UNITED STATES ENVIRONMENTAL PROTECTION AGENCY

WASHINGTON, D.C. 20460      

	OFFICE OF CHEMICAL SAFETY AND

                                                                        
                      POLLUTION PREVENTION

	

  SEQ CHAPTER \h \r 1 MEMORANDUM

Date:		25-AUG-2010.

SUBJECT:	Acequinocyl.  Petition for Use on Fruiting Vegetables, Hops,
Okra, and Edible-Podded 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  SEQ CHAPTER \h \r 1 

		Risk Assessment Branch 1 (RAB1)

		Health Effects Division (HED) (7509P)

THROUGH:	George F. Kramer, Ph.D., Senior Chemist  SEQ CHAPTER \h \r 1 

		RAB1/HED (7509P)

TO:		Barbara Madden, RM Team 05

		Registration Division (RD; 7505P)  SEQ CHAPTER \h \r 1   SEQ CHAPTER
\h \r 1 

  SEQ CHAPTER \h \r 1   SEQ CHAPTER \h \r 1 

  SEQ CHAPTER \h \r 1 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 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 Kanemite™ 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 high-performance 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  SEQ CHAPTER \h \r 1 ).  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 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 edible-podded
beans; however, the proposed tolerance for hop dried cones is too low.

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.

  SEQ CHAPTER \h \r 1 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.    

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.  

 

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/cm3	45434904

Water solubility ( 20°C)	6.69 µg/L	45434906

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 10-9 pascals	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

™ 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.

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.  

  SEQ CHAPTER \h \r 1 Based on the structural similarity of
acequinocyl-OH to parent and the presence of acequinocyl-OH 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.

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-MAY-2006; 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   SEQ CHAPTER
\h \r 1 (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  SEQ CHAPTER \h \r 1 , 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 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
acequinocyl-OH 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-FEB-2004; 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
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)].  

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, non-bell	0.602-0.635	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.

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

sidered 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 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).

  SEQ CHAPTER \h \r 1 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 acequinocyl-OH 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.  

  SEQ CHAPTER \h \r 1 860.1650 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-APR-2010) 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

  

  SEQ CHAPTER \h \r 1 860.1850/1900 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 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.

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

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-JUN-2008 (Memoranda, DP#s D351336 & D353313).

From:		S. Levy

To:		J. Hebert

Dated:		25-AUG-2010

MRID(s):	48016603-48016605

  SEQ CHAPTER \h \r 1 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



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

⁭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-dodecyl-3-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



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%
upper-confidence 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.

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



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	0.125



	0.125



	0.095



	0.105





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

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

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

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

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

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)

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

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

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

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

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

Page   PAGE  1  of   NUMPAGES  29 

