppm for CS2 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 acceptable concurrent method recovery data. 

Maximum residues of metiram, determined as CS2, in/on grapes harvested 54-56 days following 

the last of six broadcast foliar applications of the 70% WG formulation for a total seasonal rate of 

8.2-8.5 lb ai/A were 1.81 ppm; see Table 7. Maximum residues of ETU were 0.05 ppm in/on the 

respective treated grape samples. The residue decline data indicate that residues of metiram, as 

CS2, 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). The 
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highest residues typically occurred 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. HAFT2 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 

CS2 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 

CS2 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 CS2, 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 for metiram on grapes grown in Europe. A total 

of three grape field trials were conducted during the 2001 growing season 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 Italy (1 trial). Each field test consisted of one 

untreated plot and one treated plot. Grape vines received three broadcast 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). All applications were made with 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 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 from harvest to analysis was 84 days (2.8 months) 

for metiram and 85 days (2.8 months) for ETU. No storage stability data on grapes were included 

in the grape residue study. However, it was reported 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 stability data for ETU were 

submitted in support of the 2000 field trials (see DER for MRID 46501201); these data 

demonstrated that residues of ETU are relatively stable in/on grapes bearing weathered residues 

under frozen storage conditions for up to 8.5 months. 

Grape samples were analyzed for residues of metiram, determined as CS2, 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 CS2 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 373/2) with pulsed amperometric 
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detection. The reported LOQ was 0.01 ppm for ETU. Both methods are adequate for data 

collection based on acceptable concurrent method recovery data. 

Maximum residues of metiram, as CS2, in/on grapes harvested 56 days following the last of three 

broadcast foliar applications of the 70% WG formulation for a total seasonal rate of 2.96-3.00 lb 

ai/A were 1.69 ppm; see Table 8. Maximum residues of ETU were 0.012 ppm in/on the respective 

treated grape samples. The residue decline data indicate that residues of CS2 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 (62 days) in one trial. The lowest residues 

typically occurred in/on samples 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. HAFT2 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 

CS2 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 

CS2 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 CS2, and 0.01 ppm 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. 

2002- 2003 Trials

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

BASF Corporation has submitted field trial data for 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 varieties of grapes. During the 2003 growing season, three grape field 

tests were conducted on wine varieties 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) formulation 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 pyraclostrobin active ingredient are not 

reviewed herein. All applications were made with 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 after the last application (DALA), which was stated 

as the intended PHI for this formulation in France. To generate residue decline data, additional 

grape samples were collected from the treated plot at 0, 27-29, and 41-42 DALA. 

The maximum storage interval of grape samples from 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 included 
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in the current study submissions. However, it was reported in the 10/13/04 Residue Chemistry 

Chapter of the Metiram RED that 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. 

Grape samples were analyzed for residues of metiram, as CS2, using a spectrophotometry method 

(BASF Method 135/4) with HPLC/UV. The stated limit of quantitation (LOQ) was 0.03 ppm for 

CS2 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 373/2) 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 CS2, in/on grapes harvested 35 days following the 

last of three broadcast foliar applications of the 55% WG formulation 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. HAFT2 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 

CS2 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 

CS2 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 CS2, and 0.01 ppm for ETU; for calculating the median, mean, and standard 

deviation, half the LOQ was used for residues reported below the 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/proposed PHI for grapes using this formulation. 

We note that in three 2002 trials conducted in France, the control samples bore high residues of 

CS2 (0.12-0.61 ppm); the petitioner stated that the higher residues in these control samples likely 

resulted from applications of metiram 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 indicate that residues of CS2 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 fluctuated. 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 between the 1999 and 2003 growing seasons in France, 
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Germany, Italy, and Spain. The number and location of field trials are adequate for this petition 

request. 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 

CS2, in/on mature grapes were: (i) 1.5 ppm following 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 following six applications of the 

70% WG formulation for a total rate of 8.2-8.5 lb ai/A; and (iv) 1.96 ppm following three 

applications of the 55% WG formulation for a total rate of 2.9 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 0.032 

ppm. These data may be used to support the label PHI of 28 days in Italy pending submission of 

additional use pattern information. The residue data summarized above reflect a total application 

rate range of 2.9-9.8 lb ai/A. 

Data bracketing a 35/36-day PHI indicate that the maximum residues of metiram, determined as 

CS2, in/on mature grapes were: (i) 1.7 ppm following 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 ai/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 total 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 label 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 the maximum seasonal label rate in 

France). 

Data bracketing a 54/55/56-day PHI indicate that the maximum residues of metiram, determined as 

CS2, in/on mature grapes were: (i) 1.2 ppm following 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 following six applications of the 

70% WG formulation for a total rate 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 below the method LOQ (<0.01 or <0.05 ppm) to 0.012 

ppm. These data may be used to support the 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 CS2, will support a tolerance on imported grapes of 5 ppm. 
Summary of Analytical Chemistry and Residue Data

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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 followed 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) formulation of metiram, was applied ten times as 

broadcast foliar spray applications to red wine varieties of grapes grown in France during the 1997 

crop year at a target rate 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 harvested 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 CS2, 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 adequate for data collection based on acceptable 

concurrent method recovery data. The method LOQ was 0.05 ppm for CS2 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) samples 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 analysis 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 mature 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 adequately 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 those in each processed fraction resulted in 

processing factors listed below; average processing factors are presented in parentheses. The 

maximum theoretical concentration factor for grapes is 5x (OPPTS GLN 860.1520, Table 1). 
Summary of Analytical Chemistry and Residue Data

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Processed Grape Matrix Processing Factors for Metiram, 

Determined as CS2

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, >1.7x, >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) formulation of metiram, was applied six times as 

broadcast foliar spray applications to wine varieties of grapes 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 samples from the 55/56-day PHI were processed into 

must, pomace, and wine using rosé and red wine commercial procedures. A subsample was also 

processed into raisins. 

Grape and its processed samples were analyzed for residues of metiram, determined as CS2, using 

a spectrophotometry method (BASF Method 135/4) and also for residues 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 was 0.03 ppm for CS2 which corresponds to approximately 0.05 ppm of metiram 

in all sample materials. The method LOQ was 0.01 ppm for ETU. 

The maximum storage interval from harvest (collection 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 for 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 processed commodities (raisins) are required to support 

sample storage conditions and intervals from the current 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 Chemistry Chapter of the Metiram RED). Therefore, HED requests the 
Summary of Analytical Chemistry and Residue Data

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petitioner to use the same analytical laboratory (BASF Aktiengesellschaft, Limbergerhof, 

Germany), which performed the analysis of samples collected from the submitted grape processing 

study, in the generation of the requested storage 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, residues of metiram (determined as CS2) and 

ETU showed average processing factors of 3.3x and 1.7x, respectively in raisins; no data were 

generated for grape juice. A comparison of the residues in the RAC with those in each processed 

fraction resulted in processing factors listed below; average processing factors are presented in 

parentheses. The maximum theoretical concentration factor for grapes is 5x (OPPTS GLN 

860.1520, Table 1). 

Processed Grape Matrix Processing Factors for Metiram, 

Determined as CS2

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 (1.5x) 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 regulated processed commodities of grapes are 

juice and raisins. Although incomplete, the grape processing data indicate that residues of metiram 

(determined as CS2) and ETU concentrated by average processing factors of 3.3x and 1.7x, 

respectively, 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 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 Analytical Reference Standards 

Analytical standards for metiram and ETU are currently available in the National Pesticide 

Standards Repository. Analytical reference standards of metiram and ETU must be replenished as 

requested by the Repository. The reference standards should be sent to the Analytical Chemistry 

Lab, which is located at Fort Meade, to the attention 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 grapes 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 tolerances be established for residues of the fungicide tris[ammine 

[ethylenebis(dithiocarbamato)]zinc(2+)][tetrahydro 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 the tolerance expression for metiram and the 

other EBDCs such as mancozeb and maneb with registered uses. Pending input from registrants, 

the EBDC tolerance expressions will be revised to include residues of the parent EBDC only, 

calculated as CS2, 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 expression for EBDCs, 

the petitioner is required to submit a revised Section F to include residues of the parent EBDC 

only, calculated as CS2, rather than as zineb. In addition, the petitioner should delete 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 requested tolerances. Because quantifiable residues 

of metiram were observed in/on all samples of bananas, the tolerance spreadsheet was used to 

determine the appropriate tolerance level; residues were first converted from metiram equivalents 

to CS2 equivalents. Based on the calculations in the tolerance spreadsheet, the appropriate 

tolerance level for bananas is 3.0 ppm. Although several deficiencies 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 the submission of a revised Section 
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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 are 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 correct 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 recommended 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

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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: mancozeb 
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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 search 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 asterisk (*) signifies that the MRL was established at or about the limit of 

detection. 3

 Shaded rows indicate that one of the sources 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 Reregistration 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 Assessment Review Committee (MARC) 

Meeting of 1/16/02. (TXR No.0050408) 

From: Christina Swartz 

To: Yan Donovan 

Dated: 12/03/02 

MRID(s): None 
Summary of Analytical Chemistry and Residue Data

Metiram Barcode D322230 

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DP Barcode: D200791 

Subject: Response to the Metiram Reregistration 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 2003
Summary of Analytical Chemistry and Residue Data

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Appendix I. Tolerance Assessment Calculations.

The dataset used to establish a tolerance for metiram 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 label PHI, respectively. The residues values used to calculate the 

tolerance are provided in Table I-1. Because the residue values were reported in terms of metiram 

and HED has determined that tolerances for EBDCs should be expressed in terms of CS2, the 

residue values for bananas were converted to CS2 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 LOQ. Since there were no values reported below 

the LOQ, maximum likelihood estimation procedures were not needed to impute censored values. 

The metiram-banana dataset was entered into the tolerance spreadsheet. Visual inspection of the 

lognormal probability plot (Figure I-1) provided in the spreadsheet indicates that the dataset is 

reasonably lognormal. The result from the approximate Shapiro-Francia test statistic (Figure I-2) 

confirmed that the assumption of lognormality should not be rejected. 

Since the field trial data for metiram on bananas represent a small dataset (i.e., less than 15 

samples) and are reasonably lognormal, the upper bound estimate of the 95th percentile based on 

the median residue value was compared to the 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 99th percentile round to the value 4.0 ppm (Figure I-2). 

Because this value was the minimum value, 3.0 ppm is the recommended tolerance level for 

metiram, as CS2, 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 CS2

0.94 

0.65 

2.8 

0.24 

0.42 
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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 CS2

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 

99th 

Percentile 

99.9th 

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 

DistributionFree 

 1.2 

California 

Method 

μ + 3σ

3.0
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UPLMedian95th 3.0

 

Approximate Shapiro-Francia 

Normality Test Statistic 

0.9652 

p-value > 0.05 : Do not reject 

lognormality assumption 

Lognormal Probability Plot

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

3.0000

1.5000

0.7500

0.3750

0.1875

0.0938

0.0469

y = 1.0653x - 1.0834

R2

 = 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