Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C. 20460 

OFFICE OF CHEMICAL SAFETY AND

 POLLUTION PREVENTION

MEMORANDUM

Date: 25-AUG-2010.

SUBJECT: Acequinocyl. Petition for Use on Fruiting Vegetables, Hops, Okra, and EdiblePodded Beans. Summary of Analytical Chemistry and Residue Data. 

PC Code: 006329 DP Barcode: D369100

Decision No.: 417967 Registration No.: 66330-38

Petition No.: 9E7598 Regulatory Action: Section 3

Risk Assessment Type: NA Case No.: 7621

TXR No.: NA CAS No.: 57960-19-7

MRID Nos.: 478194-01 thru -04 40 CFR: §180.599

FROM: Sarah J. Levy, Chemist

Risk Assessment Branch 1 (RAB1)

Health Effects Division (HED) (7509P)

THROUGH: George F. Kramer, Ph.D., Senior Chemist

RAB1/HED (7509P)

TO: Barbara Madden, RM Team 05

Registration Division (RD; 7505P)

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

220; Rockville, MD 20850).

Executive Summary

Acequinocyl is a quinoline type miticide registered for use in the U.S. on pome fruits, citrus 

fruits, grapes, tree nuts, pistachios, and strawberries for the control of various phytophagous mite 

species. Acequinocyl is currently registered to Arysta Lifescience North America Corporation as 

a 15% suspension-concentrate (SC) formulation.

Under PP#9E7598, the Interregional Research Project No.4 (IR-4), on behalf of the Agricultural 

Experiment Station of AZ, CA, CO, FL, ID, NC, NJ, NY, OK, OR, TN, TX, VA, and WA, is 

requesting for the establishment of tolerances for the combined residues of the insecticide 

acequinocyl, 2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione, and its metabolite, 2-dodecyl-3-

hydroxy-1,4-naphthoquinone, expressed as acequinocyl equivalents in/on the following 
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commodities:

Vegetable, fruiting, group 8 .............................................................0.70 ppm

Okra..................................................................................................0.70 ppm

Bean, edible podded.........................................................................0.25 ppm

Hop, dried cones ..............................................................................3.5 ppm

The end-use product proposed for use on fruiting vegetables, hops, okra and snap beans is 

KanemiteTM 15 SC Miticide, a 1.25 lb/gal SC formulation. Up to two foliar applications are 

proposed for a maximum seasonal rate of 0.6 lb ai/A, with a 7-day preharvest interval (PHI), 

except for okra for which a 1-day PHI is proposed.

Tolerances are currently established under 40 CFR §180.599(a) for the combined residues of 

acequinocyl and its metabolite, 2-dodecyl-3-hydroxy-1,4-naphthoquinone, expressed as 

acequinocyl equivalents, in/on a number of plant and livestock commodities. Tolerances for 

plant commodities range from 0.02 ppm (tree nuts and pistachios) to 30 ppm (citrus oil), and 

tolerances for livestock commodities are established at 0.02 ppm in the fat and liver of cattle, 

goat, horse, and sheep.

The nature of acequinocyl residues in apples, oranges, and eggplants is understood based on the 

previously submitted and reviewed metabolism studies. In these crops, the metabolism of 

acequinocyl involves the loss of the acetyloxy moiety to form acequinocyl-OH, the opening of 

the quinone ring to form AKM-18, and the subsequent degradation of the quinone ring to yield 

polar metabolites that degrade to phthalic acid. For purposes of risk assessment and the tolerance 

expression, HED has determined that the residues of concern in these commodities include 

parent and acequinocyl-OH (Memo, S. Levy, 07-JAN-2004; DP# 297872).

There are no livestock feedstuffs associated with the proposed crop uses addressed herein. 

Therefore, no livestock metabolism data, enforcement methods, storage stability data, or feeding 

studies are required to support this petition.

There are adequate residue analytical methods for enforcing tolerances for acequinocyl residues 

of concern in/on the proposed/registered plant commodities. These methods include two highperformance liquid chromatography methods with tandem mass-spectroscopy detection 

(HPLC/MS/MS) for determining residues in/on fruit and nut commodities (Morse Methods 

Meth-133 and Meth-135). For each of these methods, residues are extracted with hexane or 

acetonitrile (ACN)/water and cleaned up by solvent partitioning, gel-permeation chromatography

(GPC) and/or silica-gel solid-phase extraction (SPE).

Residue data from the current field trial and processing studies were obtained using the approved 

enforcement methods, Meth-135 (tomato, pepper and hops) and Meth-133 (snap beans) with 

minor modifications. The methods are adequate for data collection based on acceptable method 

validation and concurrent method recovery data for tomato and its processed matrices, pepper, 

and snap beans. However, the data-collection method yielded consistently low recoveries 

(~53%) for acequinocyl-OH in dried hop cones; therefore, residues of the metabolite from the 

hop field trials were corrected for low recoveries. The validated limit of quantitation (LOQ) was 

0.010 ppm for acequinocyl and 0.025 ppm for acequinocyl-OH in/on tomato and pepper; 0.020 
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

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ppm each for acequinocyl and acequinocyl-OH in/on edible-podded beans; and 0.10 ppm for 

acequinocyl in/on hop dried cones. 

The data requirements for multiresidue (MRM) methods are fulfilled. Certain MRM protocols 

resulted in acceptable recoveries. The MRM testing data have been forwarded to the U.S. Food 

and Drug Administration (FDA) for further evaluation (Memo, S. Levy, 18-FEB-2004; DP#: 

298917).

The submitted concurrent storage stability data for tomato, snap bean, and hops is adequate to 

support the storage intervals and conditions incurred by the field trial studies. In addition, the 

concurrent storage stability data for the parent acequinocyl is adequate to support the sample 

storage intervals and conditions for the pepper field trials and tomato processing studies. It is 

noted that zero-day data were not provided. IR-4 is reminded that storage stability studies should 

always include a zero-day sampling interval to establish the residue levels present at the time 

samples are placed into storage [see OPPTS 860.1380(d)(6)(i)]. 

The concurrent storage stability data indicate problems with the stability of acequinocyl-OH in 

peppers and processed tomato paste and puree. Because zero-day samples were not analyzed, 

determination of residue levels present at the time samples were placed in frozen storage could 

not be made. In addition, an insufficient number of time points were analyzed in order to 

establish how much of the residue (acequinocyl-OH) was lost at various time points. 

However, because residues of acequinocyl-OH in the pepper field trial were <10% of the parent 

value or were <LOQ, correction for 51% decline would not affect the results. Furthermore, in 

the tomato processing study, because there were quantifiable residues of the parent in the raw 

agricultural commodity (RAC) and residues of acequinocyl-OH in the RAC were 

nonquantifiable, HED believes that any concentration of acequinocyl-OH residues would not 

significantly increase the total residue level. Therefore, HED is not requesting additional storage 

stability data at this time. 

The submitted magnitude of the residue data for tomatoes, peppers, edible-podded beans, and 

hops are adequate. The field trials reflect the proposed use patterns and an adequate number of 

field trials were conducted in major crop growing regions. The submitted field trial data reflect 

applications made without the use of a spray adjuvant. A revised Section B should be 

submitted incorporating an adjuvant–use restriction. The Agency’s tolerance spreadsheet as 

specified by the Guidance for Setting Tolerances Based on Field Trial Data SOP (August 2009 

version) was used to determine the appropriate tolerance levels. The field trial data will support 

tolerances of: 0.70 ppm for fruiting vegetables; 0.70 ppm for okra; 0.25 ppm for edible-podded 

beans; and 4.0 ppm for dried hop cones.

It is noted that the proposed PHI for fruiting vegetables is 7 days whereas the field trials reflect a 

1-day PHI. Residue decline trials for tomato and pepper demonstrate that residues generally

decline with later sampling intervals; therefore, the proposed/recommended tolerance will likely

overestimate anticipated residues of acequinocyl and acequinocyl-OH in/on fruiting vegetables. 

The available data support the proposed tolerances for fruiting vegetables, okra, and ediblepodded beans; however, the proposed tolerance for hop dried cones is too low.
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The tomato processing study is adequate. The results indicate that residues of acequinocyl and 

acequinocyl-OH did not concentrate in paste and puree processed from tomato fruits bearing 

quantifiable residues of acequinocyl. No tolerances are required for tomato processed matrices. 

An adequate confined rotational crop study was previously submitted. These data reflect the 

maximum proposed use pattern for rotated crops (fruiting vegetables and edible-podded beans); 

the results indicate that residues of acequinocyl do not accumulate in rotated crops. These data 

support a 30-day plantback interval (PBI) for all non-labeled crops.

Regulatory Recommendations and Residue Chemistry Deficiencies

Pending submission of revised Sections B (see requirements under Directions for Use) and F (see 

requirements under Proposed Tolerances), and submission of analytical reference standards to the 

EPA National Pesticide Standards Repository (see requirements under Residue Analytical 

Methods), there are no residue chemistry issues that would preclude granting a permanent

registration for the requested uses of acequinocyl or establishment of tolerances for residues of 

acequinocyl and acequinocyl-OH as follows: 

Vegetable, fruiting, group 8 .............................................................0.70 ppm

Okra..................................................................................................0.70 ppm

Bean, edible podded.........................................................................0.25 ppm

Hop, dried cones ..............................................................................4.0 ppm

Note to PM: According to HED’s Interim Guidance on Tolerance Expressions (5/27/09, S. 

Knizner), the tolerance expression for acequinocyl should be revised to state:

“Tolerances are established for residues of acequinocyl, including its metabolites and 

degradates, in or on the commodities in the table below. Compliance with the tolerance 

levels specified below is to be determined by measuring only the sum of acequinocyl [2-

(acetyloxy)-3-dodecyl-1,4-naphthalenedione] and its metabolite, 2-dodecyl-3-hydroxy-1,4-

naphthoquinone, calculated as the stoichiometric equivalent of acequinocyl, in or on the 

commodity.

A human health risk assessment is forthcoming.

860.1200 Directions for Use

 The proposed label (Section B) for the 1.25 lb/gal SC should be revised to specify a 30-

day PBI restriction for all non-labeled crops.

 The submitted field trial data reflect applications made without the use of a spray

adjuvant. A revised Section B should be submitted incorporating an adjuvant–use 

restriction.

 The data for fruiting vegetables supports a 1-day PHI for all fruiting vegetables. The 

petitioner may amend the label for the 1.25 lb/gal SC to reduce the proposed PHI for 

fruiting vegetables from 7 days to 1 day, based on field trial data. 
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

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860.1340 Residue Analytical Methods

 Submission of analytical reference standards to the EPA National Pesticide Standards 

Repository.

860.1550 Proposed Tolerances

 A revised Section F is required to amend the tolerances as specified in Table 7.

Background

The chemical structure and nomenclature of acequinocyl and its regulated metabolite are 

presented in Table 1, and the physicochemical properties of acequinocyl are presented in Table 2. 

Table 1. Nomenclature of Test Compound and Metabolites.

Compound

O

O

CH2(CH2)

10CH3

OCOCH3

Common name Acequinocyl

Company experimental names TM-41301 or AKD-2023

IUPAC name 3-dodecyl-1,4-dihydro-1,4-dioxo-2-naphthyl acetate

CAS name 2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione

CAS # 57960-19-7

End-use products/EP KanemiteTM 15 SC (1.25 lb ai/gal; EPA Reg. No. 66330-38)

Compound O

O

CH2(CH2)

10CH3

OH

Common name Acequinocyl-OH

Company experimental names R1

IUPAC name 2-dodecyl-3-hydroxy-1,4-napthoquinone

CAS name 2-dodecyl-3-hydroxy-1,4-naphthalenedione

CAS # 57960-31-3

Table 2. Physicochemical Properties.

Parameter Value Reference (MRID)

Melting point 59.6 C 45434906

pH 6.94 45434904

Density 1.13 g/cm345434904

Water solubility ( 20°C) 6.69 μg/L 45434906
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Table 2. Physicochemical Properties.

Parameter Value Reference (MRID)

Solvent solubility (mg/L at 20°C) 1,2-dichloroethane: >250

acetone: >250

ethyl acetate: >250

xylene: >250

methanol: 6.1

n-heptane: 36

n-octanol: 29.2

45434904

Vapor pressure at 25°C 1.69 x 10-9pascals 45434905

Dissociation constant (pKa) no measurable pKa 45434905

Octanol/water partition coefficient 

Log(KOW)

>6.2 45434906

UV/visible absorption spectrum

(max, nm)

neutral pH: 242, 248, 262, 270, 335

acid pH: 242, 248, 265, 270, 330

basic pH: 232, 245, 255, 275, 362

45434905

860.1200 Directions for Use

The petitioner provided a draft label for KanemiteTM 15 SC Miticide (EPA Reg. No. 66330-38), a 

1.25 lb/gal SC formulation of acequinocyl. The acequinocyl formulation, which is currently

registered for use on several fruit and nut crops, is proposed for use on fruiting vegetables, okra, 

edible-podded beans and hops. The proposed uses are summarized below in Table 3.

Table 3. Summary of Directions for Use of Acequinocyl.

Applic. Timing, 

Type, and 

Equip.

Formulation

[EPA Reg. 

No.]

Applic. 

Rate 

(lb ai/A)

Max. No. 

Applic. per 

Season

Max. Seasonal 

Applic. Rate

(lb ai/A)

PHI

(days)

Use Directions and 

Limitations1

Fruiting Vegetables (except cucurbits) (field grown and greenhouse grown)

[eggplant, groundcherry (Physalis spp.), pepino, pepper (includes bell pepper, chili pepper, cooking pepper, 

pimento, sweet pepper), tomatillo, and tomato] 

Postemergence,

foliar

Ground only

1.25 lb/gal 

SC

[66330-38]

0.3 2 0.6 7

Minimum spray volume 

of 100 gal/A; minimum 

RTI of 21 days.

Okra

Postemergence,

foliar

Ground only

1.25 lb/gal 

SC

[66330-38]

0.3 2 0.6 1

Minimum spray volume 

of 100 gal/A; minimum 

RTI of 21 days.

Edible-podded Beans

Postemergence,

foliar

Ground only

1.25 lb/gal 

SC

[66330-38]

0.3 2 0.6 7

Minimum spray volume 

of 100 gal/A; minimum 

RTI of 21 days.

Hops

Postemergence,

foliar

Ground only

1.25 lb/gal 

SC

[66330-38]

0.3 2 0.6 7

Minimum spray volume 

of 100 gal/A; minimum 

RTI of 21 days.

1

 RTI = retreatment interval.
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General label restrictions include: (i) do not apply through any type of irrigation system; (ii) do 

not apply by air; (iii) do not apply within 75 feet of aquatic areas; and (iv) not for indoor 

residential use. The product may be combined with most commonly used pesticides with the 

exception of strongly alkaline material, which can reduce activity; combination with Phos-ethyl 

(fosetyl) is prohibited. Broad-spectrum insect control may be obtained by tank-mixing the SC 

acequinocyl product with other miticide/insecticide products; a spray mix compatability and 

phytotoxicity trial under local conditions should first be conducted. A 12-hour restricted entry

interval (REI) is specified.

No rotational crop restrictions are specified on the label.

Conclusions: The proposed use directions are adequate to allow for evaluation of the submitted 

residue data relative to the proposed uses. The proposed uses are generally supported by the 

submitted field trial data; however, the data for fruiting vegetables supports a 1-day PHI for all 

fruiting vegetables. The petitioner may reduce the proposed PHI for fruiting vegetables from 7 

days to 1 day, based on field trial data. The submitted fruiting vegetable data do support the 1-

day PHI proposed for okra. 

Furthermore, the submitted field trial data reflect applications made without the use of a spray

adjuvant. A revised Section B should be submitted incorporating an adjuvant–use 

restriction.

An adequate confined rotational crop study was previously submitted, reflecting the maximum 

proposed use pattern for rotated crops (fruiting vegetables and edible-podded beans). These data 

support a 30-day PBI for all non-labeled crops. A revised Section B should be submitted 

incorporating the rotational crop restriction.

860.1300 Nature of the Residue - Plants

The qualitative nature of acequinocyl residues in fruit and nut crops is understood based on the 

available apple, orange, and eggplant metabolism studies (Memo, S. Levy, 10-MAR-2004; DP# 

284757). The data indicate that the metabolism of acequinocyl in these crops involves the loss of 

the acetyloxy moiety to form acequinocyl-OH, opening of the quinone ring to form AKM-18, and 

subsequent degradation of the quinone ring to yield polar metabolites that degrade to phthalic 

acid. 

Based on the structural similarity of acequinocyl-OH to parent and the presence of acequinocylOH at quantifiable levels in crops, the HED Metabolism Assessment Review Committee 

(MARC) concluded that parent and acequinocyl-OH are the residues of concern for risk 

assessment and tolerance expression in apples, oranges, and eggplant commodities (Memo, S. 

Levy, 07-JAN-2004; DP# 297872). For purposes of this petition, HED is willing to translate 

these results to hops and edible-podded beans as these two crops are low-consumption food 

items. However, if in the future the petitioner requests new uses where apple, orange, and 

eggplant metabolism data cannot be translated, HED may ask for additional plant metabolism 

data.
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860.1300 Nature of the Residue - Livestock

There are no livestock feedstuffs associated with the proposed uses. Therefore, data 

requirements for livestock metabolism are not relevant to this tolerance petition.

860.1340 Residue Analytical Methods

Enforcement methods: Adequate analytical methods are available for enforcing acequinocyl 

tolerances in/on the proposed/registered plant commodities (Memo, D. Soderberg 23-MAY2006; DP# 321753; Memo, S. Levy, 25-JUN-2008; DP#s 351336 & 353313). These methods 

include two LC/MS/MS methods for determining acequinocyl and acequinocyl-OH residues in 

fruit crops (Morse Method #Meth-133, revision #3) and nut crops (Morse Method #Meth-135). 

The three methods were forwarded by HED to the BEAD, ACB laboratory for a PMV. In lieu of 

a PMV, ACB completed a desk audit (Memo, P. Golden, 04-APR-2006; ACB#: B04-13) in 

which ACB recommended that the petitioner revise methods # Meth-133, Revision #3 (including 

the modification for orange oil), # Meth-135, and # Meth-139 Revision #2 to address 

deficiencies. The petitioner adequately addressed the modifications requested by ACB (Memo, 

P. Golden, 04-APR-2006; ACB#: B04-13). Methods #Meth-135, Revision #3, #Meth-133, 

Revision #4, and #Meth-139, Revision #3 are suitable enforcement methods for the subject crop 

and livestock matrices and no additional data concerning these methods are necessary (Memo, S. 

Levy, 25-AUG-2010; DP#380302).

Data-gathering methods: Samples of crop commodities that were collected from the magnitude 

of the residue studies were analyzed for residues of acequinocyl and acequinocyl-OH using 

modifications of the enforcement methods. Samples from the tomato, pepper and hop field trials

and tomato processing study were analyzed using Method Meth-135, and samples from the 

edible-podded bean field trials were analyzed using Method Meth-133. 

Using the modified Meth-135 method, residues in/on tomato and pepper samples were extracted 

with hexane in the presence of anhydrous sodium sulfate, centrifuged, filtered, and concentrated. 

The extract was cleaned up by silica-gel SPE using a Bond Elute-Si column, and residues were 

eluted with hexane:ethyl acetate (24:1, v:v for acequinocyl and 9:1, v:v for acequinocyl-OH). 

The eluates were concentrated to dryness, and redissolved in ACN:acetone:0.4% formic acid 

(2:2:1, v:v:v) for HPLC/MS/MS analysis.

For hops, residues in/on samples were extracted with ACN:water (60:40, v:v) and filtered. The 

extract was brought to volume with additional ACN/water for cleanup by C18 SPE, and residues 

were eluted with ACN. The eluate was then partitioned with hexane; the hexane fraction was 

mixed with 1% decanol in acetone (keeper solution), concentrated, and diluted with hexane for 

silica SPE cleanup. Residues were eluted with 5% ethyl ether in hexane, concentrated, and 

redissolved in ACN:acetone:0.4% formic acid (2:2:1, v:v:v) for HPLC/MS/MS analysis. 

Using the modified Meth-133 method, residues in/on snap bean samples were extracted with 

ACN:water (10:3, v:v). Salt (NaCl) was added to force separation of the water and ACN phases

and centrifuged. The resulting ACN fraction was filtered through sodium sulfate. Residues were 

then partitioned into hexane. The hexane fraction was mixed with 1% decanol in acetone (keeper 

solution), concentrated, and diluted with hexane for silica gel SPE; residues were eluted with 
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hexane:ethyl acetate (9:1, v:v). The eluate was evaporated to dryness and redissolved in 

acetone:ACN:0.4% aqueous formic acid (2:2:1, v/v/v) for HPLC/MS/MS analysis. 

The methods were adequate for data collection based on acceptable method validation and 

concurrent method recovery data; however recoveries for acequinocyl-OH from dried hop cones 

were consistently low (~50%) at all fortification levels (0.10-3.0 ppm). The validated LOQs

were 0.010 ppm for acequinocyl and 0.025 ppm for acequinocyl-OH for tomato fruit, paste and 

puree, and peppers; 0.020 ppm each for acequinocyl and acequinocyl-OH in edible-podded

beans; and 0.10 ppm for acequinocyl in hop dried cones (acceptable recoveries were not obtained 

for acequinocyl-OH from dried hop cones at the target LOQ of 0.10 ppm).

An interfering peak in the HPLC/MS/MS chromatograms was problematic for quantitation of 

acequinocyl-OH residues near the LLMV; therefore gas chromatography (GC)/mass-selective 

detector (MSD), analysis was used to confirm that the OH metabolite was present at <0.10 ppm 

in untreated hop samples. Treated samples were also re-extracted for GC/MSD analysis. 

GC/MSD analyses using 2 or 4 confirmatory ions were inconclusive because ion ratios found in 

treated samples did not match those of standards. But significant peaks were observed for each 

ion monitored at the corresponding retention time for acequinocyl-OH, suggesting acequinocylOH may be present along with smaller co-eluting matrix interferences with similar ions, thus 

affecting ion ratios. Therefore, the HPLC/MS/MS results for acequinocyl-OH were considered 

likely to be valid.

Conclusions: Methods #Meth-135, Revision #3, #Meth-133, Revision #4, and #Meth-139, 

Revision #3 are suitable enforcement methods for the subject crop and livestock matrices 

(Memo, S. Levy, 25-AUG-2010; DP#380302). Samples of crop commodities that were collected 

from the magnitude of the residue studies were analyzed for residues of acequinocyl and 

acequinocyl-OH using the LC/MS/MS enforcement methods, with minor modifications. The 

methods were generally adequate for data-collection based on acceptable method validation and 

concurrent method recoveries from fortified tomato fruit, paste and puree, peppers, snap beans 

and hops; however, the validation data indicate that the data collection/enforcement method may

not be suitable for quantitation of acequinocyl-OH residues from dried hop cones.

860.1360 Multiresidue Methods

Acceptable MRM method testing data were submitted for acequinocyl and acequinocyl-OH, and 

these data were forwarded to the U.S. FDA for further evaluation (Memo, S. Levy, 18-FEB2004; DP#: 298917). Acequinocyl was adequately recovered from fortified apples using Method 

302, E1 + C1 with GC/electron-capture detector (ECD), but was not recovered using Method 303 

or 304 due to poor recoveries from the Florisil cleanup. Acequinocyl-OH was completely

recovered from fortified apples using Method 402, E1 or E2 + C1 with GC/ECD, but was not 

recovered using Methods 302, 303, or 304.

860.1380 Storage Stability

Samples from the field trial and processing studies were stored frozen from harvest to analysis. 

To support the sample storage conditions and durations, concurrent storage stability was 

conducted in conjunction with the analysis of the field trial and processing samples. Untreated 
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samples of tomato fruit, puree, and paste, peppers, snap beans, and dried hop cones were fortified 

with acequinocyl or acequinocyl-OH at 0.10 ppm and stored frozen. 

Residues of acequinocyl and acequinocyl-OH were relatively stable in/on tomato fruits stored 

frozen for up to 337 days, snap beans stored frozen for up to 453 days, and hop dried cones 

stored frozen for up to 411 days. Although the storage intervals of the fortified samples did not 

encompass the longest hop and snap bean sample storage duration, only samples from one trial 

for each of the crops were stored past the demonstrated storage interval.

Residues of acequinocyl were relatively stable in tomato paste and puree stored frozen for up to 

85 and 146 days, respectively, and in bell pepper stored frozen for up to 407 days. However, for 

these crops residues of acequinocyl-OH appear not to be stable. Acequinocyl-OH residues in 

puree and paste declined to 29% and 34% following frozen storage for 119 and 146 days, 

respectively, and residues in bell pepper declined to a 51% recovery following frozen storage for 

up to 408 days. Because no 0-day data were provided with the concurrent storage stability

studies, the rate of decline of acequinocyl-OH residues in pepper, and tomato puree and paste can 

not be determined.

The storage durations and conditions of samples from the crop field trial and processing studies 

submitted to support this petition are presented in Table 4. 

Table 4. Summary of Storage Conditions and Durations of Samples from Crop Field Trial and Processing

Studies. 

Matrix 

Storage

Temperature

(°C)

Actual Storage

Duration Interval of Demonstrated Storage Stability

Tomato <-20 84-285 days 

(≤9.4 months)

Acequinocyl and acequinocyl-OH are relatively stable in/on 

fortified tomato stored frozen for up to 11 months.

Tomato, puree 90 days 

(3.0 months)

Acequinocyl is relatively stable in/on fortified puree stored 

frozen for up to 3 months; acequinocyl-OH was not stable in 

puree stored frozen for up to 4 months.

Tomato, paste 156-157 days

(5.2 months)

Acequinocyl is relatively stable in/on fortified paste stored 

frozen for up to 5 months; acequinocyl-OH was not stable in 

paste stored frozen for up to 5 months.

Pepper 329-402 days 

(≤13.2 months)

Acequinocyl is relatively stable in/on fortified pepper stored 

frozen for up to 13 months; acequinocyl-OH was not stable in 

pepper stored frozen for up to 13 months.

Bean, snap 326-480 days 

(≤15.8 months)

Acequinocyl and acequinocyl-OH are relatively stable in/on 

fortified snap bean stored frozen for up to ~15 months.

Hop, dried

cones

440-449 days

(≤14.8 months)

Acequinocyl and acequinocyl-OH are relatively stable in/on 

fortified dried hop cones stored frozen for up to ~14 months.

Conclusions: The submitted concurrent storage stability data for tomato, snap bean, and hops is 

adequate to support the storage intervals and conditions incurred by the field trial studies. In

addition, the concurrent storage stability data for the parent acequinocyl is adequate to support 

the sample storage intervals and conditions for the pepper field trials and tomato processing 

studies. It is noted that zero-day data were not provided. IR-4 is reminded that storage stability

studies should always include a zero-day sampling interval to establish the residue levels present 

at the time samples are placed into storage [see OPPTS 860.1380(d)(6)(i)]. 
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The concurrent storage stability data indicate problems with the stability of acequinocyl-OH in 

peppers and processed tomato paste and puree. Because zero-day samples were not analyzed, 

determination of residue levels present at the time samples were placed in frozen storage could 

not be made. In addition, an insufficient number of time points were analyzed in order to 

establish how much of the residue (acequinocyl-OH) was lost at various time points. 

However, because residues of acequinocyl-OH in the pepper field trial were <10% of the parent 

value or were <LOQ, correction for 51% decline would not affect the results. Furthermore, in 

the tomato processing study, because there were quantifiable residues of the parent in the RAC 

and residues of acequinocyl-OH in the RAC were nonquantifiable, HED believes that any

concentration of acequinocyl-OH residues would not significantly increase the total residue level. 

Therefore, HED is not requesting additional storage stability data at this time. 

860.1500 Crop Field Trials

DER References: 47819401.de1 (tomato)

47819402.der (pepper)

47819403.der (snap bean)

47819404.der (hop)

IR-4 submitted field trial data in support of the proposed uses on fruiting vegetables, hops, and 

edible-podded beans. The results of the field trials are summarized in Table 5. The submitted 

data are discussed below.

Table 5. Summary of Residue Data from Crop Field Trials with Acequinocyl.

Crop matrix

Total Applic. 

Rate

(lb ai/A)

PHI 

(days)

Total Acequinocyl and Acequinocyl-OH Residues (ppm)

n Min. Max. HAFT1 Median Mean Std. 

Dev.

FRUITING VEGETABLES (proposed use = 0.6 lb ai/A total application rate, 7-day PHI)

Tomato 0.600-0.642 1 30 <0.05 <0.16 0.16 0.075 0.085 0.03

Tomato 

(greenhouse)

0.622-0.630 1 6 <0.10 <0.20 0.19 0.13 0.14 0.04

Pepper, nonbell0.602-0.635 1 10 <0.035 0.338 0.307 0.108 0.160 0.117

Pepper, bell 0.601-0.636 1 16 <0.035 0.607 0.515 0.074 0.125 0.158

Pepper, bell

(greenhouse)

0.606-0.617 1 4 <0.131 0.292 0.214 0.161 0.186 0.075

EDIBLE-PODDED BEANS (proposed use = 0.6 lb ai/A total application rate, 7-day PHI)

Snap bean,

pod with seeds

0.574-0.646 6-8 20 <0.04 0.16 0.12 0.06 0.07 0.03

HOPS (proposed use = 0.6 lb ai/A total application rate, 7-day PHI)

Hop, dried 

cones2

0.588-0.641 7 6 1.32 2.83 2.74 2.09 2.11 0.577

1

 HAFT = highest-average field trial result.

2

 Determined using acequinocyl-OH residues corrected for low recoveries.
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 12 of 29

Fruiting Vegetable, Group 8

Tomato

Fifteen tomato field trials were conducted in North American Free Trade Agreement (NAFTA)

Growing Zones 1 (NY, 1 trial), 2 (GA; 1 trial), 3 (FL; 2 trials), 5 (WI; 1 trial) and 10 (CA, NM; 

10 trials), and three greenhouse trials were conducted in NAFTA Growing Zones 2 (NJ; 1 trial), 

6 (TX; 1 trial) and 9 (CO; 1 trial) during the 2003 growing season. Each trial consisted of one 

untreated and one treated plot. At each site, a 1.25 lb/gal SC formulation of acequinocyl was 

applied to tomatoes as two broadcast or directed foliar applications during fruit development at 

rates of 0.291-0.321 lb ai/A/application, with a 19- to 24-day RTI, for a total seasonal rate of 

0.600-0.642 lb ai/A (~1x the maximum proposed seasonal rate). Applications were made using 

ground equipment in volumes of 25-78 gal/A, without a spray adjuvant. Single control and 

duplicate treated samples of mature tomatoes were harvested from each site one at a 1-day PHI. 

Additional samples were taken from one field trial location and one greenhouse location at 0-, 3-,

and 7-day PHIs to assess residue decline.

Residues of acequinocyl-OH were nonquantifiable (<0.025 ppm) in/on all tomatoes (field and 

greenhouse samples) harvested one day after foliar treatments with the SC formulation for a total 

rate of 0.600-0.642 lb ai/A. Residues of parent acequinocyl were 0.02-0.13 ppm in/on tomatoes 

grown in the field, and 0.07-0.17 ppm in/on tomatoes grown in greenhouses; residues of 

acequinocyl were slightly higher in greenhouse-grown tomatoes than in those grown in the field. 

Total residues of acequinocyl and acequinocyl-OH were <0.05-<0.20 ppm in/on all tomatoes. 

In the residue decline studies, residues of acequinocyl declined steadily from the 0-day to the 7-

day sampling interval in/on tomatoes grown in the field. Residues of acequinocyl in tomatoes 

grown in a greenhouse increased initially, and then decreased steadily from the 1-day to 7-day

sampling interval.

Pepper

Eight bell pepper field trials were conducted in NAFTA Growing Zones 2 (GA, MD; 2 trials), 3 

(FL; 2 trials), 5 (WI; 1 trial), 6 (TX; 1 trial), and 10 (CA, NM; 2 trials); five non-bell pepper field 

trials were conducted in NAFTA Growing Zones (NJ; 1 trial), 3 (FL; 1 trial), 5 (MI; 1 trial), 6 

(TX; 1 trial), and 10 (NM; 1 trial); and two bell pepper greenhouse trials were conducted in 

NAFTA Growing Zones 6 (TX) and 9 (CO) during the 2003 growing season. Each trial 

consisted of one untreated and one treated plot. At each site, a 1.25 lb/gal SC formulation of 

acequinocyl was applied as two broadcast or directed foliar applications during fruit development 

at 0.297-0.327 lb ai/A/application, with a 15- to 22-day RTI, for a total rate of 0.601-0.636 lb 

ai/A (~1x the maximum proposed seasonal rate). Applications were made using ground 

equipment in spray volumes of 21-56 gal/A, without a spray adjuvant. Single control and 

duplicate treated samples of mature peppers were harvested from each site one day after the last 

application. Additional samples were taken from one non-bell and one bell field trial at 0-, 3-, 

and 7-day PHIs to assess residue decline.

Residues of acequinocyl were nonquantifiable (<0.010 ppm) to 0.564 ppm in bell peppers and 

<0.010-0.295 ppm in non-bell peppers harvested one day after foliar treatments with the SC 
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 13 of 29

formulation for a total rate of 0.601-0.636 lb ai/A; average residues of acequinocyl were slightly

higher in greenhouse-grown peppers than in those grown in the field. Residues of acequinocylOH were nonquantifiable (<0.025 ppm) to 0.043 ppm in/on bell peppers and <0.025-0.043 ppm 

in/on non-bell peppers. Total residues of acequinocyl and acequinocyl-OH were <0.035-0.607

ppm in/on bell peppers and <0.035-0.338 ppm in/on non-bell peppers.

In the residue decline studies, residues of acequinocyl in bell and non-bell peppers grown in the 

field declined steadily from the 0-day to the 7-day sampling interval. 

Conclusions: The submitted residue data for tomato and peppers are adequate with respect to the 

number and locations of field trials for the representative crops of the fruiting vegetable group 8. 

The data reflect the proposed single and maximum application rates, but the proposed PHI is 7

days for fruiting vegetables and the field trials reflect a 1-day PHI. Residue decline trials for 

tomato and pepper demonstrate that residues generally decline with later sampling intervals; 

therefore, residues at the later 7-day PHI would likely be lower than those observed in the field 

trials. The petitioner may reduce the proposed PHI from 7 days to 1 day for fruiting vegetables, 

based on the field trial data. The submitted tomato and pepper field trial data reflect applications 

made without the use of a spray adjuvant. A revised Section B should be submitted 

incorporating an adjuvant–use restriction.

Because residues of acequinocyl-OH in the pepper field trial were generally <10% of the parent 

value and quantifiable residues of acequinocyl-OH were not found in most pepper samples, 

correction for decline would not affect the results. Furthermore, in the tomato processing study, 

because there were quantifiable residues of the parent in the RAC and residues of acequinocylOH in the RAC were nonquantifiable, HED believes that any concentration of acequinocyl-OH 

residues would be covered by the parent. Therefore, HED is not requesting additional storage 

stability data at this time. 

The available residue data for total acequinocyl and acequinocyl-OH residues in/on tomato 

(field- and greenhouse-grown), bell peppers (field- and greenhouse-grown), and non-bell peppers 

were separately entered into the Agency’s tolerance spreadsheet as specified by the Guidance for 

Setting Tolerances Based on Field Trial Data SOP (August 2009 version) to determine the 

appropriate tolerance levels; see Appendix I. Based on the spreadsheet, the recommended 

tolerances are 0.25 ppm for tomato, 0.60 ppm for bell pepper, and 0.70 ppm for non-bell pepper. 

Because the minimum and maximum recommended tolerances differ by less than 5x, a crop 

group tolerance is appropriate for the vegetable, fruiting, crop group 8. The recommended value 

is 0.70 ppm, the maximum of the recommended individual tolerances.

The tomato and pepper field trial data reflect the proposed use on okra (0.6 lb ai/A maximum 

application rate with a 1-day PHI), and may be translated to okra. Okra has been recommended 

to be added as a member of the fruiting vegetable group 8; however, until okra has been officially

added to the crop group, a separate tolerance is required for okra at the same tolerance level (0.70 

ppm) as for fruiting vegetables. 

Bean, Edible Podded

Ten snap bean field trials were conducted in NAFTA Growing Zones 1 (NY; 1 trial), 2 (GA, NJ; 
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 14 of 29

2 trials), 3 (FL; 1 trial), 5 (OH, WI; 4 trials), 10 (CA; 1 trial), and 11 (ID; 1 trial) during the 2004 

growing season. Each trial consisted of one untreated and one treated plot. At each site, a 1.25 

lb/gal SC formulation of acequinocyl was applied to snap beans as two broadcast or directed 

foliar applications during vegetative development at rates of 0.263-0.332 lb ai/A/application, 

with a 13- to 17-day RTI, for a total rate of 0.574-0.646 ai/A (~1x the maximum proposed 

seasonal rate). Applications were made using ground equipment in spray volumes of 29-51 

gal/A, without a spray adjuvant. Single control and duplicate treated samples of mature snap 

beans were harvested from each site at 6- to 8-day PHIs. Additional samples were collected at 

two trials 3- or 4-, and 10- or 11-day PHIs to assess residue decline.

Residues of acequinocyl were nonquantifiable (<0.02 ppm) to 0.14 ppm, and residues of 

acequinocyl-OH were at or below the LOQ (≤0.02 ppm) in/on snap beans harvested 6-8 days 

after foliar treatments with the SC formulation for a total rate of 0.574-0.646 lb ai/A. Total 

residues of acequinocyl and acequinocyl-OH were <0.04-0.16 ppm in/on snap beans.

In one residue decline study, residues of acequinocyl declined steadily from the 4-day to the 11-

day sampling interval. In the other decline study residues increased slightly, but decreased at the 

10-day sampling interval.

Conclusions: The submitted residue data for snap beans are adequate with respect to the number 

and locations of field trials for edible-podded beans. The data reflect the proposed single and 

maximum application rates, and minimum PHI. The submitted snap bean field trial data reflect 

applications made without the use of a spray adjuvant. A revised Section B should be 

submitted incorporating an adjuvant–use restriction.

The residue data for total acequinocyl and acequinocyl-OH residues in/on snap beans were 

entered into the Agency’s tolerance spreadsheet as specified by the Guidance for Setting 

Tolerances Based on Field Trial Data SOP (August 2009 version) to determine the appropriate

tolerance level; see Appendix I. Based on the spreadsheet, the recommended tolerance is 0.25 

ppm for edible-podded beans.

Hops

Three hop field trials were conducted in NAFTA Growing Zone 11 (ID, OR, WA) during the 

2005 growing season. Each trial consisted of one untreated and one treated plot. At each site, a 

1.25 lb/gal SC formulation of acequinocyl was applied to hops as two directed foliar applications 

during cone development at rates of 0.288-0.330 lb ai/A/application, with a 19- to 28 day RTI, 

for a total rate of 0.588-0.641 lb ai/A (~1x the maximum proposed seasonal rate). Applications 

were made using ground equipment in spray volumes of 86-196 gal/A, without a spray adjuvant. 

Single control and duplicate treated samples of mature hops were harvested from each site at a 7-

day PHI.

Because method validation and concurrent recoveries were consistently low (overall average 

recovery of 52.5%) for acequinocyl-OH from dried hop cones, residues of acequinocyl-OH were 

corrected. Residues of acequinocyl and acequinocyl-OH (corrected) were 1.09-2.53 and 0.229-

1.08 ppm, respectively, in/on hop dried cones harvested 7 days following foliar applications of 

the SC formulation for a total rate of 0.588-0.641 lb ai/A. Total residues of acequinocyl and 
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 15 of 29

acequinocyl-OH (corrected) were 1.32-2.83 ppm in/on dried hop cones.

A residue decline study was not conducted, and is not required as hops are considered a minor 

crop (≤3 trials required).

Conclusions: The submitted residue data for hops are adequate with respect to the number and 

locations of field trials. The data reflect the proposed single and maximum application rates, and 

minimum PHI. The submitted hop field trial data reflect applications made without the use of a 

spray adjuvant. A revised Section B should be submitted incorporating an adjuvant–use 

restriction.

The residue data for total acequinocyl and corrected acequinocyl-OH residues in/on dried hop 

cones were entered into the Agency’s tolerance spreadsheet as specified by the Guidance for 

Setting Tolerances Based on Field Trial Data SOP (August 2009 version) to determine the 

appropriate tolerance level; see Appendix I. Based on the spreadsheet, the recommended 

tolerance is 4.0 ppm for hop, dried cones.

860.1520 Processed Food and Feed

DER Reference: 47819401.de2 (tomato)

Tomato

In a field trial conducted in NAFTA Growing Zone 10 (CA) during the 2003 growing season, a 

1.25 lb/gal SC formulation of acequinocyl was applied to maturing tomatoes as two broadcast 

foliar applications at 0.606-0.621 lb ai/A/application, with a 21-day RTI, for a total rate of 1.227 

lb ai/A (~2x the maximum proposed seasonal rate for tomato). Applications were made using 

ground equipment in spray volumes of 25-26 gal/A, without a spray adjuvant. Mature tomatoes 

were harvested at a 1-day PHI and processed into puree and paste using simulated commercial 

procedures.

Samples were analyzed for residues of acequinocyl and its metabolite acequinocyl-OH using 

HPLC/MS/MS, Morse Meth-135 with minor modifications. Meth-135 is an approved 

enforcement method for crop commodities. The method was adequate for data collection based 

on acceptable method validation and concurrent method recovery data; however, it is noted that 

low method verification recoveries were obtained for the OH metabolite in tomato paste and 

puree at higher fortification levels (i.e., 1.0 ppm). The validated LOQ was 0.01 ppm for 

acequinocyl and 0.025 ppm for acequinocyl-OH for all tomato matrices. 

Sample storage conditions and durations are reported in Table 4. The storage conditions and 

durations are supported by concurrent storage stability data conducted in conjunction with the 

analysis of the processing study samples. Based on the results of the concurrent storage stability

study, residues of acequinocyl-OH in puree and paste declined to 29% and 34% after 119 and 

146 days, respectively, of frozen storage; however, because no 0-day data were provided with the 

concurrent storage stability study, the rate of decline in puree and paste can not be determined. 

Residues of parent acequinocyl were 0.20 ppm (field sample) or 0.14 ppm (sample for 
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 16 of 29

processing) in/on tomato (RAC) harvested 1 day following foliar applications of the SC 

formulation at a total rate of 1.227 lb ai/A. Following processing, acequinocyl residues were 

0.04 ppm in/on tomato puree and 0.05 ppm in/on tomato paste. Based on the study results, 

residues of acequinocyl do not appear to concentrate in puree (0.3x), and paste (0.4x). Residues 

of acequinocyl-OH were nonquantifiable (<0.025 ppm) in both the respective RAC and 

processed samples, therefore, processing factors can not be calculated. 

A summary of the processing factors for tomato matrices is presented in Table 6. The observed 

processing factors are below the maximum theoretical concentration factors, based on loss of 

water, of 1.4x for puree and 5.5x for paste (OPPTS 860.1520, Table 2).

Table 6. Summary of Processing Factors for Acequinocyl.

RAC Processed Commodity Processing Factor

Tomato Fruit Puree 0.3x

Paste 0.4x

Conclusions: The tomato processing study is adequate to support the proposed use pattern. 

Residues of acequinocyl-OH were found to degrade significantly during storage. However, 

because there were quantifiable residues of the parent in the RAC and residues of acequinocylOH in the RAC were nonquantifiable, HED believes that any concentration of acequinocyl-OH 

residues would be covered by the parent. The available data indicate that residues of acequinocyl 

and acequinocyl-OH are not likely to concentrate with processing of tomato fruit to paste and 

puree; therefore, tolerances are not required for these commodities. 

860.1650 Submittal of Analytical Reference Standards

The available analytical standards for acequinocyl and acequinocyl-OH at the EPA National 

Pesticide Standards Repository (personal communication with Dallas Wright, ACB, 30-APR2010) expired on 19-APR-2010 and 20-APR-2010, respectively. This is a deficiency. The 

petitioner should either recertify the lot in the repository and send in an updated certificate of 

analysis (COA), or submit new standards (different lot #) if the previous lots will not be 

recertified. If new COAs are being submitted, they should be faxed to the repository at 410-305-

2999. If new standards are being submitted, they should be sent to the Analytical Chemistry Lab, 

which is located at Fort Meade, to the attention of Theresa Cole at the following address (note 

that the mail will be returned if the extended zip code is not used):

USEPA

National Pesticide Standards Repository/Analytical Chemistry Branch/OPP

701 Mapes Road

Fort George G. Meade, MD 20755-5350

 

860.1850/1900 Confined and Field Accumulation in Rotational Crops

The proposed uses under this petition include fruiting vegetables and edible-podded beans which 

are typically rotated crops. An acceptable confined rotational crop study was previously

submitted (Memo, S. Levy, 25-JUN-2008; DP#s 351336 & 353313) in support of uses on 

strawberries. The study results (47332501.der) showed the extent and nature of the residue 
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 17 of 29

uptake by crops (lettuce, turnip and wheat) planted 30-, 120- and 365-days post-application in 

soil treated with 14C-acequinocyl at 0.60 lb ai/A (1x maximum registered/proposed seasonal 

application rate to rotated crops). Residues in a majority of the rotational crop samples were 

either low or non-quantifiable (<0.01 ppm 14C-acequinocyl equivalents). The only significant 

levels of TRR occurred at the 30-day PBI in immature lettuce and turnip tops. Parent chemical 

along with its hydroxylated metabolite plus a variety of low but detectable metabolites, including 

metabolite M1, could be found only in immature crops from the 30-day PBI. Plant residues from 

other maturity stages and replant intervals were largely non-extractable with organic solvent. A 

majority of the non-extractable residues could be released by enzyme, acid and base hydrolysis. 

A vast array of products were detected by chromatographic assay in hydrolyzed samples, though 

the nature of these residues could not be further delineated due to their low level coupled with 

lack of chromatographic resolution following analysis.

The available data support a 30-day PBI for all non-labeled crops. A revised Section B should 

be submitted incorporating the rotational crop restriction.

860.1550 Proposed Tolerances

HED has determined that the residues of concern in both plant and ruminant commodities 

includes acequinocyl and acequinocyl-OH, and tolerances are currently established for the 

combined residues of acequinocyl and acequinocyl-OH, expressed as parent, in/on plant and 

livestock commodities [40 CFR §180.599(a)]. The tolerance expression proposed by IR-4 is 

appropriate.

There are currently no established Codex or Mexican maximum residue limits (MRLs) for 

acequinocyl; Canadian MRLs include the parent and metabolite, but none are established for the 

crops proposed for use under this petition.

The field trial data for tomato and pepper are considered adequate to support a crop group 

tolerance. The tomato, bell pepper and non-bell pepper datasets were separately entered into the 

tolerance spreadsheet (rev. August 2009) in the Agency’s Guidance for Setting Pesticide 

Tolerances Based on Field Trial Data; see Appendix I. The proposed tolerance (0.70 ppm) for 

the fruiting vegetable group 8 is appropriate. No tolerances are required for tomato paste or 

puree.

Okra has been recommended to be added as a member of the fruiting vegetable group 8; 

however, until okra has been officially added to the crop group, a separate tolerance is required. 

The tomato and pepper field trial data will support the proposed tolerance (0.70 ppm) for okra. 

The snap bean and hop dried cone data are adequate, and were entered into the tolerance 

spreadsheet to determine the appropriate tolerances; see Appendix I. The proposed tolerance 

(0.25 ppm) for edible-podded beans is appropriate; however, the tolerance proposed for hop dried 

cones is too low and should be increased to 0.40 ppm.

The proposed and recommended tolerances are listed in Table 7.
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 18 of 29

Table 7. Tolerance Summary for Acequinocyl.

Commodity Proposed Tolerance 

(ppm)

HED-Recommended 

Tolerance (ppm)

Comments; 

Correct Commodity Definition

Vegetable, fruiting, group 8 0.70 0.70

Okra 0.70 0.70

Bean, edible podded 0.25 0.25

Hop, dried cones 3.5 4.0

References

DP#: 297872

Subject: Acequinocyl. Report of the Metabolism Assessment Review Committee 

(MARC). Meeting Date: 17-DEC-2003.

From: S. Levy/P. Terse

To: Y. Donovan

Dated: 07-JAN-2004

MRID: None

DP#: 298917

From: S. Levy

To: M. Wirtz

Dated: 18-FEB-2004

MRID: 45651603

DP#s: 284757, 290204, 286425

Subject: Acequinocyl. Registration for Use on Pome Fruits, Citrus, Almonds, Pistachios, 

and Strawberry. Summary of Analytical Chemistry and Residue Data.

From: S. Levy

To: D. Kenny/M. Laws

Dated: 10-MAR-2004

MRID(s): 46602001-46602003

DP#: 321753

Subject: Acequinocyl. Response to Submission of MRID#s 46602001, 46602002 and 

46602003 by Morse Laboratories Addressing a Need for Confirmation of 

Acequinocyl in Fruits, Almonds and Livestock Tissues.

From: D. Soderberg and S. Levy

To: T. White

Dated: 23-MAY-2006

MRID(s): 46602001-46602003

DP#s: 330439, 337218, 337472

Subject: Acequinocyl. Petitions for Uses on Tree Nuts and Grapes. Summary of 

Analytical Chemistry and Residue Data.

From: S. Levy

To: M. Mautz

Dated: 05-SEP-2007
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 19 of 29

MRID(s): 46776602, 47032402, & 46952301

DP#s: 351336 & 353313

Subject: Acequinocyl; Review of Petitioner’s Amendment Dated 28-JUN-2008 Submitted 

in Response to the Health Effects Division (HED) Memoranda, DP# 284757 

(dated 10-MAR-2004).

From: S. Levy

To: J. Stone/J. Miller

Dated: 25-JUN-2008

MRID: 47332501

DP#s: 380302

Subject: Acequinocyl; Response to the Health Effects Division (HED) Review of 25-JUN2008 (Memoranda, DP#s D351336 & D353313).

From: S. Levy

To: J. Hebert

Dated: 25-AUG-2010

MRID(s): 48016603-48016605

Attachments: 

International Residue Limit Status (IRLS) sheet.

Appendix I -Tolerance Assessment Calculations.

RDI: G. Kramer (02-MAY-2010); RAB1 Chemists (02-MAY-2010)

S. Levy:S-10953:PY1:(703)305-0783:7509P

Template Version September 2005
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 20 of 29

INTERNATIONAL RESIDUE LIMIT STATUS

Chemical Name: 2-(acetyloxy)-

3-dodecyl-1,4-naphthalenedione

Common Name: 

Acequinocyl

X Proposed tolerance

 Reevaluated tolerance

 Other

Date: 01-MAR-2010

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: 9E7598

DP Number: 369100

Other Identifier: Decision Number: 417967

Residue definition (step 8/CXL): N/A Reviewer/Branch: S. Levy/RAB1

Residue definition: Combined residues of acequinocyl 

and acequinocyl-OH, expressed as parent

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

Vegetable, fruiting, Group 8 0.70

Okra 0.70

Bean, edible podded 0.25

Hop, dried cones 3.5

Limits for Canada Limits for Mexico1

⁭No Limits

√ No Limits for the crops requested

√ No Limits

⁭ No Limits for the crops requested

Residue definition: 2-(acetyloxy)-3-dodecyl-1,4-

naphthalenedione, including the metabolite 2-dodecyl3-hydroxy-1,4-naphthalenedione.

Residue definition: N/A

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

Notes/Special Instructions: 

1Mexico adopts Codex MRLs or US tolerances for its export purposes.

S. Funk, 01-MAR-2010
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 21 of 29

Appendix I. Tolerance Assessment Calculations.

For each of the crops listed below, the Guidance for Setting Pesticide Tolerances Based on Field 

Trial Data (SOP), along with the tolerance spreadsheet (August 2009 version), was used for 

calculating recommended tolerances. As specified in the SOP, the minimum of the 95% upperconfidence limit (UCL) on the 95th percentile and the point estimate of the 99th percentile was 

selected as the tolerance value in cases when the dataset was large (greater than 15 samples) and 

reasonably lognormal. For datasets that were small (≤15 samples) and reasonably lognormal, the 

upper bound estimate of the 95th percentile based on the median residue value was compared to 

the minimum of the 95% UCL on the 95th percentile and the point estimate of the 99th 

percentile, and the minimum value was selected as the tolerance value. For datasets that were 

not lognormal, the upper bound on the 89th percentile was selected as the tolerance value 

(distribution-free method). The rounding procedures specified in the SOP were also used.

Fruiting Vegetables

The dataset used to establish a tolerance for acequinocyl on the fruiting vegetable, crop group 8

consisted of field trial data for tomato (field and greenhouse), bell pepper (field and greenhouse) 

and non-bell pepper (the representative crops of the crop group), representing total application 

rates of 0.600-0.642 lb ai/A (2 applications at ~0.3 lb ai/A/application), with a 1-day PHI. The 

field trial application rates are within 25% of the maximum label application rate. The minimum 

label PHI is 7 days for fruiting vegetables; however, a full set of field trial samples were 

collected for tomatoes, bell peppers and non-bell peppers at a 1-day PHI. The residue values that 

were entered into the tolerance spreadsheet are provided in Table I-1.

All field trial sample results were above the combined LOQ for acequinocyl and acequinocyl-OH 

(LOQ = 0.035 ppm). The non-bell pepper dataset was small (10 samples). The tomato and bell 

pepper datasets were not small (36 and 20 samples, respectively). For tomato, bell pepper, and 

non-bell pepper, visual inspection of the lognormal probability plots (Figures I-1, I-3, and I-5) 

and the results from the approximate Shapiro-Francia test statistic (Figures I-2, I-4, and I-6)

indicated that the datasets were reasonably lognormal. 

Using the tolerance spreadsheet, the recommended tolerances are 0.25 ppm for tomato, 0.60 ppm 

for bell pepper, and 0.70 ppm for non-bell pepper. Because the minimum and maximum 

recommended tolerances differ by less than 5x, a crop group tolerance is appropriate for the 

vegetable, fruiting, group 8. The recommended value is 0.70 ppm, the maximum of the 

recommended individual tolerances.
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 22 of 29

Table I-1. Residue Data Used to Calculate Tolerance for Acequinocyl Residues on Fruiting Vegetables.

Regulator: EPA EPA EPA

Chemical: Acequinocyl Acequinocyl Acequinocyl

Crop: Tomato Bell Pepper Non-Bell Pepper

PHI: 1 day 1 day 1 day

App. Rate: 0.600-0.642 lb ai/A 0.601-0.636 lb ai/A 0.602-0.635 lb ai/A

Submitter: IR-4 IR-4 IR-4

MRID Citation: MRID 47819401 MRID 47819402 MRID 47819402

Combined Residues of Acequinocyl and Acequinocyl-OH (ppm)

0.075 0.055 0.035

0.105 0.089 0.039

0.065 0.036 0.068

0.135 0.035 0.079

0.045 0.09 0.102

0.075 0.121 0.114

0.115 0.074 0.259

0.115 0.075 0.275

0.125 0.073 0.292

0.095 0.071 0.338

0.135 0.607

0.145 0.422

0.075 0.047

0.065 0.043

0.155 0.109

0.155 0.058

0.065 0.292

0.065 0.136

0.055 0.186

0.045 0.131

0.075

0.055

0.085

0.065

0.095

0.085

0.075

0.065

0.055

0.105

0.185

0.195

0.125

0.125

0.095

0.105
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 23 of 29

Figure I-1. Lognormal probability plot of Acequinocyl field trial data for Tomato.

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

y = 0.3937x - 2.4044

R

2

 = 0.9784

Percentiles

Concentrations

EPA Acequinocyl Tomato 1 day 0.600-0.642 lb ai/A IR-4

Figure I-2. Tolerance spreadsheet summary of Acequinocyl field trial data for Tomato.

Regulator: EPA

Chemical: Acequinocyl

Crop: Tomato

PHI: 1 day

App. Rate: 0.600-0.642 lb ai/A

Submitter: IR-4

n: 36

min: 0.05

max: 0.20

median: 0.09

average: 0.10

95th Percentile 99th Percentile 99.9th Percentile

0.20 0.20 0.25

(0.20) (0.25) (--)

0.20 0.25 0.35

(0.25) (0.30) (--)

0.25

0.25

0.45

0.9784

p-value > 0.05 : Do not reject lognormality assumption

Approximate 

Shapiro-Francia 

Normality Test 

EU Method I

Normal

UCLMedian95th

95/99 Rule

EU Method II

Distribution-Free

Mean+3SD
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 24 of 29

Figure I-3. Lognormal probability plot of Acequinocyl field trial data for Bell Pepper

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

y = 0.7812x - 2.3271

R

2

 = 0.9315

Percentiles

Concentrations

EPA Acequinocyl Bell Pepper 1 day 0.601-0.636 lb ai/A IR-4

Figure I-4. Tolerance spreadsheet summary of Acequinocyl field trial data for Bell Pepper.

Regulator: EPA

Chemical: Acequinocyl

Crop: Bell Pepper

PHI: 1 day

App. Rate: 0.601-0.636 lb ai/A

Submitter: IR-4

n: 20

min: 0.04

max: 0.61

median: 0.08

average: 0.14

95th Percentile 99th Percentile 99.9th Percentile

0.40 0.50 0.60

(0.50) (0.70) (--)

0.40 0.60 1.1

(0.70) (1.3) (--)

0.30

0.60

0.45

0.9315

p-value > 0.05 : Do not reject lognormality assumption

Approximate 

Shapiro-Francia 

Normality Test 

EU Method I

Normal

UCLMedian95th

95/99 Rule

EU Method II

Distribution-Free

Mean+3SD
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 25 of 29

Figure I-5. Lognormal probability plot of Acequinocyl field trial data for Non-Bell Pepper

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

y = 0.8667x - 2.1235

R

2

 = 0.9267

Percentiles

Concentrations

EPA Acequinocyl Non-Bell Pepper 1 day 0.602-0.635 lb ai/A IR-4

Figure I-6. Tolerance spreadsheet summary of Acequinocyl field trial data for Non-Bell Pepper.

Regulator: EPA

Chemical: Acequinocyl

Crop: Non-Bell Pepper

PHI: 1 day

App. Rate: 0.602-0.635 lb ai/A

Submitter: IR-4

n: 10

min: 0.04

max: 0.34

median: 0.11

average: 0.16

95th Percentile 99th Percentile 99.9th Percentile

0.40 0.45 0.60

(0.60) (0.70) (--)

0.50 0.90 1.7

(1.5) (3.5) (--)

0.60

0.60

0.70

0.9267

p-value > 0.05 : Do not reject lognormality assumption

Approximate 

Shapiro-Francia 

Normality Test 

EU Method I

Normal

UCLMedian95th

95/99 Rule

EU Method II

Distribution-Free

Mean+3SD
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 26 of 29

Edible-Podded Beans

The dataset used to establish a tolerance for acequinocyl on edible-podded beans consisted of 

field trial data representing total application rates of 0.574-0.606 lb ai/A (2 applications at ~0.3 lb 

ai/A/application), with a 7-day PHI. 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.

Because 6 of 20 field trial sample results were below the combined LOQ for acequinocyl and 

acequinocyl-OH (LOQ = 0.04 ppm), maximum-likelihood estimation (MLE) procedures were 

needed to impute censored values. The dataset was not small (20 samples). Visual inspection of 

the lognormal probability plot (Figure I-7) and the results from the approximate Shapiro-Francia 

test statistic (Figure I-8) indicated that the dataset was reasonably lognormal. 

Using the tolerance spreadsheet, the recommended tolerance is 0.25 ppm for edible-podded

beans.

Table I-2. Residue Data Used to Calculate Tolerance for Acequinocyl Residues on Edible-podded Beans.

Regulator: EPA

Chemical: Acequinocyl

Crop: Edible-podded beans (MLE)

PHI: 6-8 days

App. Rate: 0.574-0.606 lb ai/A

Submitter: IR-4

MRID Citation: MRID 47819403

Combined Residues of Acequinocyl and Acequinocyl-OH (ppm)

0.040

0.0231

0.050

0.050

0.110

0.110

0.090

0.110

0.0261

0.0291

0.0311

0.0331

0.080

0.160

0.060

0.070

0.040

0.0381

0.070

0.070

1 MLE value calculated for residues below the LOQ (<0.04 ppm)
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 27 of 29

Figure I-7. Lognormal probability plot of Acequinocyl field trial data for Edible-podded Beans

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

y = 0.5689x - 2.8873

R

2

 = 0.9754

Percentiles

Concentrations

EPA Acequinocyl Edible podded beans (MLE) 6-8 days 0.574-0.606 lb ai/A IR-4

Figure I-8. Tolerance spreadsheet summary of Acequinocyl field trial data for Edible-podded Beans.

Regulator: EPA

Chemical: Acequinocyl

Crop: Edible podded beans (MLE)

PHI: 6-8 days

App. Rate: 0.574-0.606 lb ai/A

Submitter: IR-4

n: 20

min: 0.02

max: 0.16

median: 0.06

average: 0.06

95th Percentile 99th Percentile 99.9th Percentile

0.15 0.15 0.20

(0.20) (0.20) (--)

0.15 0.25 0.35

(0.25) (0.35) (--)

0.20

0.20

0.30

0.9754

p-value > 0.05 : Do not reject lognormality assumption

Approximate 

Shapiro-Francia 

Normality Test 

EU Method I

Normal

UCLMedian95th

95/99 Rule

EU Method II

Distribution-Free

Mean+3SD
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 28 of 29

Hops

The dataset used to establish a tolerance for the combined residues of acequinocyl and 

acequinocyl-OH on dried hop cones consisted of field trial data representing application rates of 

0.588-0.641 lb ai/A (2 applications at ~0.3 lb ai/A/application), with a 7-day PHI. 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-3.

All field trial sample results were above the combined LOQ for acequinocyl and acequinocyl-OH 

(LOQ = 0.20 ppm). The dataset was small (6 samples). Visual inspection of the lognormal 

probability plot (Figure I-9) and the results from the approximate Shapiro-Francia test statistic 

(Figure I-10) indicated that the dried hop cone dataset was reasonably lognormal. 

Using the tolerance spreadsheet, the recommended tolerance is 4.0 ppm for dried hop cones.

Table I-3. Residue data used to calculate tolerance for Acequinocyl Residues on Hops.

Regulator: EPA

Chemical: Acequinocyl

Crop: Hops

PHI: 7 days

App. Rate: 0.588-0.641 lb ai/A

Submitter: IR-4

MRID Citation: MRID 47819404

Combined Residues of Acequinocyl and Corrected Acequinocyl-OH (ppm)

2.825

2.656

1.658

1.319

2.204

1.980

Figure I-9. Lognormal probability plot of Acequinocyl field trial data for Hops
Acequinocyl Summary of Analytical Chemistry and Residue Data DP#: 369100

Page 29 of 29

Lognormal Probability Plot

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

3.0000

1.5000

0.7500

y = 0.3102x + 0.7119

R

2

 = 0.9708

Percentiles

Concentrations

EPA Acequinocyl Hops 7 days 0.588-0.641 lb ai/A IR-4

Figure I-10. Tolerance spreadsheet summary of Acequinocyl field trial data for Hops.

Regulator: EPA

Chemical: Acequinocyl

Crop: Hops

PHI: 7 days

App. Rate: 0.588-0.641 lb ai/A

Submitter: IR-4

n: 6

min: 1.32

max: 2.83

median: 2.09

average: 2.11

95th Percentile 99th Percentile 99.9th Percentile

3.5 3.5 4.0

(4.5) (6.0) (--)

3.5 4.0 5.0

(6.0) (9.0) (--)

6.0

4.0

17

0.9708

p-value > 0.05 : Do not reject lognormality assumption

Approximate 

Shapiro-Francia 

Normality Test 

EU Method I

Normal

UCLMedian95th

95/99 Rule

EU Method II

Distribution-Free

Mean+3SD