Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode 0423321 

UNITED STATES ENVIRONMENTAL PROTECTION AGENCY 

WASHINGTON, DC 20460 

OFFICE OF CHEM ICAL SAFETY AND 

PO LLUTION PREVENTION 

MEMORANDUM 

DATE: 2 September 2015 

SUBJ ECT: Acctamiprid. Proposed Label Amendments for Use of Two End-Use Products 

on Various Crops; Petition Proposing Label Amendments. and Revised 

Permanent Tolerances, for Use of the Insecticide on Clover with a Decreased PreHarvest Interval (Regional Registration). Summary of Analytical Chemistry 

and Residue Data. 

PC Code: 099050 DP Barcocles: 0423321. 04261 15. 0 4261 17 

Registration Numbers: 8033-23. 8033-36 

Regulatory Action: Section 3 

Decision Numbers: 494790. 500022. 500044 

Petition: 4E8307 

Risk Assessment Type: A 

TXR Number: A 

Case Number: 76 17 

CAS Number: 135410-20-7 

MRID Numbers: 4944380 I. 49443802 40 CFR: § 180.578 

FROM: 

THRU: 

and 

TO: 

and 

~ -

William T. Drew, Chemist W~ ~ 

Risk Assessment Branch II (RAB2) 

Health Effects Division (HED), 7509P 

Douglas A. Dotson, PhD. Senior Chemist ,J. J;t:i:nv 

RAB2/HED. 7509P 

Sarah Levy. Chemist ~( [..v./ H ~o\ 5" r'lh Le v1 

RABl/HEO, 7509P. Chemistry Se enccfXi~sory Council (ChemSAC) 

Katelynn King, Biologist r WMv..11 \~ RAB7/HED, 7509P, ChemSAC- r~ . - 0 

Barbara Madden and Sidney Jackson, RM Team 5 

Minor Use and Emergency Response Branch (MU ERB) 

Registration Division (RD), 7505 P 

Venus Eagle and Jacquelyn Marchese. RM Team I 

l nvcrtebrate-Vertebrate Branch 3 (I VB3) 

RD, 7505P 

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Acctamiprid Summary of Analytical Chemistry and Residue Data DP Barcode 0423321 

Table of Contents 

1.0 Executive Sumn1ary .................. ............................................................................ ................ 4 

2.0 Regulatory Recommendations .............. ............ .................................................................... 5 

2.1 Data Deficiencies/Data Needs ................. ................................................................ ......... 6 

2.2 Tolerance Considerations ............. ... ......... ............. ... ........ ................................. ................ 6 

2.2.1 Enforcement Analytical Method/Multi-Residue Methods ........................................ 6 

2.2.2 Recommended Tolerances .. ........ ............ ............ ............................................ .......... 7 

2.2.3 Revisions to Petitioned-For Tolerances ............. ....................................................... 7 

2.2.4 International Harmonization ..................................................................................... 7 

2.3 Label Recomn1endations ................. ............. ............................................. ....................... 7 

2.4 Submittal of /\nalytical Reference Standards (860.1650) ............................................... 8 

3.0 Chen1ical Identity ........ ......................................................................................................... 8 

3.1 Nomenclature .......... ................... ........ ..... ........ ................................................................. 9 

3.2 

3.3 

4.0 

4.1 

Physicochemical Characteristics ...................................................................................... 9 

Pesticide Use Pattern/Directions for Use (860.1200) ....... ............................................. 10 . Metabolite/Oegradate Residue Profile .. .................................................. ........................... 13 

Nature of the Residue ..................................................................................................... 13 

4.1.1 Summary of Plant and/or Livestock Metabolism (860.1300) ................................. 14 

4.1.2 Summary of Confined Rotational Crops (860.1850) ....... ........................................ 14 

4.1.3 Summary of Rat Metabolism ................................................. ................................. 14 

4.1 .4 Summary of Environmental Degradation ........... .................................................... 15 

5.0 Residue Profile ................................................................................................................... 15 

5. 1 Residue Analytical Methods (860.1340) ...................................................................... 15 

5.1.1 Data Collection Methods ........................................................................................ 15 

5.1.2 Multi-Residue Methods (860.1360) ........................................................................ 17 

5.1.3 Tolerance Enforcement Methods ............................................................................ 17 

5.2 Storage Stability (860. 1380) ..... ..................................................................................... 18 

5.3 Residue Data .................................................................................................................. 19 

5.3.1 Crop Field Trials (860.1 500) ................ .................... .............................................. 19 

5.3.2 Field Rotational Crops (860.1900) ......................................................................... 20 

5.3.3 Processed Food and reed (860.1 520) ..................................................................... 20 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode 0423321 

5.3.4 Meat, Milk. Poultry and Eggs (860.1480) .............................................................. 20 

5.3.5. Food I fandling (860. 1460) ............................................................ .......................... 22 

5.3.6 Water, Fish and Irrigated Crops (860.1400) ........................................ ...... ...... ....... 22 

5.4 Food Residue Profile ...................................................................................................... 22 

6.0 Tolerance Deri vation .......................................... ............. ................... ......................... ...... 22 

7.0 Chen1SAC Reference ......................................................................................................... 23 

References ....... ...... ....... ...... ...... ....... ....... ....... ........... ....... ....................... ......... .............................. 23 

Attachment I: International Residue Limit Status ......... .............................. ...... ...... .................... 25 

Attachment 2: OECD MRL (Tolerance) Assessment Calculations .............................................. 26 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D42332 I 

1.0 Executive Summary 

J\cctamiprid (with CAS name (I E)-N-[(6-chloro-3-pyridinyl)methyl]- '-cyano- -

methylethanimidamide) is a selecti ve insecticide intended for use against various sucking and 

chewing insect pests that feed upon fruit and vegetable crops. It is a member of the 

chloro nicotinyl (neonicotinoid) class of insecticides, which function by binding to nicotinic 

acetylcholine receptors in the post-synaptic neurons of the insect's central nervous system. This 

binding results in the opening of ion pores, causing a subsequent overload of sodium ions in the 

neurons which leads to nervous system hyper-excitatio n. and the eventual death of the insect. 

Acetamiprid is registered for use on a variety of crops. and permanent tolerances have been 

established ranging from 0.0 10 ppm to 50 ppm in plant commodities (40 CFR §180.578[aj[l]). 

and from 0.010 ppm to 0.70 ppm in li vestock commodities (40 CFR §180.578[a)[2]). There are 

also permanent tolerances (with regional registrations) established in clover forage at 0.10 ppm. 

and clover hay at 0.01 ppm (40CFR § 180.578lc]). The residue definition for risk assessment 

and tolerance enforcement is the parent compound in plant commodities, and combined residues 

of the parent compound and Metabolite IM-2-1 in livestock commodities (plus Metabolite IM-2-

1-amide in ruminant muscle for risk assessment purposes only). Acceptable analytical methods 

are available to enforce tolerances for residues of acetamiprid in plant and livestock 

commodities. 

Interregional Research Project #4 (lR-4) has submitted a petition (4E8307) requesting an 

amended use pattern, and revised tolerances in clover forage and hay. for use o f the insecticide 

acetamiprid on clover grown for seed in ID. OR and WA only. The proposed pre-harvest 

interval (PHI) is 30 days for clover, compared to the currently registered PHI of 56 days. The 

end-use products (EPs) proposed for regional registration are Assail 70WP Insectic ide (EPA 

Registration #8033-23), a wettable powder (WP) formulation containing 70% of the active 

ingredient (ai) by weight, and Assail 30SG Insecticide (EPA Registration #8033-36), a soluble 

granule (SG) formulation containing 30% of the ai by weight. 

IR-4 submitted field trial data for acetamiprid on clover grown for seed in response to an Agency 

request for two additiona l clover field trials as confirn1atory data (0364833; D. Mc eilly; 14 

October 2009). In conjunction with the petition, IR-4 has proposed the revision of established 

tolerances for residues of acetamiprid in o r o n clover forage (from 0.10 to 0.3 ppm) and clover 

hay (from 0.0 I to 1.5 ppm). with regional registration (in ID, OR and WA only). The proposed 

tolerance in clover forage is suppot1ed adequately by the current submitted field trial residue 

data, in conjunction with previously submitted field tri al data (0 364833; 0. Mc eilly: 14 

October 2009). The current submitted field trial residue data support the recommended tolerance 

in clover hay of 2.0 ppm. 

Nippon Soda Company Limited (care of isso America Incorporated) has also proposed multiple 

label amendments (0426 11 5 and 0426 11 7) for revised use patterns of the same acetamiprid EPs 

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Ace1amiprid Summary of Analytical Chemistry and Residue Data DP Barcode 0423321 

(Assail 70WP and Assail 30SG) on various crops. These amendments do not require the revision 

of any existing acetamiprid tolerances. 

Pending submission of a revised Section F (to propose tol erances in clover forage and hay in 

accordance with HED's recommendations). there are no residue chemistry issues that would 

preclude increasing the established tolerances in clover forage and hay to the levels 

recommended by HED. The specific residue chemistry findings are summari zed below. 

Additionally. HED has no objection regarding the proposed label amendments for revised use 

patterns of the acetamiprid EPs. Assail 70WP and Assail 30SG. on various crops. 

Crop field trials: Two pairs of field trials were conducted in the US in North American Free 

Trade Agreement (NAFTA) Growing Zone 11 during the 2010 (MRID #49443801) and 2012 

(MRID #49443802) growing seasons. HED has determined that the 2010 trials, which were 

separated by less than 20 miles, are repli cate tri als. Following a single fol iar broadcast 

application of the 30% SG formulation at 0.075-0.080 pounds of ai per acre (lb ai/ A), residues of 

acetamiprid (and per-trial averages) were 0.0496-0. I 69 (0.08 12-0. I 63) ppm and 0.200-0.763 

(0.450-0.753) ppm in clover forage and hay, respectively. harvested at a PHI of27-32 days. 

Residue decline was not evaluated. 

Processed food and f eed: There are no processed commodities associated with clover forage 

and hay. 

Residue analytical methods and storage stability: Validated methods are available for the 

enforcement of acetamiprid tolerances. An adequate method was used for the quantitation of 

acetamiprid residues in samples from the c lover field trials. based on acceptable method 

validation and concurrent recovery data. Adequate data are available to support sample storage 

durations and conditions. 

Meat, milk, poultry and eggs: The current action for the proposed PHI reduction (and increased 

tolerances in clover forage and hay) fo llowing use on clover does not require revisions to the 

existing tolerances in livestock commodities. 

M RL '1armo11izatio11: Codex has not established maximum residue limits (MRLs) for 

aeetamiprid in clover forage or hay. Canada's Pest Management Regulatory Agency (PMRA) 

does not establish MRLs in livestock feed items. Ergo, there are no issues with international 

harmonization that need to be addressed. 

2.0 Regulato11' Recommendations 

I-JED has examined the residue chemistry database for acecamiprid. Pending submission of a 

revised Section F (to propose tolerances in clover forage and hay in accordance with HED's 

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Acctamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D.t2332 I 

recommendations), the re are no residue chemistry issues that would preclude the establishment 

of the recommended tol erances. The recommended tolerances are listed in Table 2.2.2, below. 

H ED has no objection regarding the proposed label amendments for revised use patterns of the 

acetamiprid EPs, Assail 70WP and Assa il 30SG, on various crops. 

Notes to RD: An error has been identified with a commodity deiinition in the existing 40CFR 

entry for acetamiprid, which currently lists "'Vegetable, tuberous and co1m, group I '' under 

40CFR § I 80.578ra][l). This listing should be revised to read "Vegetable. tuberous and corm. 

subgroup IC'' when the tolerances for clover forage and hay are revised. 

The analytical reference standard for acetamiprid metabolite IM-1-4 (having expired on l April 

2015) is currently unavailable in EPA's National Pesticide Standards Repository (NPSR), per 

Email communication from Theresa Cole of the Biological and Economic Analysis Division·s 

Analytical Chemistry Branch (BEAD/ACB) on 1June2015. RD should notify the registrant 

(Nisso America Incorporated) regarding this lack of a reference standard for metabolite IM-1-4, 

and request that the registrant provide a new reference standard, or updated certificate of analysis 

(CO/\), as soon as possible. 

2.1 Da ta Deficiencies/Data Needs 

one. 

2.2 Tolerance Considerations 

2.2.1 Enforcement Ana lytica l Method/Multi-Residue Methods 

Approved tolerance enforcement methods for acetamiprid residues in crops are available. 

including gas chromatography with electron capture detection (GC/ ECD) for vegetables and 

non-citrus fruits, high performance liquid chromatography with ultraviolet detection (HPLC/UV) 

for citrus fruits only, and HPLC with tandem mass spectrometric detection (LC/MS/MS) for 

vegetables and non-citrus fruits (D394779; E. llolman; 6 March 20 12). 

Data concerning the recovery of residues of acetamiprid using Food and Drug Administration 

(FDA) multi-residue method protocols from Pesticide Analytical Manual (PAM) Volume 1 were 

submitted in conjunction with the original acetami prid petition (PP#OF6082). Based on the 

results of the testing. the multi-residue methods are not appropriate for detern1ining acetamiprid 

residues of concern. BEAD/ACB is currently working on a multi-residue method for the 

nconicotinoids (D264154; M. Doherty; 3 1 December 200 l ). 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D-123321 

2.2.2 Recommended Tolerances 

TABLE 2.2.2 Toler a nce Summary for Acetamiprid (40CFR 80.5781cl). 

Commodity Existing Proposed Recommended Correct Commodity Defi11itio11; 

Tolerance (Dpm) Tolerance (ppm) Tolerance ( ppm)' Comments 

Clover. forage 0. 102 0.3 0.30 Based on current and previous clover 

field trial data submitted by I R-4. 

Clover. hay 0.0 12 1.5 2.0 Based on current clover fie ld trial 

data submitted by IR-4. 

I. Tolerance level as recommended by HED. 

2. A tolerance is currently established at the listed tolerance level in the corresponding commodity. 

The currently established tolerance expressions for acetamiprid ( 40CFR § 180.578) are adequate, 

and include both coverage and compliance statements for enforcement purposes. 

2.2.3 Revisions to Petitioned-For Tolerances 

The submitted clover field trial data support a tolerance of2.0 ppm, instead of the proposed 

tolerance of 1.5 ppm, in clover hay. The petitioner used residues in clover hay from all field 

trials to calculate the tolerance level (PHis of 27-63 days). The draft labels stipulate a PHI of 30 

days (decreased from 56 days on the current labels). Therefore, only residues from those trials 

where hay was collected at PHls of 27-32 days were used to calculate the tolerance; residues 

from those trials where hay was collected at PH ls of 50-63 days were not used. HED utilized 

residue data for hay coll ected at PHis of 27-32 as the input dataset for the Organization for 

Economic Cooperation and Development (OECD) tolerance calculation procedure, yielding a 

different result (2.0 ppm). 

In clover forage, the recommended tolerance level includes an additional significant figure (0.30 

ppm rather than 0.3 ppm). This is in order to avoid the situation where rounding of a residue 

result to the level of precision of the tolerance expression would be considered non-violative 

(such as 0.34 ppm being rounded to 0.3 ppm). 

2.2.4 International Harmonization 

Codex has not established MRLs for acetamiprid in clover forage or hay. Canada's PMRA does 

not establish MRLs in livestock reed items. Ergo, there are no issues with international 

harmoni zation that need to be addressed. 

2.3 Label Recommendations 

None. 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode 0423321 

2.4 Submittal of Analytical Reference Standards (860.1650) 

The analytical reference standard for parent acetamiprid (expiration date of2 October 2016) is 

currently available in EPA"s NPSR, per Email communication from Theresa Cole of 

BEAD/A CB on I June 20 15. The registrant is required to maintain reasonable amounts of the 

reference standards for acetamiprid and its metabolite IM-2-1 in the NPSR as long as tolerances 

remain published in 40CFR § 180.578. When necessary, new reference standards. or updated 

COAs, should be sent to the ACB, which is located at Fort Meade. MD. They should be sent to 

the attention of either Theresa Cole or Thuy guyen at the address listed below. along with a 

letter of transmittal. Please note that the full 9-digit ZIP Code is required, or the mail will be 

returned to the registrant. 

USEPA 

National Pesticide Standards Repository 

Analytical Chemistry Branch/BEAD/OPP 

701 Mapes Road 

Fort George G. Meade, MD 20755-5350 

The letter of transmittal should include the assay of the standard, name of the analytical method 

used, a statement of principal impurities, purification procedures employed, storage 

requirements. and special precautions for safe handling. Replacement of standards. or updated 

CO As, may be required periodically if supplies are exhausted, if the standards expire. or if 

decomposition occurs during storage. Material Safety Data Sheets (MSDSs) must accompany all 

analytical standards as specified by the Occupational Safety and Health Administration (OSHA) 

in 29CFR § 1910.1200. In addition to the parent compound, various acctamiprid metabolites are 

cun-ently available in the NPSR, as listed below with their respective expiration dates. 

Acetamiprid metabolite IC-0: 18 September 2023. 

Acetamiprid metabolite IM-1-2: 14 April 2024. 

Acetamiprid metabolite IM-1-4: I April 20 15 (**Expired**). 

Acetamiprid metabolite IM-2- 1: 14 April 2020. 

Acetamiprid metabolite lM-2-2: 6 December 2024. 

3.0 Chemical Identity 

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

insect pests that feed upon fruit and vegetable crops. It is a member of the chloronicotinyl 

(neonicotinoid) class of insecticides, which function by binding to nicotinic acetylcholine 

receptors in the post-synaptic neurons of the insect's central nervous system. This binding 

results in the opening of ion pores, causing a subsequent overload or sodium ions in the neurons 

which leads to nervous system hyper-excitation, and the eventual death of the insect. The 

chemical structure and nomenclature of acctamiprid are listed in Table 3. 1, and its 

physicochemical properties arc presented in Tabl e 3.2 (below). 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D42332 I 

3.1 Nomenclature 

TABLE 3. 1 Acetamiprid Nomenclature. 

Chemical Structure 

Cl~ I ~ CH. I ~ 

N ,,,,.;;;. Nl(Cl ... 11 

N 

'cN 

Common Name Acetamiprid 

Molecular Formula Cio 11 CIN~ 

Molecular Weight 222.68 

Company Experimental Name EXP-6 I 842A, AEF 124370. NI-25 

IUPAC Name (£)-.N 1-[(6-chloro-3-pyridyl)methyl]-N 1-cyano-N 1-methylacetamid ine 

CAS Name ( I £)-N-[(6-chloro-3-pyridinyl)methyl]-N'-cyano-N-methylcthanimidamide 

CAS Registry Number 1354 10-20-7 

End-use Products (EPs) Assail 70WP (70% WP: EPA Registration #8033-23) 

Assail 30SG (30% SG: EPA Registration #8033-36) 

3.2 Physicochemical Characteristics 

TABLE3.2 Phvsicochemical Properties of Technical-Grade Acetamiprid. 

Parameter Value Reference 

Melting Point/Range (°C) 98.9 D328216: W.T. Drew: 23 October2007 

pH 6.08 (Aqueous solution at 20°C) 

Density (g/cm') 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 >20g/100g 

Chloroform >20 g/100 g 

Acetonitrile >20 g/ 100g 

Tetrahydrofuran >20g/100 g 

Benzene 2.44 g/ 100 g 

Xylene 4.01 g/ IOOg 

n-1 lexane 6.54 ppm 

Carbon disulfide 507 ppm 

Vapor Pressure (mm Hg) 7.5 X 10·9 (at 25°C) D264 I 54: M. Doherty: 31 December 

2001 

Dissociation Constant. pKa 0.7 (at 25°C) D3282 16: W.T. Drew: 23 October2007 

Octanol/Water Partition 0.8 (at 25°C) 

Coefficient. Log Kow 

UVN isiblc Absorption Spectrum Not available 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D42332 I 

Acetamiprid is a solid under ambient conditions, and has a low volatility. The compound has a 

relative ly low solubility in water, and low to high solubility in various organic solvents. Its 

octanol/water partition coefficient suggests that accumulation of acetamiprid in fatty tissues is 

unlikely. 

3.3 Pesticide Use Pattern/Directions for Use (860.1200) 

IR-4 has proposed an amended use pattern, and revised tol erances in clover forage and hay. for 

foliar broadcast use of the insecticide acetamiprid on c lover grown for seed in ID. OR and WA 

onl y. The proposed PHI is 30 days for c lover, compared to the currentl y registered Pl ll of 56 

days. The EPs proposed for regional registration are Assail 70WP Insecticide (EPA Registration 

#8033-23), a WP formulation containing 70% of the ai by weight, and Assail 30SG Insecticide 

(EPA Registration #8033-36), an SG formulation containing 30% of the ai by weight. Examples 

of the proposed labels were provided, and the proposed use directions therein are summarized in 

Table 3.3. 1, below. 

isso America has also proposed multiple label amendments for revised use patterns of the same 

acetamiprid EPs (Assail 70WP and Assail 30SG) on various crops. The requested revisions 

increase single (but not seasonal) use rates, add pests, and make additional minor changes to the 

EP labels. These label revisions do not change the amount of ai applied per acre per crop, and no 

revisions to tolerances were proposed by the registrant. Examples of the proposed labels were 

provided, and the proposed use pattern revisions therein are summarized in Table 3.3.2, below. 

TABLE 3.3. l Summary of Proposed Label Directions for Use of Acetamiprid on Clover. 

Application Use Rate Max. Uses Maximum PHl 2 Use Directions and Limitations 

Timing; Type; (lb ai/A) per Season Seasonal Use (Days) 

Eq uipment• Rate (lb ai/A) 

Assail 70WP 

Post-emergence; 0.05- I J 0.075 30 Minimum spray volume of 5 GPA~ by 

foliar broadcast: 0.075 air, or 20 GPA by ground. Begin 

ground. aerial applications when treatment thresholds 

have been reached. Thorough coverage 

is important to obtain optimum control. 

Assail 30SG 

Post-emergence; 0.047- ]l 0.075 30 Minimum spray volume of5 GPA by 

foliar broadcast; 0.075 air, or 20 GPA by ground. Begin 

ground, aerial applications when treatment thresholds 

have been reached. Thorough coverage 

is important to obtain optimum control. 

I. Not to be applied via chemigation. 

2. PHI = Pre-Harvest Interval. 

3. Implied; more than 1 application at the minimum single use rate would exceed the maximum seasonal use rate. 

4. GPA - Gallons Per Acre. 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode 0423321 

Conclusions: The use directions for application to clover are sufficient to allow for evaluation of 

the submitted residue data relative to the proposed use pattern. 

TABLE 3.3.2 Summary of Proposed Amendments to Label Directions for Use of Acetamiprid. 

C rop Pest C urrent Proposed Amendments to Use Directions a nd 

Use Ra te Use Rate Limitations 

(lb a i/A) (lb ai/A) 

Assail 70WP (EPA Registration #8033-23) 

Cotton Whitefly 0.075- 0.075- To "Do not make more than 4 applications per 

0.10 0.15 season:· add "or more than 2 applications per 

season if 2 applications of the highest labeled rate 

is applied for both applications." 

Leafy Aphid 0.035- 0.035- To "Do not make more than 5 applications per 

Vegetables 0.075 0. 10 season." add "or more than 3 applications per 

(within Crop Whitefly 0.05- 0.05-0.10 season if 3 applications of the highest labeled rate 

Group 4) 0.075 is applied for all 3 applications:· 

I lead and Stem NA1 NA NA Change " I lead and Stem Cole Crops (within 

Cole Crops Crop Subgroup 5A)'" to "Head and Stem Brassica 

(within Crop (within Crop Subgroup 5A)." 

Subgroup SA) 

Leafy Cole NA NA A Change "Leafy Cole Crops (within Crop 

Crops (within Subgroup 58)" to "Leafy Brassica (within Crop 

Crop Subgroup Subgroup SB)."' 

58) 

Fruiting Lea fhoppcr2 NA 0.05- Add "Begin applications when treatment 

Vegetables 0.075 thresholds have been reached. Thorough 

(within Crop coverage is important to obtain optimum 

Group 8- 10) control:· to the use directions for the new target 

pest. leafhopper. 

Citrus (within Asian Citrus Psyllid NA NA Add "(suooression)" note to this target pest. 

Crop Group I 0- Apple Maggot. Plum Remove "(suppression)" note from these target 

JO) Curculio. San Jose pests. 

Scale 

Grapes (within A 11 target pests A A Remove ··For ASSAIL WSP Insecticide Only ( I 

Crop Sub- to 2 packets)" from dosage per acre. Change 

Group I 3-07F) ··WSP" to "70WP" in mealybugs use directions. 

Remove ··Do not use adjuvants.·· from 

restrictions. 

Cucurbits Whitefly 0.05-0.10 0.05-0.15 To '·Do not make more than 5 applications per 

(within Crop season:· add "or more than 3 applications per 

Group 9) season if 3 applications of the highest labeled rate 

is applied for all 3 applications:· To ··oo not 

apply less than 0 days before harvest (PHI=O 

days):· add ··with application rate of2.3 oil A or 

less." Add "Do not apply less than 5 days before 

harvest (PH1=5 davs) with app lication rate of3.5 

oiJA:· to restrictions. 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D42332 l 

TABLE 3.3.2 Summary of Proposed Amendments to Label Directions for Use of Acetamiprid. 

Crop Pest Current Proposed Amendments to Use Directions and 

Use Rate Use Rate Limitations 

(1b ai/A) (lb ai/A) 

Legume Colorado Potato NA 0.044- Add "Colorado Potato Beetle: Use higher rates 

Vegetables Bectle2 0.10 when populations are high. dense foliage exists. 

(within Crop or when large larvae or adults are present. 

Sub-Groups 6A Thorough coverage is important to obtain 

and 68) optimum control." to use directions. 

Berries (within EAST of Rocky NA 0.085- Add "Spotted Winged Drosophila (larvae): Begin 

Crop Sub- Mountains Only. 0.10 applications when adults arc present and fruit is 

Groups 13-07 A Spoiled Winged ripening or already ripe. It is recommended to 

and 13-078) Drosophila (larvae )2 tankmix with an aduhicide." to use directions. 

Assail 30SG (EPA Registration #8033-36) 

Cotton Whitefly 0.075- 0.075- To "Do not make more than 4 applications per 

0.10 0.15 season." add ··or more than 2 applications per 

season if 2 applications of the highest labeled rate 

is aoolied for both applications." 

Leafy Aphid 0.038- 0.038- To ··Do not make more than 5 applications per 

Vegetables 0.075 0.10 season." add "or more than 3 applications per 

(within Crop Whitefly 0.056- 0.056- season if 3 applications of the highest labeled rate 

Group 4) 0.075 0.10 is applied for all 3 applications." 

Head and Stem NA NA NA Change "I lead and Stem Cole Crops (within 

Cole Crops Crop Subgroup 5A)'" to "Head and Stem Brassica 

(within Crop (within Crop ubgroup 5A).'' 

Subgroup 5A) 

Leafy Cole NA NA NA Change ·'Leafy Cole Crops (within Crop 

Crops (within Subgroup 58)" to "Leafy Brassica (within Crop 

Crop Subgroup Subgroup 58).'' 

58) 

Fruiting Leafhopper A 0.047- Add "Begin applications when treatment 

Vegetables 0.075 thresholds have been reached. Thorough 

(within Crop coverage is important to obtain optimum 

Group 8-10) control." to the use directions for the new target 

pest, leafhopper. 

Citrus (within Asian Citrus Psyllid NA NA Add "(suppression)" note to this target pest. 

Crop Group I 0-

I 0) 

Grapes (within A II target pests NA NA Remove "Do not use adjuvants." from 

Crop Sub- restrictions. 

Group I 3-07F) 

Cucurbits Whitefly 0.047- 0.047- To "Do not make more than 5 applications per 

(within Crop 0.10 0.15 season," acid ··or more than 3 applications per 

Group 9) season if 3 applications of the highest labeled rate 

is applied for all 3 applications." To "Do not 

apply less than 0 days before harvest (PH I 0 

days)," add ··with application rate of 5.3 ovA or 

less:· Add "Do not apply less than 5 days before 

harvest (PH1=5 davs) with application rate of8.0 

ovA.'. to restrictions. 

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TABLE3.3.2 Summary of Proposed Amendments to Label Directions for Use of Acetamiprid. 

Crop Pest Current Proposed Amendments to Use Directions and 

Use Rate Use Rate Limitations 

(lb ai/A) (lb ai/A) 

Legume Colorado Potato NA 0.047- Add "Colorado Potaro Beetle: Use higher rares 

Vegetables Beerle2 0.10 when populations are high. dense foliage exists. 

(within Crop or when large larvae or adults are present. 

Sub-Groups 6A Thorough coverage is important to obtain 

and 6B optimum control." to use directions. 

Berries (within EAST of Rocky NA 0.085- Add "Sponed Winged Drosophila (larvae): Begin 

Crop Sub- Mountains Only. 0.10 applications when adults are present and fruir is 

Groups 13-07 A Sponed Winged ripening or already ripe. Ir is recommended to 

and I 3-07B) Drosophila (larvae)2 rankmix with an adulticide.'" to use directions. 

I. NA = Not Applicable. 

2. New pcsr added to the list of target pests. 

Conclusions: HED has no objection regarding the proposed amendments to the labels· use 

directions. 

4.0 Metabolite/Degradate Residue Profile 

4.J Nature of the Residue 

Residue Chemistry Summary Document 0264154; M. Doherty; 31 December 2001 

Residue Chemistry Summary Document 0328216; W.T. Drew; 23 October 2007 

Radiolabeled metabolism studies are avai !able for canot, cabbage. cotton. apple, eggplant 

lactating goat, laying hen, and rat. In plants, there appears to be little translocation of 

acetamiprid following foliar application. In cabbage. there was uptake and translocation of 

acetamiprid to the above-ground po11ions of the plant following a soil application. Due to the 

rapid dissipation of acetamiprid in the field, root uptake is not considered to be a I ike ly source of 

residues in plants. Parent acctamiprid is the predominant residue, at >90% of total radioactive 

residues (TRR) in three of the five metabolism studi es. Confined rotational crop studies showed 

no residues of acetamiprid at the 30-day plant-back interval (PBI). 

Acctamiprid and metabolite IM-2- 1 are the major residues in all ruminant tissues except muscle. 

where I M-2-l-amide accounts for nearly 50% of the TRR. IM-2- 1-amide was not found in any 

other ruminant tissue. Metabolite IM-2-1 is the major residue in poultry tissues and eggs (50-

80% TRR). lM-2-5 is also a major residue in eggs (at roughly 20% TRR). Parent acetamiprid 

" ·as not detected in poultry tissues or eggs. The metabolism of acetamiprid in lactating goat was 

similar to the profile observed in laying hen and rat. The initial transformation appears to be 

demethylation of the parent compound. The most abundant metabolite identified (in both sexes) 

resulted from the removal of the cyanoacetamide group from demethylated parent. This removal 

(and direct removal of the group from the parent) resulted in cyanoacetamide metabolites. 

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Conclusions: The nature of the residue for acetamiprid is considered to be adequately 

understood for target crops, rotational crops. and livestock. 

4.1. l Summary of Plant and/or Livestock Metabolism (860.1300) 

MARC Decision Memo D278652; M. Do herty; 13 November 200 1 

Data have been submitted and reviewed depicting the metabolism of acetamiprid in livestock and 

numerous crops, and its degradation in the environment. HED has determined the residues of 

concern (ROCs) plants and livestock for purposes of tolerance enforcement and risk assessment 

(see Table 4. l .1, below). 

TABLE 4. 1. 1 Summa ry of Acetamiprid Metabolites a nd Degr adates to be included in the Risk 

Assessment and Tolerance Exoression. 

Matrix Residues Included in Risk Assessment Residues Included in 

Tolerance Expr ession 

Plants Primary Crop Acctamiprid Acctamiprid 

Rotational Crop NA* None at this time 

Livestock Ruminant Acetamiprid + IM-2- 1 + IM-2-1 -amide (muscle only) Acctamiprid + IM-2-1 

Poultry Acetamiprid and IM-2- 1 Acetamiprid + IM-2-1 

Drinking Water Acctamiprid NA 

• NA = Not Applicable. 

Conclusions: The nature of the residue in plants and livestock has been adequately delineated. 

-U.2 Summary of Confined Rotationa l Crops (860.1850) 

Residue Chemistry Sum ma r y Document 0 3282 16; W.T. Drew; 23 October 2007 

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 use. 

4.1.3 Summary of Rat Metabolism 

Risk Assessment Document 0 394322; E. Holma n; 19 April 2012 (PP# l E79 19) 

Several studies have examined the in vivo metabolism and distribution of acetamiprid in the rat. 

including single dose, 15-day repeated dose, biliary excretion, and metabolite characteri zation 

studies. 

Acetamiprid is rapidly absorbed and eliminated. Metabolism studies indicate 96-99% absorption 

following an oral administration. Peak blood concentrations in the rat occur within 1-2 hours, 

with nearly complete clearance from the blood by 48 hours. Acetamiprid distributes widely in 

the body, but tissue burdens rarely exceed 1 % of the administered dose. Acetamiprid is 

extensi vely metabolized, with metabolites accounting for 79-86% of the administered 

radioactivity. 6-Chloronicotinic acid is the most abundant metabolite, accounting for 24-28% of 

the dose in single-dose studies, and 8-10% in repeated-dose studies. Urinary excretion was the 

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Acetam iprid Summary of Analytical Chemisrry and Residue Data DP Barcode 0423321 

major route of elimination. accounting for 79-97% of the administered dose within 24 hours in 

single oral dose groups. Fecal excretion accounted for 2 1-35% of the administered radioactivity, 

with excretion in males being slightly higher. Excretion rates for the IV and repeated dose 

studies were similar. Biliary excretion did not vary between genders and, by 48 hours, accounted 

for about 19% of the administered radioactivity. 

As a result of the rapid absorption, metabolism, and clearance of acetamiprid in the rat, the 

pharmacokinetic parameters derived from the 15-day repeated dose study were similar to those 

derived from the single dose study. Therefore, the potential for acetamiprid to bioaccumulate is 

minimal. 

4.1.4 Summary of Environmental Degradation 

EFED Memo; 0423299; K. White; 25 March 2015 

J\cetamiprid may be transported to surface water and ground water via runoff, leaching and 

spray drift. J\cetamiprid is classified as moderately mobile using the Food and Agriculture 

Organization (F AO) classification system (Koes = 157 to 298 L/kg OC). The primary route of 

degradation is aerobic soil metabolism. Unextracted residues made up a significant amount of 

radioactivity. and the identity of the residues was unknown in metabolism studies. Therefore, 

degradation rates were estimated both for the parent alone and assuming that unextracted 

residues were the parent. Aerobic soil metabolism rates for the parent ranged from <I day to six 

days for the parent, and 2 to 99 days for the parent plus unextracted residues in nine soils. 

Aerobic aquatic metabolism rates were slower at 23 to 32 days for the parent alone. and 38 to 74 

days for parent plus unextracted residues in three sediments. Anaerobic aquatic metabolism was 

much slower, with a half-life of 325 days in a loamy sand sediment. Acetamiprid is stable to 

hydrolysis at 25°C, but does undergo aqueous photolysis (ha lf-life = 34 days). Based on the low 

octanol-water partition coefficient (log Kow = 0.08 at 25°C), acctan1iprid is not expected to 

bioconcentratc . 

5.0 Residue Profile 

5.1 Residue Analytical Methods (860.1340) 

5.1.1 Data Collection Methods 

M RIDs #49.t4380 I a nd .t9443802 (Clover field trials) 

Clover forage and hay samples were analyzed for residues of acetamiprid using an LC/MS/MS 

method with minor modifications, based on the Cerexagri Method #KP-2 I 6R I, titled 

Preliminmy LC/MS/MS Analytical Method for De1erminalion of AssailTM 70WP Insecticide 

(Acetamiprid) in Crop Matrices. A complete desc ription of the method, including a list of minor 

modifications, was included in the submission. Modifications included the e limination of a 

solid-phase extraction clean-up step, and changes to the LC/MS/MS system. 

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Briefly, samples were extracted using methanol/water (1: I, v/v), and vacuum filtered. The 

extract was diluted with methanol/water (I :1 , v/v), and the volume of the final extract was 

adjusted to be within the calibration range for LC/MS/MS analysis. 

The limit of quantitation (LOQ), determined as the lowest limit of method validation (LLMV), 

was 0.010 ppm. lt was noted that the registrant also presented calculated values for the limit of 

detection (LOO) and LOQ, based on the recoveries obtained from samples fortified with 

acetamiprid at 0.010 ppm. The LOO was calculated by multiplying the standard deviation of 

recovery measurements at the LLMY by the one-tailed t-statistic (confidence level not reported) 

for 6 to 8 replicates, and the LOQ was defined as 3X the LOO. The calculated LODs and LOQs 

were. respectively, 0.0023 and 0.0069 ppm in clover forage, and 0.0012 and 0.0035 ppm in 

clover hay from the 2010 trials. They were, respectively. 0.0025 and 0.0075 ppm in forage, and 

0.0035 and 0.0104 ppm in hay from the 2012 trials. 

Method perfo1mance was eva luated during method validation, and by use of concurrent recovery 

samples run with sample sets. For method validation. samples of untreated forage and hay were 

fortified with acetamiprid at 0.0 I 0, 0.100 and 1.00 ppm. For concurrent recovery, samples of 

forage and hay were fortified at 0.0 I 0-0.200 and 0.010-1.00 ppm, respectively. Recoveries were 

within the generally recognized acceptable range of 70-120%, except for a concurrent recovery 

from forage of 67%. Therefore, the method was considered valid for the analysis of acetamiprid 

residues in clover matrices. The fortification levels bracketed the measured residues. 

Concurrent recoveries were not corrected for apparent residues in controls. 

The detector response was reported to be linear. Coefficients of determination (r2) were 0.9956 

within the range of0.050- 1.00 ng/mL from the 20 10 study, and 0.9993 within the range of 

0.050-2.00 ng/mL from the 2012 study. Representative chromatograms of control, fortified and 

treated samples were provided. The control chromatograms generally had no peaks of interest 

above the chromatographic background. The fortified sample clu-omatograms contained only the 

analyte of interest, and peaks were symmetrical and well defined. Residues in controls were 

below the LOQ (<0.010 ppm). The reported residue values were not corrected for apparent 

residues in controls. 

Method validation and concurrent recovery results are summarized in Table 5.1.1, below. 

TABLE 5.1.l Summa ry of Method Validation and Procedural/Concurrent Recoveries of 

Acetamiprid from Clover Fora2e and Hay. 

Matrix Study Fortification Level (ppm) Sample Size (n) Recoveries'(%) Mean ± Std. Dev. (%) 

Method Validation 

Forage 2012 0.010-1.00 9 77-96 89 ± 6.7 

Hay 2010 1.00 3 81-83 82 ± 1.0 

2012 0.010- 1.00 9 84-100 93 ± 5.3 

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TABLE 5.1.1 Summary of Method Validation and Procedura l/Concurrent Recoveries of 

Acetamiprid from Clover Fora2e and Hay. 

Matrix Study Fortification Level (ppm) Sample Size (n) Recoveries1 (%) Mean ± Std. Dev.(%) 

Concurrent Recoverv1 

Forage 20 10 0.0 10 6 71-88 80 :l: 6.9 

20 12 0.0 10-0.200 4 67: 82- 101 86 ± 15 

Hay 20 10 0.0 10 6 73-82 78 ± 3.7 

20 12 0.010- 1.00 4 72- 100 82 ± 13 

1. Concurrent recoveries were not corrected fo r apparent residues in controls. 

2. For concurrent recovery. a ll values are the mean of duplicate analyses. 

Conclusions: Adequate method validation and concurrent recovery data have been submitted for 

the LC/MS/MS method used for the determination of acetarniprid residues in clover forage and 

hay. No additional data are required in support of this data collection method. which is also the 

tolerance enforcement method for residues in vegetables and non-citrus fru its. 

5.1.2 Multi-Residue Methods (860.1360) 

Residue Chemistry Summary Document D264 154; M. Doherty; 3 1 December 200 1 

Data concerning the recovery of residues of acetamiprid using FDA multi-residue method 

protocols (PAAlf Volume I) were submitted in conjunction with the o riginal acetamiprid petition 

(PP#OF6082). Based on the results of the testing. the multi-residue methods are not appropriate 

for determining acetamiprid residues of concern. BEAD/ ACB is currently working on a multiresidue method for the neonicotinoids. 

5.1.3 Tolerance Enforcement Methods 

Resid ue Chemistry Summary Document 0 394779; E. Holman; 6 March 2012 

Adequate residue analytical methods (GC/ECD and I IPLC/UY) are available for the 

enforcement of established tolerances on plant commodities. The method LOQs are 0.0 I 0 ppm 

in vegetabl es and non-citrus fruits (GC/ECD). and 0.05 ppm in citrus fruits (HPLC/UV). These 

methods have undergone successful petition method validation (PMY) tri als. ln PP#4F6833. 

isso America proposed that the LC/MS/MS method utili zed for data collection and 

confirmatory analysis (Method #KP-2 I 6RO or its modification, Method #KP-2 I 6RI) be 

designated an alternative to the established GC/ECD tolerance enforcement method. With 

submission of acceptable independent laboratory validation (IL Y) data, and the ability to analyze 

two daughter ions specifi c to acetamiprid, the LC/MS/MS method was determined to be suitable 

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

summary of the available methods is presented in Table 5.1.3 (below). 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D42332 I 

TABLE 5.l.3 Summary of Validated Analytical Methods for Acetamiprid. 

Target Matrices Method Description LOQ Method Validation 

(ppm) Fortification Recovery 

Levels (ppm) Ra n2e (%) 

Vegetables and Methanol extraction, residues partitioned into 0.010 0.0 I 0, 0.020 72-80 

Non-Citrus Fruits dichloromethanc. Florisil/silica gel column 

cleanup, and LC/MS/MS determination. 

Vegetables and Methanol extraction. residues partitioned into 0.0 10 0.0 I 0, 0.050 68-112 

Non-Citrus Fruits dichloromethane. Florisil/silica gel column 

cleanup. and GC/ECD determination. 

Citrus Fruits Acetonitrile extraction, co-extractives 0.050 0.050. 0.250 77-100 

partitioned into hexane, residues partitioned 

into dich loromethane, Florisil/C1g column 

cleanup, and HPLC/UV detem1ination. 

An approved I lPLC/UV tolerance enforcement method for livestock matrices is available. The 

LOQ is 0.0 I 0 ppm in meat, fat, milk and eggs, and 0.050 ppm in liver and kidney. 

5.2 Storage Stability (860.1380) 

MRIDs #494.&3801 and 49443802 (Clover field tria ls) 

All samples were maintained frozen at the testing faci lities, during shipping, and were stored 

frozen at the analytical laboratory until analysis. Samples of clover forage and hay were stored 

for maximum durations of 5 19 and 5 16 days (17. 1 and 17.0 months), respectively, from harvest 

to extraction. Samples were ana lyzed within I day of extraction. To support the sample storage 

durations, a concurrent storage stability study was conducted along with the field trial study. 

The results are presented in Tables 5.2. 1 and 5.2.2, below. The data demonstrate that residues of 

acetamiprid were stable in fortified samples of clover forage and hay stored frozen for intervals 

of up to 509-510 days ( 16. 7- 16.8 months); no 0-day data were provided. These data are 

acceptable to support the storage conditions and durations of samples from the submitted field 

trials. However, storage stability studies should always include a 0-day sampling interval to 

establish the residue levels present at the time samples are placed into storage (see OCSPP 

Residue Chemistry Test Guideline 860. I 380[d][6][i]). 

TABLE 5.2.l Summary of Stora2e Conditions. 

Matrix Storage Temperature Actua l Storage Dura tion1 Interval of Demonstrated 

(OC) Stor ae:e Stability 

Clover forage - -20 245-519 days (8.0-1 7.0 months) 509 days ( 16. 7 months)2 

Clover hay 2 17-5 16 days (7. 1-1 6.9 months) 510 days ( 16.7 months)2 

I. Interval from harvest to extraction. Samples were analyzed within I day of extraction. 

2. Based on the concurrent storage stability study. See Table 5.2. 1.2 (below). 

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TABLE 5.2.2 Stability of Acetamiprid Residues in Clover Forage and Hay (<-20°C). 

Clover Spike Storage Concurrent Stored Sample Mean Corrected 

Matrix Level (ppm) Interval (Days) Recoveries (%) Recoveries (%) Recovery(%) Recovery (% )* 

Forage 0. 100 509 92 96.95. 99 97 105 

Hay 510 67 72. 71. 75 73 108 

*Corrected for recovery in freshly fortified concurrent recovery samples. 

Conclusions: Although the actual storage durations for some of the field trial samples were 

slightly longer than the storage intervals of fortified samples in the concurrent stability studies, 

the storage stability data are considered adequate. because the duration/interval differences are 

relatively small (<2%), and acetamiprid residues were demonstrated to be stable during longterm frozen storage (17.0 months). Therefore. there are no storage stability issues, and no 

corrections for potential decline during storage are needed in reviewing the residue data 

submitted for clover forage and hay. 

5.3 Residue Data 

5.3.1 Crop Field Trials (860. l 500) 

MRIDs #4944380 1 and 49443802 (Clover fi eld trials} 

The clover field trial residue results are summarized in Table 5.3 .1. below. 

In response to an Agency memorandum (D364833; D. McNeilly; 14 October 2009). JR-4 has 

submitted field trial data for acetamiprid on clover grown for seed. The Agency had requested 

two additional clover field trials as confirmatory data. reflecting a use pattern comprised of a 

single foliar broadcast application of a 30% SG formulation of acctami prid (Assa il 30SG 

Insecticide) at a target rate of 0.075 lb ai/A, with a 28-day PHI for forage, and a roughly 56-day 

PHI for hay. Two pairs of field trials were conducted in the US in NAFTA Growing Zone 11 

during the 2010 (MRID #49443801) and 20 12 (MRlD #49443802) growing seasons. The 

registrant noted that the 2012 trials were conducted to provide bridging data between the original 

clover field trials and the 20 I 0 trials. because forage and hay samples from the 2010 trials were 

either sampled sooner or dried faster than those in the ori ginal study fo r which the confirmatory 

data were required. HED has detem1ined that the 20 I 0 trials, which were separated by less than 

20 miles, are replicate trials. 

Each trial consisted of one untreated plot and one treated plot. At each trial location, the treated 

plot received a single foliar broadcast application of Assail 30SG at 0.075-0.080 lb ai/A. 

Applications were made using ground equipment, in spray volumes of 16.6-29.7 gallons per acre 

(GPA). A non-ionic surfactant (NIS) or crop oil concentrate (COC) was added to the spray 

mixture for a ll applications. Samples of clover forage and hay were harvested from all trial sites 

at PHls of27-32 days. Additional samples of hay were harvested from the 2012 trials at PH ls of 

50-53 days. Hay samples were allowed to dry at the field trial sites for 3-6 days prior to 

collection. 

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Following a single foliar broadcast application of the 30% SG formulation at 0.075-0.080 lb 

ai/A, residues of acetamiprid (and per-trial averages) were 0.0496-0.169 (0.08 12-0.163) ppm and 

0.200-0.763 (0.450-0.753) ppm in clover forage and hay, respectively, harvested at a PHI of 27-

32 days. ln clover hay harvested 50-53 days following application at 0.077-0.080 lb ai/A, 

residues of acetamiprid (and per-trial averages) were 0.0592-0.116 (0.0648-0.1 11) ppm. Residue 

decline was not evaluated. 

TABLE 5.3.1 Summary of Residue Data from Clover Field Trials with Acetamiprid. 

Crop Ma trix Total Use PHI n • Residues (oom) 

Ra te (lb ai/A) (Days) Min.

1 Max.2 LAFT3 HAFT3 Median3 Mean3 SD3 

Clover forage 0.075-0.080 27-32 ... 

.} 0.0496 0.169 0.0812 0.163 0.102 0.115 0.0425 

Clover hay 0.075-0.080 27-32 3 0.200 0.763 0.450 0.753 0.462 0.555 0.172 

0.077-0.080 50-53 2 0.0592 0.116 0.0648 0.111 0.0879 0.0879 NA~ 

1. n = number of field trials. 

2. Values based on individual samples. 

3. Values based on per-trial averages. LAFT = Lowest Average Field Trial: HAFT = Highest Average Field Trial: 

D = Standard Deviation. 

4. NA = Not Applicable (standard deviation is not calculated for sample sets where n < 3). 

Conclusions: The submitted clover field trial data (in conjunction with the previously submitted 

data) are adequate, and support increasing the permanent tolerances in clover forage from 0.10 to 

0.30 ppm, and in clover hay from 0.0 I to 2.0 ppm. 

5.3.2 Field Rotational Crops (860.1900) 

Residue Chemistry Summary Document 0 3282 16; W.T. Drew; 23 October 2007 

o field rotational crop data have been submitted, and no rotational crop restrictions are 

established on the subject labels. The avail able confined rotational crop data indicate that no 

field rotational crop studi es or label restrictions for rotational crops are required to support the 

proposed use. 

5.3.3 Processed Food and Feed (860.1520) 

There are no processed commodities associated with clover forage and hay. 

5.3.4 Meat, Milk, Poultry and Eggs (860.1480) 

In the cattle feeding study and poultry feeding study, the lowest dietary feeding levels were 6 

ppm and 1.2 ppm, respectively. The current livestock tolerances are based on the residues 

observed at those lowest feeding levels. Inclusion of acetamiprid residues at the recommended 

tolerance levels in clover forage (0.30 ppm) and hay (2.0 ppm) results in livestock dietary 

burdens that are at or below the lowest feedi ng levels used in the cattle and poultry feeding 

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studies (see Table 5.3.4, below). Therefore, the existing tolerances associated with li vestock are 

adequate to cover the higher clover tolerances resulting from the decreased clover PHI. 

TABLE S.3.4 Estimated Reasonably Balanced Livestock Dietary Burdens for Acetamiprid. 

Crop Feedstuff Type1 Residue % Dry % of Dieta ry Contribution 

(ppm) Matter Diet

2 (ppm)l 

Beef Cattle 

Clover Hay R 2.0 89 10 0.225 

Cotton Gin byproducts R 20 90 5 I. I 11 

Cotton Undelinted seed p 0.60 88 5 0.034 

Field com Milled byproducts c 0.01 85 50 0.006 

Sugar beet Molasses c 0.01 75 10 0.001 

Sugarcane Molasses c 0.01 75 10 0.001 

Turnip Root c 0.0 1 15 10 0.007 

TOT AL BURDEN 100 1.385 

Dairy Cattle 

Clover Hay R 2.0 89 30 0.674 

Almond Hulls R 5.0 90 10 0.556 

Clover Forage R 0.30 30 5 0.050 

Cotton Undelinted seed p 0.60 88 10 0.068 

Field com Milled byproducts c 0.01 85 15 0.002 

Sugar beet Molasses c 0.01 75 JO 0.001 

Sugarcane Molasses c 0.01 75 10 0.001 

Turnip Root c 0.01 15 10 0.007 

TOTAL BURDEN 100 1.359 

Poultry 

Cotton Meal p 0.60 NA~ 20 0.120 

Soybean Meal p 0.03 NA 5 0.002 

Barley Grain c 0.01 NA 70 0.007 

Field com Grain c 0.01 NA 5 0.001 

TOTAL BURDEN 100 0. 130 

Swine 

Cotton Meal p 0.60 NA 15 0.090 

Field com Grain c 0.01 NA 65 0.007 

Barley Grain c 0.01 NA 20 0.002 

TOT AL BURDEN 100 0.099 

I. R = Roughage; CC = Carbohydrate Concentrate; PC = Protein Concentrate. 

2. Revisions of Feedstuffs in Table I of OPP TS Test Guideline 860. I 000 and Guidance 0 11 Constructing Ala.ximum 

Reasonahly Balanced Diets (AIRBD).; ChemSAC memorandum; 30 June 2008. 

3. Contribution = ([Residue + %DM) x %diet) for beef and dairy cattle. Contribution = (Residue x %diet) for 

poultry and swine. 

4. NA = Not Applicable. 

Conclusion: Revisions to the currently established livestock tolerances are not required for this 

petition. 

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Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode D42332 I 

5.3.5 Food Handling (860. 1460) 

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

5.3.6 Water, Fish and Irrigated Crops (860.1400) 

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

5.4 Food Residue Profile 

The data submitted in support of the current action (PP#4E8307) along with previously reviewed 

data, are adequate for purposes of risk assessment and tolerance assessment for the proposed 

revised use pattern under review. Maximum residues of acetamiprid are expected to occur at 

relatively low levels (<0.30 ppm in clover forage, and <2.0 ppm in clover hay) from the revised 

use pattern on clover grown for seed proposed in the current petition. 

Acetamiprid residues generally tend to decline or remain stable with increasing PHI, and do not 

increase to any significant degree. Follo\ving foliar applications. acetamiprid is present primarily 

as surface residues: translocation does not appear to be extensive. In cabbage, there was uptake 

and translocation of acetamiprid to the above-ground portions of the plant following a soil 

application. In general, acetamiprid residues do not tend to concentrate in processed fractions, 

other than via dehydration or from surface residues. 

Residues of acetamiprid are not expected to accumulate above the LOQ in rotational crops. 

I I ED previously concluded that rotational crop tolerances and restrictions are not required for 

acetamiprid. 

6.0 Tolerance Derivation 

The OECD tolerance calculation procedure was used for setting tolerances in clover forage and 

in clover hay, using residue data from the submitted clover field trial studies. The submitted 

clover field trial data support a tolerance of 2.0 ppm, instead of the proposed tolerance of 1.5 

ppm, in clover hay. The petitioner used residues in c lover hay from all field trials to calculate 

the tolerance (PI-lls of27-63 days). The draft labels stipulate a PHI of 30 days (decreased from 

56 days on the current labels). Therefore, only residues from those trials where hay was 

collected at PI !ls of 27-32 days (current submitted data) were used to calculate the tolerance; 

residues from those trials where hay was collected at PH ls of 50-63 days (previously submitted 

data) were not used. HED utili zed the residue data for hay collected at Pl lls of 27-32 as the 

input dataset for the OECD tolerance calculation procedure, yielding a different result (2.0 ppm). 

The proposed tolerance increase in clover forage (from 0.10 to 0.30 ppm) is supported 

adequately by the current submitted field trial residue data, in conjunction with previously 

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submitted field trial data (D364833; D. McNeilly; 14 October 2009). The current submitted field 

trial residue data support the recommended tolerance increase in clover hay (from 0.0 I to 2.0 

ppm). 

The proposed revised use pattern (decreased PHI) on clover grown for seed is for regional 

registration in ID, OR and WA only (40CFR §180.578[c]). 

HED has identified an error with a commodity definition in the existing 40CFR entry for 

acetamiprid. which currently lists "Vegetable. tuberous and corm, group 1 ··under 40CFR 

§ 180.578[a][l]. This listing should be revised to read ''Vegetable, tuberous and corm, subgroup 

1 c· when the tolerances for clover forage and hay are revised. 

An International Residue Limit Status sheet is appended as Attachment I. Data sets and results 

from the OECD tolerance calculation procedure for clover forage and hay are appended as 

Attachment 2. 

7.0 ChcmSAC Reference 

This memorandum was reviewed by ChemSAC designated reviewers, and has been revised to 

reflect the recommendations of those reviewers. 

References 

Acelamipricl. Requesl for Label Amendmenlsfor New Uses on Clover: Small Vine Climbing 

Fruils. excepl Kiwifruil. Subgroup 13-07F (amending grape use): Greenhouse-grown Tomaloes: 

and a Regional Regislrationfor Tea. Summary of Anafylical Chemist1y and Residue Da1a.; 

0 364833, D366269; 0. McNeilly; 14 October 2009. 

Acelamiprid. Petition for the Establishment of Permanent Tolerances and Regislralion for Use 

on Asparagus: Brassica. Leafy Greens. Subgroup 5B. and Turnip Greens: and Sweet Corn: and 

Updale of Crop Group Definitions for Established Tolerances for Vege1able. Frniling, Group 8-

10: Fruit. Citrus. Group 10-10: and Fruit. Pome. Group I 1-10. SwnnWIJ' of Anafylica/ 

Chemislly and Residue Data.; 0394 779; E. I Joi man; 6 March 2012. 

OF6082. Seclion 3 Registrationj(Jr Use ofAcetamiprid on Cotton. Leq/y Vegetables. Cole 

Vegetables. Fruiting Vege1ables. Citrus Frnils, Pome Fruits, Grapes. and Cano/a and M11s1ard 

Seed. Summcay of Ana/y1ical Me1hods and Residue Che111is11y DERs.; D264154: M. Doherty; 31 

December 200 I. 

Acelamiprid. Pel it ions Requesling 1he Es1ablishmenl of Permanenl Tolerances (Associaled wilh 

Section J Registration) for New Food/Feed Uses of !he Insecticide on Berries (Crop Group 13). 

Page 23of27 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP Barcode 0423321 

Bulb Vegetables (Crop Group 3), Edible Podded Legume Vegetables (Crop Subgroup 6A), 

Succulent Shelled Peer and Bean (Crop Subgroup 6B). and Strawbeny and Other low-growing 

Berries. Summcuy of Analytical Chemistry and Residue Data. Petition Numbers 6F705 J 

(Various Crops) and 6£7163 (.'Strawhen y).; 0 3282 16; W.T. Drew; 23 October 2007. 

Acetamiprid. Results of the HED Metabolism Assessment Review Commillee Meeting Held on 

October 16. 200 I.; 0278652; M. Doherty; 13 November 200 I. 

Acetamiprid: Human Ilea/th Risk Assessment.for New U~·es on Asparagus: Brassica. leafy 

Greens, Subgroup 5B. and Turnip Greens: and Sweet Corn: and Updated Crop Group 

De.flnitionsfor Fruiting Vegetables, Citrus. and Pome Fruit.; D394322; E. Holman: 19 April 

20 12 (PP# ! E7919). 

Tier I Drinking Water Exposure Assessment for A cetamiprid in Regard<; to a Proposed 

Reduction in the Preharvest Interval for Clover and Hay; 0 423299; K. White; 25 March 2015. 

Attachments 

Attachment I: International Residue Limit Status. 

Attachment 2: OEC D MRL (Tolerance) Assessment Calculations. 

Page 24of27 
Acetamiprid Summary of Analytical Chemistry and Residue Data DP 13arcodc D42332 I 

Attachment 1: International Residue Limit Status. 

Acetamiprid (PC Code 099050) 

Summary of US Tolera nces and International Maximum Residue Limits. 

Residue Defi nitions 

US (40CFR .578) Canada Codex 

Crops: [a)[I] and [c] Acetamiprid. (1£)-N-[(6-

chloro-3-pyridinyl)methyl]-N'-cyano-Nmethylethanimidamide. 

Livestock: [a][2] Acetamiprid and IM-2-1. (1£)-

N-[ ( 6-ch loro-3-pyridinyl)methy 1)-N'-cyano-Nmethylethanimidamide and (I £)-N-[(6-chloro-3-

pyridinyl)methyl]-N'-cyano-N-ethanimidamide. 

Commodity2 Tolerance Commodity MRL Commodity MRL 

(ppm)J (mg/kg) (mg/kg) 

Clover. forage 0.30 

Clover, hay 2.0 

Completed: W.T. Drew: 3 June 2015. 

I. Mexico adopts US tolerances. and/or Codex MRLs. for its export purposes. 

2. Includes only commodities of interest for this action. 

3. Tolerance values arc those recommended by HED. not those proposed by the petitioner. 

Page 25 of27 
Acctamiprid Summary of Analytical Chemistry and Residue Data 

Attachment 2: OECD MRL {Tolerance) Assessment Calculations. 

Clover hay 

Residues (mg/kg) 

0.450 

0.753 

0.462 

Acetarniprid 

Clover hay 

USA (ID, OR, WA) 

0 . 075 lb ai/A, 30-day PHI 

Total number of data (n) 

Percentage of censored data 

Number of non-censored data 

Lowest residue 

Highest residue 

Median residue 

Mean 

Standard deviation (SD) 

Correction factor for censoring (CF) 

Proposed MRL estimate 

- Highest res idue 

- Mean + 4 SD 

- CF x 3 Mean 

Unrounded MRL 

Rounded MRL 

High uncertainty of MRL estimate. 

[Small dataset] 

Page 26of27 

DP Barcode D42332 I 

3 

0% 

3 

0 . 450 

0 . 753 

0 . 462 

0 . 55 5 

0 . 1 72 

1. 000 

0 . 753 

1. 241 

1 . 66 5 

1 . 665 

2 
Aceramiprid Summary of Analytical Chemistry and Residue Data 

Clover forage 

Residues (mg/kg) 

0 . 04 5 

0 . 0 50 

0 . 010 

0 . 08 1 

0. 163 

0 . 102 

Acetamiprid 

Clover forage 

USA (ID, OR, WA) 

0.075 lb ai/A, 30-day PHI 

Total number of data {n) 

Percentage of censored data 

Number of non-censored data 

Lowest residue 

Highest residue 

Median residue 

Mean 

Standard deviation {SD) 

Correction factor for censoring (CF) 

Proposed MRL estimate 

- Highest residue 

- Mean + 4 SD 

- CF x 3 Mean 

Unrounded MRL 

Rounded MRL 

High uncertainty of MRL estimate . 

[Small dataset] 

Page 27of27 

6 

17% 

DP Barcode 042332 I 

5 

0 . 010 

0.163 

0.066 

0.075 

0.053 

0.889 

0.163 

0.289 

0 . 201 

0 . 289 

0 . 3 
Acetamiprid (PC Code 099050)/ lnterregional Project #4 (IR-4) 

B.7.6 

B.7.6.1 

B.7.6.1.1 

Document ID: 

Report: 

Guidelines: 

Residues Resulting from Supervised Trials 

(Annex IIA 6.3; Annex IHA 8.3) 

Residues in Target Crops 

Clover Grown for Seed 

MR!Ds #49443801 and 49443802 

MRID #4944380 I. R. Leonard (2013) Acetamiprid: lvfagnitude of the 

Residue on Clover. Re-amended Report. Report Numbers: A9600 and 

A9600. I 0-M lR 12. Unpublished study prepared by Interregional Research 

Project #4. 11 6 pages. 

MRfD #49443802. R. Leonard (20 13) Acelamiprid: Magnitude of the 

Residue on Clover. Report Numbers: 89600 and 89600. 12-MIR 12. 

Unpublished study prepared by Interregional Research Project #4. 107 

pages. 

EPA OCSPP Harmonized Test Guideline 860. 1500 Crop Field Trials 

(August 1996). 

PMRA Regulatory Directive DIR98-02 - Residue Chemistry Guidelines. 

Section 9 - Crop Field Trials. 

PMRA Regulatory Directive DIR2010-05 - Revisions to the Residue 

Chemistry Crop Field Trial Requirements. 

OECD Guideline 509 Crop Field Trial (September 2009). 

GLP Compliance: No deviations from regulatory requirements were reported which would 

have an impact on the va lidity of the study. 

Acceptability: 

Evaluator: 

Date: 

The study is considered scientifically acceptable. The acceptability of this 

study for regulatory purposes is addressed in the forthcoming USEPA 

Residue Chemistry Summary Document, 0 42332 1. I'~ . 

2 

William 

September 

T. Dr

20 

ew, 

l 5 

Chemist, Risk Assessment Branch Il (RAB2) lAJ & ~ 

ote: This Data Evaluation Record (DER) was originally prepared under contract by Versar. Incorporated (6850 

Versar Center. Springfield VA 22151: submitted 27 February 20 15). The DER has been reviewed by the I lea Ith 

Effects Division (HED), and revised to refiect current Office of Pesticide Programs (OPP) policies. 

EXECUTIVE SUMMARY 

In response to an Agency memorandum (0 364833: D. McNeilly; 14 October 2009), the 

Interregional Research Project #4 (lR-4) has submitted field trial data for the active ingredient 

(ai) acetamiprid on clover grown for seed. The Agency had requested two additional clover field 

trials as confirmatory data, reflecting a use pattern comprised of a single fo liar broadcast 

application of a 30% soluble granule (SG) formulation of acetamiprid (Assail 30SG Insecticide) 

at a target rate of 0.075 pound of ai per acre (lb ai/ A), with a 28-day pre-harvest interval (PHI) 

EPA MRIDs #49443801 and 49443802 Page I of8 
Acetamiprid (PC Code 099050)/lnterregional Project #4 (IR-4) 

for forage, and a roughly 56-day PHI for hay. Two pairs of field trials were conducted in the US 

in orth American Free Trade Agreement (NAf-T A) Growing Zone 11 during the 20 10 (MRID 

#4944380 1) and 20 12 (MRID #49443802) growing seasons. The registrant noted that the 201 2 

trials were conducted to provide bridging data between the original clover field trials and the 

20 I 0 trials, because forage and hay samples from the 20 I 0 trials were either sampled sooner or 

dri ed faster than those in the original study for which the conlinnatory data were required. HED 

has determined that the 20 I 0 trials, which were separated by less than 20 miles, arc replicate 

tri als. 

Each trial consisted of one untreated plot and one treated plot. At each trial location, the treated 

plot received a single foliar broadcast application of a 30% SG formulation of acetamiprid 

(Assail 30SG Insecticide) at 0.075-0.080 lb ai/A. Applications were made using ground 

equipment. in spray volumes of 16.6-29.7 gallons per acre (GPA). A non-ionic surfactant (NIS) 

or crop oil concentrate (COC) was added to the spray mixture for all applications. Samples of 

clover forage and hay were harvested from all trial sites at PHls of 27-32 days. Additional 

samples of hay were harvested from the 20 12 trials at PHis of 50-53 days. Hay samples were 

allowed to dry at the fi eld trial sites for 3-6 days prior to collection. 

All samples were maintained frozen at the testing facilities, during shipping, and were stored 

frozen at the analytical laboratory until analysis. Samples of clover forage and hay were stored 

for maximum durations of 5 19 and 5 16 days ( 17. 1 and 17.0 months), respecti vely, from harvest 

to extraction. Samples were analyzed within 1 day of extraction. To support the sample storage 

durations, a concurrent storage stability study was conducted along with the field trial study. 

The data demonstrate that residues of acetamiprid were stable in fortified samples of clover 

forage and hay stored frozen for intervals of up to 509-5 10 days (16.7- 16.8 months); no 0-day 

data were provided. These data are acceptable to support the storage conditions and durations of 

samples from the submitted field trials. However, storage stability studies should always include 

a 0-day sampling interval to establish the residue levels present at the time samples arc placed 

into storage (see OCSPP Residue Chemistry Test Guideline 860. I 380[d](6](i]). 

Samples \.vere analyzed for residues of aceramiprid via high performance liquid chromatography 

with tandem mass spectrometric detection (LC/MS/MS), using a method based on Cerexagri 

Method #KP-2 I 6Rl. Acceptable method validation and concurrent recoveries were reported for 

samples of clover forage and hay fortified with acetamiprid at 0.0 I 0-I .00 ppm, thus validating 

the method. The limit of quantitation (LOQ), determined as the lowest leve l of method 

validation (LLMY), was 0.0 l 0 ppm. The fortification levels used in concurrent method recovery 

were adequate to bracket expected residue levels. Concurrent recoveries and residues in treated 

samples were not corrected for apparent residues in controls. 

Following a single foliar broadcast application of the 30% SO fonnulation at 0.075-0.080 lb 

ail A, residues of acetamiprid (and per-trial averages) were 0.0496-0.1 69 (0.08 I 2-0.163) ppm and 

0.200-0.763 (0.450-0.753) ppm in clover forage and hay, respectively. harvested at a PHI o f 27-

32 days. ln clover hay harvested 50-53 days following application at 0.077-0.080 lb ai/A, 

EPA MRIDs #49443801and49443802 Page 2 of8 
Acetamiprid (PC Code 099050)/lnterregional Project #4 (IR-4) 

residues of acetamiprid (and per-trial averages) were 0.0592-0.116 (0.0648-0. 111) ppm. Residue 

decline was not evaluated. 

I. MATEIUALS AND METHODS 

A. MATEIUALS 

TABLE B.7.6.1.l -J Nomenclature for Acetamiprid. 

Common name Acetamiprid 

CAS name (I £)-N-[(6-chloro-3-pyridinyl)methyl]-N'-cyano-Nmethylethan im idam ide 

CAS number 135410-20-7 

Company experimental name None 

Other synonyms (ifaoolicable) None 

Empirical formula C10H11CIN4 

Molecular weight 222.7 amu 

Cl~ I THJ 

h- 1 l(CH3 

'cN 

B. Study Design 

1. Test Procedure 

Three residue tri als were conducted on clover grown for seed during the 2010 and 2012 growing 

seasons. reflecting a single foliar broadcast application with a 30% SG formulation of 

acetamiprid (Assail 30SG Insecticide). Field trial locations by NAFTA growing zone are 

summari zed in Table B.7.6. l. l-2 (below). 

The trials separated by <20 miles have been assessed for independence as detailed in the table 

below. H ED has determined that one pair of trials (20 I 0 trials; MRIO #49443801) cons ti lute a 

single trial with replicate samples for purposes of OCSPP 860. 1500 data requirements. 

Independent Trial Determination 

MRID# Crop Trial Numbers Differences Decision 

49443801 Clover OR36 and OR37 Same variety Replicates 

*No other differences in criteria 

• All assessments are based on the replicate trial guidance presented in draft memo 568_Criteria for Independence 

of Trials 23 April 2013 (EPA and PMRA). A separate tank mix was used for all applications. 

EPA MRI Os #49443801 and 49443802 Page 3 of8 
Acetamiprid (PC Code 099050)/lnterregional Project #4 (IR-4) 

TABLE B.7.6.1.1-2 Trial Numbers and Geo2t"apbical Locations. 

Crop #of Trials NAF'l'A Growing Zone T otal 1 2 3 4 s 6 7 8 9 10 11 12 

Clover Submitted' .., 

.) 3 

Required2 Ill 1/ 1 1/1 3/2 111 Ill 111 I I I I' Il l' 12/9 

I. Data were submitted in response to 0364833; D. McNeilly; 14 October 2009. 

2. As per Table 5 of OCSPP 860.1500 for clover: the second number re nects a 25% reduction in the number of field 

trials allowed for the crop as a representative commodity in support of a crop group/subgroup tolerance or 

when application results in no quantifiable residues. 

3. Either Zone is acceptable. 

Locations of, and detailed use patterns at, the trials are provided in Table B. 7 .6.1.1-3 (below). 

TABLE 8 .7.6.1.1-3 Stud1 Use Pattern. 

Location: City, EP1 Method; Timing of Volume Single 

State; Year Application (GPA) Use Rate 

!Trial IDI ~ (lb ai/A) 

2010 Trials (MRID #49443801) 

Aurora, OR: 20 I 0 30% I. Foliar broadcast 23.4 0.077 

fA9600. IO-OR36] SG~ vcg.etative. 

St. Paul, OR: 20 I 0 30% I. Foliar broadcast: 25.3 0.075 

IA9600. JO-OR371 SG vegetative. 

2012 Trials (MRLD #49443802) 

Woodburn, OR; 2012 30% I. Foliar broadcast; 29.7 

[B9600.12-0R34] SG vegetative. 

Hillsboro, OR; 2012 30% I. foliar broadcast; 16.6 

[B9600. I 2-0R35l SG vegetative. 

I. EP = End-use Product. 

2. RTI = Re-Treatment 1 nterval. 

3. NIS = Nonionic surfactant; COC = Crop oil concentrate. 

4. Assail 30SG Insecticide. a 30% SG formulation ofacetamiprid. 

5. A = Not Applicable. 

0.080 

0.077 

RTr Total Use Tank Mix 

(Days) Rate Adjuvant3 

Ob ai/A) 

NA~ 0.077 IS 

A 0.075 IS 

NA 0.080 coc 

NA 0.077 NIS 

Clover was grown and maintained according to typical agricultural practices. o 1rngation was 

used. No unusual weather conditions were reported to have adversely affected crop production 

or yield during the study. 

Sample Handling and Preparation 

Duplicate control and treated samples of clover forage and hay were harvested from all trials at 

PHis of27-32 days; additional samples of hay were harvested from the 2012 trials at PHis of 50-

53 days. Hay samples were allowed to dry at the field sites for 3-6 days prior to collection. 

Samples were placed in frozen storage at the field sites within approximately 2 hours of 

collection, and were shipped frozen via ACDS freezer truck within 2-28 days of harvest to the 

analytical laboratory, IR-4 North Central Research Center, Michigan State University (in 

Lansing, MI). At the analytical laboratory, samples were stored frozen (at roughly -20°C) prior 

EPA MRIDs #49443801 and 49443802 Page 4 of8 
Acctamiprid (PC Code 099050)/lnterregional Project 114 (IR-4) 

to preparation and analysis. The sampl es were prepared for analysis by homogenizing in the 

presence of dry ice. 

2. Description of Analytical Procedures 

Samples were analyzed for residues of acetamiprid using an LC/MS/MS method with minor 

modifications, based on the Cerexagri Method #KP-2 I 6R I, titled Preliminary LC/MS/MS 

Analytical Method for Determination of AssailTM 70WP Insecticide (Acetamiprid) in Crop 

Matrices. A complete description of the method, including a list of minor modifications, was 

included in the submission. Modifications included the elimination of a solid-phase extraction 

clean-up step, and changes to the LC/MS/MS system. 

Briefly. samples were extracted using methanol/water (I: I, v/v). and vacuum filtered. The 

extract was diluted with methanol/water (I: I, v/v), and the volume of the final extract was 

adjusted to be within the calibration range for LC/MS/MS analysis. 

The LOQ (determined as the LLMV) was 0.010 ppm. It was noted that the registrant also 

presented calculated values for the limit of detection (LOD) and LOQ, based on the recoveries 

obtained from samples fortified with acetamiprid at 0.010 ppm. The LOD was calculated by 

multiplying the standard deviation of recovery measurements at the LLMV by the one-tailed tstatistic (confidence level not reported) for 6 to 8 replicates. and the LOQ was defined as 3X the 

LOO. The calculated LODs and LOQs were, respectively, 0.0023 and 0.0069 ppm in clover 

forage. and 0.0012 and 0.0035 ppm in clover hay from the 2010 trials. They were. respectively. 

0.0025 and 0.0075 ppm in forage. and 0.0035 and 0.0 I 04 ppm in hay from the 2012 trials. 

II. RESULTS AND DISCUSSION 

Method performance was evaluated during method validation, and by use of concurrent recovery 

samples run with sample sets. For method validation, samples of untreated forage and hay were 

fortified with acetamiprid at 0.0 I 0. 0.100, and I .00 ppm. For concurrent recovery. samples of 

forage and hay were fortified at 0.0 I 0-0.200 and 0.0 I 0-1.00 ppm, respectively. Recoveries were 

within the generally recognized acceptable range of 70-120%, except for a concurrent recovery 

from forage of 67%. Therefore, the method was considered valid for the analysis of acetamiprid 

residues in clover matrices (Table B.7.6.1.1-4). The fortification levels bracketed the measured 

residues. Concurrent recoveries were not corrected for apparent residues in controls. 

The detector response was reported to be linear. Coefficients of determination (r2) were 2:0.9956 

within the range of 0.050-1.00 ng/mL from the 20 I 0 study, and 2:0.9993 within the range of 

0.050-2.00 ng/mL from the 20 12 study. Representative chromatograms of control. fortified and 

treated samples were provided. The control chromatograms generally had no peaks of interest 

above the chromatographic background. The fortified sample chromatograms contained only the 

analyte of interest. and peaks were symmetrical and well defined. Residues in controls were 

EPA MRIDs #49443801 and 49443802 Page 5 ofS 
Acetamiprid (PC Code 099050)/lnterregional Project #4 (IR-4) 

below the LOQ ( <0.0 l 0 ppm). The reported residue values were not corrected for apparent 

residues in controls. 

TABLE B.7.6.l.1-4 Summary of Method Validation and P roceduraVConcurrent Recoveries of 

Acetamiprid from Clover Fora2e a nd Hay. 

Matrix Study Fortification Level (porn) Sample Size (n) Recoveries1 (%) Mean ± Std. Dev.(%) 

Method Validation 

Forage 2012 0.0 I 0-1.00 9 77-96 

Hay 2010 1.00 3 81-83 

2012 0.0 10- 1.00 9 84- 100 

Concurrent Recoverv1 

Forage 2010 0.0 10 6 7 1-88 

2012 0.0 I 0-0.200 4 67; 82-101 

Hay 2010 0.010 6 73-82 

2012 0.0 I 0-1.00 4 72- 100 

I. Concurrent recoveries were not corrected fo r apparent residues in controls. 

2. For concurrent recovery. all values are the mean of duplicate analyses. 

89 ± 6.7 

82 ± 1.0 

93 ± 5.3 

80 ± 6.9 

86 ± 15 

78 ± 3.7 

82 ± 13 

Samples of clover forage and hay were stored for a maximum of 5 19 and 5 16 days (17. 1 and 

l 7.0 months), respectively. from harvest to extraction (Table 8. 7.6. l. l-5a). Samples were 

analyzed within I day of extraction. To support sample storage durations, a storage stability 

study was conducted concurrently with the field trial study; the results are presented in Table 

8. 7.6.1 .1-Sb (below). The data demonstrate that residues of acetamiprid were stable in fo11ified 

samples of clover forage and hay stored frozen for intervals of up to 509-5 10 days (16.7-16.8 

months); no 0-day data were provided. These data arc acceptable to support the storage 

conditions and durations of samples from the submitted clover field trials. However, storage 

stabi lity studies should always include a 0-day sampli ng interval to establish the residue leve ls 

present at the time san1plcs are placed into storage (see OCSPP 860. I 380[d]l6][i]). 

TABLE B.7.6.1.1-Sa Summarv of Stora2e Conditions. 

Matrix Storage Temperature Actual Storage Duration1 Interval of Demonstrated 

(OC) Stora2e Stability 

Clover forage - -20 245-519 days (8.0- 17.0 months) 509 days (16.7 months)2 

Clover hay 217-5 16 days (7.1 - 16.9 months) 510 days ( 16. 7 months)2 

I. Interval from harvest to extraction. Samples were analyzed within I day of extraction. 

2. Based on the concurrent storage stability study. See Table B. 7 .6. I. l-5b (below). 

TABLE B.7.6.1.1-Sb Stability of Acetamiprid Residues in Clover Forage and Hay (<--20°C). 

Clover Spike Storage Concurrent Stored Sample Mean Corrected 

Matrix Level (ppm) Interval (Days) Recoveries(%) Recoveries(%) Recovery (%) Recovery(%)* 

Forage 0.100 509 92 96,95,99 97 105 

Hay 510 67 72, 7 1. 75 73 108 

• Corrected for recovery in freshly fortified concurrent recovery samples. 

EPA MRIDs #49443801and 49443802 Page 6 of8 
Acetamiprid (PC Code 099050)/lnterrcgional Project #4 (IR-4) 

The results from the submitted field tri als are presented in Tables B.7.6.1 .. 1-6 and B.7.6.1. 1-7 

(below). Following a single foli ar broadcast application of the 30% SG formulation at 0.075-

0.080 lb ai/A, residues of acetamiprid (and per-trial averages) were 0.0496-0.169 (0.081 2-0.1 63) 

ppm and 0.200-0.763 (0.450-0.753) ppm in clover forage and hay, respectively, harvested at a 

PHI of 27-32 days. In clover hay harvested 50-53 days following application at 0.077-0.080 lb 

ai/A, residues of acetamiprid (and per-trial averages) were 0.0592-0.116 (0.0648-0. 111 ) ppm. 

Residue decline was not evaluated. 

TABLE B.7.6.1.7-6 Residue Data from Clover Field Trials with Acetamiprid. 

Location Zone Variety EP2 Rate Matrix PUP Residues4 (ppm 

(City, State; Year (lb ai/A) (Days) [Average]) 

rTrial IDJ)1 

' 

2010 Trials fMRID #49443801) 

Aurora. OR: 2010 I I Medium 30% 0.075- Forage _,_ "'? 0.0496. 0.0522, 0. 106, 

[A9600. I O-OR36] Red SG 0.077 0.11 7 [0.081 2] 

a nd Hay 29 (6) 0.207. 0.200. 0.689. 0.703 

St. Paul. OR: 20 I 0 [0.450] 

f A9600. IO-OR37] 

2012 Trials (MRID #49443802) 

Woodburn. O R: II Med ium 30% 0.080 Forage 27 0. 156. 0. 169 [0.1 63] 

20 12 [8 9600. 12- Red SG Hay 27 (3) 0.742. 0.763 [0.753] 

OR34] 50 (6) 0.0703. 0.0592 (0.0648] 

Hillsboro, OR: II Common 30% 0.077 Forage 30 0.0760, 0.1 28 [0. 102] 

2012 (89600. 12- Red SG Hay 30 (3) 0.502. 0.422 [0.462] 

OR35) 53 (6) 0. 116. 0. 106 ro.11 11 

I. I JED has determined that trials OR36 and OR37 are replicate trials. 

2. EP = End-use Product. 

3. Days that hay was allowed to dry at the field sites arc presented in parentheses. 

4. All values are the mean of duplicate ana lyses. The LOQ was 0.0 I 0 ppm. 

TABLE B.7.6.1.1-7 Summary of Residue Data from Clover Field Trials with Acetamiorid. 

Crop Matrix Total Use PHI n• Residues fonm) 

Rate (lb ai/A) (Days) Mi n. 2 Max.

2 LA.Ffl .HAFI'J Media n3 Mean3 SD3 

Clover forage 0.075-0.080 27-32 3 0.0496 0. 169 0.08 12 0. 163 0. 102 0. 11 5 0.0425 

Clover hay 0.075-0.080 27-32 3 0.200 0.763 0.450 0.753 0.462 0.5 55 0. 172 

0.077-0.080 50-53 2 0.0592 0.1 16 0.0648 0.1 11 0.0879 0.0879 NA~ 

I. n = nmnbcr of fie ld trials. 

2. Values based on individua l samples. 

3. Values based on per-rrial averages. LAFT - Lowest Average Field Trial: HAFT = Highest Average Field Trial: 

SD = Standard Deviation. 

4. NA = Not Applicable (standard deviation is not calculated for sample sets where n < 3). 

Ill. CONCLUSIONS 

The clover field trials are considered scientifically acceptable. Following a single fo li ar 

broadcast application of the 30% SG formulation at 0.075-0.080 lb ail A, residues of acetamiprid 

(and per-trial averages) were 0.0496-0. 169 (0.08 12-0. 163) ppm and 0.200-0. 763 (0.450-0. 753) 

EPA MRIDs #4944380 1 and 49443802 Page 7 of8 
Acetamiprid (PC Code 099050)/lntcrregional Project #4 (IR-4) 

ppm in clover forage and hay, respectively, harvested at a PHI of 27-32 days. ln clover hay 

harvested 50-53 days following application at 0.077-0.080 lb ai/A, residues of acetamiprid (and 

per-trial averages) were 0.0592-0.11 6 (0.0648-0.111 ) ppm. Residue decline was not evaluated. 

An acceptable method was used for residue quantitation. and adequate storage stability data were 

submitted to support sample storage durations and conditions. 

REFERENCES 

Acetamiprid. Request for Label Amendments/or New Uses on Clover: Small Vine Climbing 

Fruits, except Kiwifi·uit, Subgroup l 3-07F (amending grape use); Greenhouse-grown Tomatoes; 

and a Regional Registration/or Tea. Summary of Analytical Chemist1y and Residue Data. ; 

0 36483 3 and 0 366269; D. McNeilly; 14 October 2009. 

EPA MRI Os #4944380 1 and49443802 Page 8 of8