Acetamiprid Summary of Analytical Chemistry and Residue Data DP#s: 364833 & 366269 

Page 1 of 38

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C. 20460

OFFICE OF PREVENTION, PESTICIDE

AND TOXIC SUBSTANCES

MEMORANDUM

Date: October 14, 2009

SUBJECT: Acetamiprid. Request for Label Amendments for New Uses on Clover; Small 

Vine Climbing Fruits, except Kiwifruit, Subgroup 13-07F (amending grape use);

Greenhouse-grown Tomatoes; and a Regional Registration for Tea. Summary of 

Analytical Chemistry and Residue Data.

PC Code: 099050 DP Barcode: D364833, D366269

Decision No.: 408298 Registration Nos.: 8033-23, 8033-36, 8033-94

Petition No.: 9E7544 Regulatory Action: Amended Section 3 &

 Regional Registration for Tea

Risk Assessment Type: NA Case No.: NA

TXR No.: NA CAS No.: 135410-20-7

MRID Nos.: 47716901, 47716902, 

 47716903, 47781201

40 CFR: §180.578

FROM: Dennis McNeilly, Chemist

 Risk Assessment Branch II (RAB2)

 Health Effects Division (HED) (7509P)

THROUGH William Drew, Chemist

 Risk Assessment Branch II (RAB2)

 Health Effects Division (HED) (7509P)

and

 Christina Swartz, Chief

Richard A. Loranger, Ph.D., Senior Scientist

 Risk Assessment Branch II (RAB2)

 Health Effects Division (HED) (7509P)

TO: Barbara Madden, Team 05

RIMUERB

Registration Division (RD) (7505P)

This document was originally prepared under contract by Dynamac Corporation (1901 Research Boulevard, Suite 

220; Rockville, MD 20850). The document has been reviewed by the Health Effects Division (HED) and revised to 

reflect current Office of Pesticide Programs (OPP) policies
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 2 of 38

Executive Summary

Acetamiprid is a selective insecticide intended for use against various sucking/chewing insect 

pests that feed upon field, fruit, and vegetable crops. Acetamiprid is registered for foliar 

application to cotton, leafy vegetables, cole (Brassica) vegetables, fruiting vegetables, tuberous 

and corm vegetables, citrus fruits, pome fruits, cucurbit vegetables, stone fruits, tree nuts, berries,

bulb vegetables, succulent legume vegetables and grapes, and for seed treatment of canola and 

mustard seeds.

The Interregional Research Project Number 4 (IR-4) has submitted amended Section 3 

registration requests for new uses of acetamiprid on clover grown for seed, small vine climbing 

fruits, except kiwifruit, subgroup 13-07F (amending established grape uses), greenhouse-grown

tomatoes, and tea. The end-use products associated with this action include: (i) Assail® 30SG 

Insecticide (EPA Reg. No. 8033-36), a 30% active ingredient (ai) soluble granule (SG) 

formulation; (ii) Assail® 70WP Insecticide (EPA Reg. No. 8033-23), a 70% ai wettable powder 

(WP) formulation; and (iii) Tristar® 30SG Insecticide (EPA Reg. No. 8033-94), a 30% ai SG

formulation. 

For clover, Assail® 30SG and Assail® 70WP are proposed for a single postemergence broadcast 

foliar application at a maximum of 0.075 lb ai/A with a 28-day preharvest interval (PHI); the 

proposed use is limited to clover grown in ID, OR, and WA only. For grapes, a change to the 

registered use pattern is proposed. The current label permits up to two foliar applications on 

grapes at 0.05 lb ai/A/application for a maximum seasonal rate of 0.1 lb ai/A with a 7-day PHI. 

The requested new use on grapes (and small vine climbing fruits, except kiwifruit, subgroup 13-

07F) will permit up to two foliar applications of Assail® 30SG and Assail® 70WP at 0.1 lb 

ai/A/application for a seasonal rate of 0.2 lb ai/A with a 3-day PHI. For tomatoes, a new use on 

greenhouse-grown tomatoes is proposed. The current Assail® 30SG and Assail® 70WP labels

permit up to four foliar applications on field-grown tomatoes at 0.075 lb ai/A/application for a 

maximum seasonal rate of 0.3 lb ai/A with a 7-day PHI. The requested new use on tomatoes will 

add a greenhouse use pattern using Tristar® 30SG, with a maximum of two applications at 0.075 

lb ai/A/application (based on 10,000 plants per acre) for a maximum seasonal rate of 0.15 lb 

ai/A, applied via chemigation with a 1-day PHI. No use directions were proposed for the 

domestic use on tea grown in South Carolina. The following GAP information was provided for 

the 20% SP formulation in Japan: one application at 0.10-0.40 kg ai/ha applied in 2000-4000 

L/ha, with a 14-day PHI. Application rate GAP information for India were not provided;

however, the residue data conducted in India were a single application of 0.022 lb ai/A (0.025 kg 

ai/ha) or 0.045 lb ai/A (0.050 kg ai/ha). The shoots along with bud are (reportedly) typically

harvested at a 7-day PHI in India.

Concurrently, IR-4 has proposed the establishment of permanent tolerances for residues of 

acetamiprid in or on the raw agricultural commodities (RACs) listed below. 

Clover, forage...........................................................0.10 ppm

Clover, hay...............................................................0.01 ppm

Fruit, small, vine climbing, except fuzzy kiwifruit,

 subgroup 13-07F ...................................................0.35 ppm

Tea ........................................................................ 50.0 ppm
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 3 of 38

Tolerances have been established under 40 CFR §180.578 (a)(1) for residues of the insecticide 

acetamiprid, ranging from 0.01 to 20 ppm in/on canola seed, cotton matrices, and various fruits, 

nuts, and vegetables. Tolerances for the combined residues of acetamiprid and N1-[(6-chloro-3-

pyridyl)methyl]-N2-cyano-acetamidine have also been established for livestock commodities 

(ruminants and poultry) ranging from 0.01 to 0.20 ppm under 40 CFR §180.578(a)(2). 

Compliance with the tolerance levels listed in 40 CFR §180.578 is to be determined by

measuring only acetamiprid for plant commodities, and acetamiprid and its IM-2-1 metabolite for 

animal commodities as quantitated by the GC/ECD and LC/MS/MS analytical enforcement 

methods. 

HED has previously determined that the nature of the residue in plants and animals is adequately

understood. The residue of concern in plants is acetamiprid for both tolerance enforcement and 

risk assessment purposes. The residues of concern in livestock commodities for tolerance 

expression are acetamiprid plus its IM-2-1 metabolite. For the purpose of risk assessment, the 

residues of concern in livestock commodities (except ruminant muscle) are acetamiprid plus its 

IM-2-1 metabolite. In ruminant muscle, the residues of concern for risk assessment are 

acetamiprid plus IM-2-1 plus IM-2-1-amide.

The proposed use on clover could theoretically lead to the secondary transfer of acetamiprid 

residues of concern to beef and dairy cattle from the feeding of clover forage, hay, and silage. 

However, the proposed use on clover grown for seed is restricted to clover grown in ID, OR, and 

WA and the residues in or on the animal feed items are very low. Therefore, HED does not 

believe that the proposed use on clover would significantly increase the dietary burdens, and the

established tolerances in milk, meat, and meat byproducts need not be reassessed for the purpose 

of this petition.

Adequate gas chromatograph with electron capture detection (GC/ECD) and high performance 

liquid chromatography with ultraviolet detection (HPLC/UV) residue analytical methods are 

available for the enforcement of established tolerances on plant commodities. The method limits 

of quantitation (LOQ) are 0.01 ppm for vegetables and non-citrus fruits (GC/ECD), and 0.050 

ppm for citrus fruits (HPLC/UV). A secondary liquid chromatography with tandem mass 

spectrometric detection (LC/MS/MS) method, designated by the petitioner as an alternative to the 

established GC/ECD tolerance enforcement method, has been determined suitable for tolerance 

enforcement, and confirmatory analysis of vegetables and non-citrus fruits. The GC/ECD 

method or LC/MS/MS Method #KP-216R1 (or its modification) was used for the analysis of 

samples from the clover, grape, and tomato field trials. Acceptable recoveries were obtained in 

method validation efforts conducted prior to the analysis of field trial samples.

In a Japanese study, dried green tea leaves and brewed tea were analyzed for combined residues 

of acetamiprid and metabolites convertible to 6-chloronicotinic acid (Metabolite IC-0) using a 

common moiety GC/ECD method. Briefly, dried tea leaves were homogenized, soaked in water, 

and then extracted with methanol. Brewed tea was simply filtered. The resulting 

extracts/filtrates were partitioned with hexane, and the aqueous layer was subjected to base 

hydrolysis. Acetamiprid and metabolites were then converted to 6-chloronicotinic acid by

oxidation, then methylated (procedure not specified) and purified by silica column 

chromatography prior to GC/ECD analysis. The reported method LOD was 0.05 ppm as 

acetamiprid. In India, samples of green shoots, dried black tea leaves, brewed tea, and spent 

leaves were analyzed for residues of acetamiprid using an HPLC/UV method. The reported LOD 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 4 of 38

was also 0.05 ppm.

Adequate multiresidue methods testing data have been submitted. These data indicate that the 

multiresidue methods are not appropriate for determining residues of acetamiprid. 

The available storage stability data for acetamiprid on representative crops, and the concurrent 

storage stability data for clover and tomato are adequate to support the submitted clover, grape, 

tomato, and tea field trials.

The use pattern of the clover field trials adequately reflects the proposed label use pattern with 

the exception of the PHI for hay. The available field trial data indicate a regional tolerances for 

residues of acetamiprid in clover forage at 0.10 ppm and clover hay at 0.01 ppm, are appropriate. 

However, the submitted clover field trial data are not completely adequate to satisfy data 

requirements. The three clover field trials were all conducted in Zone 11 (OR) at the same 

location and within a very short time period of each other. Two additional clover field trials are 

required, as confirmatory data. In addition, the submitted residue data included field trial data for 

only the 70WP formulation. However, since the requested PHI is for 28 days (generally bridging 

data are required if the proposed PHI is less than or equal to 7 days), additional residue chemistry

field trial data are not required to support registration of the 30SG formulation. Use on clover 

grown for seed is to be limited to clover grown in ID, OR, and WA. Since the residue chemistry

data submitted for clover hay reflect PHIs of between 56-63 days, the PHI for clover should be 

increased to 56 days for any crop harvested as clover hay.

The submitted grape residue data included field trial data for only the 70WP formulation (the 

original field trials also used a 70WP formulation). Since the requested PHI for grape is for 3 

days, additional residue chemistry field trial data are needed to support registration of the 30SG 

formulation. As a condition of registration, HED requests that three side-by-side field trials be 

conducted and submitted to determine if residues are comparable for the two different 

formulations. In addition, the submitted grape field trials were not conducted using an adjuvant. 

The label for Assail® 30SG (EPA Reg. No. 8033-36) should be revised to remove the use of a 

spreader, methylated seed oil or crop oil from the product label, unless an adjuvant is used in the 

side-by-side testing. The number and locations of the field trials for the 70WP formulation are in 

accordance with OPPTS Guideline 860.1500 for grapes, and the use pattern of the field trials 

reflects the use pattern proposed for grapes (and other climbing vine small fruits, except fuzzy

kiwifruit, within subgroup 13-07F), except for the adjuvant use. As the representative crop of the 

fruit, small, vine climbing, except fuzzy kiwifruit, subgroup 13-07F, the available grape field 

trial data from the current submission, which reflect a higher seasonal rate and a shortened PHI

from that which is currently registered, will support a tolerance for residues of acetamiprid in 

“fruit, small, vine climbing, subgroup 13-07F, except fuzzy kiwifruit” at 0.35 ppm. The 

established individual tolerance for grape at 0.20 ppm should be concomitantly removed upon 

establishment of the subgroup 13-07F tolerance.

The application rate used in the submitted tomato residue data for the proposed greenhouse use

was 2x the proposed seasonal rate for the greenhouse tomato use. The three trials conducted are 

adequate with respect to the number of trials. Although the greenhouse trials were conducted at a 

2x application rate, no additional residue data will be required to support the proposed 

greenhouse use pattern for tomatoes provided the use is limited to the 70WP product (conditional 

data needed for SG formulation). The available tomato greenhouse trial data indicate that the 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 5 of 38

established tolerance for residues of acetamiprid in fruiting vegetables (Crop Group 8) at 0.20 

ppm will not be exceeded following applications of the Assail 70WP formulation of acetamiprid 

according to the use patterns of the tomato greenhouse trials. No residue data were provided for 

the proposed use of Tristar® 30SG on greenhouse tomatoes, the only formulation requested for 

this use on greenhouse tomatoes. HED does have side-by-side formulation trials (WP and 

soluble liquid formulation) for acetamiprid in undelinted cottonseed and cotton gin byproducts. 

These data indicate that residue levels are comparable for the two different formulation, i.e., WP 

and soluble liquid. In view of these data and the 70WP data reflecting 2x the seasonal rate, HED 

requests submission of only one side-by-side formulation trial (rather than the normal three sideby-side trials) to support the use of Tristar® 30SG on greenhouse tomatoes as a condition of 

registration. 

The submitted magnitude of the residue data for tea reflect application of a 20% SP formulation 

of acetamiprid to green tea grown in Japan at 0.13 lb ai/A (0.15 kg ai/ha) and 0.27 lb ai/A (0.30 

kg ai/ha) and to black tea grown in India at 0.022 lb ai/A (0.025 kg ai/ha) and 0.045 lb ai/A 

(0.050 kg ai/ha). Samples of tea leaves (and shoots) were harvested at PHIs of 7, 14, and 21 

days in the Japan study and 0, 1, 3, 5, 7, 9, 11, 15, and 21 days in the India study and were 

processed into dried tea leaves and brewed tea; spent tea leaves were also analyzed in the India 

study. Acceptable methods were used for quantitating residues of acetamiprid and metabolites 

determined as acetamiprid. No U.S. residue field trial data were submitted and proposed 

domestic use directions were not provided. At least one U.S. field trial study is required to 

establish a tolerance for domestic use of acetamiprid on tea. At this time HED can recommend 

for a 50 ppm tolerance on tea with no U.S. registration.

An acceptable grape processing study was previously reviewed, which reported processing 

factors of 1.5x for juice and 0.9x for raisins. Based on these data, no tolerances are needed for 

juice or raisins as a result of the proposed use, because any residues in these commodities are 

expected to be less than the RAC tolerance.

An acceptable tomato processing study was also previously reviewed, which reported processing 

factors of 1.4x for puree and 3.0x for paste. Based on the observed processing factor of 3.0x and 

a HAFT of 0.1 ppm, a tolerance of 0.40 ppm was established for residues of acetamiprid in 

tomato paste. A tolerance was not needed for puree because any expected residues in puree 

would be less than the RAC tolerance. The proposed use on greenhouse-grown tomatoes will not 

change the expected residues in puree or paste. 

An acceptable confined rotational crop study is available. HED has determined that the residue 

of concern in rotational crops is parent only, and that tolerances would not be needed on 

rotational crops. The available confined rotational crop data indicate that field rotational crop 

studies and label restrictions for rotational crops are not required to support the proposed uses.

An analytical standard for acetamiprid is currently available in the National Pesticide Standards 

Repository. However, analytical standards for the IM-2-1 and IM-2-1-amide metabolites are not 

available at the Repository. Analytical reference standards of these metabolites should be 

supplied and supplies replenished as requested by the Repository.

 

Regulatory Recommendations and Residue Chemistry Deficiencies
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 6 of 38

HED has examined the residue chemistry database for acetamiprid. Pending submission of

revised Section B (see requirements under Directions for Use) and analytical reference standards 

(see requirements under Submittal of Reference Standards), there are no residue chemistry issues 

that would preclude granting a conditional registration for the requested uses of acetamiprid. The 

data that HED recommends be required as a condition of registration are specified below. 

Provided that the forthcoming human health risk assessment does not identify any issues of 

concern, the submitted data support the establishment of permanent tolerances for acetamiprid, 

including its metabolites and degradates, under 40 CFR §180.578, as listed below. Compliance 

with tolerance levels specified below is to be determined by measuring acetamiprid only.

Clover, forage*.........................................................0.10 ppm

Clover, hay*.............................................................0.01 ppm

Fruit, small, vine climbing, subgroup 13-07F,

 except fuzzy kiwifruit .........................................0.35 ppm

Tea**......................................................................50.0 ppm

* Tolerances with regional restrictions [40 CFR §180.578(c)].

** Tolerance without a U.S. registration.

The established individual tolerance for grape at 0.20 ppm should be concomitantly removed 

upon establishment of the subgroup 13-07F tolerance. 

No change is needed with regard to the established tolerance for residues of acetamiprid in 

fruiting vegetables (Crop Group 8) at 0.20 ppm as a result of adding greenhouse use on tomatoes.

860.1200 Directions for Use

Because the grape field trial data submitted with this petition did not reflect the use of a 

surfactant in the application sprays, the label directions regarding use of a spreader, methylated 

seed oil or crop oil should be removed from the product label of Assail® 30SG (EPA Reg. No. 

8033-36).

The PHI for clover harvested for hay should be increased to 56 days on the 30SG and 70WP 

labels.

Use directions for the domestic use of acetamiprid on tea were not submitted. HED cannot 

evaluate the data without proposed use directions for acetamiprid use on tea in South Carolina. 

GAP information was provided for Japan and India. The use directions are adequate to establish 

a tolerance without U.S. registrations (an “import” tolerance). 

860.1650 Submittal of Analytical Reference Standards

Analytical standards for the IM-2-1 and IM-2-1-amide metabolites are not available at the 

Repository and should be supplied. The reference standards should be sent to the Analytical 

Chemistry Lab, which is located at Fort Meade, to the attention of Theresa Cole at the following 

address:
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 7 of 38

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.)

860.1550 Proposed Tolerances

The final tolerances for subgroup 13-07F should reflect the correct commodity definition as 

specified in Table 8. A revised Section F is no needed for this minor change. The established 

individual tolerance for grape at 0.20 ppm should be concomitantly removed with establishment 

of the subgroup 13-07F tolerance.

Conditional Data Requirements

 Two clover field trials reflecting the same use pattern utilized in the submitted studies.

 Three side-by-side field trials on grapes to demonstrate that residues from the 30SG 

formulation are comparable to or less than those from the 70WP product. The spray in 

the plots for the SG formulation should contain adjuvant (spreader, methylated seed oil, 

or crop oil) if a label statement recommending such additives is desired.

 One side-by-side greenhouse trial on tomatoes to demonstrate that residues from the SG 

formulation are comparable to or less than those from the 70WP product.

Background

The nomenclature of acetamiprid and its metabolites is summarized in Table 1, and the 

physicochemical properties of acetamiprid are summarized in Table 2.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 8 of 38

Table 1. Acetamiprid Nomenclature.

Chemical Structure

Common Name Acetamiprid

Molecular Formula C10H11ClN4

Molecular Weight 222.68

Company Experimental Name EXP-61842A, AEF124370, NI-25

IUPAC Name (E)-N 1-[(6-chloro-3-pyridyl)methyl]-N

2

-cyano-N 1-methylacetamidine

CAS Name (1E)-N-[(6-chloro-3-pyridinyl)methyl]-N'-cyano-N-methylethanimidamide

CAS Registry Number 135410-20-7

End-use Products (EPs) Assail® 30SG (30% SG; EPA Reg. No. 8033-36)

Assail® 70WP (70% WP; EPA Reg. No. 8033-23)

Tristar® 30SG (30% SG; EPA Reg. No. 8033-94)

Chemical Structure of 

Acetamiprid Metabolite 

IM-2-1

N 1-[(6-chloro-3-pyridyl)methyl]-N

2

-cyano-acetamidine

Chemical Structure of 

Acetamiprid Metabolite 

IM-2-1-amide 

(also referred to as IM-2-2)

N

2

-aminocarbonyl-N 1-[(6-chloro-3-pyridyl)methyl]acetamidine

Table 2. Physicochemical Properties of Technical-Grade Acetamiprid.

Parameter Value Reference

Melting Point/Range (C) 98.9 DP# 328216, W. Drew, 10/23/2007

pH 6.08 (Aqueous solution at 20C)

Density (g/cm3) 1.33 (at 20C)

Water Solubility (g/L) 4.25 (at 25C)

Solvent Solubility (at 25C) Acetone >20 g/100 g

Methanol >20 g/100 g

Ethanol >20 g/100 g

Dichloromethane >20 g/100 g

Chloroform >20 g/100 g

Acetonitrile >20 g/100 g

Tetrahydrofuran >20 g/100 g

Benzene 2.44 g/100 g

Xylene 4.01 g/100 g

n-Hexane 6.54 ppm

Carbon disulfide 507 ppm

N N

CH3

Cl

CH3

N

CN

N N

H

Cl

CH3

N

CN

N N

H

Cl

CH3

N

O

NH2
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 9 of 38

Table 2. Physicochemical Properties of Technical-Grade Acetamiprid.

Parameter Value Reference

Vapor Pressure (mm Hg) 7.5 x 10-9

(at 25C) DP# 264154, M. Doherty; 12/31/2001

Dissociation Constant, pKa 0.7 (at 25C) DP# 328216, W. Drew, 10/23/2007

Octanol/Water Partition 

Coefficient, Log KOW

0.8 (at 25C)

UV/Visible Absorption Spectrum Not available

860.1200 Directions for Use

A list of acetamiprid end-use products (EPs) relevant to this registration action is presented 

below in Table 3. All listed EPs are registered to Nippon Soda Co., Ltd. (c/o Nisso America, 

Inc.). 

Table 3. List of Acetamiprid End-Use Products Associated with PP#9E7544.

Trade Name Reg. No. ai (% of formulation) Formulation Type Label Date

Assail® 30SG Insecticide 8033-36 30% by wt Soluble granule 3/4/2009 (draft)

Assail® 70WP Insecticide 8033-23 70% by wt Wettable powder 3/4/2009 (draft)

Tristar® 30SG Insecticide 8033-94 30% by wt Soluble granule 3/4/2009 (draft)

A summary of the proposed or amended use patterns is presented in Table 4. For clover, new use 

is proposed for Assail® 30SG and Assail® 70WP. For grapes, a change to the registered use 

pattern is proposed. The current labels permit up to two foliar applications on grapes at 0.05 lb 

ai/A/application for a maximum seasonal rate of 0.1 lb ai/A with a 7-day preharvest interval 

(PHI). The requested new use on grapes (and small vine climbing fruits, except kiwifruit, 

subgroup 13-07F) will permit up to two applications of Assail® 30SG or Assail® 70WP at 0.1 lb 

ai/A/application for a seasonal rate of 0.2 lb ai/A with a 3-day PHI. For tomatoes, new use is 

proposed for greenhouse-grown tomatoes. The current Assail® 30SG and Assail® 70WP labels

permit up to four foliar applications on field-grown tomatoes at 0.075 lb ai/A/application for a 

maximum seasonal rate of 0.3 lb ai/A with a 7-day PHI. The requested new use on tomatoes will 

add a greenhouse use pattern for Tristar® 30SG, with a maximum of two applications (reduced 

from four for resistance management) at 0.075 lb ai/A/application (based on 10,000 plants per 

acre) for a maximum seasonal rate of 0.15 lb ai/A, applied via chemigation with a 1-day PHI. 

There were no rotational crop restrictions listed on any of the acetamiprid draft labels.

Table 4. Summary of Directions for Use of Acetamiprid.

Applic. Timing, 

Type, and 

Equip.

Trade Name

[EPA Reg. 

No.]

Applic. 

Rate 

(lb ai/A)

Max. No. 

Applic. per 

Season 1

Max. Seasonal 

Applic. Rate

(lb ai/A)

PHI

(days)

Use Directions and 

Limitations

Clover 2

Postemergence

Broadcast foliar

spray

Ground/aerial

Assail®

30SG;

[8033-36]

Assail® 

70WP

[8033-23]

0.047-

0.075 1 0.075 28

Proposed use is limited to 

clover grown in ID, OR, 

and WA only. Begin 

applications when 

treatment thresholds have 

been reached. Apply in 

minimum spray volumes 

of 5 GPA by air or 20 

GPA by ground.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 10 of 38

Table 4. Summary of Directions for Use of Acetamiprid.

Applic. Timing, 

Type, and 

Equip.

Trade Name

[EPA Reg. 

No.]

Applic. 

Rate 

(lb ai/A)

Max. No. 

Applic. per 

Season 1

Max. Seasonal 

Applic. Rate

(lb ai/A)

PHI

(days)

Use Directions and 

Limitations

Grapes and Other Climbing Vine Small Fruits (Except Fuzzy Kiwifruit) (Within Crop Subgroup 13-07F): Amur 

River Grape; Gooseberry; Hardy Kiwifruit; Maypop; Schisandra Berry; and Cultivars, Varieties, and/or Hybrids

Postemergence

Broadcast foliar

spray

Ground/aerial

Assail®

30SG;

[8033-36]

Assail® 

70WP

[8033-23]

0.047-0.1 2 0.2 3

Begin applications when 

treatment thresholds have 

been reached. Do not 

apply more than once 

every 14 days. Apply in 

minimum spray volumes 

of 5 GPA by air or 20 

GPA by ground. Assail® 

30SG states that the 

addition of a spreader, 

methylated seed oil or 

crop oil will enhance pest

control. 

Greenhouse-Grown Tomatoes

Postemergence

Drip or micro

 irrigation

Tristar®

30SG

[8033-94]

0.075 lb 

ai/A of 

crop 

(based on 

10,000 

plants/A)

2 0.15 1

For use in greenhousegrown tomato production. 

May be applied by 

injection into drip 

irrigation or microirrigation (spaghetti tube 

or emitter) systems, soil 

drenching, or by handheld or motorized 

calibrated irrigation 

equipment directed to the 

plant roots. Application 

should be made only to 

mature tomato plants 

grown in non-soil media 

such as rock wool, 

vermiculite, perlite, or 

other soil-less media.

Some cultivars may 

exhibit sensitivity and 

therefore treatment of a 

few plants is 

recommended prior to 

treating an entire 

greenhouse. Begin 

applications when 

treatment thresholds have 

been reached. 

1

 The number of treatments allowed per season when the EP is applied at the maximum single application rate.

2

 Section G of the petition specifies that the EP is proposed for use on red clover grown for seed. The draft label 

does not specify that use is for clover grown for seed.

TEA

No use directions were proposed for the domestic use of acetamiprid on tea grown in South 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 11 of 38

Carolina. The following GAP information was provided for the 20% SP formulation in Japan: 

one application at 0.10-0.40 kg ai/ha applied in 2000-4000 L/ha, with a 14-day PHI. GAP 

information was also provided for India: one application at 0.022 lb ai/A (0.025 kg ai/ha) or 

0.045 lb ai/A (0.050 kg ai/ha), shoots along with bud are typically harvested at a 7-day PHI.

Conclusions. The submitted labels are adequate to allow evaluation of the residue data relative 

to the proposed use, except for the use on tea in South Carolina for which directions were not 

proposed. The available field trial data reflect the proposed use patterns for all of the submitted 

field trials except those submitted for grapes and clover hay. Because the grape field trial data 

submitted with this petition did not reflect the use of a surfactant in the application sprays, the 

label directions regarding use of a spreader, methylated seed oil or crop oil should be removed 

from the product label of Assail® 30SG (EPA Reg. No. 8033-36). The PHI for clover harvested 

for hay should be increased to 56 days on the 30SG and 70 WP labels.

860.1300 Nature of the Residue - Plants

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)

MARC Decision Memo, DP# 278652, 11/13/2001, M. Doherty

Plant metabolism studies with acetamiprid on apple, cabbage, carrot, cotton, and eggplant were 

submitted as part of the data package for the original acetamiprid petition (PP#0F6082), which 

adequately delineate the qualitative nature of the residue in plants. It was found that in most 

plants, acetamiprid is demethylated at the N1amine to form IM-2-1, which may then be further 

metabolized to form IM-0 and IC-0. IM-0 is then metabolized to form the glucose conjugate IM0-Glc. The HED has previously determined that the residue of concern in plants is acetamiprid

for both tolerance enforcement and risk assessment purposes.

860.1300 Nature of the Residue - Livestock

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)

MARC Decision Memo, DP# 278652, 11/13/2001, M. Doherty

The qualitative nature of acetamiprid residues in livestock is adequately understood. HED has 

previously determined that the tolerance expression for enforcement purposes in livestock 

commodities should be acetamiprid plus its IM-2-1 metabolite. For the purpose of risk 

assessment, the residues of concern in livestock commodities (except ruminant muscle) are 

acetamiprid plus its IM-2-1 metabolite. In ruminant muscle, the residues of concern for risk 

assessment are acetamiprid plus IM-2-1 plus IM-2-1-amide. These conclusions are based on 

acceptable metabolism studies with lactating goats (1 ppm or 8.6 ppm dosing levels administered 

for 7 days) and laying hens (1.1 ppm or 12.5 ppm dosing levels administered for 14 days). 

Metabolism data indicate that levels of IM-2-1-amide will not exceed 10x the level of IM-2-1 in 

ruminant muscle tissue. Acetamiprid is metabolized in goats via loss of an amine methyl group, 

forming IM-2-1, which can further hydrolyzed to form IM-2-3 and IM-2-4. IM-2-2 can be 

formed as an intermediate in the metabolism of IM-2-1 to IM-2-4. In poultry, IM-2-2 can be 

converted to IM-2-5 through loss of the acetamide group.

860.1340 Residue Analytical Methods

Residue Chemistry Memo DP#s 342549 & 355773, 11/05/2008, W. Drew
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 12 of 38

Residue Chemistry Memo DP# 328216, 10/23/2007, W. Drew (PP#6F7051 and PP#6E7163)

Residue Chemistry Memo DP# 303623, 11/05/2004, W. Drew (PP#4F6833)

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)

Enforcement methods: Adequate residue analytical methods (GC/ECD and HPLC/UV) are 

available for the enforcement of established tolerances on plant commodities. The method LOQs 

are 0.010 ppm for vegetables and non-citrus fruits (GC/ECD), and 0.050 ppm for citrus fruits 

(HPLC/UV). These methods have undergone successful petition method validation (PMV)

trials. Under PP#4F6833, Nisso America proposed that the LC/MS/MS method utilized for data 

collection and confirmatory analysis (Method #KP-216R0 or its modification, Method #KP216R1) be designated an alternative to the established GC/ECD tolerance enforcement method. 

With submission of acceptable independent laboratory validation (ILV) data and the ability to 

analyze two daughter ions specific to acetamiprid, the LC/MS/MS method, was determined to be 

suitable for tolerance enforcement and confirmatory analysis of vegetables and non-citrus fruits

(DP#s 342549 & 355773). A summary of the available methods is presented in Table 5.

Table 5. Summary of Validated Analytical Methods for Acetamiprid.

Target Matrices Method Description

LOQ 

(ppm)

Method Validation

Fortification 

Levels (ppm)

Recovery 

Range (%)

Vegetables and 

Non-Citrus Fruits

Methanol extraction, residues partitioned into 

dichloromethane, Florisil/silica gel column 

cleanup, and LC/MS/MS determination.

0.010 0.010, 0.020 72-80

Vegetables and 

Non-Citrus Fruits

Methanol extraction, residues partitioned into 

dichloromethane, Florisil/silica gel column 

cleanup, and GC/ECD determination.

0.010 0.010, 0.050 68-112

Citrus Fruits Acetonitrile extraction, co-extractives partitioned 

into hexane, residues partitioned into 

dichloromethane, Florisil/C18 column cleanup, 

and HPLC/UV determination.

0.050 0.050, 0.250 77-100

Data-collection methods: Samples from the clover and grape field trials submitted in

conjunction with the subject petition were analyzed for residues of acetamiprid using LC/MS/MS 

Method #KP-216R1 or a modification of Method #KP-216R1. Samples from the tomato field 

trials were analyzed for residues of acetamiprid using a GC/ECD working method entitled 

“Residue Analysis of Acetamiprid on Tomato (greenhouse) by GC/EC Detection”, adapted with 

modifications from the reference method, “Methods for the Analysis of Acetamiprid (NI-25) in 

Plants and Plant Process Fractions.” Acceptable recoveries were obtained in method validation 

conducted prior to the analysis of field trial samples and/or concurrent method validation using 

clover forage, clover hay, grapes, and tomatoes fortified with acetamiprid at levels ranging from 

the lowest limit of method validation (LLMV; 0.010 ppm) and up to 1.00 ppm. The fortification 

levels used in method validation and concurrent method validation were adequate to bracket the 

expected residue levels for all trials.

Tea: In the Japan study, samples of dried green tea leaves and brewed tea were analyzed for 

combined residues of acetamiprid and metabolites convertible to 6-chloronicotinic acid 

(Metabolite IC-0) using a common moiety GC/ECD method. Briefly, dried tea leaves were 

homogenized, soaked in water, and then extracted with methanol. Brewed tea was simply

filtered. The resulting extracts/filtrates were partitioned with hexane, and the aqueous layer was 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 13 of 38

subjected to base hydrolysis. Acetamiprid and metabolites were then converted to 6-

chloronicotinic acid by oxidation, then methylated (procedure not specified) and purified by

silica column chromatography prior to GC/ECD analysis. The reported method LOD was 0.05 

ppm as acetamiprid. 

In the India study samples of green shoots, dried black tea leaves, brewed tea, and spent leaves 

were analyzed for residues of acetamiprid using an HPLC/UV method. Briefly, green shoots, 

and dried and spent leaves were extracted with acetonitrile, then filtered. The filtrate was 

concentrated and transferred to a separatory funnel containing petroleum ether:5% NaCl solution 

(5:5, v:v). Following shaking and phase separation, the organic phase was washed twice with 

NaCl solution, and the aqueous phases were combined and partitioned with dichloromethane 

(DCM; 4x). The resulting extracts were concentrated to dryness, reconstituted in acetone:hexane 

(5:5, v:v), and purified by silica-carbon column chromatography; residues were eluted with 

acetone/hexane prior to HPLC/UV analysis. Samples of brewed tea were extracted with DCM 

(4x), and the organic layers were combined and concentrated for analysis by HPLC/UV. The 

reported LOD was 0.05 ppm. 

Only limited details were provided for the analytical phase for both studies and that no raw data 

were included for either study.

Conclusions: Adequate residue analytical methods (GC/ECD, HLPC/UV and LC/MS/MS) are 

available for the purpose of tolerance enforcement. The GC/ECD and LC/MS/MS Methods used 

for the analysis of samples from the clover, grape, and tomato field trials are similar to the 

enforcement methods, and were adequate as data-collection methods based on acceptable method 

validation recoveries from clover forage, clover hay, grapes, tomatoes, and tea.

860.1360 Multiresidue Methods

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)

The petitioner submitted data concerning the recovery of residues of acetamiprid using FDA 

multiresidue method protocols (PAM Volume I) in conjunction with the original acetamiprid 

petition (PP#0F6082). These data have been forwarded to FDA for evaluation. Based on the 

results of the testing, the multiresidue methods are not appropriate for determining acetamiprid 

residues of concern. The Biological and Economic Analysis Division (BEAD) is currently

working on a multi-residue method for the neonicotinoids.

860.1380 Storage Stability

Residue Chemistry Memo DP# 303623, 11/05/2004, W. Drew (PP#4F6833)

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)

Storage stability data submitted with PP#6F7051 indicate that residues of acetamiprid are 

relatively stable under frozen storage conditions for up to 12 months in/on fortified samples of an 

oilseed (cotton seed), a leafy vegetable (head lettuce), a Brassica leafy vegetable (cabbage), a 

cucurbit vegetable (cucumber), and fruits (apple and orange), as well as the processed 

commodities of apple, cotton, and orange. In addition, the stability of acetamiprid during shortterm storage at ambient temperatures was evaluated. Samples of cottonseed, cotton gin 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 14 of 38

byproducts, cotton seed oil, whole grapes, grape juice, raisins, whole oranges, whole tomatoes, 

and tomato paste spiked with acetamiprid at 0.100 and 0.250 ppm were stored at ambient 

temperatures for 7 days (15 days for raisins). Under these conditions, residues of acetamiprid 

were stable in all commodities. 

IR-4 conducted concurrent storage stability studies with the analysis of the field trial samples in 

conjunction with the clover and tomato field trials. Although no 0-day data were provided, the 

data indicate that residues of acetamiprid are relatively stable under frozen storage conditions 

in/on fortified samples of clover forage for up to 239 days (7.9 months), clover hay for up to 213 

days (7.0 months), and tomatoes for up to 114 days (3.7 months). The storage durations and 

conditions of samples from the submitted crop field trials are presented below in Table 6. 

Table 6. Summary of Storage Conditions and Durations of Samples from Crop Field Trial Studies. 

Matrix Storage Temperature

(°C)

Actual Storage Duration Interval of Demonstrated Storage 

Stability

Clover forage -29 to -10 224-227 days (7.4-7.5 months) Up to 239 days in/on frozen clover forage.

Clover hay 195-204 days (6.4-6.7 months) Up to 213 days in/on frozen clover.

Grape -28 to -10 49-125 days (1.6-4.1 months) Up to 12 months in/on diverse representative 

crops, including fruits.

Tomato -21 ± 7 20-99 days (0.7-3.3 months) Up to 114 days in/on frozen tomato.

Conclusions. The available storage stability data for acetamiprid on representative crops, and the 

submitted concurrent storage stability data for clover and tomato are adequate to support the 

submitted clover, grape, tomato, and tea field trials. There is no need for correction of residues, 

as no decline in residue was observed. 

860.1480 Meat, Milk, Poultry, and Eggs

The proposed use on clover could theoretically lead to the secondary transfer of acetamiprid 

residues of concern to beef and dairy cattle from the feeding of clover forage, hay, and silage. 

However, the proposed use on clover is to be restricted to that grown in ID, OR, and WA only. 

Therefore, HED does not believe that the proposed use on clover would significantly increase the 

dietary burdens, and the established tolerances in milk, meat, and meat byproducts need not be 

reassessed for the purpose of this petition.

860.1500 Crop Field Trials
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 15 of 38

DER Reference List 47716901.der.doc (Clover)

47716902.der.doc (Grapes)

47716903.der.doc (Greenhouse Tomatoes)

47782101.der.doc (Tea)

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)

Minutes of the 11/16/2005 Meeting of the HED Chemistry SAC

IR-4 has submitted magnitude of the residue data for acetamiprid on red clover, grapes, and 

tomato, and tea to support the new uses on clover and greenhouse tomatoes, tea and amended use 

on grapes (also expanded to small vine climbing fruits, except fuzzy kiwifruit, subgroup 13-07F). 

A summary of the residue data is presented in Table 7a and 7b.

Table 7a. Summary of Residue Data from Crop Field Trials with Acetamiprid.

Crop Matrix

Total Applic. Rate

(lb ai/A)

PHI 

(days)

Residue Levels (ppm)

n Min. Max. HAFT1 Median Mean Std. 

Dev.

Clover

(Proposed use = One broadcast foliar spray treatment at a maximum of 0.075 lb ai/A; 28-day PHI)

Clover forage 0.074-0.079 28-34 6 <0.01 0.05 0.05 0.05 0.04 0.02

Clover hay 56-63 6 <0.01 <0.01 <0.01 0.01 0.01 --

Grapes and Other Climbing Vine Small Fruits (Except Fuzzy Kiwifruit) (Within Crop Subgroup 13-07F)

(Current registered use on Grapes = 0.1 lb ai/A total application rate; 7-day PHI)

(Proposed amended use = 0.2 lb ai/A total application rate; 3-day PHI)

Grape 0.195-0.206 2-3 36 0.01 0.25 0.25 0.08 0.11 0.07

Tomatoes

(Current registered field use = 0.3 lb ai/A total application rate; 7-day PHI)

(Proposed greenhouse use = 0.15 lb ai/A total application rate; 1-day PHI)

Tomato 0.300-0.324 1 6 <0.01 0.052 0.050 0.027 0.029 0.018

1

 HAFT = Highest average field trial result.

TABLE 7b. Summary of Residue Data from Crop Field Trials with Acetamiprid.

Commodity Total Applic. 

Rate, 

lb ai/A

[kg ai/ha]

PHI

(days)

Residue Levels (ppm)

n Min. Max. HAFT1 Median

(STMdR)

Mean

(STMR)

Std. Dev.

Japan Study - Combined residues of acetamiprid and residues convertible to Metabolite IC-0

Green tea - dried 

leaves

0.13-0.27

[0.15-0.30]

6-7 8 13.6 40.9 39.3 23.9 25.3 9.82

13-14 8 8.15 17.2 16.6 13.1 12.8 4.19

20-21 8 2.30 5.44 5.44 3.64 3.75 1.19

Green tea -

brewed tea*

0.13-0.27

[0.15-0.30

6-7 8 7.74 27.7 27.0 17.3 17.4 7.29

13-14 8 5.17 12.7 12.6 9.21 9.07 3.38

20-21 8 1.57 3.30 3.27 1.87 2.15 0.70

India Study (wet and dry season tea) - Residues of acetamiprid per se (only mean values reported)2

Black tea - green 

shoots

0.022-0.045

[0.025-0.050]

0 12 3.96 9.53 9.53 NC36.54 NC

7 12 0.20 0.51 0.51 NC 0.33 NC

15 12 0.03 0.11 0.11 NC 0.06 NC

21 12 <0.05 <0.05 <0.05 <0.05 <0.05 0

Black tea - dried 

leaves

0.022-0.045

[0.025-0.050]

0 12 11.2 26.4 26.4 NC 18.5 NC

7 12 0.54 1.47 1.47 NC 0.95 NC

15 12 <0.05 0.26 0.26 NC 0.11 NC

21 12 <0.05 <0.05 <0.05 <0.05 <0.05 0

Black tea - 0.022-0.045 0 12 5.4 12.6 12.6 NC 8.92 NC
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 16 of 38

TABLE 7b. Summary of Residue Data from Crop Field Trials with Acetamiprid.

Commodity Total Applic. 

Rate, 

lb ai/A

[kg ai/ha]

PHI

(days)

Residue Levels (ppm)

n Min. Max. HAFT1 Median

(STMdR)

Mean

(STMR)

Std. Dev.

brewed tea* [0.025-0.050] 7 12 0.24 0.61 0.61 NC 0.41 NC

15 12 <0.05 0.13 0.13 NC 0.07 NC

21 12 <0.05 <0.05 <0.05 <0.05 <0.05 0

Black tea - spent 

leaves

0.022-0.045

[0.025-0.050]

0 12 4.6 10.2 10.2 NC 7.5 NC

7 12 0.20 0.51 0.51 NC 0.36 NC

15 12 <0.05 0.09 0.09 NC 0.06 NC

21 12 <0.05 <0.05 <0.05 <0.05 <0.05 0

1 HAFT = Highest Average Field Trial. 

2

 The reported LOD (0.05 ppm) was used for calculation of median, mean, and 

standard deviation where appropriate. Only the 0-day PHI and PHIs relevant for comparison to the Japan trials were 

included in the summary. 

3

 NC = Not calculated. Median and standard deviation could not be calculated because only 

mean values were reported for each sample set. 

4

 NA = Not applicable when all residues are nonquantifiable (<0.05 

ppm). * The relatively high residues in the brewed tea, which HED expected to be much lower than the residues in or 

on the dried tea leaves, may reflect a back calculation of what the residues would have been on the dried tea leaves. 

Otherwise, HED can not account for why the residues were not diluted by the water used for making the tea.

Clover

Three red clover field trials were conducted in the U.S. in Zone 11 (OR) during the 2006 growing 

season. Each trial site consisted of one untreated plot and one treated plot. Red clover was 

treated with a single broadcast foliar application of Assail® 30SG, a 30% SG formulation of 

acetamiprid, at a rate of 0.074-0.079 lb ai/A (ca. 1x the maximum proposed seasonal rate on 

clover). Application was made when the crop was in the vegetative stage to blooming stage 

using ground equipment in 23-25 GPA spray volumes, without an adjuvant. Samples of clover 

forage were harvested 28 to 34 days following application. Additionally, hay samples were cut at 

a normal harvest time (coinciding with PHIs of 56-63 days) and allowed to dry in the field prior 

to collection.

Samples were analyzed for residues of acetamiprid using an LC/MS/MS working outline based 

on Cerexagri Method No. KP-216R1. The adequacy of the method for data collection was 

verified by analysis of untreated samples of red clover forage and hay fortified with acetamiprid 

at 0.01-1.0 ppm. Overall method recoveries ranged 75% to 96% for forage, and 75% to 100% 

for hay. The fortification levels used in method validation adequately bracketed the expected 

residues in/on treated clover forage and hay. The validated LOQ (and LLMV) was 0.01 ppm in 

both clover forage and hay.

Samples were held in frozen storage prior to analysis. The maximum sample storage durations, 

from harvest to analysis, were 227 days (7.5 months) for clover forage, and 204 days (6.7 

months) for clover hay. Sample storage conditions and durations are supported by concurrent 

storage stability data. 

The results of the clover field trials are summarized in Table 7. Residues of acetamiprid were 

<0.01-0.05 ppm in/on red clover forage harvested 28-34 days following a single broadcast foliar 

application of the 30% SG at 0.074-0.079 lb ai/A. Residues were below the LLMV (<0.01 ppm) 

in/on clover hay harvested 56-63 days following treatment.

Conclusions: The use pattern of the clover field trials adequately reflects the proposed label use 

pattern with the exception of the PHI for hay. The available field trial data indicate a regional 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 17 of 38

tolerances for residues of acetamiprid in clover forage at 0.10 ppm and clover hay at 0.01 ppm, 

are appropriate. However, the submitted clover field trial data are not completely adequate to 

satisfy data requirements. The three clover field trials were all conducted in Zone 11 (OR) 

during the 2006 growing season, at the same location and within a very short time period of each 

other. The number of trials are adequate to support restricted use on clover in ID, OR and WA 

(Zones 11 and 12) according to OPPTS Guideline 860.1500, Attachment 11; however the 

guidelines state that for crops requiring 8 or more trials nationally (12 are required for clover), 

the trials for regional registrations must be conducted in multiple years to account for variability

due to climate conditions. As a condition of registration, HED recommends that two additional 

clover field trials be required, as confirmatory data. In addition, the submitted reside data 

included field trial data for only the 70WP formulation (the original field trials also used a 70WP 

formulation). However, since the requested PHI is for 28 days, additional residue chemistry field 

trial data are not required to support registration of the 30SG formulation (generally bridging data 

are required if the proposed PHI is less than or equal to 7 days). Use on clover grown for seed is 

to be limited to clover grown in ID, OR, and WA. Since the residue chemistry data submitted for 

clover hay reflect PHIs of between 56-63 days, the PHI for acetamiprid use on clover should be 

increased to 56 days for any clover crop which will be harvested for hay.

No residue decline data were included in the clover field trials. However, residue decline studies 

on cotton, head lettuce, oranges, pears, and peppers were submitted in conjunction with 

PP#0F6082 (D264154, 12/31/2001, M. Doherty). These data indicated that residues of 

acetamiprid did not increase in the subject crops with increasing harvest intervals. Given the 

long PHI (28-days) for clover and available residue decline data on other crops, residue decline 

data will not be required to support the clover field trials. The available field trial data will 

support tolerances with regional registration for residues of acetamiprid in clover forage at 0.10 

ppm (with a 28-day PHI) and clover hay at 0.01 ppm (with a 56-day PHI); the tolerance 

calculations for clover forage are presented in Appendix I. 

Grape; Fruit, Small Vine Climbing, Subgroup 13-07F, Except Fuzzy Kiwifruit

Eighteen grape field trials were conducted in the U.S. and Canada in Zones 1 (NY; 1 trial), 2 (NJ; 

2 trials), 5 (ON; 4 trials), 5A (MI; 1 trial), 10 (CA; 8 trials), 11 (BC; 1 trial), and 11/12 (WA; 1 

trial) during the 2005 growing season. Mature grape vines in established orchards were treated 

with two directed foliar applications of Assail® 70WP, a 70% WP formulation of acetamiprid, at 

0.096-0.103 lb ai/A/application, with a 13- to 14-day retreatment interval (RTI), for a total rate of 

0.195-0.206 lb ai/A (ca. 1x the maximum proposed seasonal rate on grapes and other climbing 

vine small fruits). Applications were made during the crop’s fruiting to berry ripening stages 

using ground equipment in 22-130 GPA spray volumes, without an adjuvant. Samples of mature 

grape fruits were harvested 2 to 3 days after the second application.

Samples were analyzed for residues of acetamiprid using an LC/MS/MS method based on 

Cerexagri Method No. KP-216R1. The adequacy of the method for data collection was verified 

by analysis of untreated samples of grapes fortified with acetamiprid at 0.01-1.0 ppm. Overall 

method recoveries ranged from 80% to 98%. The fortification levels used in method validation 

adequately bracketed the expected residues in/on treated grapes. The validated LOQ (and 

LLMV) was 0.01 ppm in grape.

Samples were held in frozen storage prior to analysis. The maximum sample storage duration 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 18 of 38

from harvest to analysis was 125 days (4.1 months) for grape. Adequate storage stability data are 

available for acetamiprid demonstrating that residues are stable in/on diverse representative crops 

(including fruits) for up to one year. 

The results of the grape field trials are summarized in Table 7. Residues of acetamiprid were 

0.01-0.25 ppm in/on grapes harvested 2-3 days following the last of two directed foliar 

applications of the 70% WP at a total rate of 0.195-0.206 lb ai/A. No residue decline data were 

included in the grape field trial study.

Conclusions: The submitted grape residue data included field trial data for only the 70WP 

formulation (the original field trials also used a 70WP formulation). Since the requested PHI for 

grape is for 3 days, additional residue chemistry field trial data are needed to support registration 

of the 30SG formulation. As a condition of registration, HED requests that three side-by-side 

field trials be conducted and submitted to determine if residues are comparable for the two 

different formulations.

The submitted grape field trial data are adequate for the 70 WP formulation pending label 

revision. Because the grape field trial data did not reflect the use of a surfactant in the 

application sprays, the label directions regarding use of a spreader, methylated seed oil or crop oil

should be removed from the product label of Assail® 30SG (EPA Reg. No. 8033-36). The 

number and locations of the field trials are in accordance with OPPTS Guideline 860.1500 for 

grapes, and the use pattern of the field trials reflects the use pattern proposed for grapes (and 

other climbing vine small fruits, except fuzzy kiwifruit, within subgroup 13-07F), except for the 

adjuvant use. 

No residue decline data were included in the grape field trials. The residue decline studies from 

PP#0F6082 (DP# 264154, 12/31/2001, M. Doherty), which indicated that residues of acetamiprid 

did not increase in various crops with increasing harvest intervals, will be used to fulfill the 

requirements for residue decline data. The available field trial data from the current submission, 

which reflect a higher seasonal rate and a shortened PHI from those which are currently

registered for grape, will support a tolerance for residues of acetamiprid at 0.35 ppm; the 

tolerance calculations for grape are presented in Appendix I. 

Grape is the representative crop of the fruit, small vine climbing, subgroup 13-07F, except fuzzy

kiwifruit, and the available grape data will support a subgroup tolerance at 0.35 ppm. The 

established individual tolerance for grape at 0.20 ppm should be deleted when the subgroup 13-

07F tolerance is established.

Tomatoes (Greenhouse Study)

Three trials were conducted on tomatoes in the U.S. and Canada in Zones 4 (TN), 5 (ON), and 6 

(TX) during the 2002 and 2003 growing seasons. Each trial site included one untreated plot and 

one treated plot. Tomato plants grown in rock wool substrate under greenhouse conditions were 

treated at the fruiting stage with four simulated drip-irrigation (chemigation) treatments of 

Assail® 70WP, a 70% WP formulation of acetamiprid, at rates equivalent to 0.074-0.081 lb 

ai/A/application. Applications were made with 7-day RTIs, for a total rate of 0.300-0.324 lb ai/A 

(ca. 2x the maximum proposed seasonal rate for greenhouse-grown tomato); no adjuvant was 

used. Samples of mature tomato were harvested one day after the last application. At the TX 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 19 of 38

trial, additional treated samples were harvested 3, 5, and 7 days after the last application to 

generate residue decline data.

Samples were analyzed for residues of acetamiprid using a GC/ECD working method entitled 

“Residue Analysis of Acetamiprid on Tomato (greenhouse) by GC/EC Detection”, adapted with 

modifications from the reference method, “Methods for the Analysis of Acetamiprid (NI-25) in 

Plants and Plant Process Fractions.” The adequacy of the method for data collection was verified 

by analysis of untreated samples of tomato fruit fortified with acetamiprid at 0.01-1.0 ppm. 

Overall method recoveries ranged from 86% to 120%. The fortification levels used in method 

validation adequately bracketed the expected residues in/on treated tomato. The validated LOQ 

(and LLMV) was 0.01 ppm in tomato.

Tomato samples were held under frozen storage conditions for a maximum duration of 99 days 

(3.3 months) prior to residue analysis. Sample storage conditions and durations are supported by

concurrent storage stability data. 

The results of the greenhouse grown tomato field trials are summarized in Table 7. Residues of 

acetamiprid ranged from below the LLMV (<0.01 ppm) to 0.052 ppm in/on greenhouse-grown 

tomatoes harvested one day following the last of four drip-irrigation (chemigation) treatments of 

the 70% WP at a total rate of 0.300-0.324 lb ai/A. The decline data show that residues 

accumulated slightly, from an average of 0.027 ppm at the 1-day PHI to an average of 0.037 ppm 

at the 7-day PHI.

Conclusions: The submitted tomato data do not reflect the proposed greenhouse use pattern 

because the application rate used in the trials is 2x the proposed seasonal rate for tomatoes grown 

under greenhouse conditions. In addition, the three trials conducted are marginally adequate with 

respect to the number of trials. Because the established field tomato uses differ from the 

proposed greenhouse-grown tomato use, HED (ChemSAC 11/16/05 minutes) typically requires

data depicting residues from 4 greenhouse sites, with 4 samples per site. For chemicals with 

tomato tolerances resulting from a field use and for which the field and greenhouse use patterns 

are similar, any of the following 3 study designs would generally be found to be appropriate: (i) 

residue data from 3 greenhouse sites with 2 samples per site; (ii) residue decline data, 

encompassing the proposed PHI, from 2 greenhouse sites with 2 samples per time interval; or

(iii) residue data from 2 greenhouse sites with 4 samples per site.

Although the greenhouse trials were conducted at a 2x rate and the number of trials is marginal, 

no additional residue data will be required to support the proposed greenhouse use pattern for 

tomatoes if use is limited to the WP formulation. The tomato greenhouse data indicate that 

resulting acetamiprid residues resulting from applications of Assail 70WP formulation of 

acetamiprid according to the proposed use pattern would not exceed the established tolerance for 

residues of acetamiprid in fruiting vegetables, crop group 8 (0.20 ppm). No data were provided 

for the proposed use of Tristar® 30SG on greenhouse tomatoes. HED does have side-by-side 

formulation trials (WP and soluble liquid formulation) for acetamiprid in undelinted cottonseed 

and cotton gin byproducts (D330540, M. Doherty, 30 Oct 2007). These data indicate that residue 

levels are comparable for the two different formulations at the same use rate. In view of these 

data and the 70WP data reflecting 2x the seasonal application rate, HED requests only one sideby-side formulation trial (rather than the normal of three trials) to support the use of Tristar® 

30SG on greenhouse tomatoes as a condition of registration.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 20 of 38

Tea

The Interregional Research Project No. 4 (IR-4) has submitted a report summarizing the results 

of two studies on tea conducted in Japan (by Nippon Soda Co., Ltd.) and India (by the Institute of 

Himalayan Bioresource Technology; IHBT). No raw data were included in the submission, all 

data presented herein are as reported in the original studies.

Nippon Soda Co, Ltd. conducted two trials in the Mie Prefecture and the Fukuoka Prefecture of 

Japan investigating the magnitude of the residue in dried green tea leaves and brewed tea 

following a single foliar application of a 20% water-soluble powder (SP) formulation of 

acetamiprid made to green tea in separate plots at 0.13 lb ai/A (0.15 kg ai/ha) and 0.27 lb ai/A 

(0.30 kg ai/ha). Applications were made in spray volumes of 321 gal/A (3000 L/ha). The 

following Good Agricultural Practice (GAP) information was provided for the 20% SP 

formulation in Japan: one foliar application at 0.10-0.40 kg ai/ha applied in 2000-4000 L/ha, 

with a 14-day preharvest interval (PHI). Duplicate samples of green tea leaves were harvested 6-

7, 13-14, and 20-21 days after application, and were processed into dried leaves and brewed tea 

(green tea drink) according to standard procedures for green tea. 

In a separate study, the Institute of Himalayan Bioresource Technology (IHBT) conducted two 

sets of trials in Palampur (Himachal Pradesh, India) investigating the magnitude of the residue in 

black tea for green shoots, dried tea leaves, brewed tea, and spent leaves after brewing. 

Acetamiprid was applied to black tea in separate plots as a single foliar application of a 20% SP 

formulation of acetamiprid at 0.022 lb ai/A (0.025 kg ai/ha) and 0.045 lb ai/A (0.050 kg ai/ha) in 

spray volumes of 43 gal/A (400 L/ha). The application rates were reported to be 1x and 2x the 

recommended application rate for acetamiprid on tea. Two sets of trials were conducted, one 

during the dry season (June) and the second during the wet season (August). The following GAP 

information was provided for India: shoots along with bud are typically harvested at a 7-day

PHI. Samples of green shoots (consisting of two leaves and a bud) were collected 0 (2 hours post 

application), 1, 3, 5, 7, 9, 11, 15, and 21 days after application; three replicate samples were 

collected from each plot at each sampling interval. Samples were processed into dried tea leaves 

and brewed tea (infusion) using standard procedures for black tea production; samples of spent 

leaves following brewing were also collected. 

Samples of dried green tea leaves and brewed tea from the Japan study were analyzed for 

residues of acetamiprid and its metabolites convertible to 6-chloronicotinic acid (Metabolite IC0) using a common moiety gas chromatography method with electron capture detection 

(GC/ECD). Using this method, acetamiprid and metabolites are converted to Metabolite IC-0 

and methylated prior to determination by GC/ECD; residues are expressed as acetamiprid. The 

reported method limit of detection (LOD) is 0.05 ppm as acetamiprid. Samples of green shoots, 

dried black tea leaves, brewed tea, and spent leaves from the India study were analyzed for 

residues of acetamiprid using a high performance liquid chromatography method with ultraviolet 

detection (HPLC/UV). The reported LOD was 0.05 ppm. Both methods are adequate for data 

collection based on the submitted concurrent recovery data; however, we note that the 

fortification levels used in concurrent method validation in the Japan study did not encompass 

residues found in dried green tea leaves or brewed tea. 

Regarding the common moiety method used in the Japan study, we note that, although 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 21 of 38

Metabolite IC-0 is not a residue of concern for tolerance enforcement or risk assessment, based 

on the available plant metabolism studies, it may constitute a significant portion of the total 

residues (e.g., up to 24% total radioactive residues (TRR) in cotton seed and 31% TRR in carrot 

flesh; refer to D278652, 11/13/01, H. Bietlot and M. Doherty). Therefore, the residues reported 

for the Japan study may reflect an overestimation of expected residues of acetamiprid per se in 

green tea.

Samples of dried green tea leaves and brewed tea from the Japan study were stored frozen from 

collection to analysis for up to 3.5 and 1.7 months, respectively. Storage conditions and 

durations for samples of green shoots, dried black tea leaves, brewed tea, and spent leaves from 

the India study were not reported; however, the study indicated that samples were analyzed 

immediately after receipt in the laboratory and that extensive storage was not required. HED 

believes there are sufficient storage stability data available for acetamiprid, demonstrating that 

residues are stable in crop commodities stored frozen for up to 12 months and crop commodities 

stored at ambient temperatures for up to 7 days, to support both studies (refer to D264154, 

12/31/01, M. Doherty).

Following a single foliar application of the 20% SP formulation of acetamiprid at 0.13-0.27 lb 

ai/A (0.15-0.30 kg ai/ha) to green tea grown in Japan, combined residues of acetamiprid and 

metabolites were 13.6-40.9 ppm in dried green tea leaves harvested 6-7 days after application and 

were 8.15-17.2 and 2.30-5.44 ppm in dried leaves harvested 13-14 and 20-21 days after 

application, respectively. In brewed tea produced from the dried leaves harvested at the 6- to 7-, 

13- to 14-, and 20- to 21-day PHIs, residues were 7.74-27.7, 5.17-12.7, and 1.57-3.30 ppm, 

respectively.

Following a single foliar application of the 20% SP formulation of acetamiprid at 0.022-0.045 lb 

ai/A (0.025-0.050 kg ai/ha) to black tea grown in India during the wet and dry seasons, combined 

residues of acetamiprid in green shoots harvested at 0-, 7, -15, and 21-day PHIs were 3.96-9.53, 

0.20-0.51, 0.03-0.11, and <0.05 ppm, respectively. Residues in dried black tea leaves processed 

from the shoots were generally higher at the 0-, 7-, and 15-day PHIs, 11.2-26.4, 0.54-1.47, and 

<0.05-0.26 ppm, respectively, and were <0.05 ppm at the 21-day PHI. Residues were 5.4-12.6, 

0.24-0.61, and <0.05-0.13 ppm, respectively, in brewed tea, and 4.6-10.2, 0.20-0.51, and <0.05-

0.09 ppm, respectively, in spent leaves from tea harvested at the 0-, 7-, and 15-day PHIs, and 

were <0.05 ppm in brewed tea and spent leaves at the 21-day PHI.

The study report also contained a list of multiresidue method analysis results for residues of 

acetamiprid in tea received in commercial shipments from various countries. Although residues 

were nondetectable in the majority of green and black tea samples received from Argentina, 

Bangladesh, Burundi, China, Ecuador, Ethiopia, India, Indonesia, Iran, Kenya, Malawi, 

Mozambique, Rwanda, Sri Lanka, South Africa, Tanzania, Turkey, Uganda, Vietnam, 

Zimbabwe, detectable residues of acetamiprid were found in tea samples from China (0.03-0.04 

ppm; n=3), Indonesia (0.03 ppm; n=1), and Vietnam (0.03-0.12 ppm; n=7). The source of these 

data was not identified.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 22 of 38

860.1520 Processed Food and Feed

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)

No new processing studies were submitted with this petition request. 

Grape

An acceptable grape processing study (MRID 44988620) was reviewed under PP# 0F6082 which 

reported processing factors of 1.5x for juice and 0.9x for raisins. Expected residues, based on the 

new HAFT (0.25 ppm) for grape from the amended use, would be 0.375 ppm in juice and 0.225 

ppm in raisins. Based on these data, no tolerance is needed in grape raisins as a result of the 

proposed use because any expected residues in raisins are less than the RAC tolerance. 

Considering that the maximum theoretical concentration factor for grape juice is 1.2 (Guideline 

860.1520), HED also expects residues in grape juice, resulting from the proposed use, will not 

exceed the RAC tolerance of 0.35 ppm; therefore, a separate tolerance is not needed for grape 

juice. 

Tomato

An acceptable tomato processing study (MRID 44988621) was reviewed under PP# 0F6082 

which reported processing factors of 1.4x for puree and 3.0x for paste. Based on the observed 

processing factor of 3.0x and a HAFT of 0.1 ppm, a tolerance of 0.40 ppm was established for 

residues of acetamiprid in tomato paste. A tolerance was not needed in puree because any

expected residues in puree would be less than the RAC tolerance (0.20 ppm). The proposed use 

on greenhouse-grown tomatoes will not change the expected residues in puree or paste. 

860.1650 Submittal of Analytical Reference Standards

An analytical standard for acetamiprid is currently available in the National Pesticide Standards 

Repository (personal communication with Dallas Wright, ACB, 07/06/2009). However, 

analytical standards for the IM-2-1 and IM-2-1-amide metabolites are not available at the 

Repository. Analytical reference standards of these metabolites must be supplied and supplies 

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 Theresa Cole at the 

following address:

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

Residue Chemistry Memo DP# 328216, 10/23/2007, W. Drew (PP#6F7051 and PP#6E7163)

Residue Chemistry Memo DP# 264154, 12/31/2001, M. Doherty (PP#0F6082)
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 23 of 38

No new confined rotational crop data were submitted with this petition; the nature of the residue 

in rotational crops is understood. A confined rotational crop study was reviewed in conjunction 

with PP#0F6082. In the study, acetamiprid was not detected in any rotational crop matrix 

(mustard greens, radish, and grain crops) at any of the plantback intervals (PBIs), which were 30-

, 58-, 120- and 365 days after treatment (DAT) following application to bare soil at 0.66 lb ai/A. 

The major metabolite identified in rotational crops was IM-1-4, at 2.94-56.65% TRR (<0.001-

0.040 ppm). Two other metabolites were identified in most rotational crops: IM-0-Glc, at 1.11-

15.23% TRR (<0.001-0.010 ppm), and IC-0, at 2.75-24.19% TRR (<0.001-0.014 ppm). Storage 

stability data, required as a condition of registration in the original petition PP#0F6082, have 

been submitted and determined to rectify deficiencies under PP#6F7051. 

HED has determined that the residue of concern in rotational crops is parent only, and that 

tolerances would not be needed on rotational crops. The available rotational crop data are 

adequate to support the uses proposed in this petition. 

860.1900 Field Accumulation in Rotational Crops

Residue Chemistry Memo DP# 328216, 10/23/2007, W. Drew (PP#6F7051 and PP#6E7163)

No field rotational crop data have been submitted, and no rotational crop restrictions have been 

proposed. The available confined rotational crop data indicate that no field rotational crop 

studies or label restrictions for rotational crops are required to support the proposed uses.

860.1550 Proposed Tolerances

Tolerances are currently established under 40 CFR §180.578 (a)(1) for residues of the 

insecticide, acetamiprid, in or on crop matrices. The tolerance expression proposed by IR-4 in 

this petition is consistent with 40 CFR §180.578(a)(1).

Adequate field trial data were submitted for clover. Provided confirmatory data are submitted as 

a condition of registration, the available field trial data will support the proposed regional 

tolerances for residues of acetamiprid in clover forage at 0.10 ppm and clover hay at 0.01 ppm. 

The tolerance spreadsheet in the Agency’s Guidance for Setting Pesticide Tolerances Based on 

Field Trial Data was utilized for determining the appropriate tolerance level for clover forage; 

see Appendix I. The tolerance spreadsheet was not used to determine the tolerance level on

clover hay because all treated samples (n=6) bore residues below the LLMV (<0.01 ppm). 

The submitted field trial data for grapes are adequate pending label revision to remove use of a 

spreader, methylated seed oil or crop oil from the product label of Assail® 30SG. The available 

grape field trial data from the current submission, which reflect a higher seasonal rate and a 

shortened PHI from those which are currently registered on grapes, will support the proposed 

tolerance for residues of acetamiprid in “fruit, small, vine climbing, subgroup 13-07F, except 

fuzzy kiwifruit” at 0.35 ppm. The tolerance spreadsheet in the Agency’s Guidance for Setting 

Pesticide Tolerances Based on Field Trial Data was utilized for determining the appropriate 

tolerance level for grape; see Appendix I. The established individual tolerance for grape at 0.20 

ppm should be concomitantly removed upon the establishment of the Subgroup 13-07F (except 

fuzzy kiwifruit) tolerance. HED notes that side-by-side trials on grapes comparing residues from 

the WP and SG formulations are recommended as a condition of registration.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 24 of 38

Although the tomato greenhouse trials were conducted at 2x and the number of trials is marginal, 

the submitted data indicate that the established tolerance for residues of acetamiprid in fruiting 

vegetables (Crop Group 8) at 0.20 ppm will not be exceeded following applications of Tristar® 

30SC according to the use patterns of the tomato greenhouse trials. HED notes that side-by-side 

trials on tomatoes comparing residues from the WP and SG formulations are recommended as a 

condition of registration.

Acceptable grape and tomato processing studies are available. The grape processing studies 

reported processing factors of 1.5x for juice and 0.9x for raisins. The tomato processing studies 

reported processing factors of 1.4x for puree and 3.0x for paste. Based on these data, no 

tolerances are needed in grape raisins and tomato puree as a result of proposed uses because any

expected residues in these processed commodities are estimated to be less than the respective 

RAC tolerances. Based on the observed processing factor of 3.0x and a HAFT of 0.1 ppm, a 

tolerance of 0.40 ppm was established under 40 CFR §180.578[a][1] for residues of acetamiprid 

in tomato paste; this tolerance remains appropriate with the proposed use on greenhouse 

tomatoes. Considering that the maximum theoretical concentration factor for grape juice is 1.2 

(Guideline 860.1520), HED also expects residues in grape juice, resulting from the proposed use, 

will not exceed the RAC tolerance of 0.35 ppm; therefore, a separate tolerance is not needed for 

grape juice.

Although the tolerance spreadsheet recommends a 40 ppm level for dried tea, one residue value 

(40.9 ppm) exceeded that level and Japan has an established 50 ppm MRL for tea. Therefore, 

HED recommends a 50 ppm tolerance as well. Given the data for brewed tea and understanding 

that FDA would adjust residues measured on instant tea back to a dried tea basis for enforcement 

purposes, a separate instant tea tolerance is not required

The established tolerances on animal commodities need not be reassessed for this petition. The 

proposed use on clover could theoretically lead to the secondary transfer of acetamiprid residues 

of concern to beef and dairy cattle from the feeding of clover forage, hay, and silage. However, 

the proposed use on clover is to be restricted to that grown in ID, OR, and WA only and the 

residues on the clover RAC are very low. Therefore, HED does not believe that this would 

significantly increase the dietary burdens.

Tolerances on rotational crops are not needed. Residues of acetamiprid were not detected in any

rotational crop matrix (mustard, lettuce, radish, sorghum, or wheat) at any PBI (30, 58, 120, or 

365 DAT).

There are no Codex maximum residue limits (MRLs) established for residues of acetamiprid on 

crop or animal commodities; no Mexican MRLs are established on crops associated with this 

petition. Canada has established an MRL for acetamiprid residues in grapes at 0.20 ppm. The 

recommended U.S. tolerance for Subgroup 13-07F tolerance at 0.35 ppm is not harmonized with 

the Canadian MRL, presumably because of differences in good agricultural practices. Japan has 

a 50 ppm MRL for tea and HED recommends setting the tolerance at the same level. An 

International Residue Limit Status (IRLS) sheet is appended to this document.

The final tolerance for subgroup 13-07F should reflect the correct commodity definitions, as 

specified in Table 8. A revised Section F does not need to be submitted for this minor change.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 25 of 38

Provided that the forthcoming human health risk assessment does not identify any issues of 

concern, the submitted data support the establishment of permanent tolerances for acetamiprid, 

including its metabolites and degradates under 40 CFR §180.578, as listed in Table 8, below. 

Compliance with tolerance levels specified below is to be determined by measuring acetamiprid 

only.

Table 8. Tolerance Summary for Acetamiprid.

Commodity Established/Proposed 

Tolerance (ppm)

Recommended 

Tolerance (ppm)

Comments; Correct Commodity 

Definition

Clover, forage 0.10 0.10 Recommended tolerances are for 

Clover, hay regional registration. 0.01 0.01

Fruit, small, vine climbing, 

except fuzzy kiwifruit, 

subgroup 13-07F

0.35 0.35 Pending label revision to remove use 

of a spreader, methylated seed oil or 

crop oil. Fruit, small, vine climbing, 

except fuzzy kiwifruit, subgroup 13-

07F.

Grape 0.20 Remove Grapes will be covered under the 

subgroup 13-07F tolerance.

Tea, dried 50.0 50.0 Tolerance without a U.S. registration.

References

D342549/355773. Acetamiprid. Request for Label Amendment (TriStar 30SG) Allowing 

Food/Feed Use of the Insecticide on Vegetable Transplants; Independent Laboratory Validation 

Study (Assail 70WP), Submitted as Supplementary Data Pursuant to HED Memorandum of 5 

November 2004 (D303623). W. Drew, 11/05/2008. MRID: 47185401.

D328216. Acetamiprid. Petitions Requesting the Establishment of Permanent Tolerances 

(Associated with Section 3 Registration) for New Food/Feed Uses of the Insecticide on Berries 

(Crop Group 13), Bulb Vegetables (Crop Group 3), Edible Podded Legume Vegetables (Crop 

Subgroup 6A), Succulent Shelled Pea and Bean (Crop Subgroup 6B), and Strawberry and Other 

Low-growing Berries. Summary of Analytical Chemistry and Residue Data. Petition Numbers 

6F7051 (Various Crops) and 6E7163 (Strawberry). W. Drew, 10/23/2007. MRIDs: 46785502-

46785504 and 47013601

D303623. Acetamiprid. Tolerance Petition Requesting Section 3 Registration for Food Use of 

the Insecticide Acetamiprid on Cucurbit Vegetables (Crop Group 9), Stone Fruits (Crop Group 

12), and Tree Nuts (Crop Group 14). Summary of Analytical Chemistry and Residue Data. 

Petition Number 4F6833. W. Drew, 11/05/2004. MRIDs: 46265701-46265703.

D306191. Acetamiprid. Tolerance Petition Requesting Section 3 Registration for Food Use of 

the Insecticide Acetamiprid on Tuberous and Corm Vegetables (Crop Subgroup 1C) and NonFood Use on Tobacco. Summary of Analytical Chemistry and Residue Data. Petition Number 

3F6575. W. Drew, 11/03/2004. MRIDs: 45900506-45900509.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 26 of 38

D264154. 0F6082. Section 3 Registration for Use of Acetamiprid on Cotton, Leafy Vegetables, 

Cole Vegetables, Fruiting Vegetables, Citrus Fruits, Pome Fruits, Grapes, and Canola and 

Mustard Seed. Summary of Analytical Methods and Residue Chemistry DERs. M. Doherty, 

12/31/2001. MRIDs: 44988518-44988524, 44988526, 44988529, 44988532-44988535, 

44988601-44988603, 44988610, 44988611, 44988616, 44988618-44988623, 4498862.

D278652. Acetamiprid. Results of the HED Metabolism Assessment Review Committee 

Meeting Held on October 16, 2001. H. Bietlot, M. Doherty, and P. Hurley, 11/13/2001. MRID: 

None.

Attachments: 

International Residue Limit Status sheet

Appendix I - Tolerance Assessment Calculations
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 27 of 38

INTERNATIONAL RESIDUE LIMIT STATUS

Chemical Name: Common Name:

Acetamiprid

X Proposed tolerance

 Reevaluated tolerance

 Other

Date: 07/06/2009

Updated: Oct 5, 2009 

with the tea MRL 

information.

Codex Status (Maximum Residue Limits) U. S. Tolerances

X No Codex proposal step 6 or above

 No Codex proposal step 6 or above for the crops 

requested

Petition Number: 9E7544

DP Barcode: D364833

Other Identifier: 

Residue definition (step 8/CXL): N/A Reviewer/Branch: Dennis McNeilly/RAB2

Residue definition: acetamiprid [N1-[(6-chloro-3-

pyridyl)methyl]-N2-cyano-N1-methylacetamidine]

Crop (s) MRL (mg/kg) Crop(s) Tolerance (ppm)

Clover, forage 0.10

Clover, hay 0.01

Fruit, small, vine climbing, 

except fuzzy kiwifruit, 

subgroup 13-07F

0.35

Tea 50.0

Limits for Canada Limits for Mexico

 No Limits

 No Limits for the crops requested

 No Limits

X No Limits for the crops requested

Residue definition: (E )-N-[(6-chloro-3-

pyridinyl)methyl]-N’ -cyano-N-methylethanimidamide

Residue definition: acetamiprid

Crop(s) MRL (mg/kg) Crop(s) MRL (mg/kg)

Grapes 0.2

Notes/Special Instructions:

S. Funk, 07/07/2009. Note: There are no MRLs for acetamiprid in Codex. There is no MRL for 

acetamiprid on tea in Australia. There is no MRL for acetamiprid on tea in Canada. Japan has a 50 

ppm MRL for tea.

Rev. 1998
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 28 of 38

Appendix I

Tolerance Assessment Calculations

Clover forage

The dataset used to establish a tolerance for acetamiprid on clover forage consisted of field trial 

data representing a single application at rates of 0.074-0.079 lb ai/A with a 28- to 34-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 residue values that were entered into the tolerance 

spreadsheet are provided in Table I-1.

2 of 6 field trial sample results were below LOQ (LOQ = 0.01 ppm), entering the LOQ and using 

maximum likelihood estimation (MLE) procedures for the censored values both yielded a 

recommended tolerance of 0.1 ppm. Visual inspection of the lognormal probability plot (Figure 

I-1) and the result from the approximate Shapiro-Francia test statistic (Figure I-2) indicated that 

the assumption of lognormality should be rejected.

Since the field trial data for acetamiprid on clover forage are not lognormal, the upper bound on 

the 89th percentile should be selected as the tolerance value (distribution-free method). Using the 

rounding procedure as outlined in the SOP, the upper bound on the 89th percentile rounds to the 

value 0.10 ppm. Therefore, 0.10 ppm is the recommended tolerance level for acetamiprid in/on 

clover forage.

Table I-1. Residue data used to calculate tolerance for acetamiprid on clover forage.

Regulator: EPA

Chemical: Acetamiprid

Crop: Clover Forage (MLE)

PHI: 28-34 Days

App. Rate: 1 at 0.074-0.079 lb ai/A

Submitter: IR-4

MRID Citation: MRID 47716901

Residues of Acetamiprid (ppm)

0.05

0.04

0.05

0.05

0.01 

0.01
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 29 of 38

Figure I- 1. Lognormal probability plot of acetamiprid field trial data for clover forage.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 30 of 38

Figure I- 2. Tolerance spreadsheet summary of acetamiprid field trial data for clover forage.

Regulator: EPA

Chemical: Pymetrozine

Crop: LeafLettuce

PHI: 0-1 Day

App. Rate:

Submitter:

n: 6

min: 0.01

max: 0.05

median; 0.05

average: 0.04

95th Percentile 99th Percentile 99.9th Percentile

0.07 0.09 0.10

(0.15) (0.15) (--)

0.15 0.20 0.35

(0.60) (1.7) (--)

0.10

0.10

UPLMedian95th 0.60

0.7235

0.05 >= p-value > 0.01 : Reject lognormality assumption

Approximate

Shapiro-Francia 

Normality Test 

EU Method II

Distribution-Free

California Method

μ + 3σ

EU Method I

Normal

EU Method I

Log Normal

Grapes

The dataset used to establish a tolerance for acetamiprid on grape consisted of field trial data 

representing application rates of 0.195-0.206 lb ai/A (2 applications at ~0.10 lb ai/A/application) 

with a 2- to 3-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 residue values that were entered 

into the tolerance spreadsheet are provided in Table I-2.

All 36 field trial sample results were equal to or greater than the LOQ (LOQ = 0.01 ppm). Visual 

inspection of the lognormal probability plot (Figure I-3) and the result from the approximate 

Shapiro-Francia test statistic (Figure I-4) indicated that the assumption of lognormality should be 

rejected. 

Since the field trial data for acetamiprid on grape are not lognormal, the upper bound on the 89th

percentile should be selected as the tolerance value (distribution-free method). Using the 

rounding procedure as outlined in the SOP, the upper bound on the 89th percentile rounds to the 

value 0.35 ppm. Therefore, 0.35 ppm is the recommended tolerance level for acetamiprid on 

grape. 

Table I-2. Residue data used to calculate tolerance for acetamiprid on grapes.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 31 of 38

Regulator: EPA

Chemical: Acetamiprid

Crop: Grape

PHI: 2-3 Days

App. Rate: 2 at 0.10 lb ai/A/application

Submitter: IR-4

MRID Citation: MRID 47716902

Residues of Acetamiprid (ppm)

0.050

0.050

0.030

0.030

0.010

0.010

0.080

0.080

0.170

0.150

0.080

0.090

0.080

0.080

0.200

0.210

0.240

0.250

0.100

0.110

0.060

0.060

0.220

0.220

0.040

0.040

0.070

0.060

0.040

0.030

0.150

0.150

0.240

0.220

0.130

0.130
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 32 of 38

Figure I- 3. Lognormal probability plot of acetamiprid field trial data for grape.

Lognormal Probability Plot

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

1.0000

0.5000

0.2500

0.1250

0.0625

0.0313

0.0156

0.0078

y = 0.8301x - 2.4867

R

2

 = 0.9355

Percentiles

Concentrations

EPA Acetamiprid Grape 2-3 Days 2 at 0.10 lb ai/A IR-4

Figure I- 4. Tolerance spreadsheet summary of acetamiprid field trial data for grape.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 33 of 38

Regulator: EPA

Chemical: Acetamiprid

Crop: Grape

PHI: 2-3 Days

App. Rate: 2 at 0.10 lb ai/A

Submitter: IR-4

n: 36

min: 0.01

max: 0.25

median: 0.08

average: 0.11

95th Percentile 99th Percentile 99.9th Percentile

0.25 0.30 0.35

(0.30) (0.35) (--)

0.35 0.60 1.2

(0.60) (1.1) (--)

0.35

0.35

0.40

0.9355

0.05 >= p-value > 0.01 : Reject lognormality assumption

Approximate 

Shapiro-Francia 

Normality Test 

EU Method I

Normal

UCLMedian95th

95/99 Rule

EU Method II

Distribution-Free

Mean+3SD

Tea

The dataset used to establish a tolerance for acetamiprid on tea consisted of a report summarizing 

the results of two studies on tea conducted in Japan (by Nippon Soda Co., Ltd.) and India (by the 

Institute of Himalayan Bioresource Technology; IHBT), submitted by the Interregional Research 

Project No. 4 (IR-4). The dataset used to establish a tolerance for acetamiprid on tea consisted of 

field trial data representing application rates of 0.022-0.27 lb ai/A (1 foliar application) with a 6-

to 14-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 residue values that were entered into 

the tolerance spreadsheet are provided in Table I-2.

The common moiety method used in the Japan study included the metabolite IC-0 which is not a 

residue of concern for tolerance enforcement or risk assessment but, based on the available plant 

metabolism studies, it may constitute a significant portion of the total residues (e.g., up to 24% 

total radioactive residues (TRR) in cotton seed and 31% TRR in carrot flesh; refer to D278652, 

11/13/01, H. Bietlot and M. Doherty). Therefore, the residues reported for the Japan study may

reflect an overestimation of expected residues of acetamiprid per se in green tea.

All 38 field trial sample results were equal to or greater than the LOD (LOD = 0.05 ppm). Visual 

inspection of the lognormal probability plot (Figure I-3) and the result from the approximate 

Shapiro-Francia test statistic (Figure I-4) indicated that the assumption of lognormality should be 

rejected. 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 34 of 38

Since the field trial data for acetamiprid on tea are not lognormal, the upper bound on the 89th

percentile should be selected as the tolerance value (distribution-free method). Using the 

rounding procedure as outlined in the SOP, the upper bound on the 89th percentile rounds to the 

value 40.0 ppm. However, one residue value is above the 40 ppm level (40.9 ppm) and Japan 

has already established a 50.0 ppm MRL for acetamiprid on tea; therefore, HED recommends for 

a 50 ppm tolerance. 

Given our understanding that FDA would adjust residues measured on instant tea back to a dried 

tea basis for enforcement purposes, HED believes that the 50.0 ppm tolerance for dried tea is 

adequate to cover residues in or on instant tea and hence is not recommending for a separate 

instant tea tolerance. HED notes that the 50.0 ppm tolerance harmonizes with Japan. The 

residue data from Japan included the IC-0 metabolite, which is not in the U.S. tolerance 

expression and therefore the data are considered conservative.
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 35 of 38

Table I-3. Residue data used to calculate tolerance for acetamiprid on tea.

Regulator: EPA

Chemical: Acetamiprid

Crop: Tea

PHI: 6-14 Days

App. Rate:

Submitter: IR-4

MRID Citation: MRID 47781201

Residues of Acetamiprid (ppm)

16.4

17.2

8.15

8.45

16.5

16.7

13.6

14.0

9.32

9.78

0.24

0.15

0.07

0.51

0.42

0.23

0.68

0.45

0.21

1.47

1.21

0.62

0.2

0.12

0.06

0.38

0.26

0.15

0.54

0.38

0.18

1.1

0.67

0.38

37.7

40.9

22.5

23.6
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 36 of 38

Figure I- 4. Lognormal probability plot of acetamiprid field trial data for tea.

Lognormal Probability Plot

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

41.0000

20.5000

10.2500

5.1250

2.5625

1.2813

0.6406

0.3203

0.1602

0.0801

0.0400

y = 1.9873x + 0.3103

Percentiles

Concentrations

EPA Acetamiprid Tea 6-14 Days
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 37 of 38

Figure I- 5. Tolerance spreadsheet summary of acetamiprid field trial data for tea.

Regulator: EPA

Chemical: Acetamiprid

Crop: Tea

PHI: 6-14 Days

App. Rate:

Submitter:

n: 38

min: 0.06

max: 40.90

median: 0.65

average: 6.99

95th Percentile 99th Percentile 99.9th Percentile

25 35 40

(30) (40) (--)

40 160 750

(110) (580) (--)

30

40

3.5

0.9046

p-value <= 0.01: Reject lognormality assumption

Approximate 

Shapiro-Francia 

Normality Test 

EU Method I

Normal

UCLMedian95th

95/99 Rule

EU Method II

Distribution-Free

Mean+3SD
Acetamiprid Summary of Analytical Chemistry and Residue Data DP#: 364833

Page 38 of 38

Regulator: EPA

Chemical: Acetamiprid

Crop: Tea

PHI: 7-14 Days

App. Rate:

Submitter:

n: 38

min: 0.06

max: 40.90

median; 0.65

average: 6.99

95th Percentile 99th Percentile 99.9th Percentile

25 35 40

(30) (40) (--)

40 160 750

(110) (580) (--)

30

40

UPLMedian95th 3.5

0.9046

p-value <= 0.01: Reject lognormality assumption

Approximate

Shapiro-Francia 

Normality Test 

EU Method II

Distribution-Free

California Method

μ + 3σ

EU Method I

Normal

EU Method I

Log Normal