ETOFENPROX (184)...CAS number 80844-07-1 CIPAC number 471 Molecular mass: 376.47 g/mol Molecular...

Etofenprox 405

ETOFENPROX (184)

First draft prepared by Mr David Lunn, New Zealand Food Safety Authority, Wellington, New Zealand

EXPLANATION

Residue and analytical aspects of etofenprox were evaluated by the JMPR in 1993 and the compound was listed in the Periodic Re-Evaluation Program at the Forty-second Session of the CCPR for periodic review by the 2011 JMPR. The most recent toxicological review was in 1993 when an ADI of 0–0.03 mg/kg bw was established for etofenprox. Specifications for etofenprox technical material, emulsifiable concentrate, wettable powder and emulsion (oil-in-water) have been published by FAO in July 2007 (http://www.fao.org/ag/AGP/AGPP/Pesticid/Specs/docs/Pdf/new/Etofenprox07.pdf).

Etofenprox, a pyrethroid-like insecticide, active through contact or ingestion, is effective against a range of agricultural and horticultural isect pests and is also used as an indoor non-food crack and crevice insecticide, a spot treatment for pets, and as an outdoor fogger to control a variety of flying and crawling insect pests.

Authorisations exist for the agricultural uses of etofenprox (EC and SC formulations) in Italy, Germany, Brazil and Japan with use in rice in USA being a granular formulation for aerial application. The manufacturer submitted studies on metabolism, analytical methods, supervised field trials, processing, freezer storage stability, environmental fate in soil and rotational crop residues.

In this evaluation, the values presented in the tables are as reported in the various studies, but in the accompanying text, they have generally been rounded to two significant digits.

IDENTITY

ISO common name: Etofenprox

Code number MTI-500

IUPAC name: 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether

Chemical Abstracts name:

1-[[2-(4-ethoxyphenyl)-2-methylpropoxy]methyl]-3-phenoxybenzene

CAS number 80844-07-1

CIPAC number 471

Molecular mass: 376.47 g/mol

Molecular formula C25H28O3

Structural formula:

Physical and chemical properties

Pure active ingredient

A detailed chemical and physical characterisation of the active ingredient is given in Table 1.

O

CH3CH2O C CH3

CH3

CH2O CH2

http://www.fao.org/ag/AGP/AGPP/Pesticid/Specs/docs/Pdf/new/Etofenprox07.pdf

406 Etofenprox

Table 1 Physical and chemical data of etofenprox

Property Result Test material purity

Reference

Melting point 37.4 °C > 99% 718830 Temperature of decomposition

200 °C > 99% 692730

Relative density 1.17 g/cm3 at 2.7 °C > 99% 692728 Vapour pressure 2.16 ×10-3 Pa at 80 °C

7.01 × 10-3 Pa at 90 °C 8.13 × 10-7 Pa at 25°C (extrapolated)

> 99% 751803

Henry's law constant (calculated)

0.0136 Pa m3 mol-1 751803

Appearance white crystalline solid yellowish liquid or yellowish viscous paste

> 99% 06-alpha-74

Solubility in water etofenprox buffer at pH 4 5.2 µg/L at 20 °C buffer at pH 9 12 µg/L at 20 °C distilled water at pH 7 22.5 µg/L at 20 °C α-CO metabolite buffer at pH 4 & 9 not measurable (degraded) distilled water at pH 7 42.5 µg/L at 20 °C

> 98% 576.09 MBq/mmol 99.7% 14C-α-CO radiolabel

755515 21386

Solubility in organic solvents

methanol 49 g/l at 20°C ethanol 98 g/l at 20 °C heptane 621 g/l at 20 °C hexane 667 g/l at 20 °C ethyl acetate 837 g/l at 20°C xylene 856 g/l at 20 °C toluene 862 g/l at 20 °C acetone 877 g/l at 20 °C dichloromethane 924 g/l at 20 °C

> 98% 692752

n-Octanol/water partition coefficient

etofenprox: log Pow 6.9 at 20 °C α-CO metabolite log Pow 6.5 at 22 °C

> 99% 99.7%

692763 21024

Hydrolysis Hydrolytically stable at pH 4, 7 and 9 under dark, sterile conditions

> 98.9 2-14C-propyl- and α-14C-benzyl- labels

731158

Phototransformation DT50 = 4.7 days (1st order) in buffer at pH 7 (Quantum yield: Φ = 0.248) DT50 = 7.9 days (1st order) in pond water at pH 7 (Quantum yield: Φ = 0.147) Photoproducts > 10% are α-CO and PENA

100% 2-14C-propyl- and α-14C-benzyl- labels

755526

Dissociation in water Etofenprox has no sites which can either be protonated or dissociate at pH 3 to 10

692741

The technical material is a white crystalline solid or yellowish liquids or paste containing not

less than 980 g ai/kg with a maximum water content of 5 g/kg and a pH range of 5.5–7 [FAO Specification 471/TC of July 2007].

Formulations

Etofenprox is formulated for agricultural use as emulsifiable concentrates (EC) containing 287.5 or 300 g ai/L, a 100 g ai/L suspension concentrate (SC), a 100 g ai/L oil-in water emulsion (EW) and a 30 g ai/kg granule (GR).

Etofenprox 407

METABOLISM AND ENVIRONMENTAL FATE

The Meeting received etofenprox metabolism studies on animals (rats, lactating goats and laying hens), plants (winter rape, grape, lettuce and rice), water/sediment systems and rotational crops. Etofenprox radiolabelled on the benzyl ring or the propyl ring were in a 1:1 mixture used in these studies. The label positions are given below:

Major metabolites identified in these studies and discussed in this evaluation are listed below.

Table 2 Major etofenprox metabolites identified in plant and animal matrices

Codes (Names)

Names Molecular formula Occurrence

MTI-500 (etofenprox)

2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether

α-CO (alpha-CO)

2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzoate

Oil seed rape

Grape

Lettuce

Rice

Aqueous photolysis

Water/Sediment

Rat

4-AcO 2-(4-acetoxyphenyl)-2-methylpropyl 3-

phenoxybenzyl ether

Rice

4’-OH (4’-hydroxy-etofenprox)

2-(4-ethoxyphenyl)-2-methylpropyl 3-(4-hydroxyphenoxy) benzyl ether

Oil seed rape

Rice

Water/Sediment

Goat

Hen

Rat

PENA 2-(4-ethoxyphenyl)-2-methylpropyl alcohol

Oil seed rape

Grape

Rice

Aqueous photolysis

Hen

Rat

O

CH3CH2O C CH3

CH3

CH2O CH2

C2H5O C

CH3

CH3

CH2O C

OO

O C

CH3

CH3

CH2 O CH2

O

CCH3

O

C2H5O C

CH3

CH3

CH2 O CH2

O OH

O C

CH3

CH3

CH2 OHC2H5

408 Etofenprox

Codes (Names)

Names Molecular formula Occurrence

DE (desethyl-etofenprox)

3-phenoxybenzyl 2-(4-hydroxyphenyl)-2-methylpropyl ether

Oil seed rape

Grape

Lettuce

Rice

Water/Sediment

Goat

Hen

Rat

EPMP 2-(4-ethoxyphenyl)-2-methylpropionic acid

Oil seed rape

Grape

Lettuce

Goat

Rat

DP (desphenyl-etofenprox)

3-hydroxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether

Oil seed rape

Grape

Rice

Water/Sediment

Hen

Rat

m-PB-acid

(PB-acid)

3-phenoxybenzoic acid O

CHO

O

Oil seed rape

Grape

Rice

Aqueous photolysis

Water/Sediment

Goat

Rat

m-PB-alc 3-phenoxybenzyl alcohol

Oil seed rape

Grape

Water/Sediment

Goat

Hen

Rat

OH-P-Alc 2-(4-hydroxyphenyl)-2-methylpropyl alcohol

Rice

Hen

4’-OH-PB-acid 3-(4-hydroxyphenoxy) benzoic acid

Rice

Goat

Rat

HO C

CH3

CH3

CH2

O

CH2O

O C

CH3

CH3

C

O

C2H5 OH

C2H5O C

CH3

CH3

CH2

OH

CH2O

O

CH2HO

HO C

CH3

CH3

CH2 OH

O

COOH

OH

Etofenprox 409

Animal metabolism

The Meeting received animal metabolism studies on rats, lactating goats and laying hens, following oral dosing with [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox.

Rats

In rats, dosed with a 1:1 mixture of [α-14C-benzyl] and [2-14C-propyl], absorbtion was rapid, but incomplete, with residues in plasma reaching a maximum in 3-5 hours. Distribution was rapid and depletion from tissues was rapid except for fat (estimated DT50 5-8.5 days). About 3% AR remained in the carcase after 7 days. No unchanged etofenprox was found in urine but it was a major component in faeces, most likely due to unabsorbed material. Cleavage of the parent molecule did not appear to be a significant metabolic process, although a numner of radiolabelled entities were not identified. Desethyletofenprox (DE) occurred at 19.5%-25.1% of the dose and etofenprox hydroxylated in the 4΄ position of the phenoxybenzyl moiety (4’-OH) occurred at 7.2-13.8% of the dose. Other primary metabolic steps involved oxidation of carbons on either side of the ether linkage, one of which (α-CO) is a major metabolite in plants, soil and in photo-degradation studies.

Lactating goats

The metabolism of etofenprox was investigated in lactating goats by Burri, 2002 [Ref: 799233] where Saanen goats were dosed twice daily for 7 days with a 1:1 mixture of [α-14C-benzyl] and [2-14C-propyl] labelled etofenprox in gelatine capsules at dietary equivalent levels of 1.5 ppm or 13.5 ppm per day. Based on an average food consumption of 1.67 kg/day and 1.87 kg/day, the goats received two oral daily doses of either 1.25 mg or 12.5 mg test item respectively, at approximately 8 am and 4 pm after milking and before feeding. At the end of the 7-day dosing period, the goats were sacrificed 21 hours after the last administration.

The body weight of the goats (47–53 kg) remained stable during acclimation and administration. The regular food consumption (1.67–1.87 kg/day) and milk production (1.56–1.78 kg/day) proved that the health of the goats was not affected by the laboratory conditions and the treatment.

Blood samples were taken prior to dosing, immediately prior to each administration and at sacrifice. Urine and faeces were collected prior to dosing (urine only), at 24-hour intervals during dosing, and after the last administration until sacrifice. The goats were milked prior to dosing, during treatment twice daily at approximately 08.00 and 16.00 hours, shortly before each administration, and immediately before sacrifice. At sacrifice, the cages were washed for determination of the remaining radioactivity. Liver, kidneys, five types of muscles (flank, round, loin, shoulder and shank), two types of fat (omental and perirenal), bile and the gastro-intestinal tract were sampled.

Radioactivity in milk was determined by LSC after solubilisation. Milk sampled at 5 days after the first administration was further analysed, by measuring radioactivity in milk fat (centrifuged) and whey and after partitioning with dichloromethane/ethyl acetate) were analysed by TLC/HPLC.

Tissues (liver, kidney, muscle) were homogenised for radioactivity determination. Thereafter, the samples were extracted with acetonitrile, acetonitrile/water (8:2), dichloromethane (liver, kidney) and methanol/water (8:2, soxhlet; liver). After partitioning against hexane and dichloromethane (liver, kidney) or ethyl acetate (muscle), the organic extracts were analysed by HPLC/TLC. Fat was extracted with acetonitrile and dichloromethane, and the radioactivity in the two phases was analysed separately by HPLC/TLC. Urine was directly analysed by HPLC/TLC. Faeces was homogenised in acetonitrile/water, and the samples collected on day 2 and 7 were analysed by HPLC/TLC after further extraction with acetonitrile and acetonitrile/water (8:2). Aliquots of the extracts were analysed by reverse phase HPLC and TLC.

Radioactivity in all morning and afternoon milk samples was < 0.1% of the applied radiolabel (AR), reaching a maximum after about 3 days. At sacrifice (21 hours after the last administration), total recoveries were 97-99% AR with 77-83% AR being excreted. Radioactivity levels (corrected for

410 Etofenprox

background radioactivity) in organs/tissues were highest in fat (2.2–2.8% AR) and muscle (0.5–0.7% AR) and were < 0.2% AR in other tissues.

Table 1 Balance of radioactivity and distribution pattern in lactating goats after oral dosing with [14C]-etofenprox twice daily for 7 days at the dietary equivalent of 1.5 ppm and 13.5 ppm

Animal Goat 1 Goat 2 Treatment 1.5ppm dose 13.5ppm dose mg/kg equiv % AR mg/kg equiv % AR

Urine 17.3 18.4 Faeces 58.45 62.77 Milk After am dose–day 1 After pm dose–day 1

0.003 0.007

0.01 0.04

0.019 0.068

0.01 0.05

After am dose–day 2 After pm dose–day 2

0.009 0.009

0.03 0.06

0.11 0.094

0.04 0.06


0.012 0.018

0.04 0.04

0.139 0.086

0.05 0.06


0.011 0.007

0.04 0.04

0.138 0.141

0.05 0.09


0.005 0.012

0.01 0.07

0.134 0.107

0.05 0.06


0.015 0.006

0.04 0.03

0.193 0.083

0.06 0.05


0.006 0.006

0.02 0.03

0.1 0.097

0.04 0.06

21 hrs after last dose 0.007 0.02 0.139 0.03 Total in milk (0-173 hours) 0.52 0.76 Edible organs/tissues (at sacrifice, 21 hrs after last dose)

Bile 0.409 0.04 3.444 0.01 Liver 0.045 0.19 0.214 0.09 Kidney 0.02 0.01 0.08 0.01 Muscle 0.005 0.66 0.052 0.53 Fat 0.075 2.75 0.737 2.24 Blood < 0.001 0.02 0.028 0.06 Total in edible tissues/organs and blood 3.67 2.94 Content intestinal tract 16.33 12.85 Cage wash 1.05 1.55 Total excreted 77.32 83.48 Total recovered 97.32 99.27

The majority of radioactivity (93-100% TRR) in milk, liver, kidney, muscle (high dose only)

and fat was extracted using organic solvent, organic solvent/water and soxhlet extraction. The radioactivity of the pooled organic extracts (except the soxhlet and dichloromethane extracts of liver and kidney) was partitioned into the organic phase and made up about 77%–93% TRR in the two dose groups. Only a minor amount of the radioactivity remained in the aqueous phase (0.4%–9.5%).

The milk fat contained a significant proportion of radioactivity recovered from the milk, measuring about 47% (0.007 mg/kg eq) and 68% (0.132 mg/kg eq) in the low and high dosed animals respectively. Negligible amounts were measured in milk proteins (< 0.001 mg/kg eq) and the amounts in the whey (defatted and deproteinised milk) were 51.5% (0.008 mg/kg eq, low dose) and 31.5% (0.061 mg/kg eq, high dose).

Etofenprox 411

Table 4 Characterisation of radioactivity in liver, kidney, fat and muscle of lactating goats dosed orally (14X) with [14C]-etofenprox for 7 days. Values are % TRR with mg/kg parent equivalents in brackets)

Animal: Goat 1 Goat 2 Treatment: Low dose (1.5 ppm) High dose (13.5 ppm) Tissue/organ: Liver a Kidney a Fat Liver a Kidney a Fat b Muscle

Extraction: Extracted 92.7

(0.042) 93.3 (0.019)

99.7 (0.075)

94.9 (0.203)

94.5 (0.076)

98.8 (0.728)

94.8 (0.049)

Post-extraction solids (3)

7.3 (0.003)

6.7 (0.001)

0.3 (< 0.001)

5.1 (0.011)

5.5 (0.004)

1.2 (0.009)

5.2 (0.003)

Total 100 (0.045)

100 (0.02)

100 (0.075)

100 (0.214)

100 (0.08)

100 (0.737)

100 (0.052)

Partitioning: Organic phase 77.4

(0.035) 92.9 (0.019)

– 87 (0.186)

84.5 (0.067)

– 93.4 (0.048)

Aqueous phase c 6.2 (0.003)

0.4 (< 0.001)

– 3.2 (0.007)

9.5 (0.008)

– 1.4 (0.001)

Total 83.6 (0.038)

93.3 (0.019)

– 90.2 (0.193)

94 (0.075)

– 94.8 (0.049)

a Soxhlet and dichloromethane extracts not partitioned or analysed b Acetonitrile and dichloromethane extracts analysed separately by TLC and HPLC c not further analysed

Table 5 Characterisation of radioactivity in milk from lactating goats dosed orally with [14C]-etofenprox twice daily and sampled 120–128 hours (5 days) after the first administration

Animal: Goat 1 Goat 2 Treatment: Low dose (1.5 ppm diet) High dose (13.5 ppm diet) % TRR mg/kg eq % TRR mg/kg eq

Milk fat 47.3 0.007 68.3 0.132 Whey acetone (1st extraction) acetone (2nd extraction) methanol

37.3 7.7 6.5

0.006 0.001 0.001

27.5 2.9 1.1

0.053 0.006 0.002

Whey total 51.5 0.008 31.5 0.061 Post-extraction solids (protein pellet) 1.2 0.001 0.2 0.00 Total 100 0.015 100 0.193

Analysis of the extracted radioactivity by HPLC/TLC identified etofenprox and seven

metabolites in the animal matrices. In milk, etofenprox was the predominant residue, at 93% TRR. In fat and muscle, etofenprox was also the predominant residue (93–97% TRR).

In liver, etofenprox was the major residue (38% TRR, 0.08 mg/kg) with the DE and m-PB-alc/PENA metabolites also being found at about 10% TRR and 12% TRR.

In kidney, etofenprox was found at about 0.026 mg/kg (33% TRR), with the EPMP and m-PB-acid metabolites each present at about 25–26% TRR (0.02 mg/kg parent equivalents).

412 Etofenprox

Table 6 Identification of radioactivity in milk and tissues from lactating goats dosed orally for 7 days with a dietary equivalent of 13.5 ppm [14C]-etofenprox.

Tissue/organ: Milk Liver Kidney Muscle Fat %TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg

etofenprox 24.8 (W) 68.3 (F) 93.1 (T)

0.048 (W) 0.132 (F) 0.18 (T)

37.9 0.081 33.1 0.026 93.4 0.048 97.2 0.716

DE – – 9.8 0.021 – – – – – – EPMP – – – – 26.3 0.021 – – – – m-PB-acid – – – – 25.1 0.02 – – – – m-PB-alc/PENA – – 11.7 0.025 – – – – – – 4’-OH – – – – – – – – – – 4’-OH-PBAcid 2.7 (W) 0.005 (W) – – – – – – – – Unidentified 2.7 (W) 0.005 (W) 27.6 0.059 – – – – 1.6 0.012 Not analysed 1.3 0.003 7.9 0.017 10.0 0.009 1.4 0.001 – – Total 99.8 0.19 94.9 0.203 94.5 0.076 94.8 0.049 98.8 0.728

(W) = whey, (F) = milk fat, (T) = Total of whey and milk fat

The proposed metabolic pathways involve desethylation of the ethoxyphenyl group to form

the DE metabolite, hydroxylation of the phenoxy ring (to form the 4’-OH metabolite) and the formation of the α-CO by oxidation of the benzyl methylene group. Cleavage of these primary metabolites at the ether linkage produces the EPMP, m-PB-acid, PENA and m-PB-alc which are subsequently conjugated by glucuronidation and sulfation.

Figure 1 Proposed metabolic pathway of etofenprox in lactating goats

etofenprox

4’-OH

DE

m-PB-Acid

PENA

+conjugates

EPMP

m-PB-alc

α-CO

4’-OH-PB-acid

Etofenprox 413

Laying hens

The metabolism of etofenprox was investigated in laying hens by Burri, 2003 [Ref: 799244] where 5 white leghorn hybrid hens per dose group were dosed each morning for 14 days with a 1:1 mixture of [α-14C-benzyl] and [2-14C-propyl] labelled etofenprox in gelatine capsules at dietary equivalent levels of 0.9 ppm or 9.6 ppm. Based on average daily food consumptions of 0.174 kg/hen and 0.159 kg/hen for the two dose groups, the 5–8 month old hens received once daily an oral dose of either 0.15 mg or 1.5 mg test item in the morning after egg sampling and before feeding. At the end of the 14-day dosing period, the hens were sacrificed about 24 hours after the last administration.

The body weight of the hens (1.4–1.6 kg) remained stable during acclimation and administration. The regular food consumption (160–174 g/day) and egg production proved that the health of the hens was not affected by the laboratory conditions and the treatment.

Eggs were collected prior to dosing and during administration twice daily (just before dosing and 5 to 8 hours later). The eggs were separated into yolk, white and shells per hen and per sampling interval, and samples from each 24 hours period were pooled by animal. Excreta of individual hens were sampled at 24-hour intervals during administration and sacrifice. At sacrifice, samples were taken of blood, liver, muscle (breast and thigh), fat (peritoneal), skin (including subcutaneous fat), developing eggs in the oviduct (these eggs were pooled with the eggs laid during the last time interval).

Radioactivity in egg yolks and whites was determined per hen and time interval. Yolks and whites of eggs laid on day 8 and 14 were pooled per group for protein precipitation (acetone) and extraction with acetonitrile (2×), acetonitrile/water (2×), methanol (Soxhlet) and HCl (hydrolysis, egg yolk only). Extracts (except the Soxhlet extract) were partitioned against hexane and dichloromethane, and the partitioned fractions were analysed by TLC/HPLC. The aqueous phase of high dose egg samples were lyophilised and re-dissolved in methanol for analysis by TLC.

Liver samples were homogenised and extracted with acetonitrile (3×), acetonitrile/water (neutral conditions; 2×), dichloromethane (2×), acetonitrile/water (acidic conditions; 2×), and methanol/water (Soxhlet). High dose samples were further hydrolysed with HCl and extracted with pronase. The acetonitrile extracts were partitioned with hexane and dichloromethane under neutral and acidic conditions. The pooled partitioned organic fractions were analysed by HPLC/TLC, either directly or after purification using silica gel columns. The dichloromethane extracts were partitioned with acetonitrile for analysis by TLC. However, because only 62.4% of the radioactivity in the liver was extracted using the above method, a second extraction was conducted using incubation with pronase, extractions with methanol/water (1×), acetonitrile (3×) and dichloromethane (3×) and hydrolysis with HCl. The acetonitrile and dichloromethane extracts were pooled separately and analysed by TLC/HPLC. Pronase and methanol extracts were pooled, lyophilised, re-dissolved in methanol and analysed by TLC/HPLC.

Muscle samples were extracted with acetonitrile (3×) and acetonitrile/water with the pooled extracts being partitioned with hexane and dichloromethane, and the partitioned organic fraction analysed by TLC/HPLC.

Fat and skin samples were extracted with acetonitrile (3×) and dichloromethane (2×) and the acetonitrile extracts were concentrated, redissolved in hexane and directly analysed by TLC/HPLC while the dichloromethane extracts were partitioned with acetonitrile for analysis by TLC.

At sacrifice (24 hours after the last administration), recoveries of the administered radioactivity (AR) were 86.4% (low dose) and 94.5% (high dose), most of which was excreted or in the cage wash (83–92%). Small amounts of radioactivity were detected in edible organs/tissues (2.2–2.7%. A comparison of the levels of radioactive residues in the tissues at the two dose levels showed a good dose response.

414 Etofenprox

Low radioactivity (about 0.5% AR) was detected in egg yolks collected from day 1 to 14. Radioactivity levels reached a plateau of about 0.09 mg/kg eq (low dose) and 0.9 mg/kg eq (high dose) after about the 8th and 11th administration, respectively. Radioactivity in egg whites did not exceed 0.1% AR, reaching a maximum of 0.003 mg/kg eq for the low dose and 0.012 mg/kg eq for the high dose.

The highest residue levels were found in fat (0.217 mg/kg eq, low dose; 1.789 mg/kg eq, high dose), followed by skin (0.071 mg/kg eq, low dose; 0.481 mg/kg eq, high dose) and liver (0.035 mg/kg eq, low dose; 0.343 mg/kg eq, high dose).

Table 7 Balance of radioactivity and distribution pattern in laying hens after oral doses of [14C]-etofenprox at mean dietary concentrations equivalent to 0.9ppm and 9.6ppm

Animal Group 1 Group 2 Treatment 0.9ppm dose 9.6ppm dose mg/kg equiv

(mean) % AR mg/kg equiv % AR

Eggs yolk white yolk white yolk white yolk white Day 1 0.002 0.002 0.001 0.001 Day 2 0.006 0.002 0.009 0.008 Day 3 0.014 0.002 0.138 0.009 Day 4 0.032 0.003 0.345 0.009 Day 5 0.05 0.002 0.47 0.009 Day 6 0.068 0.003 0.614 0.009 Day 7 0.078 0.002 0.668 0.01 Day 8 0.086 0.002 0.827 0.01 Day 9 0.088 0.002 0.866 0.01 Day 10 0.084 0.003 0.881 0.012 Day 11 0.084 0.002 0.906 0.011 Day 12 0.083 0.002 0.932 0.012 Day 13 0.084 0.002 0.9 0.009 Day 14 0.087 0.002 0.889 0.011 Total in eggs (Max residue) (0.1 0.003) 0.5 0.1 (0.999 0.012) < 0.1 0.5 Edible organs/tissues (at sacrifice, 24 hrs after last dose)

Liver 0.035 0.1 0.343 0.1 Muscle 0.004 0.1 0.016 < 0.1 Fat 0.217 1.9 1.789 1.6 Skin 0.071 0.6 0.481 0.4 Blood 0.004 < 0.1 0.018 < 0.1 Plasma 0.005 Total in edible tissues/organs 2.7 2.2 Excreta 81.6 90.2 Cage wash 1.6 1.5 Total excreted 83.2 91.7 Total recovered 86.4 94.5

Radioactive residues in egg yolk were extracted by using organic solvent, organic

solvent/water soxhlet extraction and HCl-hydrolysis (high dose only). For the two dose levels and the two sampling intervals (day 8 and 14), extracted residues accounted for 91–96% TRR in yolks, most of which could be partitioned into hexane and dichloromethane (84% to 88% TRR). In egg whites, about 90–91% TRR was extractable. These results indicated that [14C]-etofenprox and/or its metabolites did not accumulate in the protein fraction of egg yolk and egg white.

Etofenprox 415

Most of the radioactivity in liver, muscle, fat and skin was extracted using sequential organic solvent, organic solvent/water and organic solvent/diluted acid partitioning, soxhlet extraction and pronase incubation. Extraction rates were generally higher than 96% except in egg yolks (90–91% TRR extracted) and in liver, where 79–83% TRR was extracteable.

Fat and skin extracts were directly analysed without partitioning. For muscle, 95.5% of the extracted radioactivity (0.015 mg/kg eq) was partitioned into the organic phase and in case of liver, 0.019 mg/kg eq (low dose) and 0.135 mg/kg eq (high dose) were recovered in the organic phase (with 0.004 mg/kg eq and 0.022 mg/kg eq being found in the respective aqueous phases.

Table 8 Characterisation of radioactivity from eggs, liver, skin, fat and muscle of laying hens dosed orally with [14C]-etofenprox for 14 days. Values are % TRR with mg/kg parent equivalents in brackets

Animal: Group 1 Group 2 Treatment: Low dose (0.9 ppm diet) High dose (9.6 ppm diet) Tissue/organ: Egg

yolk a Liver b Fat b Skin Egg

white a Egg yolk a

Liver(2) Muscle Fat Skin

Total extracted (0.087) (0.035) (0.217) (0.071) (0.011) (0.889) (0.343) (0.343) (0.016) (1.788)

Extraction: 1st extract 2nd extract 1st extractions c 88.8

(0.077) 64.6 (0.023)

94 (0.204)

72.4 (0.051)

89.1 (0.01)

90.2 (0.802)

45.6 (0.157)

34.9 (0.12)

96.6 (0.015)

94.8 (1.695)

72.3 (0.347)

Subsequent extractionsd

2.5 (0.002)

18.4 (0.006)

5.7 (0.012)

23.8 (0.017)

1.3 (0.0)

5.8 (0.051)

16.8 (0.057)

44.0 (0.151)

– 5.0 (0.089)

24.0 (0.116)

Post-extraction solids e

8.7 (0.008)

17.0 (0.006)

0.3 (0.001)

3.8 (0.003)

9.6 (0.001)

4.0 (0.036)

37.6 (0.129)

21.1 (0.072)

3.4 (0.001)

0.2 (0.004)

3.7 (0.018)

Partitioning: Organic phase 83.7

(0.073) 53.4 (0.019)

– – – 85.0 (0.756)

39.1 (0.135)

95.5 (0.015)

– –

Aqueous phase e 5.1 (0.004)

11.2 (0.004)

– – – 5.2 (0.046)

6.5 (0.022)

1.1 (< 0.001)

– –

Total f 88.8 (0.077)

64.6 (0.023)

– – – 90.2 (0.802)

45.6 (0.157)

96.6 (0.015)

– –

a egg yolk and white samples collected on day 14 b values for the low dosed samples from first extraction, for the high dosed samples from first and second (pronase) extraction c Acetone and acetonitrile extracts, pooled for partitioning d Extractions involving dichloromethane and/or Soxhlet MeOH, pronase incubation or HCl-hydrolysis e not further analysed f total radioactivity in the pooled organic extracts

In egg yolk, etofenprox made up about 80% of the extracted radioactivity with several

unidentified metabolite fractions being detected in minor amounts.

In muscle, fat and skin, the extracted radioactivity was mostly the unchanged parent (69–93% TRR). The remaining radioactivity was not identified. In liver, the parent compound accounted for 15-30% TRR with two other unidentified fractions making up about 25% TRR.

Table 9 Identification of radioactivity in egg yolk and tissues from laying hens dosed orally for 14 days at the dietary equivalent of 9.6 ppm [14C]-etofenprox.

Tissue/organ Egg yolk (day 8) Egg yolk (day 14)

Liver Muscle Fat Skin

%TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg

Organic phase

etofenprox 80.0 0.692 80.4 0.715 14.7 0.051 88.0 0.013 89.0 90.6(a)

1.591 1.62a

67.5 0.324

416 Etofenprox

Tissue/organ Egg yolk (day 8) Egg yolk (day 14)

Liver Muscle Fat Skin

%TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg DE 0.032

0.075 a

Unidentified 0.05 0.041 0.084 0.002 0.072 nda

0.023

Aqueous phase etofenprox 1.2 0.01 nd nd nd nd 4.7 0.084 22.3 0.108 Unidentified 6.5 0.057 5.2 0.046 8.4 0.028 0.3 0.005 1.7 0.008

a = first values before acidic hydrolysis, second values after acidic hydrolysis and partitioning into hexane nd not detected

The proposed metabolic pathways involve desethylation of the ethoxyphenyl group to form

the DE metabolite, hydroxylation of the phenoxy ring (to form the 4’-OH metabolite) and the loss of the phenoxy group to form the DP metabolite. Cleavage of these primary metabolites produces the 4’-OH-PB-acid and PENA, OH-P-alc and m-PB-alc.

Figure 2 Proposed metabolic pathway in laying hen

Plant metabolism

The Meeting received plant metabolism studies on grapes, lettuce, winter rape and rice following foliar applications of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox and on rice following a pre-harvest soil application.

etofenprox

4’-OH

DE

m-PB-Acid

PENA

+conjugates

EPMP

m-PB-alc

α-CO

4’-OH-PB-acid

Etofenprox 417

Grapes

In a study reported by Völkel, 2002 [Ref: 784168], a 1+1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox was applied to four ‘Verdelet’ grape vines (4-5 years old) grown outdoors, as single foliar sprays at rates equivalent to 0.3 kg ai/ha (50 g ai/hL) and 3.0 kg ai/ha (500 g ai/hL). Each treatment rate was applied to two vines, either 28 or 14 days before harvest.

At harvest, mature grape bunches were sampled and washed with water and then ethanol to determine the surface radioactivity. The washed bunches were then separated into stems and grapes with the grapes being homogenised and the juice separated from pulp, skin and pips by centrifugation.

Washing solutions were lyophilized and analysed by HPLC. Pulp and skin were extracted twice with acetonitrile and once with methanol/water (8:2, v/v). The extracts were concentrated to the water phase, mixed with methanol and analysed by HPLC/TLC. Aliquots of the extracted solid were combusted to determine their content of radioactivity by capturing the produced 14CO2. Grape juice was purified by solid phase extraction and the eluted extracts were analysed by HPLC. Stems were dried by lyophilization and combusted to determine their content of radioactivity. After all solvent extractions, the solid residue (skin and pulp) was further subjected to acidic and alkaline “harsh” extraction, acid hydrolysis, alkaline hydrolysis, and cellulase treatment, and the radioactivity in the solutions was determined by LSC.

The TRR in grape bunches from the vine treated with the lower rate (0.3 kg ai/ha) were 5.44 mg/kg eq (14 day PHI) and 2.66 mg/kg eq (28 day PHI) and the corresponding residues in bunches from the higher rate were 58.32 mg/kg eq and 28.19 mg/kg eq. Most of the radiolabel was removed by water/ethanol washing (81–82% from the 14-day PHI bunches and 60-75% from the 28-day PHI bunches.

In the washed grapes, radioactive residues were 12–14% TRR in the 14-day PHI grapes, and 20–23% in the 28-day grapes, mostly in the solids (pulp, skin and pips), with only 0.9 to 3.5% TRR in the juice. The un-extracted residue in the washed grapes was low, amounting only to 0.9–2.6% TRR and radioactivity in stems accounted for 4.0–17.1% TRR (0.124–4.825 ppm).

Table 10 Characterisation and distribution of radioactivity in grapes after single foliar applications of [14C]-etofenprox.

Plant-No. 1 2 3 4 PHI (days) 28 28 14 14 Rate (kg ai/ha) 0.3 3.0 0.3 3.0 Fraction mg/kg eq %TRR mg/kg eq %TRR mg/kg eq %TRR mg/kg eq %TRR

1st wash of bunches (water)

0.06 2.3 0.168 0.6 0.206 3.8 6.335 10.9

2nd wash of bunches (ethanol)

1.944 73.0 16.664 59.1 4.258 78.3 40.827 70.0

Total surface wash 2.004 75.2 16.831 59.7 4.464 82.1 47.162 80.9 Juice 0.092 3.5 0.834 3.0 0.052 0.9 1.242 2.1 Pulp, skin, pip extract 0.372 14.0 4.965 17.6 0.642 11.8 5.096 8.7 Un-extracted 0.054 2.0 0.732 2.6 0.063 1.2 0.548 0.9 Total grapes (washed) 0.518 19.5 6.53 23.2 0.756 13.9 6.886 11.8 Stems 0.124 5.3 4.825 17.1 0.215 4.0 4.277 7.3 Total bunch 2.664 100.0 28.186 100.0 5.436 100.0 58.325 100.0

Up to 13 radioactive fractions were detected in surface wash, grape juice and in the extracts of

the solid parts of grapes (pulp, skin, pips). Etofenprox was the main radioactive fraction. α-CO was a significant metabolic fraction. Fractions characterized as metabolites DE, DP, m-PB-Acid, m-PB-alc, EPMB and/or PENA were found at low concentrations.

418 Etofenprox

Etofenprox was the main fraction in surface washes (76–77% TRR in the 14-day PHI bunches and 54–72% TRR in the 28-day PHI bunches). Low levels of up to eight metabolites were also detected.

In juice, neither etofenprox nor the α-CO metabolite were detected, with three unknown metabolic fractions being found (at not more than 2% TRR). Etofenprox was also the major residue in grape pulp and skin, present at 7.7–15% TRR, with the major metabolite (α-CO) also present but at low levels.

Chemical hydrolysis and enzymatic treatment were performed to further characterise the residue in pulps and skin not extracted with solvents. At room temperature, alkaline extractions released more of the residue than acid hydrolysis. For each treatment, about 10% of the non-extracted residue was dissolved by 1N sodium hydroxide solution, whereas the acid hydrolysis released a maximum of 3.9%. Hydrolysis under reflux conditions with 6N hydrochloric acid did not release more radioactivity than at room temperature with diluted acid. However, the alkaline hydrolysis with 6N sodium hydroxide solution under reflux conditions dissolved a major part of the non-extracted residues with 52%–101% of the residue in the post-extraction solids (PES) being solubilised. Treatment with cellulase released the lowest amount of radioactivity, not exceeding 2.1% of the PES residues.

Table 11 Identification of radioactivity in grape plants treated with [14C]-etofenprox, 14 days before harvest. Values are % TRR with mg/kg parent equivalents in brackets

Plant-No. 3 4 PHI (days) 14 14 Dose (kg ai/ha) 0.3 (normal dose) 3.0 (high dose) Fraction 1st wash

(H2O) 2nd wash (EtOH)

Juice Pulp & skin

Total bunch

1st wash (H2O)

2nd wash (EtOH)

Juice Pulp & skin

Total bunch

Extracted 3.8 (0.2)

78.3 (4.3)

0.95 (0.2)

11.8 (0.64)

94.9 (5.3)

10.9 (6.3)

70.0 (41.0)

2.1 (1.2)

8.7 (5.1)

91.7 (53.5)

etofenprox 3.4 (0.18)

72.5 (3.9)

– 10.8 (0.59)

86.8 (4.7)

10.2 (5.9)

66.6 (38.9)

– 7.7 (4.5)

84.6 (49.3)

α-CO 0.17 (0.01)

5.8 (0.327)

– 0.56 (0.031)

6.52 (0.37)

0.46 (0.28)

2.94 (1.78)

– 0.33 (0.2)

3.72 (2.255)

DE 0.03 (0.002)

– – – 0.03 (0.002)

– 0.21 (0.113)

– – 0.21 (0.113)

m-PB-Acid 0.07 (0.002)

– – – 0.07 (0.002)

0.04 (0.014)

– – – 0.04 (0.014)

m-PB-alc – – – – – 0.02 (0.007)

– – – 0.02 (0.007)

EPMP+ PENA

– – – – – 0.03 (0.011)

– – – 0.03 (0.011)

Post-extraction solids (grapes+stems)

5.11 (0.28)

8.72 (4.83)

Table 12 Identification of radioactivity in grape plants treated with [14C]-etofenprox, 28 days before harvest. Values are % TRR with mg/kg parent equivalents in brackets



Juice Pulp & skin

Total bunch

1st wash (H2O)

2nd wash (EtOH)

Juice Pulp & skin

Total bunch

Extracted 2.25 (0.06)

73.0 (1.95)

3.4 (0.092)

14.0 (0.37)

92.7 (2.47)

0.59 (0.16)

59.1 (16.7)

3.0 (0.83)

17.6 (4.98)

80.3 (22.7)

Etofenprox 419



Juice Pulp & skin

Total bunch

1st wash (H2O)

2nd wash (EtOH)

Juice Pulp & skin

Total bunch

etofenprox 2.0 (0.054)

70.0 (1.86)

– 12.4 (0.33)

84.4 (2.25)

0.41 (0.12)

53.8 (15.2)

– 15.1 (4.26)

69.3 (19.5)

α-CO 0.09 (0.002)

2.99 (0.083)

– 0.73 (0.02)

3.81 (0.105)

0.04 (0.011)

4.26 (1.244)

– 1.06 (0.309)

5.35 (1.564)

DP – – – – – 0.01 (0.003)

– – – 0.01 (0.003)

m-PB-Acid – – – – – 0.02 (0.004)

– – – 0.02 (0.004)

Post-extraction solids (grapes+stems)

7.36 (0.196)

19.7 (5.557)

Lettuce

In a study reported by Mamouni, 2002 [Ref: 815084], a 1+1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox was applied to pots of 4 lettuce plants (35 days after planting) and grown outdoors, as foliar sprays at rates equivalent to 0.18 kg ai/ha and 1.8 kg ai/ha.

At harvest (8 days after treatment), lettuce leaves were washed with water and then with a mixture of water/ethanol (1:1). The washing solutions were submitted to LSC to measure surface radioactivity. Washed, lyophilised leaves were extracted with acetonitrile (3×), methanol/water (8:2, 3×) and water (1×). In addition, a Soxhlet extraction using acetonitrile/water (8:2) was performed after the extractions at ambient temperature. The radioactivity in each solvent extract was quantified by LSC. The post-extraction solids (PES) for each sample were dried and weighed, and the radiocarbon content was determined by LSC after combustion of 5 sub-samples. Finally, an extraction under reflux conditions for about 4 hours using acetonitrile/water (6:4) was performed. The extracts obtained under reflux conditions were purified by solid phase extraction and the eluted extracts were concentrated and analysed by HPLC and TLC.

The TRR in the lettuce were 2.43 mg/kg parent equivalents in the plants treated at the low rate and 19.2 mg/kg eq. in the plants treated at the high rate. About half of the applied radioactivity was found on the surface of the plants with 45-63% TRR being washed off with surface washes. Most of the remaining radioactivity (36–53.5% TRR) could be sequentially extracted from lettuce leaves with acetonitrile (26–39% TRR) and methanol/water (9–13.5% TRR). The remaining non-extractable radioactive residues accounted for less than 2% TRR.

Table 13 Characterisation and distribution of radioactivity in lettuce (leaves), 8 days after single foliar applications of [14C]-etofenprox

Treatment 0.18 kg ai/ha (low rate) 1.8 kg ai/ha (high rate) Concentration TRR Concentration TRR

[mg/kg eq] [%] [mg/kg eq] [%]

Washings: 1st wash (water) 0.204 8.38 4.781 24.9 2nd wash (EtOH/water) 0.833 36.3 7.307 38.06 Total washings 1.086 44.69 12.089 62.97 Extractions: ACN (3X) 0.952 39.16 4.999 26.04 MeOH/water (3X) 0.327 13.47 1.771 9.22 Water (1X) 0.003 0.14 0.02 0.11 Soxhlet (ACN/water) 0.004 0.18 0.03 0.16

420 Etofenprox

Treatment 0.18 kg ai/ha (low rate) 1.8 kg ai/ha (high rate) Concentration TRR Concentration TRR

[mg/kg eq] [%] [mg/kg eq] [%] Reflux (ACN/water) 0.014 0.58 0.06 0.31 Total extracted 1.301 53.53 6.88 35.84 Total extractable 2.388 98.21 18.969 98.81 Not-extracted 0.043 1.79 0.229 1.19 Total 2.431 100.0 19.198 100.0

Etofenprox was the most important radioactive fraction accounting for 88–90% TRR. Apart

from the α-CO metabolite, none of the other 15 radioactive fractions exceeded 5% TRR.

Table 14 Identification of radioactivity in lettuce (leaves) treated 8 days before harvest with 14C-etofenprox

Surface washes Extracts Total plant Fraction: water EtOH/water ACN MeOH/water +

water Soxhlet (ACN/water)

Reflux (ACN/water)

% TRR mg/kg % TRR

mg/kg % TRR

mg/kg % TRR mg/kg % TRR mg/kg % TRR mg/kg % TRR mg/kg

Treatment 0.18 kg ai/ha (low rate) Extracted 8.38 0.2 36.3 0.88 39.2 0.95 13.6 0.33 0.18 0.004 0.58 0.014 98.2 2.39 etofenprox 7.86 0.19 34.4 0.84 38.1 0.93 7.6 0.19 0.06 0.002 0.09 0.002 88.2 2.15 α-CO 0.26 0.006 1.74 0.042 0.78 0.019 0.16 0.004 < 0.01 < 0.001 2.95 0.072 DE – 0.004 0.006 0.003 < 0.001 0.001 0.014 EPMP 0.26 0.06 – 0.01 < 0.001 0.27 0.007 Treatment 1.8 kg ai/ha (high rate) Extracted 24.9 4.78 38.1 7.31 26.0 5.0 9.33 1.79 0.16 0.03 0.31 0.06 98.8 18.97 etofenprox 24.4 4.69 35.7 6.85 25.3 4.85 4.52 0.87 0.08 0.015 0.10 0.019 90.1 17.29 α-CO 0.5 0.096 2.17 0.417 0.62 0.12 – 0.03 0.005 3.32 0.637 DE – 0.044 0.025 – – 0.005 0.074 EPMP – – – – 0.01 0.002 – 0.01 0.002

Winter rape

In a study reported by Völkel, 2002 [Ref: 784170], a 1+1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox was applied to pots of ‘Express’ winter rape plants (grown outdoors) at flowering (about 7 months after planting) as foliar sprays at rates equivalent to 0.12 kg ai/ha and 1.2 kg ai/ha and mature seeds and foliage were sampled at harvest, 8 weeks after treatment.

The seeds were homogenised and extracted with organic or aqueous solvent mixtures (3× hexane, 1× acetonitrile, 2× acetonitrile/water). The radioactivity present in the individual extracts was quantified with LSC. The residual debris of each sample was dried and the radiocarbon content was quantified by LSC after combustion. The individual non-polar (hexane) and polar (acetonitrile and acetonitrile/water) extracts were separately processed for further analysis by HPLC and TLC. After all solvent extractions, the solid residue of seeds was further submitted to acid and alkaline “harsh” extractions, and the radioactivity in the extracts was quantified by LSC.

Foliage was extracted with polar solvents (acetonitrile, acetonitrile/water). After extraction, liquid and solid phases were separated and the radioactivity present in each extract was quantified by LSC. Extracts were then pooled and concentrated prior to analysis by HPLC and TLC. Radioactivity in the residual debris was quantified after combustion.

Etofenprox 421

Total radioactive residue (TRR) in the rape plant was very low. Only 3.3% and 7.6% of the amount applied was detected in the low and high rate plants, respectively, corresponded to 0.1 and 3.49 mg/kg parent equivalents. For all plant parts, the radioactive residues increased with the application rate and at both application rates, the major part was found in the foliage.

Most of the radioactivity in seeds was extractable (73–78% TRR) with up to 18 radioactive fractions being detected. Etofenprox (parent) was the predominant residue, found at levels of 0.02 mg/kg (62% TRR) and 0.14 mg/kg (56.5% TRR) in the low and high rate samples. The metabolite α-CO was also identified at about 5% TRR–0.002 mg/kg eq (low rate) and 3% TRR–0.008 mg/kg eq (high rate). None of the other identified metabolites (DE, DP, m-PB-Acid, m-PB-alc, EPMP, PENA and 4’-OH) exceeded 3% of the seed TRR. Most of the radioactivity not extracted from the seeds by organic solvents could be solubilised by acid and alkaline hydrolysis, leaving only 6.2% to 14.5% TRR unextracted for the plants treated with the low and high rates respectively. The hydrolytic treatment probably released metabolites or fragments of metabolites from conjugates in the plant.

In leaves, about 90–92% TRR was extracted, with etofenprox and the α-CO metabolite being the only fractions identified. Etofenprox was found at levels of 0.01 mg/kg (7.9% TRR) and 1.33 mg/kg (35.2% TRR) in the foliage of the low and high rate plants respectively, with the comparable levels of the α-CO metabolite being 0.001 mg/kg eq (1.1% TRR) and 0.2 mg/kg eq (5.2% TRR). Up to 19 radioactive fractions were detected, none of these (polar metabolites) exceeded 0.02 mg/kg eq for the low rate treatment and 0.26 mg/kg eq for the high dose treatment.

Table 15 Identification of radioactivity in winter rape (seeds, leaves) treated with 14C-etofenprox at flowering, 8 weeks before harvest

Treatment 0.12 kg ai/ha (low rate) 1.2 kg ai/ha (high rate) Matrix Seeds (0.09% AR) Foliage (3.2% AR) Seeds (0.05% AR) Foliage (7.5% AR) Fraction mg/kg %TRR mg/kg %TRR mg/kg %TRR mg/kg %TRR

TRR 0.032 0.11 0.25 3.78 Extracted 0.025 77.6 0.1 89.6 0.18 72.6 3.5 92.4 etofenprox 0.02 62.1 0.009 7.9 0.143 56.5 1.33 35.2 α-CO 0.002 4.9 0.001 1.1 0.008 3.2 0.2 5.2 DE < 0.001 0.3 – – 0.001 0.2 – – DP – – – – < 0.001 0.2 – – m-PB-Acid < 0.001 0.4 – – 0.002 0.7 – – m-PB-alc – – – – 0.001 0.2 – – EPMP < 0.001 0.1 – – < 0.001 0.1 – – PENA < 0.001 0.2 – – 0.001 0.3 – – 4’-OH < 0.001 0.6 – – < 0.001 0.2 – – Identified 0.023 68.6 0.01 9.0 0.157 61.6 1.54 40.4 Post-extraction solids 0.007 22.4 0.012 10.4 0.069 27.4 0.29 7.6

422 Etofenprox

Figure 3 Proposed metabolic pathway of etofenprox in rape, grapes and lettuce

Rice

In a study reported by Panthani, 2002 [Ref: 013194-1], designed to simulate rice-paddy treatments, a 1+1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox was applied to rice plants grown outdoors, either as foliar sprays (0.2 kg ai/ha and 2.0 kg ai/ha), 21 days before harvest or as soil treatments (0.45 kg ai/ha and 2.0 kg ai/ha), 35 days before harvest.

etofenprox

4’-OH

α-CO

DE

m-PB-Acid

PENA

DP

14C, bound residues and minor metabolites

EPMP

m-PB-alc

observed in all matrices

observed in grapes and rape

observed in rape only

Legend:

Etofenprox 423

Rice seedlings (at the 3–5 leaf stage) were transplanted into pots filled with soil and water and the water depth in the pot was maintained at 3–5 cm throughout the study. The soil used was a silt loam (pH 7.3 with a silt:sand:clay ratio of 76:16:8 and with an organic matter content of 2% and a CEC of 9.3 meq/100g). In both treatment groups, the water was temporarily drained from the pots and the 14C-etofenprox was applied to the soil by pipette or by hand-sprayer to the foliage and the pots re-flooded to maintain a water depth of 3–5 cm until 14 days before harvest.

Immature plants were cut just above the waterline, 28 days after the soil treatment and 14 days after the foliar spray and were separated into green seed heads and leaf/stem (straw). Mature rice plants were also cut above the water line 35 days after the soil treatment and 21 days after the foliar spray and separated into seed heads, straw (leaf/stem) and roots (washed root balls). The seed head and straw samples were washed twice with acetonitrile to extract surface residues (for LSC analysis) and the washed seed heads were dried and the grain (brown rice) separated from the chaff.

To measure the total radioactive residue (TRR), solid samples were combusted before LSC analysis and the TRR in aqueous samples was determined by direct LSC. The TRR in straw was calculated as the sum of the TRR in surface wash and in solid fraction. For whole grain, the TRR in seed heads surface wash, in brown rice and in chaff were summed.

Residues in the immature seed heads, straw and soil were extracted twice with acetonitrile and with 60:40 v/v acetonitrile:water (60:40) while the samples of mature brown rice, chaff, straw and soil were first extracted 2–3 times with acetonitrile/water (90:10) and then with acetonitrile/water (60:40). Filtered extracts were quantified by LSC analysis.

Soil application

Total radioactive residues in the rice matrices from plants treated with 0.45 kg ai/ha were 0.18 mg/kg eq in straw, 0.036–0.042 mg/kg in whole grain and brown rice and about 0.02 mg/kg eq in chaff. In the high rate plants, total residues were 0.62 mg/kg eq in straw, 0.11–0.12 mg/kg in whole grain and brown rice and about 0.08 mg/kg eq in chaff.

Extracted residues ranged from 64–79% TRR in straw, 43–47% TRR in chaff, 16–19% TRR in whole grain and 8-9% TRR in brown rice. Surface washing of the straw removed about 12% TRR from the low rate plants and 7.4% TRR from the high rate plants. Further investigation showed that the majority of the unextracted radioactivity the brown rice was the result of incorporation of 14CO2 into natural products (carbohydrate, protein and lignin).

Etofenprox was the major residue in straw (11–44%TRR) and chaff (8–16% TRR), but made up less than 3% TRR in whole grain and was not detected in brown rice. More than 9 metabolites were identified, mostly found individually at less than 10% TRR except in straw, where OH-PAlc, α-CO and PENA made up about 17% TRR, 12%TRR and 11% TRR respectively. PENA also made up about 12% of the TRR in chaff.

Table 16 Identification of radioactivity in rice harvested 35 days after soil treatment with 0.45 kg ai/ha 14C-etofenprox. Whole grain Brown Rice Chaff Straw mg/kg % TRR mg/kg % TRR mg/kg % TRR mg/kg % TRR

Extracted 0.008 19.3 0.004 8.0 0.017 46.8 0.144 79.7 Etofenprox 0.001 2.7 nd nd 0.006 15.7 0.081 44.3 α-CO < 0.001 0.6 nd nd 0.001 3.3 0.023 12.5 m-PB-Acid a 0.001 1.8 0.001 1.3 0.002 4.6 0.006 3.3 PENA a 0.001 1.8 < 0.001 0.6 0.003 8.1 0.013 7.0 4’-OH-PBAcid a < 0.001 0.5 < 0.001 0.4 < 0.001 0.9 0.005 2.6 OH-PAlc 0.001 3.3 0.002 3.8 0.001 1.8 0.007 3.9 Unextracted 0.035 80.7 0.041 92.0 0.019 53.2 0.037 20.3

a Sum of free and conjugated forms. nd = not detected.

424 Etofenprox

Table 17 Identification of radioactivity in rice harvested 35 days after soil treatment with 2.0 kg ai/ha 14C-etofenprox Whole Grain Brown Rice Chaff Straw mg/kg % TRR ppm % TRR ppm % TRR ppm % TRR

Extracted 0.018 16.3 0.011 9.3 0.035 43.3 0.4 64.5 Etofenprox 0.001 1.3 nd nd 0.007 8.4 0.069 11.1 α-CO 0.001 0.5 nd nd 0.002 3.0 0.029 4.6 m-PB-Acid a 0.002 2.0 0.002 1.6 0.004 4.6 0.054 8.6 PENAa 0.003 2.5 0.001 0.7 0.01 12.4 0.067 11.0 4’-OH-PBAcid a 0.001 0.8 0.001 0.5 0.002 2.9 0.052 8.3 OH-PAlc 0.005 4.6 0.005 4.5 0.005 5.9 0.105 16.9 Unextracted 0.09 83.7 0.107 90.7 0.046 56.7 0.222 35.5

a Sum of free and conjugated forms nd = not detected.

Soil samples were analysed at harvest, 14 and 28 days before harvest from the 0.45 kg ai/ha

soil application group. Etofenprox residues in soil were about 0.3 mg/kg (51.9% TRR) at the 28-day PHI decreasing to 0.075 mg/kg (35% TRR) at final harvest. The estimated half-life of etofenprox in soil was 13 days. Residues in soil at final harvest ranged from 0.21 mg/kg (0.45 kg ai/ha) to 1.0 mg/kg (2.0 kg ai/ha). From 48–74% TRR was extracted from the soil, mostly as etofenprox (35–61% TRR respectively) with minor metabolites (less than 10% TRR) including α-CO, 4’-OH, DE, DP, PENA and m-PBAcid.

Foliar application

TRR in whole grain were 1.8 mg/kg eq for the 0.2 kg ai/ha application and 22.7 mg/kg from the 2.0 kg ai/ha plants. Surface washing removed about 29% TRR (0.53 mg/kg eq) and 44% TRR (10 mg/kg eq) from the grain samples from plants treated with the high and low rates respectively. After the washed whole grain was separated into brown rice and chaff, TRR in brown rice were 0.075 mg/kg eq (0.2 kg ai/ha) and 1.12 mg/kg (2.0 kg ai/ha). The TRR in chaff were 5.9 mg/kg and 54.7 mg/kg respectively. TRR in straw were about 4.4 mg/kg (0.2 kg ai/ha) and 40.5 mg/kg (2.0 kg ai/ha), with 7–11% TRR being removed by surface washing. Solvent-extracted residues ranged from 85–96% TRR in all matrices.

Etofenprox was the major residue all matrices, making up 49–76 % TRR and the only other metabolites present at levels above 5% TRR were the α-CO metabolite, found in whole grain (15–16% TRR), brown rice (7–12% TRR), chaff (15% TRR) and straw (22%TRR) and the m-PB-Acid in brown rice at 6–14% TRR.

Table 18 Identification of residues in rice harvested 21 days after foliar treatment with 0.2 kg ai/ha 14C-etofenprox. Surface wash Whole grain Brown rice Chaff Straw mg/kg eq % TRR mg/kg eq % TRR mg/kg eq % TRR mg/kg eq % TRR mg/kg eq % TRR

Extracted 0.53 100.0 1.622 89.6 0.069 91.3 5.014 85.0 3.979 89.9 Etofenprox 0.316 59.6 1.057 58.4 0.04 53.4 3.425 58.1 2.167 48.9 α-CO 0.102 19.3 0.293 16.2 0.009 12.2 0.886 15.0 0.952 21.5 4’-OH 0.019 3.6 0.022 1.2 nd nd 0.018 0.3 0.065 1.5 DE 0.018 3.4 0.037 2.0 nd nd 0.09 1.5 0.13 3.0 DP 0.007 1.3 0.007 0.4 nd nd nd nd 0.058 1.3 m-PB-Acid a nd nd 0.039 2.2 0.011 14.1 0.15 2.6 0.214 4.9 PENA a 0.019 3.5 0.066 3.7 0.003 3.7 0.22 3.7 0.078 1.8 4’-OH-PBAcid a nd nd 0.01 0.6 0.003 4.3 0.037 0.6 0.136 3.1

Etofenprox 425

Surface wash Whole grain Brown rice Chaff Straw mg/kg eq % TRR mg/kg eq % TRR mg/kg eq % TRR mg/kg eq % TRR mg/kg eq % TRR Unextracted -- -- 0.189 10.4 0.007 8.7 0.886 15.0 0.452 10.2


Table 19 Identification of residues in rice harvested 21 days after foliar treatment with 2.0 kg ai/ha 14C-etofenprox

Surface wash Whole grain Brown rice Chaff Straw ppm % TRR ppm % TRR ppm % TRR ppm % TRR ppm % TRR

Extracted 10.05 100.0 21.86 96.4 1.06 94.8 51.11 93.4 38.07 94.0 Etofenprox 7.23 72.0 15.7 69.2 0.85 76.4 36.33 66.4 22.71 55.1 α-CO 1.65 16.4 3.411 15.0 0.079 7.1 7.892 14.4 9.03 22.3 4-AcO nd nd 0.022 0.1 nd nd 0.102 0.2 nd nd 4’-OH 0.264 2.6 0.284 1.3 nd nd 0.092 0.2 0.754 1.9 DE 0.154 1.5 0.236 1.2 nd nd 0.506 0.9 0.826 2.0 DP 0.066 0.7 0.139 0.6 nd nd 0.337 0.6 0.342 0.8 m-PB-Acid a nd nd 0.38 1.6 0.72 6.5 1.515 2.8 1.62 4.0 PENA a 0.12 1.2 0.56 2.5 0.018 1.6 1.973 3.6 0.53 1.3 4’-OH-PBAcid a nd nd 0.104 0.5 0.018 1.6 0.417 0.8 0.51 1.3 Unextracted -- -- 0.821 3.6 0.059 5.2 3.603 6.6 2.413 6.0


The proposed metabolic pathways involve the formation of the α-CO by oxidation of the

benzyl methylene group, hydrolysis of the ether linkage to form the DE and DP metabolites and hydroxylation of the phenoxy ring (to form the 4’-OH metabolite). Further reaction and cleavage of these primary metabolites produce the EPMP, m-PB-acid, PENA, m-PB-alc, OH-P-alc and OH-PB-acid, with subsequent conjugation.

426 Etofenprox

Figure 4 Proposed metabolic pathway in rice

Environmental fate

The meeting received information on hydrolysis, aqueous photolysis, degradation in water/sediment systems and on the metabolism of etofenprox in rotational crops.

Hydrolysis

The hydrolytic stability of etofenprox was reported by van der Gaauw, 2011 [Ref: 731158]. A 1:1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox in acetonitrile was incubated in sterile aqueous buffered solutions at pH 4, 7 and 9 at 50°C in the dark for 5 days and analysed by TLC at various times: immediately after treatment, after 2.4 hours, 24 and 120 hours of incubation.

At the end of the 5 days of incubation the recovered radioactivity was higher than 95% of the initial amount applied and no degradation (<10% hydrolysis) was observed at each of the three pH values investigated.

The rate of breakdown of the α-CO metabolite of etofenprox was investigated by Clayton et al, 2003 [Ref: 21993]. In this study a 1:1 mixture of α- and propyl-labelled 14C-CO was incubated in aqueous buffer: acetonitrile solution (9:1, v/v) at pH 4, 7 and 9 at 35°C and 45°C for up to 25 days in the dark. Samples were taken at various intervals and analysed by TLC and HPLC. The amount of radioactivity in test solutions and vessel washes was determined by LSC.

Hydrolytic half-lives (DT50 and DT90) were calculated by linear regression analysis, assuming first-order kinetics. The rate constant at 25 °C was interpolated using the Arrhenius equation.

Following incubation at 50 °C, [14C]-α-CO was stable at pH 4 and pH 7 but hydrolysed at pH 9 and [14C]-α-CO was also hydrolysed at 25°C at pH 9 but at a much slower rate.

Experiments at 35 °C and 45 °C indicated that [14C]-α-CO was hydrolysed to two main components, m-PB-acid and PENA. Quantitative recoveries of 96% to 91% of the applied

Etofenprox 427

radioactivity were obtained. The calculated DT50 values were 9.6 days (35 °C) and 2.4 days (45 °C), with corresponding DT90 values of 32 days (35 °C) and 7.9 days (45 °C).

The predicted rate of reaction at 25 °C was calculated using the Arrhenius equation. This yielded values of 42.8 days and 142 days for the DT50 and DT90 values, respectively.

Photolysis

Photolytic degradation of a 1:1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox in a sterile aqueous buffer solutions (pH 7) at 25 °C and in natural pond water was reported by van der Gaauw, 2003 [Ref: 755526]. Samples were radiochemically quantified by LSC and analysed by HPLC and TLC and the quantum yield [Φ] of disappearance of 14C-etofenprox was determined with the ECETOC method. Mean recoveries for both aqueous systems were about 92% AR for the irradiated samples and 90 to 105% for the dark control samples.

In the buffer solution at pH 7, the concentration of etofenprox was observed to decline steadily to 9.4% of the radioactivity applied after 15 days of irradiation. A DT50 of 4.7 days was calculated using 1st order regression kinetics with up to 8 photoproducts being found. Photoproducts greater than 10% were identified as α-CO and PENA after 15 days of irradiation. No unknown photodegradates greater than 10% of the applied radioactivity were formed during irradiation.

In the natural pond water, the concentration of etofenprox decreased steadily to about 33% of the applied radioactivity at the end of the 15 day irradiation period and a DT50 of 7.9 days was calculated using 1st order regression kinetics. Up to 7 photoproducts were found, mostly the α-CO and PENA metabolites.

In both solutions, etofenprox was stable in samples kept in the dark and no radiolabelled CO2 and organic volatiles were detected.

Using the UV absorption data and the degradation kinetics, the quantum yield of etofenprox was determined to be Φ = 0.248 in buffer solution (pH 7) and Φ = 0.147 in natural pond water.

Table 20 Identification of radioactive residues after photolysis of [2-14C-propyl]- and [α-14C-benzyl]-etofenprox in buffer solution at pH 7 and natural pond water (values given in % of applied radioactivity)

Condition Exposure [days]

14CO2 Etofenprox α-CO PENA m-PB-acid

M1 M2 M3 M4 M5

Buffer solution at pH 7 irradiated 0 - 100.0 nd nd nd nd nd nd nd nd

1.0 - 81.1 12.4 2.1 nd 1.5 3.0 nd nd nd 1.8 - 76.5 16.0 3.0 nd nd 1.5 3.7 nd nd 4.6 - 48.2 35.6 4.2 nd 5.6 nd 3.5 nd nd 11.7 - 20.1 54.9 10.8 nd 4.7 4.6 2.4 2.6 nd 15.0 - 9.4 63.6 12.0 5.0 1.7 nd 4.3 nd 4.0

dark 1.8 - 95.9 4.1 - - - - - - - 4.6 - 100.0 nd - - - - - - - 6.7 - 100.0 nd - - - - - - - 11.7 - 95.2 4.8 - - - - - - - 15.0 - 96.2 3.8 - - - - - - -

Natural pond water irradiated 0 - 100 nd nd nd nd nd nd nd nd

1.0 - 87.9 4.8 2.6 nd nd nd 3.2 nd nd 1.8 - 82.0 10.7 3.5 nd nd nd 3.8 nd nd 4.6 - 64.6 22.3 7.3 nd nd nd 5.9 nd nd 6.7 - 43.4 31.3 13.3 nd nd 3.7 9.4 0.8 nd

428 Etofenprox

Condition Exposure [days]

14CO2 Etofenprox α-CO PENA m-PB-acid

M1 M2 M3 M4 M5

13.5 - 38.6 37.6 11.4 4.0 2.7 1.7 2.0 2.0 nd 15.0 - 32.5 37.8 14.4 3.8 3.3 2.9 5.3 nd nd

dark 1.8 - 96.4 3.60 - - - - - - -

4.6 - 97.2 2.80 - - - - - - - 6.7 - 96.1 3.93 - - - - - - - 11.7 - 94.0 6.05 - - - - - - - 15.0 - 90.6 6.50 - - - - - - -

The photoproducts greater than 10% are in highlighted bold nd = not detected or below limit of detection

Water/sediment studies

The degradation and metabolism of etofenprox in water-sediment systems was investigated by Lewis, 2001 [Ref: D2142]. In this study, a mixture (1 + 1) of [2-14C-propyl]-etofenprox and [α-14C-benzyl]-etofenprox was incubated in two natural water-sediment systems (Mill stream pond and Emperor Lake) in the dark over a period of 99 days. In the Emperor Lake water-sediment system the degradation of [14C]-etofenprox was determined following a 12 h dark/12 h light photoperiod.

Each test vessel (glass cylinders of 4.5 cm diameter) contained a 2.5 cm sediment layer (dry weight of 16.5 g for Mill stream pond and 24.8 g for Emperor lake systems) covered with water to a depth of 6 cm (weight of 97.1 and 99.4 g for Mill stream pond and Emperor lake systems, respectively). Prior to application, the water-sediment units were pre-incubated for 67 days (Mill stream pond, Expt A) or 74 days (Emperor Lake, Expt B) in the dark at 20 ± 2 °C until equilibration. Moistened CO2-free air was drawn over the water surface. An additional incubation group consisted of the Emperor Lake water-sediment system (Expt C) acclimatised under a 12 h fluorescent lighting/12 h dark regime.

After pre-incubation for 67–74 days, [14C]-etofenprox was applied each water-sediment system at a rate equivalent to 0.2 kg ai/ha and incubated in the dark (Expts A and B) or under a 12 h light/dark cycle (Expt C) at 20 ± 2 °C for 99 days. At each sampling date, the surface water was partitioned twice with dichloromethane and the sediment was extracted 3 times with methanol and then with methanol/HCl (95:5), with residues being analysed by HPLC and TLC. Sediments for fractionation into fulvic acid, humic acid and humin were extracted with NaOH, and the radioactivity in the humin fraction was determined by combustion followed by LSC.

Recovery rates were above 90% of the applied radioactivity over the study period in the Emperor Lake experiments (except in the Expt B (dark) samples taken at day 99. In the Mill stream pond experiment, the overall recovery rates decreased from the initial 96–93% AR to 88% AR after 14 days and 84% after 59 and 99 days.

At the end of the 99 day study period, 28, 18 and 19% of the applied radioactivity present in the NaOH traps was shown to be 14CO2 in the Mill stream pond sysytem, the Emperor Lake system incubated in the dark and in the Emperor Lake system incubated under a light/dark cycle, respectively. No other volatile products could be detected (≤ 0.1% of applied radioactivity).

The initial levels etofenprox in the surface water were 22–32% of the applied radioactivity in the three incubated experiments. Not more than 1% AR was detected after 14 days, 30 or 59 days after application in experiments A, C and B, respectively. The initial decrease was more rapid in the Mill stream pond system than in the Emperor Lake system and more rapid under a light/dark cycle than in the dark. Levels of etofenprox in the sediment decreased from 62–70% of applied radioactivity to between 8–25% at 99 days, in all groups.

Etofenprox 429

Only one degradate (4’-OH) exceeded 10% of applied radioactivity, mostly found in the sediments and reaching maximum levels of about 12–21% AR after 7–14 days and decreasing to < 10% AR after 30 days.

Table 21 Degradation of etofenprox and formation of metabolites in water/sediment systems incubated in the dark

% applied radioactivity Days after application 0 7 14 30 59 99

Test system Mill stream pond in the dark (experiment A) Water phase 23.3 10.3 23.8 4.9 0.9 0.7 extracted 22.4 8.2 19.6 3.0 0.3 0.2 Etofenprox 22.3 2.2 0.7 – – – 4’-OH nd 0.6 0.5 – – – DP nd 0.3 1.2 – – – m-PB-acid nd 0.3 nd – – – EPMP a nd 1.5 1.7 – – – not extracted 0.9 2.1 4.2 1.9 0.6 0.5 Sediment 72.6 80.2 62.6 64.4 54.8 55.3 extracted 72.5 76.2 51.7 35.5 31.3 32.7 Etofenprox 70.1 42.3 15.1 10.7 7.2 7.8 4’-OH nd 21.4 17.1 7.0 7.4 6.1 DP nd 1.8 4.3 3.0 3.1 2.4 m-PB-acid nd nd nd nd nd 1.0 EPMP a nd 0.1 1.0 1.8 0.3 0.1 not extracted 0.1 4.0 10.9 28.9 23.5 22.6 14CO2 n.a. 2.1 1.5 17.0 27.6 28.2 TOTAL 95.9 92.8 88.3 86.8 83.6 84.4 Test system Emperor Lake, dark (experiment B) Water phase 33.2 18.7 19.8 12.6 6.4 1.3 extracted 32.6 18.0 19.2 11.6 4.1 0.5 Etofenprox 32.1 29.6 12.9 4.1 0.1 – 4’-OH nd 0.8 2.2 0.7 nd – DP nd 0.4 1.1 0.6 nd – m-PB-acid nd 0.9 0.6 0.8 0.2 – EPMP a nd 1.2 1.0 1.9 1.5 – not extracted 0.6 0.7 0.6 1.0 2.3 0.8 Sediment 64.6 60.2 72.4 82.2 70.5 62.8 extracted 64.5 58.8 70.1 78.3 47.0 32.0 Etofenprox 63.1 45.6 47.3 55.1 13.8 7.6 4’-OH nd 3.9 12.2 9.3 2.5 1.5 DP nd 1.1 2.4 1.9 3.8 3.8 m-PB-acid nd 0.7 0.5 nd nd nd EPMP a nd nd 0.2 0.5 1.0 0.6 not extracted 0.1 1.4 2.3 3.9 23.5 30.8 14CO2 n.a. 0.2 0.2 0.9 14.9 17.8 TOTAL 97.8 95.3 96.0 95.9 92.3 82.9

n.a. not applicable nd not detected – not analysed a runs together with P-alc (PENA/EPMP)

430 Etofenprox

Table 22 Degradation of etofenprox and formation of metabolites in water/sediment systems incubated under a 12 hour dark/light cycle

% applied radioactivity Days after application 0 7 14 30 59 99

Test system Emperor Lake, light/dark cycle (experiment C) Water phase 33.1 12.9 17.2 9.0 3.9 0.7 extracted 32.0 11.9 16.4 7.7 2.1 0.2 Etofenprox 31.5 3.2 7.6 0.5 – – 4’-OH nd 1.8 1.7 nd – – DP nd 1.0 0.6 0.7 – – m-PB-acid nd 1.1 1.6 1.0 – – EPMP a nd 2.5 3.5 3.7 – – not extracted 1.1 1.0 0.8 1.3 1.8 0.5 Sediment 64.2 83.2 75.6 82.4 81.6 72.7 extracted 64.0 72.7 69.9 67.4 66.9 45.4 Etofenprox 61.9 45.2 44.0 37.0 46.6 24.9 4’-OH nd 14.4 12.3 7.6 4.6 1.9 DP nd 4.1 3.9 6.3 2.9 2.1 m-PB-acid nd 1.2 0.9 0.2 0.7 0.9 EPMP a nd 1.1 1.4 1.7 0.5 nd not extracted 0.2 10.5 5.7 15.0 14.7 27.3 14CO2 n.a. 1.4 1.0 4.9 7.2 19.3 TOTAL 97.3 98.1 94.1 96.5 93.0 92.8

a runs together with P-alc (PENA/EPMP)

A supplementary study was conducted by Lewis, 2003 [Ref: D2194], to validate the results of

the main study (where relatively low recovery rates were achieved in the Mill stream pond system). In this study, the same water-sediment system and procedures were used but the two radiolabels were applied to separate test systems (instead of being applied as a 1:1 mixture) and slightly different extraction procuders were used.

At each sampling date, the surface water was added to NaCl, diluted with acetonitrile, mixed with dichloromethane and neutralised with HCl before partitioning with dichloromethane (3X). The sediment was extracted twice acetonitrile and then with methanol/HCl (95:5).

Overall recovery rates ranged from 96 to 101% AR for [2-14C-propyl]-etofenprox and from 91 to 99% for [α-14C-benzyl]-etofenprox. At 100 days, recovery was 98% and 96%, respectively.

The results obtained the degradation products and their dissipation rates were similar to those reported in the main study. The DT50 for etofenprox was calculated to be 6.5 days for the entire system and for the major degradate (4’-OH) a DT50 of 57 days was calculated for the whole system.

Table 23 Degradation of etofenprox and formation of metabolites in water/sediment systems following incubation with 14C-propyl- or 14C-benzyl-etofenprox in the dark

Test system Mill stream pond system in the dark Days after application 0 3 7 14 30 62 100

Label [2-14C-propyl]-etofenprox –% applied radioactivity Water phase 29.5 9.4 10.8 5.0 2.3 1.8 1.2 Etofenprox 29.7 2.9 1.0 0.2 n.a. n.a. n.a. 4’-OH nd 0.6 1.0 nd n.a. n.a. n.a. DP nd 0.2 0.6 nd n.a. n.a. n.a. DE nd nd nd nd n.a. n.a. n.a.

Etofenprox 431

Test system Mill stream pond system in the dark Days after application 0 3 7 14 30 62 100 m-P-alc/m-P-acid nd nd nd nd n.a. n.a. n.a. α-CO nd nd nd nd n.a. n.a. n.a. Sediment 69.7 91.4 87.4 83.3 73.4 69.9 61.6 extracted (1) 68.8 85.5 81.7 65.9 45.8 43.0 42.8 Etofenprox 65.7 63.8 53.8 43.7 19.0 20.1 22.4 (1) 4’-OH nd 13.5 19.3 11.1 13.5 9.4 8.5 (1) DP nd nd 0.5 0.4 0.5 0.3 1.4 (1) DE nd nd nd nd 0.2 nd 0.7 (1) m-P-alc/m-P-acid nd nd nd 0.3 nd nd 0.2 (1) α-CO nd nd nd nd nd 0.1 0.2 (1) not extracted 0.9 6.0 5.7 17.4 27.6 26.9 18.8 Volatile (2) n.a. 0.5 0.4 8.2 19.8 25.4 34.7 TOTAL 99.2 101.3 98.6 96.6 95.6 97.2 97.6 Label [α-14C-benzyl]-etofenprox –% applied radioactivity Water phase 29.6 8.4 7.7 3.3 0.7 2.4 0.6 Etofenprox 30.7 4.0 0.3 n.a. n.a. n.a. n.a. 4’-OH nd 0.4 0.2 n.a. n.a. n.a. n.a. DP nd 0.3 0.4 n.a. n.a. n.a. n.a. DE nd nd nd n.a. n.a. n.a. n.a. m-PB-acid nd 0.6 nd n.a. n.a. n.a. n.a. m-PB-alc nd nd nd n.a. n.a. n.a. n.a. α-CO nd nd nd n.a. n.a. n.a. n.a. Sediment 69.7 88.0 79.9 75.6 76.9 55.4 58.2 extracted a 69.0 82.5 69.0 60.5 63.7 36.3 36.1 Etofenprox 65.9 60.5 38.4 43.5 44.6 24.3 15.5 (1) 4’-OH nd 13.9 17.7 7.5 9.6 2.0 7.0 (1) DP nd nd 0.9 0.4 nd nd 2.1 (1) DE nd nd nd nd nd nd nd m-PB-acid nd nd nd 0.2 nd nd nd m-PB-alc nd nd nd nd nd nd nd α-CO nd nd nd nd nd nd nd not extracted 0.7 5.5 11.0 15.1 13.2 19.1 22.1 Volatile b n.a. 2.0 3.4 17.4 19.6 37.9 36.8 TOTAL 99.3 98.4 91.2 96.3 97.4 96.0 96.2

nd not detected n.a. not applicable a radioactivity in acetonitrile and in acidified methanol extracts of sediment b mostly radioactivity present in the NaOH traps, assumed to be 14CO2

Based on these results, the degradation rates of etofenprox in the water phases and entire

systems were calculated assuming first order kinetics. The degradation rates of the metabolite 4’-OH were calculated only for the total system, because most of the compound was present in the sediment phase. The DT50- and DT90-values for the 3 incubation systems are listed below.

432 Etofenprox

Table 24 Degradation of etofenprox and its 4’-OH metabolite in aquatic systems (calculated DT50 and DT90 values assuming 1st order kinetics)

Incubation system

Mill stream pond (dark) (main study) Emperor Lake (dark) Emperor Lake (light/dark) main study (D2142] supplementary study [D2149] main study (D2142] main study (D2142]

Etofenprox Water phase DT50 = 2.1 days

DT90 = 7.1 days R2: 0.999

DT50 = 1 days DT90 = 3.2 days R2: 0.999

DT50 = 10.4 days DT90 = 34.5 days R2: 0.999

DT50 = 2.1 days DT90 = 7.1 days R2: 1.000

Entire system DT50 = 6.5 days DT90 = 23.8 days R2: 0.982

DT50 = 6.5 days DT90 = 143days R2: 0.994

DT50 = 20.1 days DT90 = 71.0 days R2: 0.998

DT50 = 7 or 22 days a DT90 = > 99 or 104 days a R2: 0.686 a

4’-OH metabolite Entire system DT50 = 29.7 days

DT90 = 97.9 days R2: 0.872

DT50 = 57 days DT90 = 185 days R2: 0.798

DT50 = 21.8 days DT90 = 59.8 days R2: 0.99

DT50 = 27 days DT90 = 87.1 days R2: 0.989

R2 = correlation coefficient a Actual values show that about 50% AR is present at 7 days and that about 25% is present at 99 days (therefore the DT90 is > 99 days). Computed values using the poor fit curve suggest a DT50 of 22 days and DT90 of 104 days.

The principle etofenprox degradation pathway in water-sediment systems appears to be by

hydroxylation to the 4’-OH degradates which is further degraded to bound residues and carbon dioxide. Intermediates in the degradation of the 4’-OH probably include the P-acid. Minor pathways involve cleavage of the ether linkage between the two benzene rings to form the DP component.

Residues in rotational crops

Confined accumulation studies

The metabolism of etofenprox in lettuce, carrots and spring barley grown in bare soil treated with 14C-etofenprox was studied by Diehl, 2003 [Ref: 843640]. In this study, a 1 + 1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox was applied to bare soil at a rate equivalent to 0.312 kg ai/ha by hand sprayer using a spray volume equivalent of 600 L/ha. After about 4 weeks aging, lettuce, barley and carrots were planted/sown in the treated soil. Plants were harvested at half maturity (71, 87 and 105 days after treatment respectively) and at full maturity (84, 119 and 125 days after treatment).

Lettuce leaves and carrot roots were washed twice with water and the barley samples were air-dried and separated into grain and straw (mature plants). Aliquots were combusted to determine the TRR and samples of lettuce, barley grain and straw were extracted with acetonitrile, methanol/water (4:1) and water at room temperature, and in addition under Soxhlet (acetonitrile/water, 4:1) and reflux (acetonitrile/water, 3:1) conditions. The radioactivity in each extract was quantified by LSC. Unextracted radioactivity was determined by combustion of sub samples and further characterised by weak and strong acid/base hydrolysis, surfactant and cellulase treatment. After each treatment, the liquid and solid phases were separated and the radioactivity in the supernatants determined by LSC. The harsh acid and base extracts were concentrated and further analysed by TLC.

The highest TRRs were found in barley (dry weight) at 0.058 mg/kg eq (whole plant), 0.022 mg/kg eq (grain) and 0.069 mg/kg eq (straw). Lower residues were found in lettuce (fresh weight, before washing) at 0.008 mg/kg eq (half-mature) and 0.018 mg/kg eq (mature plants). The lowest TRR was detected in carrots at 0.004–0.005 mg/kg eq after surface water washing.

Only very low amounts of TRR (≤ 25%) were extracted, even by using harsh extraction techniques under Soxhlet and reflux conditions. The fact that most radioactivity remained unextracted indicated that the major portion of 14C may have entered the carbon pool of the plants and was no

Etofenprox 433

longer associated with the parent structure. Analysis of the extracted radioactivity was not undertaken because of the low amount of residues and binding to the extracted/dissolved tissues.

Table 25 Characterisation and distribution of radioactivity in rotational crops planted 30 days after bare soil treatment with 0.312 kg ai/ha 14C-etofenprox

Crop matrix Lettuce leaves Carrot Barley grain Barley straw mg/kg a %TRR mg/kg a %TRR mg/kg a %TRR mg/kg a %TRR

TRR 0.02 0.007 0.022 0.069 Washings (2× H2O 0.002 10.1 0.002 b 26.7 – – – – Combustion 0.018 89.9 0.005 73.3 0.022 0.069 Extractions: Acetonitrile < 0.001 1.9 < 0.001 1.9 < 0.001 0.6 MeOH/water < 0.001 4.9 0.001 5.4 < 0.001 1.3 Water < 0.001 4.0 < 0.001 4.4 0.002 2.2 Soxhlet < 0.001 4.9 0.002 7.0 0.003 4.1 Reflux 0.002 9.3 < 0.001 4.1 0.005 6.9 Total extracted 0.006 25.1 0.005 22.8 0.010 15.0 Extracted+washings 0.007 35.2 0.005 22.8 0.010 15.0 Post-extraction solids 0.013 64.8 0.017 77.2 0.059 85.0

a Concentration (mg/kg parent equivalents), calculated for fresh weight (lettuce) or dry weight (barley) of samples b Residues attributed to soil retention

Radioactivity in the post-extraction solids was further characterised by treatments with

different solutions of hydrochloric acid and sodium hydroxide (weak and strong acid/base hydrolysis), with a surfactant and an enzyme (cellulase). Strong acid and base hydrolysis under reflux conditions released substantial amounts of bound residues, up to 37% of TRR in barley grain following acid hydrolysis and up to about 47% of TRR in lettuce following alkaline hydrolysis. These extracts contained a high matrix content and further detailed analysis was not conducted. However, TLC analysis showed that for the barley straw no parent was present. Further evidence that the radioactivity probably entered the carbon pool of the plants was found by analysis of the hydrolysis extracts which showed that the main radioactive fraction remained at the origin of the TLC plate. It was therefore concluded that most of the radioactivity taken up by the plants was due to 14CO2 assimilation.

Table 26 Characterisation of residues in post-extraction solids by treatment with different solutions (weak and strong acid/base hydrolysis, surfactant and cellulose)

Crop matrix Lettuce leaves Barley grain Barley straw % Released a % TRR % Released a TRR % Released a TRR [%] [%] [%] [%] [%] [%]

Treatment: 1 M HCl (Room Temp) 4.4 2.9 0.5 0.4 1.6 1.4 1 M NaOH (Room Temp) 16.8 10.9 35.5 27.4 17.5 14.9 6 M HCl (reflux) 39.2 25.4 48.0 37.0 32.5 27.8 6 M NaOH (reflux) 58.9 38.2 55.0 42.4 33.3 28.5 Triton X-100 (2%) 6.7 4.3 1.9 1.5 1.9 1.6 Cellulase (37°C) 8.3 5.4 1.9 1.5 1.9 1.6

a Percentage of the post-extraction solids radioactivity

434 Etofenprox

METHODS OF RESIDUE ANALYSIS

Analytical methods

The meeting received analytical method descriptions and validation data for etofenprox and its major metabolite α-CO) in crop and animal commodities.

These methods summarised below are suitable for the determination of residues of etofenprox and its α-CO metabolite (as defined for both enforcement and/or risk assessment). The principle of most methods involves extraction steps using organic solvents (predominantly acetone), liquid/liquid partition (commonly hexane), and column chromatographic clean-up (alumina, silica gel, Florisil) and analysis by GC/ECD, GC/MS, HPLC or LC-MS/MS.

Table 27 Summary of Analytical Methods for Etofenprox and metabolites Plant material Mitsui, 2001 [Ref: 200102] Analytes: Etofenprox, α-CO metabolite GC/MS Method MT-200102 LOQ: 0.01 mg/kg Description Samples are extracted (overnight) in acetone, filtered and the acetone removed by evaporation. The crude

extract is partitioned with hexane:5% sodium chloride solution (100:250 mL). For dark green vegetable samples or samples with high fat/oil, a further clean-up step can be used, with the partially cleaned-up extract being partitioned three times with hexane:hexane-saturated acetonitrile (30:40 mL) and the acetonitrile phase then being further partitioned with hexane:5% sodium chloride solution (100:250 mL). After filtration through anhydrous sodium sulphate the hexane extracts are evaporated, re-dissolved in hexane and eluted through an alumina column using hexane:ethyl ether (7:3) for analysis of etofenprox and through a silica gel column using hexane:ethyl ether (100:3) for analysis of α-CO. If necessary, further cleanup through a florisil column using hexane:ethyl ether (85:15) can be included before analysing for the α-CO metabolite. Residues are detected by GC/MS (m/z etofenprox–163, 376; m/z α-CO–163, 390)

Plant material Class, 2003 [Ref: 692-G] Analytes: Etofenprox, α-CO metabolite GC/MS Method 692-G LOQ: 0.01 mg/kg Description A modification of Method 200102 involving the same extraction and partitioning steps and with the crude

acetone extracts being cleaned-up using silica gel and florasil column chromatography (i.e. omitting the alumina column clean-up step). Analysis for both etofenprox and the α-CO metabolite is by GC/MS

Apple, peach Freschi, 2003 [Ref: SIP 1354 & SIP 1355] Analytes: Etofenprox, α-CO metabolite HPLC Method SIPCAM 1354 LOQ: 0.01 mg/kg Description Homogenised samples are extracted with dichloromethane, filtered through anhydrous sodium sulphate,

evaporated and reconstituted in dichloromethane:hexane (70:30) and eluted through a silica gel column using dichloromethane. After evaporating to dryness and reconstitution in methanol, residues of etofenprox and its α-CO metabolite are measured by HPLC-UV (at 225 nm) using methanol:water (85:15) eluent

Rice, rice straw Nixon, 2006 [Ref: 236C-136] Analytes: Etofenprox, α-CO metabolite LC-MS/MS Method 236C-136 LOQ: 0.01 mg/kg Description Samples are extracted by blending in acetone and after centrifugation, the supernatant is cleaned-up by

elution through an SPE column using dichloromethane. After evaporation to dryness under nitrogen, the extracts are reconstituted in acetonitrile:water:formic acid (50:50:0.1) and residues of etofenprox and its α-CO metabolite are measured by LC-MS/MS operating in positive ion MRM mode, monitoring transitions of 359 → 183 amu (etofenprox) and 177 → 107 amu (α-CO).

Plant material Ciscato & Gebara, 1999 [Ref: 119/99, 34/99] Analytes: Etofenprox GC/NPD, ECD, MSD Method MT-GLC LOQ: 0.01 mg/kg Description Samples are extracted in acetone, filtered and the acetone removed by evaporation. The extract is partitioned

with dichloromethane: sodium chloride solution and the dried extract is reconstituted in ethyl acetate:cyclo-hexane (1:1) and cleaned-up gel permeation chromatography and by elution through a silica gel column before GC analysis using NPD, MSD or ECD.

Etofenprox 435

Plant material Komoto, 1989 [Ref: 25] Analytes: Etofenprox GC/ECD Method MT-PBI LOQ: 0.01 mg/kg Description Samples are extracted in acetone, filtered and the acetone removed by evaporation. The extract is partitioned

with hexane:5% sodium chloride solution (100:250 ml) and then with hexane:hexane-saturated acetonitrile (30:40 mL), with the acetonitrile phase also being further partitioned with hexane:5% sodium chloride solution (100:250 mL). After filtration through anhydrous sodium sulphate the hexane extracts are evaporated, re-dissolved in hexane and eluted through an alumina column using hexane:ethyl ether (7:3) and evaporated. The residue is then dissolved in chloroform and reacted with iodotrimethylsilane to form iodo-3-phenoxybenzyl (PBI) which is partitioned in hexane:sodium thiosulphate. The deydrated hexane phase is eluted through a silica gel column using hexane:dichloromethane (95:5) and and the derivatised etofenprox residues are measured by GC/ECD.

Meat, eggs, milk Mitsui, 2001 [Ref: 200104B, 200104E, 200104M] Analytes: Etofenprox, α-CO metabolite GC/MS Method MT-200104 LOQ: 0.01 mg/kg Description Samples are extracted in acetone (meat) or methanol (eggs) and after filtration and solvent evaporation,

extracts are partitioned with hexane:5% sodium chloride solution (100:250 mL). Milk samples are mixed with water, potassium chloride and ethanol (40:1:50) and partitioned into hexane:ethyl ether (1:1). The dried extracts are then partitioned three times with hexane:hexane-saturated acetonitrile (30:40 mL) and the acetonitrile phase then being further partitioned with hexane:5% sodium chloride solution (100:250 mL). After filtration through anhydrous sodium sulphate the hexane extracts are evaporated, re-dissolved in hexane and eluted through an alumina column using hexane:ethyl ether (7:3) for analysis of etofenprox and through a silica gel column using hexane:ethyl ether (100:3) for analysis of α-CO. If necessary, further cleanup through a florisil column using hexane:ethyl ether (85:15) can be included before analysing for the α-CO metabolite. Residues are detected by GC/MS (m/z etofenprox 163, 376; m/z α-CO 163, 390)

Meat, eggs, milk Wolf, 2003 [Ref: 791245] Analytes: Etofenprox, α-CO metabolite GC/MS Method 791245 LOQ: 0.01 mg/kg Description A modification of method MT-200104, using acetone extraction for all matrices and the same hexane-water

and hexane-acetonitrile partition steps but involving silica gel clean-up, eluting with hexane:ether (100:3) and florisil clean-up, eluting with hexane:ether (9:1) before evaporation and reconstitution in dodecane for analysis of both etofenprox and α-CO by GC/MS (m/z etofenprox 163, 376; m/z α-CO 163, 390)

Data collection methods

Method MT-GLC (plant matrices)

GLC methods for measuring residues of etofenprox in plant matrices, involving ECD or NPD detection (and summarised above) have been described and reported by Ciscaro & Gebara, 1999 [Ref: 119/99 and 34/99] and were evaluated by the 1993 JMPR. Samples from supervised field trials on crops conducted in Brazil (1999) were analysed using this method. LOQs were 0.01-0.05 mg/kg and concurrent recovery rates in these trials are summarised below.

Table 28 Concurrent recovery values for analytical method MT-GLC for the determination of etofenprox in crops using using GC/NPD, GC/MSD or GC/ECD

Matrix Detector Fortification level [mg/kg]

Recovery rate [%] SD n Reference mean range

Apple MSD 0.5–5.0 76.2 7.8 10 RS925, RS926, RS927 Bean ECD 0.01–0.1 85.5 2 32/99 Bean ECD 0.01–0.1 74 2 118/99 Bean NPD 0.01–0.1 74 2 RS144 Beans MSD 0.05–0.5 85.7 11.8 7 RS723, RS724, RS725 Beans MSD 0.05–0.5 113 7.2 6 RS533 Coffee bean MSD 0.05–0.5 90.2 16.8 10 RS928, RS929, RS930

436 Etofenprox



Coffee bean MSD 0.05–0.5 93.7 15 6 RS427, RS428, RS429 Corn ECD 0.01–1.0 84 2 33/99 Corn MSD 0.05–0.5 80.1 4.9 7 RS729, RS730, RS731 Corn MSD 0.05–0.5 100 16.7 6 RS535 Corn NPD 0.01–0.1 87 2 RS142 Corn NPD 0.01–0.1 87 2 116/99 Cotton ECD 0.01–0.1 76.5 2 RS135, 137/99, 139/99 Cotton MSD 0.05–0.5 84.7 15.6 7 RS732, RS733, RS734 Cotton MSD 0.05–0.5 84.5 18 6 RS536, RS536B Orange MSD 0.05–0.5 89.5 14.1 6 RS389, RS390, RS391 Peach MSD 0.05–0.5 84.8 11.5 12 RS919, RS920, RS921 Potato MSD 0.05–0.5 85 14 7 RS538 Potato NPD 0.01–0.1 82 2 126/99 Rice MSD 0.05–0.5 105.8 11 10 RS922, RS923, RS924 Soybean ECD 0.01–0.1 79.5 2 122/99 Soybean ECD 0.01–1.0 80 2 34/99 Soybean MSD 0.05–0.5 82.7 12.3 6 RS727 Soybean MSD 0.05–0.5 83.9 11.7 7 RS726, RS728 Soybean MSD 0.05–0.5 103.2 12.5 6 RS534, RS534B Soybean NPD 0.01–0.1 79.5 2 117/99 Tomato NPD 0.01–0.1 92.5 2 119/99, 120/99, RS141 Tomato NPD 0.02 84 2 USP-1991-T Wheat ECD 0.02 87 2 USP-1991-W Wheat NPD 0.01–0.1 77 2 RS145

Method MT-PBI (plant matrices)

A modification of the MT-GLC method has been described and reported by Komoto, 1989 [Ref: 25]. In this method (summarised above), an additional derivitisation step was included to convert etofenprox to 3-phenoxybenzyl iodide (3-PBI) by reacting the purified extract with trimethylsilane iodide before the final silica-gel cleanup step. Samples from supervised field trials on soya beans, bean, potato, maize conducted in Brazil (1999) and paddy rice trials in Japan (1989–96) were analysed using this method. LOQs were 0.02–0.05 mg/kg and concurrent recovery rates in these trials are summarised below.

Table 29 Concurrent recovery values for analytical method MT-PBI for the determination of etofenprox in crops using using GC/ECD


Recovery rate [%] SD n Reference

mean range

Soybean GC/ECD 0.05–1.0 83 3 2 USP-1995-S

Bean GC/ECD 0.05–1.0 77 6 2 2273/97

Potato GC/ECD 0.05–1.0 77 2 USP-1994-P

Maize GC/ECD 0.05–1.0 87 2 2144/96

Brown rice GC/ECD 0.04 90.8 [MT] 91.5 [IL]

2 2

MT-39

Brown Rice GC/ECD 0.04 89.7 [IL] 3.6 4 MT-49

Brown Rice GC/ECD 0.04 89.9 [MT] 2.3 4 MT-61

Etofenprox 437


Recovery rate [%] SD n Reference

mean range

Brown Rice GC/ECD 0.04 91.9 [MT] 97.5 [IL]

2 2

MT-25

[MT] = samples analysed by the Mitsui laboratory [IL] = duplicate samples analysed by an independent laboratory

Method MT-200102 (plant matrices)

A GC/MS method (MT-200102) was developed by the manufacturer (Mitsui, 2001) [Ref: 200102] to analyse plant matrices for both the parent compound and its α-CO metabolite and is summarized above. Independent validation studies were conducted with samples of apples, peaches, head cabbage, rape seed, cucumbers and grapes fortified at 0.01–5.0 mg/kg with recovery rates of 89–99% (etofenprox) and 92–99% (α-CO). The LOQ was 0.01 mg/kg and recoveries are summarized below.

Table 30 Validation recovery values for analytical method MT-200102 for the determination of etofenprox and its α-CO metabolite in crops using using GC/MS

Matrix Analyte Fortification level [mg/kg]

Recovery rate [%] RSD [%]

n Reference mean range

Rape seed Etofenprox 0.01 0.10 2.00

93.3 94.9 77.5

81.5–110.5 90.6–100.5 72.0–84.0

12.8 4.7 6.9

5 5 5

789390

α-CO 0.01 0.10

103.9 91.6

99.4–107.8 79.8–99.3

3.1 7.8

5 5

Cabbage Etofenprox 0.01 0.10 2.00

98.4 104.4 101.2

87.0–108.1 102.7–108.1 97.1–106.9

7.9 2.1 3.6

5 5 5

814588

α-CO 0.01 0.10

100.9 88.7

97.9–104.8 82.3 –96.5

3.1 6.9

5 5

Cucumber Etofenprox 0.01 0.10 2.00

99.3 89.7 88.7

86.3–112.4 77.3–111.8 73.9–112.5

11.6 15.7 17.0

5 5 5

789377

α-CO 0.01 0.10

102.8 103.3

95.9–108.9 96.6–111.7

4.7 7.0

5 5

Grape Etofenprox 0.01 0.10 5.00

105.1 106.7 101.4

99.1–109.6 101.4–109.5 89.7–104.8

3.7 2.9 6.5

5 5 5

789401

α-CO 0.01 0.10 0.50

108.0 95.4 80.0

106.0–109.9 87.0–100.3 70.7–91.7

1.3 5.7 11.5

5 5 5

Peach Etofenprox 0.01 2.0

85.6 93.4

76.0–108.1 70.1–107.2

15.3 16.0

5 5

A-32-02-02

α-CO 0.01 0.50

97.6 78.7

90.2–105.7 64.8–89.1

5.8 12.2

5 5

Apple Etofenprox 0.01 2.0

83.0 96.0

75.2–95.4 86.7–104.5

10.6 8.7

5 5

A-32-02-01

α-CO 0.01 0.50

97.4 95.0

81.8–107.0 84.1–105.9

9.8 10.4

5 5

Crop field trials conducted in Europe were analysed using method MT-200102 and

concurrent recovery values in these trials are summarized below.

438 Etofenprox

Table 31 Concurrent recovery values for GC/MS analytical method MT-200102 for the determination of etofenprox and its α-CO metabolite in crops



Grape Etofenprox α-CO

0.01–0.1 0.01–0.1

100.9 105.2

6.2 8.3

4 4

820350


0.01–0.1 0.01–0.1

106.3 106.8

2 2

843559


0.01–0.1 0.01–0.1

105.1 100.9

0.9 5.9

3 4

820348


0.01–0.1 0.01–0.1

107.9 102.8

2 2

843558


0.01–1.0 0.01–1.0

96.8 88.3

16 4.8

6 6

4-alpha-08

Grape juice Etofenprox α-CO

0.01–0.1 0.01–0.1

109.3 89.6

1.6

4 2

820350

Apple Etofenprox α-CO

0.01–2.0 0.01–0.05

102.4 84.9

8.1 11.9

4 4

848643

Apple pureé Etofenprox α-CO

0.01–2.0 0.01–0.05

91.9 104.1

2 2

848643

Apple juice Etofenprox α-CO

0.01–2.0 0.01–0.05

93.9 100.9

2 2

848643

Apple press cake Etofenprox α-CO

2.0 0.5

103.2 110.8

1 1

848643

Peach Etofenprox α-CO

0.01–2.0 0.01–0.05

94.8 99.6

2 2

848642

Peach juice Etofenprox α-CO

0.01–2.0 0.01–0.05

82.5 72.5

2 2

848642

Peach jam Etofenprox α-CO

0.01–2.0 0.01–0.05

88.3 74.2

16.4 3 2

848642

Peach pureé Etofenprox α-CO

0.01–2.0 0.01–0.05

103.2 86.0

12.6 3 2

848642

Cabbage Etofenprox α-CO

0.01–2.0 0.1

93.9 110

2 1

820337


0.01–0.1 0.01–0.1

108.2 101.1

2 2

843554


0.01–2.0 0.01

94.5 114.4

2 1

820326


0.01–0.1 0.01–0.1

104.1 106.7

2 2

843555

Rape seed Etofenprox α-CO

0.01–2.0 0.01–0.1

78.4 94.7

2 2

807017


0.01–2.0 0.01–0.1

73.4 103.3

2 2

843556


0.01–2.0 0.01–0.1

88.7 87.3

2 2

807028


0.01–2.0 0.01–0.1

79.2 97.5

2 2

843557

Rape seed oil Etofenprox α-CO

0.01–2.0 0.01–0.1

85.1 91.1

2 2

807028

Rape seed cake Etofenprox α-CO

0.01–2.0 0.01–0.1

97.1 98.6

2 2

807028

Rape seed oil (refined) Etofenprox α-CO

0.01–2.0 0.01–0.1

85.1 91.1

2 2

807028

Etofenprox 439

Method 692-G (plant matrices)

A modification of the GC/MS method MT-200102, omitting the initial alumina column clean-up step was independently validated by Class, 2003 [Ref: 692-G] to analyse plant matrices for both the parent compound and its α-CO metabolite and is summarized above. The LOQ was 0.01 mg/kg and the validation studies were conducted with samples of apples, cucumbers and rape seed fortified at 0.01 mg/kg and 0.1 mg/kg with recovery rates of 69–109% (etofenprox) and 72–106% (α-CO). Recoveries are summarized below.

Table 32 Validation recovery values for analytical method 692-G for the determination of etofenprox and its α-CO metabolite in crops using using GC/MS [Ref: 692-G]

Matrix Analyte Fortification level [mg/kg] Recovery rate [%] RSD [%] n mean range

Cucumber Etofenprox 0.01 0.10

78 74

74–83 70–83

5 7

5 5

α-CO 0.01 0.10

85 91

72–92 83–100

9 7

5 5


94 98

90–98 88–109

4 9

5 5

α-CO 0.01 0.10

92 97

88–96 89–106

4 8

5 5

Rape seed Etofenprox 0.01 0.10

81 81

76–89 68–93

6 13

5 5

α-CO 0.01 0.10

89 88

85–96 74–101

6 13

5 5

Crop field trials conducted in Europe were analysed using method 692-G and concurrent

recovery values in these trials are summarized below.

Table 33 Concurrent recovery values for GC/MS analytical method 692-G for the determination of etofenprox and its α-CO metabolite in crops




0.01–1.0 0.01–1.0

82.5 75.3

10.5 9.5

4 4

05-alpha-22


0.01–1.0 0.01–1.0

98.5 75.2

14.1 16

4 4

05-alpha-21

Raisin Etofenprox α-CO

0.01–1.0 0.01–1.0

91.7 77.5

18.9 3 2

05-alpha-21


0.01–0.1 0.01–0.1

84 73

2 2

05-alpha-21

Red wine Etofenprox α-CO

0.01–0.1 0.01–0.1

75 77.5

2 2

05-alpha-21


0.01–0.5 0.01–0.5

92 80

11.7 19.6

6 6

05-alpha-20

Apple washing water Etofenprox α-CO

0.01–0.1 0.01–0.1

89.5 96

2 2

05-alpha-20

Apple juice Etofenprox α-CO

0.01–0.1 0.01–0.1

83.5 72.5

2 2

05-alpha-20

Apple pureé Etofenprox α-CO

0.01–0.1 0.01–0.1

83.5 58

2 2

05-alpha-20

Apple dried pomace Etofenprox α-CO

0.01–0.1 0.01–0.1

89 74.5

2 2

05-alpha-20


0.01–1.0 0.01–1.0

91.8 86.5

11.8 16.9

6 6

05-alpha-19

440 Etofenprox



Peach washing water Etofenprox α-CO

0.01–0.1 0.01–0.1

81 78.9

2 2

05-alpha-19


0.01–0.1 0.01–0.1

78 76

2 2

05-alpha-19

Method SIPCAM 1354 (plant matrices)

An HPLC method (SIPCAM 1354) was developed and reported by Freschi, 2003 [Ref: SIP1354, SIP1355] to measure residues of etofenprox and its α-CO metabolite in plant matrices and is summarized above. This method has been validated for apples and peaches using acetonitrile:water (75:25) eluent. The LOQ for both analytes was 0.01 mg/kg. Validation recoveries are summarized below.

Table 34 Validation recovery values for analytical method SIPCAM 1354 for the determination of etofenprox and its α-CO metabolite in crops using using HPLC




Peach Etofenprox 0.01 0.1

94 92.4

90.8–96.1 89–95.7

2.5 3.6

4 4

SIP1355

α-CO 0.01 0.1

85 89.4

72.6–90.5 85.4–92.2

9.8 3.4

4 4


89.9 90.7

84.2–95.1 77.2–96.7

5.0 10.1

4 4

SIP1354

α-CO 0.01 0.1

91 88.9

83.4–95.5 76.1–94.1

5.8 9.7

4 4

Crop field trials conducted in Europe were analysed using method SIPCAM 1354 and

concurrent recovery values in these trials are summarized below.

Table 35 Concurrent recovery values for HPLC-UV analytical method SIPCAM 1354 for the determination of etofenprox and its α-CO metabolite in crops




0.01–1.0 0.01–1.0

88.1 82.1

8.7 9.7

5 5

ET4 + SIP 1327 ET 4/I/01, ET 4/I/02


0.01–0.1 0.01–0.1

92.4 88.2

2 2

ET4 + SIP 1327 ET 4/I/01

Young wine Etofenprox α-CO

0.01–0.1 0.01–0.1

83.2 83.7

2 2

ET4 + SIP 1327 ET 4/I/01

Bottled wine Etofenprox α-CO

0.01–0.1 0.01–0.1

82.6 82.9

2 2

ET4 + SIP 1327 ET 4/I/01


0.01–0.5 0.01–0.5

91.2 89.7

7.1 5.0

7 7

ET5/ME


0.01–0.1 0.01–0.1

89.4 95.8

5.6 4.1

4 4

ET2/PC


0.01–0.1 0.01–0.1

89.6 88.2

4.9 4.8

6 6

ET5/PS


0.01–1.0 0.01–1.0

86.9 86.6

4.6 9.7

5 5

ET1/PC


0.01–1.0 0.01–1.0

91.6 89.4

6.0 4.4

6 6

ET4

Etofenprox 441




0.01–0.11 0.01–0.11

92.3 93.2

2 2

ET1/PC


0.01–0.1 0.01–0.1

92.8 93.2

2 2

ET4


0.01–0.11 0.01–0.11

84.9 85.8

2 2

ET1/PC


0.01–0.1 0.01–0.1

75.5 76.6

2 2

ET4


0.01–1.0 0.01–1.0

90.3 91.1

0.7 0.6

3 3

ET1/PC


0.01–0.1 0.01–0.1

90.7 91.4

2 2

ET4

Method 236C-136 (plant matrices)

An LC-MS/MS method (236C-136) was developed and reported by Nixon, 2006 [Ref: 236C-136] to measure residues of etofenprox and its α-CO metabolite in rice and rice straw and is summarized above. An independent validation of this method for brown rice has been conducted by Cassidy, 2006 [Ref: 019820-1], using methylene chloride as the SPE eluent. The LOQ for both analytes was 0.01 mg/kg. Validation recoveries are summarized below.

Table 36 Validation recovery values for analytical method 236C-136 for the determination of etofenprox and its α-CO metabolite in crops using using LC-MS/MS




Rice Etofenprox 0.01 0.1

95 95

88.3–97.9 94.4–99.1

3.4 3.2

7 5

236C-136

α-CO 0.01 0.1

101 82.5

93.3–107 85.4–92.2

4.9 3.9

7 5

Rice straw Etofenprox 0.01 0.1

86 91

84–92.5 90–94

3.4 1.8

7 5

236C-136

α-CO 0.01 0.1

101 82.5

93–107 79–87

4.9 3.9

7 5

Brown rice Etofenprox 0.01 0.02 0.1

84 97 109

71–91 90–102 90–118

8a 5a 11a

5 5 5

019820-1

α-CO 0.01 0.02 0.1

92 98 108

83–111 93–104 93–117

11a 4a 9a

5 5 5

Rice grain Etofenprox α-CO

0.01–0.1 0.01–0.1

91 83.6

2 2

43406A027


0.01–0.1 0.01–0.1

92.6 87.6

7.5 a 10.4 a

6 6

43406A028


0.01–0.1 0.01–0.1

102.3 91.3

9.0 a 8.4 a

12 12

43406A029

Rice hulls Etofenprox α-CO

0.01–0.1 0.01–0.1

102.6 76.5

8.4 a 8.2 a

4 4

43406A029

Rice bran Etofenprox α-CO

0.01–0.1 0.01–0.1

91.8 84.1

15.8 a 13.4 a

4 4

43406A029

a Standard deviation

442 Etofenprox

Method MT 791245 (animal matrices)

A GC/MS method (MT-200104) was developed by the manufacturer (Mitsui, 2001) to measure residues of etofenprox and its α-CO metabolite in meat [Ref: 200104M], milk [Ref: 200104M] and eggs [Ref 200104E]. A modification of this method was developed and reported by Wolf, 2003 [Ref 791245] and is summarized above. The LOQ for all animal matrices tested was 0.01 mg/kg. This method has been validated by Class, 2003 [Ref: P/B 701-G] and validation recovery results are summarized below.

Table 37 Recovery values with analytical method MT-791245 for the determination of etofenprox and its α-CO metabolite in animal matrices using using GC/MS

Matrix Analyte

Fortification level [mg/kg]

Recovery rate [%] RSD [%] n Reference mean range

Cattle meat Etofenprox 0.01 0.5 5.0

101.9 95.8 97.3

98.2–103.8 93.4–101.2 96.8–97.8

2.1 3.3 0.4

5 5 5

791245

α-CO 0.01 0.1 1.0

104.0 101.5 105.7

93.7–109.1 96.4–109.5 104.6–107.0

6.2 4.9 0.9

5 5 5

Chicken meat Etofenprox 0.01 0.5 5.0

103.0 97.5 100.2

98.1–108.9 92.0–105.3 95.9–107.0

4.1 5.9 4.4

5 5 5

α-CO 0.01 0.1 1.0

104.4 89.6 99.1

102.3-105.8 82.7–101.8 90.5–103.2

1.3 9.0 5.2

5 5 5

Egg (yolk) Etofenprox 0.01 0.5 5.0

93.3 78.5 90.6

85.0–101.5 71.2–99.4 73.3–104.7

7.2 15.0 17.5

5 5 5

α-CO 0.01 0.1 1.0

104.4 83.3 74.5

99.9–106.9 74.5–107.3 71.8–76.8

2.6 16.3 2.5

5 5 5

Egg (white) Etofenprox 0.01 0.5 5.0

102.9 77.8 79.1

100.3–104.7 74.5–80.3 75.9–81.6

1.7 2.7 3.3

5 5 5

α-CO 0.01 0.1 1.0

102.5 78.4 78.8

101.0-105.2 74.2–80.2 75.4–82.4

1.6 3.1 3.4

5 5 5

Milk Etofenprox 0.01 0.5 5.0

78.9 94.0 92.8

72.8–84.3 91.6–95.1 91.5–93.8

6.7 1.5 1.1

5 5 5

α-CO 0.01 0.1 1.0

75.2 106.3 97.6

70.5–82.0 101.3-108.6 95.9–98.6

7.1 3.1 1.2

5 5 5

Cattle fat Etofenprox 0.01 0.5 5.0

102.2 96.6 89.6

97.5–106.2 95.2–97.3 86.9–95.4

4.1 1.9 3.9

5 5 5

α-CO 0.01 0.1 1.0

99.8 91.2 90.5

99.4–100.2 90.9–91.4 87.7–98.8

0.4 0.2 5.2

5 5 5

Milk Etofenprox 0.01 0.10

94 91

91-103 79-100

5 11

5 5

P/B 701-G

α-CO 0.01 0.10

91 87

83-103 75-99

10 12

5 5

Cattle meat Etofenprox 0.01 0.10

90 84

69-106 74-97

19 10

5 5

α-CO 0.01 0.10

76 88

65-87 85-99

11 7

5 5

Etofenprox 443

Matrix Analyte

Fortification level [mg/kg]

Recovery rate [%] RSD [%] n Reference mean range

Egg Etofenprox 0.01 0.10

78 80

65-95 77-82

14 2

5 5

α-CO 0.01 0.10

95 93

88-104 85-97

6 5

5 5

Cattle fat Etofenprox 0.01 0.10

73 79

70-76 66-105

3 19

5 5

α-CO 0.01 0.10

85 83

72-98 73-100

11 13

5 5

Enforcement methods

Multi-residue methods (Plant matrices)

The suitability of the US PAM multi-residue method was assessed in a study with rice in 2007 by Martin & Nixon [Ref: 236C-146]. Etofenprox and α-CO could be extracted from rice as prescribed in Protocol D and E of the Manual and although both compounds failed Protocol C, they can be analysed by GC-MSD.

Stability of residues in stored analytical samples

Plant matrices

The Meeting received information on the stability of residues of etofenprox and its α-CO metabolite in various substrates with a high water content (apples, cabbage, peaches), a high starch content (rice grain), a high oil content (rape seed) and a high acid content (grapes) stored at freezer temperatures for 7–24 months.

In a series of studies on rape seed (Wolf, 2003) [Ref: 802888 & 810900], cabbages (Wolf, 2005) [Ref: 843556], apples and peaches (Dubey, 2005) [Ref: A-32-02-03], grape bunches (Wolf, 2005) [Ref: 843535] and in rice grain and straw (MacGregor & Nixon, 2006 [Ref: 236C-138], homogenised samples of cabbages, apples, peaches and grapes and un-homogenised samples of rape seed were fortified separately with 0.5 mg/kg etofenprox and α-CO dissolved in acetone. Rice (grain) was fortified separately with 0.1 mg/kg etofenprox and α-CO dissolved in methanol.

Initial 0-day samples were taken for analysis and other samples were stored in sealed containers in the dark at about -20 °C for up to 24 months, with samples taken for analysis at intervals of 1 (rape seed, cabbage, grape), 3, 6, 7 (rice grain) 12, 18 and 24 months. At each storage interval, the stored samples and freshly fortified control samples were analysed using LC/MS/MS Method 236C-136 for rice and GC/MS Method MT-200102 for the other commodities.

During storage, no significant decomposition was observed and the concentrations of etofenprox and α-CO showed no significant difference when compared to the freshly fortified samples. The results, expressed in terms of the corrected recovery are summarised below.

Table 38 Residue stability of etofenprox in plant matrices spiked at 0.5 mg/kg (0.1 mg/kg in rice grain) and stored ≤ -20 °C

Commodity Storage interval (months)

Residues in spiked sample (mg/kg)

Residues in stored samples (mg/kg) % Residues remaining

Procedural recovery (%)

Grape 0 1 3 6 12 18 24

0.376 0.452 0.532 0.532 0.48 0.503

0.533; 0.542; 0.399; 0.55 0.357; 0.418; 0.395 0.479; 0.443; 0.447 0.544; 0.538 0.531; 0.535; 0.534 0.482; 0.487; 0.485 0.398; 0.402; 0.386

101 78 91 108 107 97 79

101 75 91 106 106 96 101

444 Etofenprox





Apple 0 1 3 6 12 18 24

- 0.408 0.449 0.373 0.393 0.438

0.523; 0.523; 0.551 - 0.469; 0.431 0.47; 0.466 0.426; 0.422 0.436; 0.414 0.477; 0.442

106 90 94 85 85 92

106 82 90 75 79 88

Peach 0 1 3 6 12 18 24

- 0.405 0.413 0.391 0.461 0.446

0.525; 0.537; 0.528 - 0.43; 0.429 0.446; 0.443 0.421; 0.323 0.407; 0.426 0.426; 0.493

106 86 89 75 83 92

106 81 83 78 92 89

Cabbage 0 1 3 6 12 18 24

0.519 0.358 0.543 0.517 0.499 0.488

0.504; 0.478; 0.496; 0.497 0.53; 0.546; 0.551 0.355; 0.357 0.457; 0.437; 0.422 0.428; 0.437; 0.433 0.499; 0.507; 0.466 0.404; 0.406; 0.355

99 109 71 88 87 98 78

99 104 72 109 103 100 98

Rape (seed) 0 1 3 6 12 18 24

0.538 0.541 0.453 0.364 0.531 0.362

0.536; 0.541; 0.537; 0.441 0.482; 0.45; 0.463 0.54; 0.533; 0.545 0.43; 0.445; 0.363 0.477; 0.39; 0.433 0.47; 0.487; 0.503 0.529; 0.425; 0.393

103 93 108 83 87 97 90

103 108 108 91 73 106 73

Rice (grain) 0 14 weeks 30 weeks

0.098; 0.105 0.099; 0.1

0.096; 0.099; 0.094; 0.091; 0.094 0.113; 0.109; 0.109 0.094; 0.098; 0.095

95 110 95

95 101 99

Rice (straw) 0 14 weeks 30 weeks

0.098; 0.098 0.085; 0.083

0.091; 0.09; 0.091; 0.09; 0.094 0.099; 0.096; 0.0.094 0.079; 0.077; 0.083

91 96 80

91 98 84

Table 39 Residue stability of the α-CO metabolite of etofenprox residues in plant matrices spiked at 0.5 mg/kg (0.1 mg/kg in rice grain) and stored ≤ -20 °C





Grape 0 1 3 6 12 18 24

0.355 0.357 0.489 0.42 0.55 0.384

0.592; 0.534; 0.507; 0.458 0.431; 0.389; 0.424 0.354; 0.353 0.463; 0.51; 0.505 0.369; 0.353; 0.355 0.55; 0.537; 0.534 0.41; 0.438; 0.457

105 83 71 99 72 108 87

105 71 71 98 84 110 77

Apple 0 1 3 6 12 18 24

- 0.356 0.437 0.354 0.403 0.424

0.382; 0.424; 0.452 - 0.352; 0.384 0.445; 0.505 0.399; 0.473 0.418; 0.407 0.449; 0.44

84 74 95 87 83 89

84 75 87 71 81 85

Etofenprox 445





Peach 0 1 3 6 12 18 24

- 0.39 0.504 0.364 0.372 0.443

0.378; 0.487; 0.404 0.39; 0.388 0.465; 0.422 0.485; 0.327 0.427; 0.383 0.491; 0.414

85 78 89 81 81 91

85 78 101 73 74 89

Cabbage 0 1 3 6 12 18 24

0.42 0.351 0.532 0.514 0.479 0.437

0.538; 0.491; 0.499; 0.454 0.441; 0.467; 0.538 0.355; 0.368; 0.492 0.538; 0.542; 0.545 0.539; 0.518; 0.464 0.457; 0.466; 0.471 0.395; 0.462; 0.457

99 96 81 108 101 93 88

99 84 70 106 103 96 87

Rape (seed) 0 1 3 6 12 18 24

0.471 0.052 (2) 0.449 0.526 - 0.532

0.532; 0.523; 0.544; 0.512 0.516; 0.531; 0.532 0.525; 0.551; 0.497 0.463; 0.416; 0.489 0.474; 0.36; 0.352 0.453; 0.525; 0.518 0.537; 0.515

106 105 105 91 79 100 105

106 94 105 90 105 - 107

Rice (grain) 0 14 weeks 30 weeks

0.099; 0.098 0.098; 0.099

0.087; 0.084; 0.079; 0.081; 0.081 0.097; 0.095; 0.098 0.091; 0.097; 0.096

83 96 94

83 98 99

Rice (straw) 0 14 weeks 30 weeks

0.084; 0.091 0.091; 0.086

0.1; 0.078; 0.082; 0.08; 0.079 0.098; 0.098; 0.0.097 0.077; 0.081; 0.084

84 8 81

84 88 89

USE PATTERNS

Information on etofenprox GAP in Brazil, Europe, Japan and USA was provided to the Meeting. Relevant uses listed on authorised labels or advised by national authorities are summarised in the following table.

Table 40 Registered uses of etofenprox

Crop Country Application Max no

PHI (days)

Comments

form method kg ai/ha kg ai/hL water L/ha

Apple Italy EC foliar 0.008-0.014 1500 7 Apple Japan WP foliar 0.01-0.02 3 14 Apricot Italy EC foliar 0.014 1500 7 Bean Brazil SC foliar 0.03-0.12 250 3 4-15 d intervals if needed Bean Brazil EC foliar 0.15 300-400 3 7-15 d intervals if needed Bean (Broad) Italy EC foliar 0.014 700-1500 7 Bean (common)

Japan EC foliar 0.02 2 7

Bean (French) Italy EC foliar 0.014 700-1500 7 Brassica (head)

Italy EC foliar 0.014 700-1500 7 incl Br sprouts

Cabbage Japan AL, EC, SC, EW

foliar 0.01-0.02 3 3

Cherry Italy EC foliar 0.014 1500 7 incl cherry plum

446 Etofenprox


PHI (days)

Comments


Citrus Brazil SC foliar 0.001-0.0025 8 L/plant 2 7 31d intervals (borer) 7d intervals (leafhopper)

Citrus Italy EC foliar 0.014 1500 7 Citrus Japan EC foliar 0.01-0.02 3 14 Cotton Brazil SC foliar 0.05-0.075 150 15 Cotton Brazil EC foliar 0.075-0.3 300-400 15 5-15 d intervals Eggplant Italy EC foliar 0.014-0.028 700-1500 3 Grape Italy EC foliar 0.014-0.028 14 Lentils Italy EC foliar 0.014 700-1500 7 incl chick peas, lupin Maize Brazil SC foliar 0.01-0.014 300 3 Maize Brazil EC foliar 0.021-0.03 300-400 3 7-15 d intervals if needed Maize Italy EC foliar 0.014 700-1500 28 Maize Japan EC foliar 0.02 4 7 Oilseed Rape Germany EC foliar 0.058 200 2 - min 7 d interval. No PHI

required, recommended use is before flowering

Oilseed Rape France EC foliar 0.059 1 70 Peach Italy EC foliar 0.014 1500 7 Peach Japan WP foliar 0.01-0.02 14 Pear Italy EC foliar 0.008-0.014 1500 7 Pear Japan WP foliar 0.01-0.02 3 14 Pepper Italy EC foliar 0.014-0.028 700-1500 7 Plum Italy EC foliar 0.014 1500 7 Potato Italy EC foliar 0.008-0.014 700-1500 7 Potato Japan EW,

EC foliar 0.01-0.02 3 14

Potato Japan SC foliar 0.02 3 7 Pulses Japan EC 0.02 2 14 except soya bean (dry) &

adzuki bean Rice Japan EC, SC aerial 0.1 1.25 8 2 21 Rice Japan EW aerial 0.1 1.25 8 2 14 Rice Japan SC aerial 0.1 10 1 3 14 Rice Japan GR broadcast 0.3-0.45 3 21 Rice Japan EW,

EC, SC, WP

foliar 0.01-0.02 3 21

Rice Japan EC, EW, SC

foliar lv 0.083-0.17 0.033-0.067 250 3 21

Rice Japan SC foliar lv 0.086-0.13 0.034-0.052 250 3 21 Rice USA GR aerial 0.2-0.3 1 60 Apply 1-7 d after

flooding Soya bean Brazil EC, SC foliar 0.01-0.15 100-250 15 7-15 d intervals if needed Soya bean (dry)

Japan EW, SC

aerial 0.1-0.2 1.25-2.5 8 2 14

Soya bean (dry)

Japan EC, SC aerial lv 0.1 1.25 8 2 21

Soya bean (dry)

Japan EW foliar 0.1 2 14

Etofenprox 447


PHI (days)

Comments


Soya bean (dry)

Japan EC, SC foliar 0.01-0.02 2 14

Soya bean (immature)

Japan EC, EW

foliar 0.01-0.02 2 21

Soya bean (immature)

Japan SC foliar 0.02 2 14

Tomato Brazil SC foliar 0.02 300 3 Tomato Brazil EC foliar 0.012-0.018 600-1200 3 7-15 d intervals if needed Tomato Italy EC foliar 0.014 700-1500 3 Tomato Japan EC,

EW foliar 0.01-0.02 2 1

Wheat Brazil SC foliar 0.03 100 16 Wheat Brazil EC foliar 0.03-0.15 100-250 15 7-15 d intervals if needed Wheat Japan EW,

SC aerial 0.1 1.25 8 2 14

Wheat Japan EC, EW

foliar 0.01 2 14

RESIDUES RESULTING FROM SUPERVISED TRIALS

The Meeting received information on supervised field trials involving foliar sprays or broadcast granular applications of etofenprox to the following crops.

Crop Commodity Region/Country Table No.

Citrus Orange Brazil Table 41

Pome fruit Apple Brazil, Europe Table 42

Stone fruit Peach Brazil, Europe Table 43

Berries & small fruit Grapes Europe Table 44

Brassica vegetables Cabbage Europe Table 45

Fruiting vegetables Tomato Brazil Table 46

Legume vegetables Beans (without pods) Brazil Table 47

Root & tuber vegetables Potato Brazil Table 48

Pulses Soya bean (dry) Brazil Table 49

Cereals Wheat, Maize, Rice Rice (broadcast granules)

Brazil, Japan USA

Tables 50-52 Table 53

Seeds for beverages and sweets

Coffee Brazil Table 54

Oilseeds Cotton, Oilseed rape Brazil, Europe Tables 55-56

The supervised trials were well documented with laboratory and field reports. Laboratory

reports included procedural recoveries from spiking at residue levels similar to those occurring in samples from the supervised trials. Dates of analyses or duration of residue sample storage were also

448 Etofenprox

provided. Intervals of freezer storage between sampling and analysis were recorded for all trials and were covered by the conditions of the freezer storage stability studies.

In trials where duplicate field samples from an unreplicated plot were taken at each sampling time and analysed separately, each figure is presented individually but the mean value (calculated before rounding) has been used for intake risk assessment and residue estimation. Where replicate analyses were conducted on the same field samples, the mean residue values have been reported. Although trials included control plots, no control data are recorded in the tables unless residues in control samples exceeded the LOQ. In such cases, the residues found are noted as “c= x mg/kg”.

When residues were not detected they are shown as below the LOQ (e.g. < 0.01 mg/kg). In some trials, samples were taken just before the final application and then, again on the same day after the spray had dried. In the data tables the notation for these two sampling times is '-0' and '0' respectively.

Residue data are recorded unadjusted for recovery and rounded (generally to two significant digits) with the results used in estimating maximum residue limits being underlined.

Oranges

Results from supervised trials from Brazil on oranges were provided to the Meeting. In these trials, 2 applications of etofenprox (EC formulations) were made to mature trees 11-18 days apart as foliar sprays using motorised knapsack sprayers or hand guns, applying 0.01 or 0.02 kg ai/hL in 2000 L water/ha. Plot sizes in these trials ranged from 21-42 square metres and involved at least 4 trees per plot.

Unreplicated samples of at least 2 kg fruit were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 12 months before whole fruit analysis for etofenprox using GC/MSD (Method MT-GLC), with an LOQ of 0.05 mg/kg.

Table 41 Residues in oranges from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

ORANGE Country, year Location (variety)

Application PHI, (days)

Residues (mg/kg) Reference & Comments

form no kg ai/ha kg ai/hL

water (L/ha)

matrix Etofenprox α-CO

Brazil, 2000 Cosmopólis (SP) (Pera Rio)

10 SC 2 0.2 0.01 2000 7 Fruit 0.06 RS391 Plantec-02

10 SC 2 0.4 0.02 2000 7 Fruit 0.2 RS391 Plantec-03

Brazil, 2000 Engenherio Coelho (SP) (Natal)

10 EC 2 0.2 0.01 2000 7 Fruit 0.08 RS390 Plantec-02


Brazil, 2000 Iracemápolis (SP) (Natal)

10 EC 2 0.2 0.01 2000 0 3 7

Fruit 0.1 0.1 0.1

RS389 Plantec-02


Apple

Results from supervised trials from Southern Europe and Brazil on apples were provided to the Meeting. In the European trials, etofenprox (EC formulations) was applied to mature trees, once

Etofenprox 449

before the end of flowering and then twice just before harvest (7 days apart) using airblast or pressurised knapsack single nozzle sprayers. Plot sizes in these trials ranged from 40–240 square metres and involved at least 7 trees per plot. In the Brazilian trials, two preharvest applications were made, 14 days apart, to 12 square metre plots (6 trees) using pressurised knapsack single-nozzle sprayers.

Unreplicated samples of at least 12 fruit (min 2 kg) were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 5 months before whole fruit analysis for etofenprox and its α-CO metabolite using HPLC Method SIPCAM 1354 or using the GC/MS methods MT-200102 or 692-G (LOQs of 0.01 mg/kg). Whole fruit from the Brazilian trials were analysed for etofenprox using the GC-MSD method MT-GLC (LOQ 0.5 mg/kg).

Table 42 Residues in apples from supervised trials in France, Italy, Spain and Brazil involving foliar applications of etofenprox (EC formulations)

APPLE Country, year Location (variety)




water (L/ha)

matrix Etofenprox (mean) α-CO

Italy, 2002 Camposanto (Gala max)

28 EC 1+ 2

0.22 0.175

0.015 0.012

1500 1500

7 Fruit 0.13 0.13 0.02 ET5/ME ET5/I/10ME

Italy, 2002 Begosso di Terrazzo (Imperatore)

28 EC 1+ 2

0.21 0.175

0.014 0.012

1500 1500

7 Fruit 0.24, 0.27 0.26 0.03, 0.03 ET5/ME ET5/I/11ME

Italy, 2002 Fabbrico (Royal Gala)

28 EC 1+ 2

0.22 0.18

0.018 0.015

1200 1200

0 1 3 5 7

Fruit 0.12 0.14 0.09 0.13 0.1

< 0.01 0.01 < 0.01 0.01 0.01

ET5/ME ET5/I/12ME

Italy, 2002 Salerno Sul Lambro (Golden B)

28 EC 1+ 2

0.21 0.175

0.021 0.018

1000 1000

0 1 3 5 7

Fruit 0.39 0.48 0.37 0.23 0.34

0.02 0.02 0.02 0.01 0.02

ET5/ME ET5/I/13ME

Spain, 2003 Aitona (Golden Supreme)

30 EC 1+ 2

0.22 0.19

0.015 0.013

1500 1500

0 1 3 5 7

Fruit 0.46 0.43 0.39 0.39 0.25

0.04 0.05 0.05 0.05 0.04

848643 A/SP/I/03/52

Spain, 2003 Villena (Golden)

30 EC 1+ 2

0.23 0.19

0.015 0.012

1500 1500

0 1 3 5 7

Fruit 0.32 0.23 0.41 0.50 0.2

0.03 0.03 0.05 0.06 0.03

848643 A/SP/I/0/3/53

Spain, 2003 Termens (Golden Shumutti)

30 EC 1+ 2

0.23 0.19

0.015 0.012

1500 1500

7 Fruit 0.18 0.03 848643 A/SP/I/03/54 processing study

Spain, 2003 Villena (Starking)

30 EC 1+ 2

0.227 0.18

0.014 0.012

1500 1450

7 Fruit 0.22 0.04 848643 A/SP/I/03/55 processing study

France (S), 2005 Mauguio (Gala galaxy)

30 EC 2 0.16 0.011 1400 6 Fruit 0.12, 0.11 0.12 0.02, 0.02 05-alpha-20 X05 170 520 FR01 processing study

450 Etofenprox





water (L/ha)


Brazil, 2006 Veranópolis (Fuji)

10 EC 2 0.225 0.015 1500 7 Fruit < 0.5 RS927 R/05/RS927/PL Dose X

10 EC 2 0.45 0.03 1500 7 Fruit < 0.5 RS927 R/05/RS927/PL Dose2 X

Brazil, 2005 Gentil (Fuji)

10 EC 2 0.225 0.015 1500 7 Fruit < 0.5 RS926 R/05/RS926/PL Dose X

10 EC 2 0.45 0.03 1500 7 Fruit < 0.5 RS926 R/05/RS926/PL Dose 2X

Brazil, 2006 Iracemápolis (Ana)

10 EC 2 0.225 0.015 1500 0 3 5 7 10

Fruit < 0.5 < 0.5 < 0.5 < 0.5 < 0.5

RS925 R/05/RS925/PL Dose X

10 EC 2 0.45 0.03 1500 7 Fruit < 0.5 RS925/PL R/05/RS925/PL Dose 2X

Peach

Results from supervised trials from Southern Europe and Brazil on peaches were provided to the Meeting. In these trials, 2 applications of etofenprox (EC formulation) were applied to mature trees, 7 days apart (in the European trials) or 15 days apart (in the Brazilian trials) as foliar sprays using pressurised knapsack sprayers or motorised airblast backpack sprayers, applying 0.175–0.225 kg ai/ha (and 0.45 kg ai/ha in the Brazilian trials) in 1250–1500 L water/ha. Plot sizes in these trials ranged from 30–245 square metres and involved at least 4 trees per plot.

Unreplicated samples of at least 12 fruit (min 2 kg) were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up 12 months (European trials) or 7 months (Brazilian trials) before analysis. In the European trials, etofenprox and its α-CO metabolite were measured using either the GC/MS methods MT-200102 or 692-G or the HPLC method SIPCAM 1354 with LOQs of 0.01 mg/kg. In the Brazilian trials, residues of etofenprox were measured using the GC/MSD method MT-GLC with an LOQ of 0.05 mg/kg.

Table 43 Residues in peaches from supervised trials in Italy, Spain, France and Brazil involving foliar applications of etofenprox (EC formulations)

PEACH Country, year Location (variety)



form no kg ai/ha kg ai/hL water (L/ha)


Spain, 2001 Alfarras (Amarillo de Octubre)

28 EC 2 0.21 0.015 1400 0 1 3 7

Fruit 0.58 0.42 0.45 0.37

0.03 0.02 0.03 0.04

ET1/PC & SIP 1314 ET1/PC/S-01

Spain, 2001 Cieza (Miraflores)

28 EC 2 0.22 0.017 1500 7 Fruit 0.23 0.03 ET1/PC & SIP 1314 ET1/PC/S-02 processing study

Etofenprox 451






Spain, 2002 Albesa Peach (Rojo de Albesa)

28 EC 1+ 1

0.205 0.22

0.016 0.017

1250 1250

0 1 3 7

Fruit 0.53 0.14 0.26 0.2

0.03 0.01 0.03 0.02


Spain, 2002 Cieza (Murcia) (Andros)

28 EC 2 0.22 0.017 1250 7 Fruit 0.14 0.02 ET2/PC & SIP 1395 ET2/PC/S-02

Italy, 2001 Imola Peach (Elegant Lady)

28 EC 2 0.21 0.014 1500 7 Fruit 0.01 0.02 ET4/SIP & SIP 1326 ET4/I/03PS processing study

Italy, 2001 Terrazzo Peach (Maria Delizia)

28 EC 2 0.21 0.014 1500 0 1 3 6

Fruit 0.23 0.25 0.25 0.18

0.01 0.02 0.02 0.02

ET4/SIP & SIP 1326 ET4/I/04PS

Italy, 2002 Valeccio sul Mincio (Lagnasco)

28 EC 2 0.175 0.012 1500 6 Fruit 0.18 0.02 ET5/PS & SIP 1351 ET5/I/07P

Italy, 2002 Castel Bolognese (Big Top)

28 EC 2 0.21 0.014 1500 7 Fruit 0.08 < 0.01 ET5/PS & SIP 1351 ET5/I/08P

Italy, 2002 Salerano sul Lambro (Franca)

28 EC 2 0.175 0.018 1000 0 1 3 5 7

Fruit 0.20 0.14 0.10 0.10 0.08

< 0.01 < 0.01 < 0.01 < 0.01 < 0.01

ET5/PS & SIP 1351 ET5/I/09PS

Spain, 2003 Chulilla (Federica)

30 EC 2 0.22 0.014 1500 0 1 3 5 7 0 1 3 5 7

Fruit with stone Fruit without stone

0.51 0.52 0.35 0.4 0.21 0.56 0.58 0.39 0.44 0.23

0.05 0.06 0.05 0.07 0.04 0.05 0.07 0.05 0.07 0.05

848642 A/SP/I/03/51 processing study

France, 2005 Mauguio (Red Top)

30 EC 2 0.2 0.013 1500 7 Fruit 0.1, 0.09 0.1 0.02, 0.01 05-alpha-19 X05 170 519 FR01 processing study

France, 2005 Grenade (Red Star)

30 EC 2 0.2 0.013 1500 -0 0 1 3 7

Fruit 0.07 0.26 0.12 0.14 0.12

0.02 0.02 0.01 0.02 0.02

05-alpha-19 X05 170 519 FR02

Brazil, 2005 Gentil (Biuti)

10 SC 2 0.225 0.015 1500 7 Fruit < 0.05 RS921 R/05/RS921/PL Dose X

10 SC 2 0.45 0.03 1500 7 Fruit < 0.05 RS921 R/05/RS921/PL Dose 2X

452 Etofenprox






Brazil, 2005 Jundiaí (Biuti)


10 SC 2 0.450 0.03 1500 7 Fruit < 0.05 RS920 R/05/RS920/PL Dose 2X

Brazil, 2005 Iracemápolis (Biuti)


10 SC 2 0.45 0.03 1500 7 Fruit < 0.05 RS919 Trial R/05/RS919/PL Dose 2X

Grapes

Results from supervised trials from Europe on grapes were provided to the Meeting. In these trials, foliar applications of etofenprox (EC formulations) were applied to grape vines using motorised knapsack (airblast) sprayers with single nozzles or by hand gun, applying 0.14–0.17 kg ai/ha in 970–1140 L water/ha. Plot sizes in these trials ranged from 15–400 square metres. In these trials, 2 applications were made late season (at 14 day intervals in the month before harvest) and in some trials 2 earlier applications were made over the flowering to early fruit formation period.

Unreplicated samples of at least 12 bunches or part-bunches (approx 1–2 kg) were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 12 months before analysis for etofenprox and its α-CO metabolite using GC/MS Methods MT-200102 or 692-G or HPLC Method SIPCAM 1354 with reported LOQs of 0.01 mg/kg .

Table 44 Residues in grapes from supervised trials in France, Germany, Italy and Spain involving foliar applications of etofenprox (EC formulations)

GRAPE Country, year Location (variety)




water (L/ha)


Italy, 2001 Costiglione d’Asti (Barbera)

30 EC 4 0.15 0.015 1000 0 3 7 14

Grapes 3.1 2.2 1.6 1.4

0.34 0.4 0.38 0.31

820350 A/IT/I/01/41 processing study

30 EC 2 0.15 0.015 1000 82 Grapes 0.12 0.02 820350 A/IT/I/01/41 15d before 3rd application

Italy, 2001 Peverati Casssine (Moscato Bianco)

30 EC 4 0.15 0.015 1000 14 Grapes 0.96 0.08 820350 A/IT/I/01/42 15d before 3rd application processing study

30 EC 2 0.15 0.015 1000 44 Grapes 0.13 0.02 820350 A/IT/I/01/42

Italy, 2002 Cassine (Moscato Bianco)

30 EC 4 0.15 0.015 1000 0 3 7 14

Grapes 0.28 0.3 0.53 0.35

< 0.01 0.03 0.04 0.03

843559 A/IT/I/02/35

Etofenprox 453





water (L/ha)



30 EC 4 0.15 0.015 1000 14 Grapes 0.29 0.08 843559 A/IT/I/02/36

Spain, 2001 Los ruices (Planta Nova)

30 EC 2 0.15 0.015 1000 95 Grapes 0.04 0.01 820348 A/SP/I/01/43 14d before 3rd application

30 EC 4 0.15 0.015 1000 0 3 7 14

Grapes 0.55 0.5 0.56 0.39

0.1 0.12 0.22 0.14

820348 A/SP/I/01/43

Spain, 2001 Casas de Eufemia (Tempranillo)

30 EC 2 0.15 0.015 1000 60 Grapes 0.04 0.02 820348 A/SP/I/01/44 14d before 3rd application

30 EC 4 0.15 0.015 1000 14 Grapes 0.39 0.18 820348 A/SP/I/01/44

Italy, 2001 Pietra de’ Giorgi (Barbera)

28 EC 2 0.14 0.014 1000 14 Grapes 0.25 0.03 ET4 & SIP1327 ET4/I/01 VI processing study

Italy, 2001 Brentino Belluno (Lambrusco frastagliato)

28 EC 2 0.14 0.014 1000 0 1 3 7 15

Grapes 1.3 1.4 1.0 0.92 0.63

0.05 0.08 0.08 0.09 0.08

ET4 ET4/I/02 VI

France (S) 2002 Parlesboscq (Ugni Blanc)

30 EC 4 0.15 0.015 1000 0 3 7 14

Grapes 0.56 0.8 0.58 0.53

0.03 0.05 0.05 0.06

843558 A/SF/I/02/37

France (S), 2002 Monreal du Gers (Cabernet Sauvignon)

30 EC 4 0.15 0.015 1000 14 Grapes 0.38 0.06 843558 A/SF/I/02/38

France (N), 2004 Nogent l’Abbesse (Chardonnay / 41 B)

30 EC 2 0.15 0.015 1000 14 Grapes 0.36 0.02 04-alpha-08 S04LKRALPHGG58

France (N), 2004 Sainte Marie la Blanche (Pinot noir)

30 EC 2 0.15 0.015 1000 14 Grapes 0.26 0.03 04-alpha-08 S04LKRALPHTD62

France (N), 2004 Pommard (Pinot noir)

30 EC 2 0.15 0.015 1000 0 3 7 14

Grapes 0.31 0.35 0.37 0.32

< 0.01 0.02 0.02 0.03

04-alpha-08 S04LKRALPHTD63

France (N), 2005 Furdenheim (Pinot noir)

30 EC 1+ 1

0.19 0.17

0.018 0.015

1000+ 1120

-0 0 3 7 14

Grapes 0.41 0.52 0.78 0.43 0.35

0.04 0.06 0.09 0.05 0.07

05-alpha-21 A5115 AN1 processing study

France (N), 2005 Bennwihr (Riesling)

30 EC 1+ 1

0.18 0.15

0.018 0.015

1000 1000

14 Grapes 0.32 0.04 05-alpha-21 A5115 AL1

France (N), 2005 Reuilly (Pinot noir)

30 EC 1+ 1

0.2 0.15

0.019 0.015

1000 1000

13 Grapes 0.21 0.045 05-alpha-21 A5115 CT1 processing study

454 Etofenprox





water (L/ha)


Germany, 2005 Ihringen (Pinot blanc)

30 EC 1+ 1

0.18 0.16

0.018 0.015

1000 1000

-0 0 3 7 14

Grapes 0.16 0.32 0.5 0.33 0.28

0.02 0.04 0.09 0.08 0.05

05-alpha-22 A5116 GE1

Germany, 2005 Hammelburg (Domina)

30 EC 1+ 1

0.18 0.15

0.018 0.015

1000 1000

14 Grapes 0.2 0.08 05-alpha-22 A5116 HA1

Cabbages, Head

Results from supervised trials from Europe on head cabbages were provided to the Meeting. In these trials, 2 applications of etofenprox (EC formulations) were made 14–16 days apart to 25–38 square metre cabbage plots using knapsack sprayers with 4-nozzle mini-booms or single nozzle hand lances motorised backpack sprayers, applying 0.14–0.16 kg ai/ha in 200-300 L water/ha.

Unreplicated samples of at least 12 half-cabbages (without wrapper leaves) were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 9 months before analysis for etofenprox and its α-CO metabolite using GC/MS Method MT-200102 (LOQs of 0.01 mg/kg).

Table 45 Residues in head cabbage from supervised trials in Italy and Spain involving foliar applications of etofenprox (EC formulations)

CABBAGE Country, year Location (variety)




water (L/ha)


Italy, 2001 Lavagna (F1 KK Cross)

30 EC 2 0.14 0.075 200 0 1 3 7

Heads a 0.14 0.85 0.67 0.12

< 0.01 0.05 0.04 0.02

Report 820337 Trial A/IT/I/01/45

Italy, 2001 Colombano (Quisto F1)

30 EC 2 0.15 0.075 200 7 Heads 0.04 < 0.01 Report 820337 Trial A/IT/I/01/46

Italy, 2002 Carmagnola (Winchester)

30 EC 2 0.15 0.075 200 0 1 3 7

Heads 0.04 0.03 0.02 0.01

< 0.01 < 0.01 < 0.01 < 0.01

Report 843554 Trial A/IT/I/02/41

Italy, 2002 Roverchiara (Hybrid variety)

30 EC 2 0.15 0.075 200 7 Heads 0.01 < 0.01 Report 843554 Trial A/IT/I/02/42

Spain, 2001 Almussafes (Centinel)

30 EC 2 0.15 0.05 300 0 1 3 7

Heads < 0.01 0.01 < 0.01 < 0.01

< 0.01 < 0.01 < 0.01 < 0.01

820326 A/SP/I/01/47

Spain, 2001 Almussafes (Bronco)

30 EC 2 0.15 0.05 300 7 Heads < 0.01 < 0.01 820326 A/SP/I/01/48

Spain, 2001 Picassent (Centinel)

30 EC 2 0.16 0.05 300 0 1 3 7

Heads 0.03 0.03 0.02 < 0.01

< 0.01 < 0.01 < 0.01 < 0.01

843555 A/SP/I/02/39

Etofenprox 455

CABBAGE Country, year Location (variety)




water (L/ha)


Spain, 2001 Meliana (Bronco)

30 EC 2 0.15 0.05 300 7 Heads < 0.01 < 0.01 843555 A/SP/I/02/40

a with wrapper leaves

Tomato

Results from supervised trials from Brazil on tomatoes were provided to the Meeting. In these trials, 3–4 applications of etofenprox (EC formulations) were made to tomatoes at 14–15 day intervals as foliar sprays using pressurised plot sprayers or backpack sprayers with single nozzles or 3-nozzle mini-booms to apply 0.2–0.6 kg ai/ha in 200 or 1000 L water/ha.

Samples of at least 2 kg mature fruit were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 5 months before whole fruit analysis for etofenprox using GC Method MT-GLC with NPD detection with LOQs of 0.01 mg/kg (0.02 mg/kg in the 1991 study).

Table 46 Residues in tomatoes from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

TOMATO Country, year Location (variety)




water (L/ha)


Brazil, 1999 Engenheíro Coelho (Raysa)

10 SC 4 0.2 0.02 1000 0 3 7

Fruit 0.02 < 0.01 < 0.01

119/99 125 aS/99-20

10 SC 4 0.4 0.04 1000 0 3 7

Fruit 0.05 0.01 < 0.01

119/99 125 aS/99-40

Brazil, 1999 Bragança Paulista (Raysa)

10 SC 4 0.2 0.02 1000 3 Fruit < 0.01 120/99 126 aS/99-20

10 SC 4 0.4 0.04 1000 3 Fruit < 0.01 120/99 126 aS/99-40

Brazil, 1999 Engenheíro Coelho (Raysa)

30 EC 4 0.3 0.03 1000 3 Fruit < 0.01 RS141 Plantec 126 aS/99-30

30 EC 4 0.6 0.06 1000 3 Fruit < 0.01 RS141 Plantec 126 aS/99-60

Brazil, 1991 Municipality of Piedade (Cláudia)

30 EC 3 0.3 0.15 200 1 3 7

Fruit 0.23 0.21 0.12

USP-1991-T Trial 1

30 EC 3 0.6 0.3 200 1 3 7

Fruit 0.42 0.35 0.31

USP-1991-T Trial 2

Potato

Results from supervised trials from Brazil on potatoes were provided to the Meeting. In these trials, 1 or 4 applications of etofenprox (EC formulations) were made to potato plants as foliar sprays using

456 Etofenprox

knapsack or pressurised plot sprayers with single nozzles or mini-booms (3–6 nozzles), applying 0.18–1.8 kg ai/ha in 500–600 L water/ha. Plot sizes in these trials ranged from 20–30 square metres.

Unreplicated samples of about 2 kg tubers were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 20 months before analysis for etofenprox using GC/MS Method MT-GLC or MT-PBI with LOQs of 0.05 mg/kg (0.01 mg/kg in the 1999 studies).

Table 47 Residues in potatoes from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

POTATO Country, year Location (variety)



form no kg ai/ha

kg ai/hL

water (L/ha)


Brazil, 2001 Iracemápolis (Binje)

30 EC 4 0.9 0.15 600 15 Tuber < 0.05 RS538 R/99/RS538/Plantec-02

30 EC 4 18 0.3 600 15 Tuber < 0.05 RS538 R/99/RS538/Plantec-03

Brazil, 1999 Bragança Paulista (Bintje)

30 EC 4 0.3 0.05 600 3 Tuber < 0.01 126/99 R/99/RS140/Plantec R/99/RS140/Plantec-01

30 EC 4 0.6 0.1 600 3 Tuber < 0.01 126/99 R/99/RS140/Plantec R/99/RS140/Plantec-02

Brazil, 1993 São Manuel (Achat)

30 EC 1 0.18 0.04 500 15 30

Tuber < 0.05 < 0.05

USP-1994-P Trial 1

30 EC 1 0.36 0.07 500 15 30

Tuber < 0.05 < 0.05

USP-1994-P Trial 2

Beans (dry)

Results from supervised trials from Brazil on beans (without pods) were provided to the Meeting. In these trials, 2–3 applications of etofenprox (EC formulations) were made to bean plants as foliar sprays using knapsack or pressurised plot sprayers with single nozzle lances or 3–6 nozzle hand-held booms, applying 0.15 or 0.3 kg ai/ha in 400 L water/ha. Plot sizes in these trials ranged from 30–120 square metres.

Unreplicated samples of 1–2 kg of bean seeds were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 8 months before seeds were analysed for etofenprox using GC/MS Method MT-GLC or MT-PBI with LOQs of 0.05 mg/kg (0.01 mg/kg in the 1999 studies).

Table 48 Residues in beans from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

BEAN Country, year Location (variety)




water (L/ha)


Brazil, 1999 Fazenda Capuava Paranapanema (Pérola)

30 EC

3 0.15 0.038 400 3 seeds < 0.01 RS144 R/99/RS144/Plantec-01

Etofenprox 457

BEAN Country, year Location (variety)




water (L/ha)


30 EC


Brazil, 1996 Fazenda Lajeado (Carioca 80)

30 EC

2 0.675 0.15 450 3 7 14 21

seeds < 0.05 < 0.05 < 0.05 < 0.05

2273/97 Trial 1

30 EC

2 1.35 0.3 450 3 7 14 21

seeds < 0.05 < 0.05 < 0.05 < 0.05

2273/97 Trial 2

Brazil, 2004 Assis Chateaubriand (Carioca 80)

10 SC

2 0.15 0.075 200 3 seeds < 0.05 RS725 R/04/RS725/PL-02

10 SC

3 0.3 0.15 200 3 seeds < 0.05 RS725 R/04/RS725/PL-03

Brazil, 2004 Iracemápolis (Carioca 80)

10 SC

3 0.15 3 seeds < 0.05 RS723 R/04/RS723/PL-02

10 SC

3 0.3 3 seeds < 0.05 RS723 R/04/RS723/PL-03

Brazil, 2004 Vargem Grande Do Sul (Pérola)

10 SC

3 0.15 0.038 400 3 seeds < 0.05 RS724 R/04/RS724/PL-02

10 SC

3 0.3 0.075 400 3 seeds < 0.05 RS724 R/04/RS724/PL-03

Brazil, 2001 Iracemápolis (Pérola)

10 SC


10 SC

3 0.3 0.075 400 3 seeds 0.4 RS533 R/99/RS533/Plantec-03

Brazil, 1999 Fazenda Lageado, Botucatu (Carioca)

10 SC

3 0.15 0.038 400 0 3 7

seeds < 0.01 < 0.01 < 0.01

32/99 Trial 111-01-X

10 SC

3 0.3 0.075 400 0 3 7

seeds < 0.01 < 0.01 < 0.01

32/99 111-02-2X

Brazil, 1999 Fazenda Capuava, Paranapanema (Pérola)

10 SC

3 0.15 0.038 400 3 seeds < 0.01 118/99 124 aS/99-02

10 SC

3 0.3 0.075 400 3 seeds < 0.01 118/99 124 aS/99-03

Soya bean (dry)

Results from supervised trials from Brazil on soybeans were provided to the Meeting. In these trials, 1–3 applications of etofenprox (EC formulations) were made to 24–100 square metre soya bean plots as foliar sprays using pressurised plot sprayers with single nozzle or 3–6 nozzle mini-booms to apply 0.015–0.6 kg ai/ha in 100–300 L water/ha.

458 Etofenprox

Unreplicated samples of 1–6 kg beans (without pods) were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 20 months (35 months in one trial) before analysis for etofenprox using Method MT-GLC or GC/MS Method 692-G. The reported LOQs in these studies was 0.05 mg/kg (0.01 mg/kg in the 1999 studies).

Table 49 Residues in soya bean (dry) from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

SOYA BEAN Country, year Location (variety)




water (L/ha)


Brazil, 1999 Engenherio Coelho (BR16)

30 EC

2 0.15 0.06 250 15 pods & seeds

< 0.01 122/99 R/99/RS143/Plantec R/99/RS143/Plantec-01

30 EC

2 0.3 0.12 250 15 pods & seeds

< 0.01 122/99 R/99/RS143/Plantec R/99/RS143/Plantec-02

Brazil, 1991 Municípo de Passo Fundo (Cobb)

30 EC

1 0.3 0.30 100 7 seeds < 0.05 USP-1995-S Trial 1

30 EC

1 0.6 0.60 100 7 seeds < 0.05 USP-1995-S Trial 2

Brazil, 2004 Assis Chateaubriant (Embrapa 48)

10 SC 3 0.5 0.025 200 15 seeds < 0.05 RS727 R/04/RS727/PL-02

10 SC 3 0.1 0.05 200 15 seeds < 0.05 RS727 R/04/RS727/PL-03

Brazil, 2004 Iracemápolis (BR16)

10 SC 3 0.5 0.025 200 15 seeds < 0.05 RS726 R/04/RS727/PL-02

10 SC 3 0.1 0.05 200 15 seeds < 0.05 RS726 R/04/RS727/PL-03

Brazil, 2004 Gentil (Embrapa 48)

10 SC 3 0.5 0.025 200 15 seeds < 0.05 RS728 R/04/RS728/PL-02

10 SC 3 0.1 0.05 200 15 seeds < 0.05 RS728 R/04/RS728/PL-03

Brazil, 2004 Gentil (BR154)

10 SC 3 0.15 0.0075 200 15 seeds < 0.05 RS534B R/99/RS534B/Plantec-02

10 SC 3 0.3 0.015 200 15 seeds < 0.05 RS534B R/99/RS534B/Plantec-03

Brazil, 2001 Iracemápolis (IAC 19)

10 SC 3 0.15 0.0075 200 15 seeds < 0.05 RS534 R/99/RS534/Plantec-02-15

10 SC 3 0.3 0.015 200 15 seeds 0.07 RS534 R/99/RS534/Plantec-03-15

Brazil, 1999 Botucatu (BR16)

10 SC 2 0.15 0.0075 300 7 15 21

seeds < 0.01 < 0.01 < 0.01

34/99 Trial 110-01-X

10 SC 2 0.3 0.015 300 7 15 21

seeds < 0.01 < 0.01 < 0.01

34/99 Trial 110-01-2X

Etofenprox 459

SOYA BEAN Country, year Location (variety)




water (L/ha)


Brazil, 1999 Engenheíro Coelho (BR16)

10 SC 2 0.15 0.0075 300 7 seeds < 0.01 117/99 Trial 123 aS/99-X

10 SC 2 0.3 0.015 300 7 seeds < 0.01 Report 117/99 Trial 123 aS/99-2X

Maize

Results from supervised trials from Brazil on maize were provided to the Meeting. In these trials, 2 applications of etofenprox (EC formulations) were made to maize plants, 7–17 days apart as foliar sprays using pressurised plot sprayers or knapsack sprayers with hand lances or mini-booms (3–4 nozzles), applying 0.03 and 0.06 kg ai/ha in 200–400 L water/ha. Plot sizes in these trials ranged from 24–120 square metres.

Unreplicated samples of at least 1 kg of maize kernels were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 16 months before analysis for etofenprox using GC/MS Method MT-GLC or MT-PBI, with LOQs of 0.05 mg/kg (0.01 mg/kg in the 1999 studies).

Table 50 Residues in maize kernels from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations).

MAIZE Country, year Location (variety)




water (L/ha)


Brazil, 1999 São Manuel (SL 678 Brascalb)

30 EC

2 0.03 0.015 200 3 kernels < 0.01 RS142 Plantec-01

30 EC

2 0.06 0.03 200 3 kernels < 0.01 RS142 Plantec-02

Brazil, 1995 Botucatu (ICI 8452)

30 EC

2 0.03 0.008 380 3 7 14 21

kernels < 0.05 < 0.05 < 0.05 < 0.05

2144/96 Trial 1

30 EC

2 0.06 0.016 380 3 7 14 21

kernels < 0.05 < 0.05 < 0.05 < 0.05

2144/96 Trial 2

Brazil, 2004 Assis Chateaubriand (DKB 950)

10 SC 2 0.03 0.015 200 3 kernels < 0.05 RS730 R/04/RS730/PL-02


Brazil, 2004 Gentil (DKB 950)



Brazil, 2004 Iracemápolis (C 333 B)

10 SC 2 0.03 3 kernels < 0.05 RS729 R/04/RS731/PL-02

10 SC 2 0.06 3 kernels < 0.05 RS729 R/04/RS731/PL-03

460 Etofenprox

MAIZE Country, year Location (variety)




water (L/ha)


Brazil, 2001 Iracemápolis (Dekalb 733 (Hybrid))

10 SC 2 0.03 0.01 300 3 kernels < 0.05 RS535/PL R/99/RS535/Plantec-02-03

10 SC 2 0.06 0.02 300 3 kernels < 0.05 RS535/PL R/99/RS535/Plantec-03-03

Brazil, 1999 Fazenda Lageado, Botucatu Estado de Sao Paulo (Cargill 435)

10 SC 2 0.02 0.008 250 0 3 7

kernels < 0.01 < 0.01 < 0.01

33/99 109-01-X

10 SC 2 0.04 0.016 250 0 3 7

kernels < 0.01 < 0.01 < 0.01

33/99 109-02-2X

Brazil, 1999 São Manuel (XL 678 Braskalb)

10 SC 2 0.02 0.008 250 3 kernels < 0.01 116/99 122 aS/99-02

10 SC 2 0.04 0.016 250 3 kernels < 0.01 116/99 122 aS/99-03

Wheat

Results from supervised trials from Brazil on wheat were provided to the Meeting. In these trials, 2–3 applications of etofenprox (EC formulations) were made to wheat plants at 9–15 day intervals as foliar sprays using pressurised plot sprayers with 2–3 nozzle mini-booms, applying 0.03–0.06 kg ai/ha in 200 L water at one site and 0.45–0.9 kgai/ha in 100 L water at the other site. Plot sizes in these trials ranged from 50–64 square metres.

Unreplicated samples of at least 1 kg mature grain were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 12 months before analysis for etofenprox using Method MT-GLC (LOQ of 0.01 mg/kg).

Table 51 Residues in wheat from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

WHEAT Country, year Location (variety)




water (L/ha)


Brazil, 1998 Botucatu (IAC 24)

30 EC 2 0.03 0.015 200 3 Grain < 0.01 RS145 Plantex-01

30 EC 2 0.06 0.03 200 3 Grain < 0.01 RS145 Plantex-02

Brazil, 1990 Passo Fundo (CEP 24)

30 EC 3 0.45 0.45 100 16 25 36

Grain 0.4 0.06 < 0.02

USP-1991-W Trial 1

30 EC 3 0.9 0.9 100 16 25 36

Grain 1.0 0.1 0.02

USP-1991-W Trial 2

Etofenprox 461

Rice

Results from supervised trials on upland rice from Brazil and paddy rice from Japan and USA were provided to the Meeting. In the Brazilian trials, 2 applications of etofenprox (SC formulations) were made to 120 square metre plots as foliar sprays, 15 days apart using pressurised single-nozzle plot sprayers to apply 0.1 or 0.2 kg ai/ha in 200 L water/ha. Unreplicated samples of at least 1 kg grain were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 4 months before analysis for etofenprox using Method MT-GLC with an LOQ of 0.05 mg/kg.

In four reverse decline trials on rice in Japan, 20–75 square metre plots were treated with 3 foliar sprays of 0.125–0.2 kg ai/ha etofenprox (SC or EW formulations) using pressurised knapsack sprayers and hand-held 1–4 nozzle mini-booms. Treatments were applied 14 days apart, with the last applications on different plots being 14, 21 or 28 days before harvest. At harvest, plant samples were cut, allowed to dry in the sun or in greenhouses for 1–4 weeks before threshing and hulling. Samples of brown rice were then taken, frozen within 24 hours and stored at -18°C or below for up to 5 months before analysis by two independant laboratories for etofenprox using Method MT-PBI (with an LOQ of 0.02 mg/kg).

Table 2. Residues in rice from supervised trials in Brazil and Japan involving foliar applications of etofenprox (EC or SC formulations)

RICE Country, year Location (variety)




water (L/ha)


Brazil, 2006 Botucatu (IAC 25)

10 SC 2 0.1 0.05 200 14 Grain < 0.05 RS924 R/05/RS924/PL Dose X

10 SC 2 0.2 0.1 200 14 Grain < 0.05 RS924 R/05/RS924/PL Dose 2X

Brazil, 2006 Londrina (IAC 25)

10 SC 2 0.1 0.05 200 14 Grain < 0.05 RS923 R/05/RS923/PL Dose X



10 SC 2 0.1 0.05 200 0 3 7 14 21

Grain < 0.05 < 0.05 < 0.05 < 0.05 < 0.05



Japan, 1988 Chiba (Hatsu-boshi) Paddy rice

10 EW 3 0.2 0.01 2000 14 brown rice 0.11, 0.06 0.09 MT25 25-1-A Results from 2 independent laboratories

10 EW 3 0.2 0.01 2000 21 brown rice 0.07, 0.04 0.05 MT25 25-1-B Results from 2 independent laboratories

10 EW 3 0.2 0.01 2000 28 brown rice 0.04, 0.03 0.04 MT25 25-1-C Results from 2 independent laboratories

462 Etofenprox





water (L/ha)


Japan, 1988 Ishikawa (Koshi-hikari) Paddy rice


10 EW 3 0.2 0.01 2000 21 brown rice 0.06, 0.04 0.05 MT25 25-2-B Results from 2 independent laboratories

10 EW 3 0.2 0.01 2000 28 brown rice 0.02, 0.02 0.02 MT25 25-2-C Results from 2 independent laboratories



10 EW 3 0.15 0.01 1500 21 brown rice 0.01, 0.02 0.02 2.2

MT39 39-1-B Results from 2 independent laboratories

10 EW 3 0.15 0.01 1500 28 brown rice < 0.01, 0.01 0.01 MT39 39-1-C Results from 2 independent laboratories

Japan, 1991 Miyazaki (Koshi-hikari) Paddy rice


10 EW 3 0.15 0.01 1500 21 brown rice 0.01, 0.01 0.01 39 39-2-B Results from 2 independent laboratories

10 EW 3 0.15 0.01 1500 28 brown rice < 0.01, 0.01 0.01 MT39 39-2-C Results from 2 independent laboratories

Japan, 1993 Chiba (Koshi-hikari) Paddy rice

10 EW 3 0.125 0.05 250 21 brown rice 0.02, 0.02 0.02 MT49 49-1

Japan, 1993 Nagano (Koshi-hikari) Paddy rice

10 EW 3 0.125 0.05 250 21 brown rice 0.02, 0.02 0.02 MT49 49-2

Japan, 1995 Ibaraki (Koshi-hikari) Paddy rice

6.2 SC 3 0.13 0.052 250 21 brown rice 0.01, 0.02 0.02 MT61 61-1

Etofenprox 463





water (L/ha)


6.2 SC 3 0.13 0.01 1250 21 brown rice 0.01, 0.01 0.01 MT61 61-2


6.2 SC 3 0.13 0.052 250 21 brown rice < 0.01, 0.01 0.01 MT61 61-3

6.2 SC 3 0.13 0.01 1250 21 brown rice 0.02, 0.02 0.02 MT61 61-4

In a series of trials from USA, single broadcast treatments of etofenprox (granules) were

applied by hand-spinner or tractor-mounted granule spreaders over the top of the rice plants, 2–41 days after the plots were flooded. Plot sizes ranged from 93–2000 square metres. Plots were either harvested by hand and threshed using a stationary thresher or were combine harvested, with samples of grain (min 1 kg) being frozen within 24 hours of sampling and stored at -18°C or below for up to 3 months before analysis for etofenprox and its α-CO metabolite using LC/MS/MS Method 236C-136 (LOQs of 0.01 mg/kg).

Table 53 Residues in rice from supervised trials in USA involving broadcast granular applications of etofenprox




form no kg ai/ha matrix Etofenprox (mean) α-CO

USA, 2005 Arkansas (Wells)

1.5% G 1 0.3 72 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A027 860.1500-05-434-06C-06

USA, 2005 California (M206)

1.5% G 1 0.3 97 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A027 860.1500-05-434-06C-07


0.9% G 1 0.3 80 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-08


0.9% G 1 0.316 79 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-09

USA, 2006 Arkansas (Clearfield XL8)

0.9% G 1 0.309 98 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-10

USA, 2006 Arkansas (Francis)

0.9% G 1 0.29 77 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-11


0.9% G 1 0.3 83 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-12

USA, 2006 Louisiana (Cocodrie)

0.9% G 1 0.276 76 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-13

USA, 2006 Louisiana (Cheniere)

0.9% G 1 0.3 65 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-14


0.9% G 1 0.3 52 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-15

464 Etofenprox





USA, 2006 Mississippi (Cocodrie)

0.9% G 1 0.306 72 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-16


0.9% G 1 0.318 87 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-17


0.9% G 1 0.326 94 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-18

USA, 2006 Missouri (Wells)

0.9% G 1 0.3 89 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-19

USA, 2006 Texas (Cocodrie)

0.9% G 1 0.3 64 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-20


0.9% G 1 0.3 63 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 < 0.01, < 0.01

43406A028 860.1500-06-434-06C-21


0.9% G 1 0.3 103 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-22


0.9% G 1 0.295 102 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-23

USA, 2006 Arkansas (Cheniere)

0.9% G 1 1.5 86 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A029 860.1520-06-434-06C-01


0.9% G 1 1.5 64 grain < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A029 860.1520-06-434-06C-02

Coffee beans

Results from supervised trials from Brazil on coffee were provided to the Meeting. In these trials, 2 applications of etofenprox (EC formulations) were made to coffee trees 15–17 days apart as foliar sprays using pressurised or motorised knapsack sprayers and hand lances, applying 0.1 or 0.2 kg ai/ha in 500 L water/ha. Plot sizes in these trials were 7–8 square metres and involved at least 6 trees per plot.

Unreplicated samples of 1 kg coffee beans (with pulp removed) were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 16 months before analysis for etofenprox using GC Method 692-G with a reported LOQ of 0.05 mg/kg.

Table 54 Residues in coffe beans from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

COFFEE BEANS Country, year Location (variety)




water (L/ha)


Brazil, 2005 Machado (Mundo Novo)

10 SC

2 0.1 0.02 500 14 Beans < 0.05 RS930 R/05/RS930/PL Dose X

Etofenprox 465

COFFEE BEANS Country, year Location (variety)




water (L/ha)


10 SC

2 0.2 0.04 500 14 Beans < 0.05 RS930 R/05/RS930/PL Dose 2X

Brazil, 2005 Espírito Santo do Pinhal (Mundo Novo)

10 SC

2 0.1 0.02 500 14 Beans < 0.05 RS929 R/05/RS929/PL Dose X

10 SC


Brazil, 2005 Iracemápolis (Mundo Novo)

10 SC

2 0.1 0.02 500 0 7 14 21 28

Beans < 0.05 < 0.05 < 0.05 < 0.05 < 0.05


10 SC


Brazil, 2001 Machado (Mundo Novo)

10 SC

2 0.1 0.02 500 3 7 14

Beans < 0.05 < 0.05 < 0.05

RS428 R/99/RS428/Plantec-02

10 SC

2 0.2 0.04 500 7 Beans < 0.05 RS428 R/99/RS428/Plantec-03

Brazil, 2001 Espírito Santo Do Pinhal (Mundo Novo)

10 SC


10 SC


Brazil, 2001 Iracemápolis (Catuai)

10 SC


10 SC


Rape seed

Results from supervised trials from Germany and UK, on winter rape were provided to the Meeting. In these trials, a single application of etofenprox (EC formulations) was made at flowering (GS BBCH 64–65) as foliar sprays using pressurised knapsack sprayers with 3–6 nozzle mini-booms, applying about 0.06 kg ai/ha in 400 L water/ha. Plot sizes in these trials ranged from 50–144 square metres.

Unreplicated samples of rape seed (0.5–1 kg) were harvested from each plot by hand or using a plot combine harvester, frozen within 24 hours of sampling and stored at -18°C or below for up to 22 months before whole analysis for etofenprox and its α-CO metabolite using GC/MS Method MT-200102 (LOQ of 0.01 mg/kg.

466 Etofenprox

Table 55 Residues in winter rape seed from supervised trials in Germany and UK involving foliar applications of etofenprox (EC formulations)

RAPE SEED Country, year Location (variety)




water (L/ha)


Germany, 2001 Otzberg (Express)

30 EC 1 0.058 0.015 400 50 Seeds < 0.01 < 0.01 807017 A/GE/I/01/28

Germany, 2001 Reichenberg (Naplus)

30 EC 1 0.059 0.015 400 61 Seeds < 0.01 < 0.01 807017 A/GE/I/01/29

Germany, 2002 Otzberg (Express)

30 EC 1 0.056 0.015 370 67 Seeds < 0.01 (mean) < 0.01 843556 A/GE/I/02/3

Germany, 2002 Reichenberg (Naplus)

30 EC 1 0.064 0.015 420 70 Seeds < 0.01 < 0.01 843556 A/GE/I/02/32

UK, 2001 Castor (Apex)

30 EC 1 0.059 0.015 400 77 Seeds < 0.01 < 0.01 807028 A/UK/I/01/26

UK, 2001 Upton Snodsbury (Pronto)

30 EC 1 0.057 0.015 400 79 Seeds < 0.01 < 0.01 807028 A/UK/I/01/27

UK, 2002 Upton Snodsbury (Courage)

30 EC 1 0.06 0.015 400 89 Seeds < 0.01 < 0.01 843557 A/UK/I/02/33

UK, 2002 Castor (Apex)

30 EC 1 0.06 0.015 400 89 Seeds < 0.01 < 0.01 843557 A/UK/I/02/33

Cotton seed

Results from supervised trials from Brazil on cotton seed were provided to the Meeting. In these trials, 3–4 applications of etofenprox (EC or SC formulations) were applied to cotton plants 7 or 14 days apart as foliar sprays using pressurised backpack plot sprayers with 1–6 nozzle lances or mini-booms to apply 200–250 L spray mix/ha. Plot sizes in these trials ranged from 40–120 square metres.

Unreplicated samples of at least 1 kg delinted cotton seed were taken from each plot, frozen within 24 hours of sampling and stored at -18°C or below for up to 18 months before analysis for etofenprox using either GC/ECD Method MT-GLC (LOQ 0.01 mg/kg) or GC/MS Method 692-G (LOQ 0.05 mg/kg).

Table 56 Residues in cotton seed from supervised trials in Brazil involving foliar applications of etofenprox (EC formulations)

COTTON SEED Country, year Location (variety)




water (L/ha)


Brazil, 1999 Engenheiro Coelho (Delta Pine)

30 EC 4 0.3 0.12 250 15 Seeds < 0.01 RS135 Plantec-02 Spray intervals 39:14:14 days

30 EC 4 0.6 0.24 250 15 Seeds < 0.01 RS135 Plantec-03

Etofenprox 467

COTTON SEED Country, year Location (variety)




water (L/ha)


Brazil, 2004 Assis Chateaubriand (Delta Pine)

10 SC 3 0.15 0.075 200 15 Seeds < 0.05 RS733 R/04/RS733/PL-02

10 SC 3 0.3 0.15 200 15 Seeds < 0.05 RS733 R/04/RS733/PL-03

Brazil, 2004 Iracemápolis (Delta Opa)

10 SC 3 0.15 0.075 200 15 Seeds < 0.05 RS732 R/04/RS732/PL-02

10 SC 3 0.3 0.15 200 15 Seeds < 0.05 RS732 R/04/RS732/PL-03

Brazil, 2004 Jaiba (Delta Pine)

10 SC 3 0.15 0.075 200 15 Seeds < 0.05 RS734 R/04/RS734/PL-02

10 SC 3 0.3 0.15 200 15 Seeds < 0.05 RS734 R/04/RS734/PL-03


10 SC 3 0.075 0.038 200 15 Seeds 0.08 RS536 R/99/RS536/PL-02

10 SC 3 0.15 0.075 200 15 Seeds 0.4 RS536 R/99/RS536/PL-03

Brazil, 2001 Jaíba (Delta Opa)

10 SC 3 0.075 0.038 200 15 Seeds 0.1 RS536B R/99/RS536B/PL-02

10 SC 3 0.15 0.075 200 15 Seeds 0.5 RS536B R/99/RS536B/PL-03

Brazil, 1999 Botucatu (Delta Pine)

10 SC 3 0.075 0.038 200 15 Seeds < 0.01 RS153 R/99/RS153/PL-01

10 SC 3 0.15 0.075 200 15 Seeds < 0.01 RS153 R/99/RS153/PL-02

Brazil, 1999 Engenheiro Coelho (Delta Pine)

10 SC 3 0.075 0.038 200 15 Seeds < 0.01 RS152 R/99/RS152/PL-02

10 SC 3 0.15 0.075 200 15 Seeds < 0.01 RS152 R/99/RS152/PL-03

Miscellaneous animal feed commodities

Rice straw

Results from supervised trials on paddy rice from Japan and USA were provided to the Meeting. In four reverse decline trials from Japan, 20–75 square metre plots were treated with 3 foliar sprays of 0.125–0.2 kg ai/ha etofenprox (SC or EW formulations) using pressurised knapsack sprayers and hand-held 1–4 nozzle mini-booms. Treatments were applied 14 days apart, with the last applications on different plots being 14, 21 or 28 days before harvest. At harvest, plant samples were cut, allowed to dry in the sun or in greenhouses for 1–4 weeks before threshing and hulling. Samples of rice straw (min 2 kg) were then taken, frozen within 24 hours and stored at -18°C or below for up to 5 months

468 Etofenprox

before analysis by two independant laboratories for etofenprox using Method MT-PBI (with an LOQ of 0.02 mg/kg).

Table 57 Residues in rice straw from supervised trials in Japan involving foliar applications of etofenprox (EC or SC formulations)

RICE STRAW Country, year Location (variety)




water (L/ha)



10 EW 3 0.2 0.01 2000 14 rice straw 2.9, 3.0 3.0 MT25 25-1-A Results from 2 independent laboratories

10 EW 3 0.2 0.01 2000 21 rice straw 1.4, 2.4 1.9 MT25 25-1-B Results from 2 independent laboratories

10 EW 3 0.2 0.01 2000 28 rice straw 0.96, 0.82 0.89 MT25 25-1-C Results from 2 independent laboratories

Japan, 1988 Ishikawa (Koshi-hikari) Paddy rice








Japan, 1991 Miyazaki (Koshi-hikari) Paddy rice


Etofenprox 469





water (L/ha)


10 EW 3 0.15 0.01 1500 21 rice straw 1.7, 1.7 1.7 39 39-2-B Results from 2 independent laboratories


Japan, 1993 Chiba (Koshi-hikari) Paddy rice

10 EW 3 0.125 0.05 250 21 rice straw 1.8 1.8 MT49 49-1


10 EW 3 0.125 0.05 250 21 rice straw 4.3 4.3 MT49 49-2

Japan, 1995 Ibaraki (Koshi-hikari) Paddy rice

6.2 SC 3 0.13 0.052 250 21 rice straw 2. 6 2.6 MT61 61-1

6.2 SC 3 0.13 0.01 1250 21 rice straw 1.5 1.5 MT61 61-2


6.2 SC 3 0.13 0.052 250 21 rice straw 2.0 2.0 MT61 61-3

6.2 SC 3 0.13 0.01 1250 21 rice straw 3.3 3.3 MT61 61-4

In a series of trials from USA, single broadcast treatments of etofenprox (granules) were

applied by hand-spinner or tractor-mounted granule spreaders over the top of the plants, 2–41 days after the plots were flooded. Plot sizes ranged from 93–2000 square metres. Plots were either harvested by hand and threshed using a stationary thresher or were combine harvested, with samples of straw (min 0.5 kg) being frozen within 24 hours of sampling and stored at -18°C or below for up to 3 months before analysis for etofenprox and its α-CO metabolite using LC/MS/MS Method 236C-136 (LOQs of 0.01 mg/kg).

Table 58 Residues in rice straw from supervised trials in USA involving broadcast granular applications of etofenprox






1.5% G 1 0.3 72 rice straw 0.01, < 0.01 0.01 0.01, < 0.01 43406A027 860.1500-05-434-06C-06


1.5% G 1 0.3 97 rice straw 0.02, 0.03 0.02 < 0.01, < 0.01 43406A027 860.1500-05-434-06C-07


0.9% G 1 0.3 80 rice straw < 0.01, 0.01 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-08

470 Etofenprox






0.9% G 1 0.316 79 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-09

USA, 2006 Arkansas (Clearfield XL8)

0.9% G 1 0.309 98 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-10


0.9% G 1 0.3 83 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-12

USA, 2006 Louisiana (Cocodrie)

0.9% G 1 0.276 76 rice straw 0.06, 0.01 0.04 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-13


0.9% G 1 0.3 65 rice straw 0.03, 0.02 0.025 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-14


0.9% G 1 0.3 52 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-15


0.9% G 1 0.306 72 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-16


0.9% G 1 0.326 94 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-18

USA, 2006 Missouri (Wells)

0.9% G 1 0.3 89 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-19


0.9% G 1 0.3 64 rice straw 0.02, < 0.01 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-20


0.9% G 1 0.3 63 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-21


0.9% G 1 0.3 103 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-22


0.9% G 1 0.295 102 rice straw < 0.01, < 0.01 < 0.01 < 0.01, < 0.01 43406A028 860.1500-06-434-06C-23

FATE OF RESIDUES IN STORAGE AND IN PROCESSING

Nature of the Residue in Processing

The hydrolytic behaviour of etofenprox and its α-CO metabolite under simulated processing conditions was investigated in an aqueous hydrolysis radiolabel study reported by Adam (2006) [Ref: A39598].

Duplicate samples of standard buffer solutions at pH values of 4, 5 and 6 were fortified with [14C α]-etofenprox or [14C α]-α-CO. The fortified samples (about 0.1 mg ai/litre) were subjected to hydrolysis conditions reflecting pasteurisation, baking/brewing/boiling and sterilization.

Etofenprox 471

Temperature (°C)

Duration (min)

pH Process simulated

90 20 4 Pasteurisation 100 60 5 Baking, Brewing, Boiling 120 20 6 Sterilisation

The buffer solutions were continuously heated in a round-bottomed flask in an oil bath. After

incubation, the samples were partitioned with ethyl acetate (3 times) and the radioactivity was measured in the combined organic and aqueous phases. The radioactivity remaining in the aqueous phase after partition was ≤ 0.1% for both test items and therefore only the organic phases were combined, evaporated, re-dissolved in 1:1 acetonitrile/water and analysed by HPLC (with mean radiolabel recovery rates of were 93–96% for 14C-etofenprox and 94–99% for 14C-α-CO and an LOQ of 0.001 mg ai/L).

Table 59 Stability of etofenprox and its α-CO metabolite under hydrolysis conditions simulating sterilization, pasteurisation and baking/brewing/boiling

Test item Hydrolysis conditions Initial concentration Post-processing concentration %AR mg/l mg ai/l

14C-etofenprox pH 4–90 ˚C–20 min 0.116 0.111 95.6 pH 5–100 ˚C–60 min 0.114 0.106 93 pH 6–120 ˚C–20 min 0.114 0.107 94.3

14C-α-CO pH 4–90 ˚C–20 min 0.104 0.103 99.3 pH 5–100 ˚C–60 min 0.107 0.1 93.8 pH 6–120 ˚C–20 min 0.1 0.099 99.5

Results are the sum of the mean concentrations in the organic and aqueous phases

Etofenprox and its α-CO metabolite are stable under the three simulated processing conditions

(pasteurisation, baking/brewing/boiling and sterilisation.

Magnitude of the residue in processing

Information was provided to the Meeting on the effects of simulated commercial processing on residues of etofenprox and its α-CO metabolite in apples, grapes, peaches and rape seed and on the effects of milling on rice grain.

Apples

Apples from three European field trials were processed into pureé, juice and pomace (wet and dried), simulating household processing or commercial practices.

In these trials, 2–3 applications of etofenprox (EC 30 formulations) were made as foliar sprays to plots of at least 7 mature trees, once over flowering at 0.23 kg ai/ha (in one trial) and twice just before harvest (7 days apart) at 0.16–0.19 kg ai/ha using knapsack sprayers to apply 1400–1500 L spray mix/ha.

Unreplicated samples of at least 10 kg were taken 6–7 days after the last application and either processed or frozen within 24 hours of sampling and stored at -18 °C or below for 2–3 days until processing (using procedures which simulated commercial practices).

In the 2003 studies, apples were washed, peeled, cored and chopped before being cooked for 14–15 minutes and sieved. The resulting pureé was preserved in sealed glass containers by heating at 90 °C for about20 minutes and stored frozen for analysis. Apple juice was prepared from washed chopped fruit using a commercial juice extractor and preserved by cooking for 1–2 minutes at about 90 °C. Both the juice and press cake were stored frozen until analysis.

In the 2005 study, apple juice was obtained by crushing and pressing unwashed apples (ca. 15 kg per sample). After pressing, pectolytic enzymes were added to the juice, and the remaining pomace

472 Etofenprox

was dried in an oven at 60 °C to constant weight. The juice was allowed to settle for at least 12 hours before decantating, filtering and adjustment to pH 3.5 with citric acid. The juice was then pasteurised at 82–85 °C for one minute and stored in glass bottles. Samples of washing water, washed apples, wet and dry pomace and juice were taken and stored frozen until analysis.

Canned apples were prepared from unwashed, peeled apples that had been blanched in boiling water for up to two minutes before coring and chopping. A 20% sugar syrup (adjusted to pH 3.5 with citric acid) was added to the chopped apples in a 2:1 proportion and the mixture was pasteurized at 90–95 °C in glass jars and stored frozen until analysis.

For the pureé, the unwashed apples were blanched (to avoid enzymic browning), crushed, sieved and mixed with white sugar before heating until the Brix levels reached 24°. The pH of the pureé was lowered to 3.5 by adding citric acid and sterilised in glass bottles at 115–120 °C for ten minutes before being stored frozen until analysis.

The residue levels of etofenprox and α-CO in all the collected fractions were determined by GC/MS using Method 692-G. Mean recovery rates in these studies ranged from 83–102% for etofenprox in all matrices and from 73–111% for α-CO (except for apple pureé where a recovery rate of 58% (SD 28, n=2) was noted.

Table 60 Residues in apples and processed apple fractions from supervised trials in France and Spain, involving 2-3 foliar applications of etofenprox (30 EC), 6–7 day PHI


Application Residues (mg/kg) Reference & Comments

form no kg ai/ha

kg ai/hL

water (L/ha)


Spain, 2003 Termens (Golden Shumutti)

30 EC 1+ 2

0.23 0.19

0.015 0.012

1500 1500

Fruit Pureé Juice Press cake

0.18 0.05 < 0.01 0.4

0.03 0.02 < 0.01 0.10

848643 A/SP/I/03/54

Spain, 2003 Villena (Starking)

30 EC 1+ 2

0.227 0.18

0.014 0.012

1500 1450

Fruit Pureé Juice Press cake

0.22 0.07 0.01 0.48

0.04 0.04 0.01 0.10

848643 A/SP/I/03/55

France (S), 2005 Mauguio (Gala galaxy)

30 EC 2 0.16 0.011 1400 Fruit Washed fruit Wash water Juice Fruit (canned) Pureé Wet pomace Dried pomace

0.12, 0.11 0.07 < 0.01 < 0.01 < 0.01 < 0.01 0.41 1.5

0.02, 0.02 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 0.04 0.19

05-alpha-20 X05 170 520 FR01

Peaches

The fate of etofenprox and its α-CO metabolite was studied in peach juice, jam and pureé from three field trials in Europe (2001 and 2003) and in washed and canned fruit, juice, jam, pureé, wet and dry pomace waste water and peel from one field trial in France (2005).

In these trials, 2 applications of etofenprox (EC formulations) were made to mature trees, 7 days apart as foliar sprays using pressurised knapsack sprayers or motorised airblast backpack sprayers, applying 0.2–0.22 kg ai/ha in 1500 L water/ha. Plot sizes in these trials ranged from 72–220 square metres and involved at least 5 trees per plot.

Unreplicated samples of at least 5 kg were processed 1–5 days after harvest and processed samples were stored at -18 °C or below for up 8 months before analysis for etofenprox and its α-CO metabolite using either the GC/MS methods MT-200102 or 692-G or the HPLC method SIPCAM 1354. The reported LOQs in these methods, for all matrices was 0.01 mg/kg.

Etofenprox 473

In the 2001 studies, peaches were stoned, chopped and centrifuged twice, with the juice being filtered, pasteurised (95 °C for 1 hour) and stored frozen for analysis. Chopped fruit was also heated to about 70 °C and mashed to produce pureé which was then heated to 85–90 °C for 10 minutes before being sealed and stored frozen for analysis. Jam (marmalade) was also prepared from pureé by adding sugar (600 g/kg) and pectin (12 g/kg) and boiling for 10–15 minutes before being sealed and stored frozen for analysis.

Peaches from the 2003 field trial were washed, juice from the stoned, chopped fruit was extracted using a commercial juice extractor and pureé prepared by cooking for about 40–50 minutes, sieved and preserved by heating to about 90 °C for approximately 10 minutes. Marmalade was made from washed, peeled, stoned fruit by cooking to a pulp for 35–40 minutes with an equal amount of sugar and preserving by heating to about 90 °C for approximately 20 minutes.

In the 2005 study, unwashed peaches were stoned, crushed and sieved to separate the juice from the wet pomace. The juice was pasteurized at 82–85 °C for 1 minute and stored frozen in sealed glass jars until analysis. Wet pomace samples were oven-dried at 60 °C to a constant weight.

Canned peaches were prepared from unwashed peaches that were blanched in boiling water for two minutes maximum, cooled, peeled and stoned. A 20% sugar syrup (adjusted to pH 3.1 with citric acid) was added to the peaches (2:1 ratio) in glass jars that were then sealed and pasteurized at 90–95 °C for one minute.

Jam (marmalade) was made from unwashed peaches that were peeled, stoned and crushed. After the addition of sugar, the jam was heated up till the Brix degree reached 24%, sterilised in sealed glass bottles at 115–120 °C for ten minutes and stored frozen until analysis.

Unwashed peaches, after the removal of the stones, were also processed into pureé by crushing and sieving (to separate the pureé from the peels). Sugar was added to the sieved peaches and the mixture was heated to reach 24% degree Brix. Samples were then sterilized in sealed glass jars at 115–120 °C for 10 minutes and then stored frozen until analysis.

Table 61 Residues in peaches and processed peach fractions from supervised trials in France and Spain, involving 2–3 foliar applications of etofenprox (30 EC), 7 day PHI





Spain, 2001 Cieza (Miraflores)

28 EC 2 0.22 0.017 1500 fruit juice jam pureé

0.23 < 0.01 0.10 0.38

0.03 < 0.01 0.02 0.03


Italy, 2001 Imola Peach (Elegant Lady)


0.01 < 0.01 0.04 0.09

0.02 < 0.01 < 0.01 0.01

ET4/SIP & SIP 1326 ET4/I/03PS

Spain, 2003 Chulilla (Federica)


0.21 < 0.01 0.01 0.14

0.04 < 0.01 < 0.01 0.05

848642 A/SP/I/03/51

474 Etofenprox





France, 2005 Mauguio (Red Top)

30 EC 2 0.2 0.013 1500 fruit washed fruit wash water juice canned fruit blanch water pureé jam skins wet pomace dry pomace

0.1, 0.09 0.17 < 0.002 0.03 < 0.01 < 0.002 0.03 < 0.01 0.95 0.33 2.0

0.02, 0.01 < 0.01 < 0.002 0.015 < 0.01 < 0.002 0.01 < 0.01 0.09 0.09 0.16

05-alpha-19 X05 170 519 FR01

Grapes

Grapes obtained from five field trials located in Italy and France were processed into wine, juice and raisins using simulated commercial practices.

Grapes from two trials in Italy (2001) were defrosted after about 11 months in frozen storage and juice was pressed from 6 kg samples using a laboratory (constant pressure) juicer and stored frozen for about 5 weeks before GC/MS analysis for etofenprox and its α-CO metabolite using method MT-200102.

Grape samples (50 kg) from one other trial in Italy (2001) were crushed within 1 day after harvest, and the skins and must were separated after heating at 60 °C for 2 hours and pressing. The must was heated at 85–88 °C for 5 minutes and allowed to cool and settle overnight. The clear juice (about 2 L) was collected by aspiration, filtered, sterilized and stored frozen for up to 6 months before HPLC analysis for etofenprox and its α-CO metabolite using method SIPCAM 1354.

Grape samples from two trials in France (2005) were shipped and stored for 1–5 days under refrigerated conditions before being stemmed and crushed. The must was treated with bisulphite (4 g/hL) and heated at 70 °C for 20 minutes. After separation of the pomace, the juice was allowed to clarify at about 2 °C for ca. 15 hours. The clear juice was separated from lees and pasteurised, stored deep-frozen for up to 6 months before GC/MS analysis for etofenprox and its α-CO metabolite using method 692-G.

Red wine was also produced from grape samples from the above field trials in Italy (2001) and France (2005). In the 2001 study, grapes (50 kg) were crushed within 1 day after harvest and the must and skins were left to ferment for four days at room temperature. The obtained juice was collected and filtered. Bisulphite was added (10 g/hL) and fermentation continued after mixing. At the end of the fermentation, the wine was collected by aspiration and filtered. 10 g/hL bisulphite was then added and mixed to the clear wine. The young wine was then bottled and stored deep-frozen. Bottled wine was obtained following the same procedure till the second addition of bisulphite. Thereafter, instead of being bottled, the wine was left to settle for 15–20 days and again filtered. The decantation and filtration steps were repeated every 20–30 days for four months. The wine was then bottled and stored deep-frozen for up to 6 months before HPLC analysis for etofenprox and its α-CO metabolite using method SIPCAM 1354.

In the 2005 studies, grape samples from two field trials in France were shipped and stored for 1–5 days under refrigerated conditions before being stemmed and crushed. The must was treated with bisulphite (6 g/hL) and alcoholic fermentation was started by addition of yeast. At the end of alcoholic fermentation, the drop wine was run off and pomace pressed. Drop wine and pressed wine were blended and stored in closed containers. After the end of malolactic fermentation the wine put into closed containers to be clarified and stabilized at cold temperature for about three weeks. Then the

Etofenprox 475

wine was filtered, bottled and analysed within 5 days for etofenprox and its α-CO metabolite using GC/MS method 692-G.

Grapes from the two field trials in France (2005) were also processed into raisins, with 5 kg samples of grape bunches being manually separated into berries and stalks. The berries were then dipped in an alkaline solution of potassium carbonate and ethyl oleate and dried in an oven at about 40 °C until the remaining humidity was ca. 16%.

Table 62 Residues in grapes and processed grape fractions from supervised trials in France and Italy involving foliar applications of etofenprox (EC formulations): 13–14 day PHI


Application Residues (mg/kg) Reference & Comments form no kg ai/ha kg

ai/hL water (L/ha)



30 EC 4 0.15 0.015 1000 Grapes Juice

1.37 0.01

0.31 < 0.01

820350 A/IT/I/01/41

Italy, 2001 Peverati Casssine (Moscato Bianco)

30 EC 4 0.15 0.015 1000 Grapes Juice

0.96 < 0.01

0.08 < 0.01

820350 A/IT/I/01/42

Italy, 2001 Pietra de’ Giorgi (Barbera)

28 EC 2 0.14 0.014 1000 Grapes Juice Young wine Bottled wine

0.25 < 0.01 < 0.01 < 0.01

0.03 < 0.01 < 0.01 < 0.01

ET4 & SIP1327 ET4/I/01 VI

France (N), 2005 Furdenheim (Pinot noir)

30 EC 1+ 1

0.19 0.17

0.018 0.015

1000 1120

Grapes Raisins Juice Wine

0.35 0.88 < 0.01 < 0.01

0.07 0.08 < 0.01 < 0.01

05-alpha-21 A5115 AN1

France (N), 2005 Reuilly (Pinot noir)

30 EC 1+ 1

0.2 0.15

0.019 0.015

1000 1000

Grapes Raisins Juice Wine

0.21 0.33 < 0.01 < 0.01

0.045 0.04 < 0.01 < 0.01

05-alpha-21 A5115 CT1

Rice

In two field trials from the USA, no residues of etofenprox or its α-CO metabolite were measured in either the unprocessed grain or in any of the processed fractions (brown rice, polished rice, bran and hulls). It was therefore not possible to evaluate the effects of processing on etofenprox residues in rice grain.

Rape seed

In one field trial from the UK, no residues of etofenprox or its α-CO metabolite were measured in either the unprocessed rape seed or in any of the processed fractions (press cake, crude and refined oil). It was therefore not possible to evaluate the effects of processing on etofenprox residues in rape seed

Table 63 Summary of selected processing factors for etofenprox

Raw agricultural commodity

Processed commodity Calculated processing factors a Processing factor (mean or median)

Apples Washed fruit 0.61 0.61

Pureé 0.32, 0.28, < 0.09 0.23 (best estimate)

Canned fruit < 0.09 < 0.09

Juice < 0.09, < 0.06, 0.045 < 0.06 (median)

Press cake (wet pomace) 3.6, 2.2, 2.2 4 (mean)

476 Etofenprox


Processed commodity Calculated processing factors a Processing factor (mean or median)

Dry pomace 13 13

Peach Juice <1 (excluded), 0.32, < 0.05, < 0.04 < 0.05 (median)

Jam 4 (excluded), 0.43, < 0.11, 0.05 0.75 (mean)

Pureé 9 (excluded), 1.7, 0.67, 0.32 0.67 (median)

Canned fruit < 0.11 < 0.11

Skins 10 10

Wet pomace 3.5 3.5

Dry pomace 21 21

Grape Juice < 0.05, < 0.04, < 0.03, < 0.01, 0.007 < 0.03 (median)

Wine < 0.05, < 0.04, < 0.03 < 0.04 (median)

Raisins 2.5, 1.6 2.1 (mean) a Ratio of the total residue in the processed item/total residue in the RAC (if above the LOQ).

RESIDUES IN ANIMAL COMMODITIES

Farm animal feeding studies

Lactating dairy cows

A feeding study with etofenprox on lactating dairy cows was reported by Roberts et al, 1987 [Ref: 132/87587]. In this study, Friesian dairy cows (4–9 years old and weighing 470–610 kg) were dosed orally for 28–30 days with etofenprox premixed in corn oil and incorporated into the concentrate diet, fed twice daily at milking time (about 4 kg/cow/day, supplemented with about 16 kg meadow hay/cow/day). No clinically abnormal signs, no changes in food consumption, and no abnormalites during macroscopic post-mortem examination of tissues that could be associated with the treatment were observed. Mean milk production showed a slight overall decline in all groups but were not treatment-related.

Dosing levels for each group of 3 cows were 0, 5 and 15 mg etofenprox/kg concentrate, or about 0, 0.5 and 1.5 ppm in the diet (equivalent to 0, 10 and 30 mg ai/cow/day, assuming an average consumption of 20 kg feed/day) and one group of 5 cows was dosed with a higher level of 500 mg ai/kg concentrate or 50 ppm in the diet (1000 mg ai/cow/day). The dose groups were designated 0×, 1×, 3× and 200×.

Group Number of animals

Treatment Dose level [mg/cow/day]

Days of dosing Day of sacrifice Withdrawal time [days]

0× 3 control 0 1–28 29/43 a 0/14 b 1× 3 etofenprox 10 1 c–28 29 0 b 3× 3 etofenprox 30 1 c–29 30 0 b 200× 3 etofenprox 1000 1–30 31 0 b 200× 2 etofenprox 1000 1–28 43 14 d

a one control cow was sacrificed after each 0 and 14 days withdrawal period, one control cow was not sacrificed. b animals sacrificed 17–24 hours after the last dose. c 2× doses were administered on days 1 and 2 d animals were not dosed during the withdrawal period (i.e. last dosing on day 28).

Individual milk samples (4× 100 mL) were taken from each 24-hour milk production and

pooled for analysis. Samples from the 200× dose group were analysed daily and the samples collected on days -1, 7, 14, 28 and 43 from the other dose groups were also analysed. Animals were sacrificed

Etofenprox 477

17–24 hours after the last dose and samples of liver, kidney, skeletal muscle (pooled from 2–3 sites), peritoneal fat (omental/perirenal mixed sample) and subcutaneous fat were stored at -20 °C for up to 10 weeks before analysis using a modification of the MT-PBI method developed to measure etofenprox residues in plant material.

Etofenprox was extracted from milk and tissue samples into ethyl acetate/hexane (1:1), concentrated by rotary evaporation, subjected to acetonitrile/hexane partition (tissue extracts only), and eluted through a florisil column using hexane/ethyl acetate (98:2). The concentrated eluent containing etofenprox was derivatised with iodotrimethylsilane to form iodo-3-phenoxybenzyl (PBI), partitioned into hexane and subjected to silica gel column clean-up using hexane/methanol (99:1). The derivatised etofenprox residues were measured using GC/ECD with an LOQ of 0.05 mg/kg for all matrices. Concurrent recoveries obtained from control samples spiked with the test item were used to validate the method.

Table 64 Concurrent recovery values for the analytical method used to measure etofenprox residues in milk and animal tissues

Matrix Spiking level (mg/kg) No of samples % Recovery SD

Milk 0.05–0.50 9 93.5 30.2 Liver 0.05–0.20 3 92.4 28.0 Kidney 0.05–0.50 3 91.3 21.8 Skeletal muscle 0.05–0.20 3 86.9 17.0 Peritoneal fat 0.10 –20.00 3 93.4 20.6 Subcutaneous fat 0.20–0.50 3 95.8 13.1

Residues in milk of the 1× and 3× dose groups were at or below the LOQ (0.05 mg/kg) and in

the 200× dose group, residues of 0.66 mg/l were detected on day 2 of the dosing period, increasing to a maximum of 2.11 mg/l. An approximate plateau level of 1.36 mg/l was calculated as the mean of 10 values from day 5 to day 28. Over the withdrawal period, residues declined rapidly during the first 5–6 days with a slower decline over the last 7–8 days.

Table 65 Residues of etofenprox in milk

Day Group (Dose level) Control (0 mg/cow/day)

1× 0.5 ppm (10 mg/cow/day)


200× 50 ppm (1000 mg/cow/day)

-1 < 0.05 < 0.05 < 0.05 < 0.05 2 n.a. n.a. n.a. 0.66 5 n.a. n.a. n.a. 1.42 7 < 0.05 < 0.05 0.05 1.91 10 n.a. n.a. n.a. 0.84 12 n.a. n.a. n.a. 1.12 14 < 0.05 < 0.05 0.05 1.08 18 n.a. n.a. n.a. 1.05 21 n.a. n.a. n.a. 1.63 23 n.a. n.a. n.a. 2.11 25 n.a. n.a. n.a. 1.12 28 < 0.05 < 0.05 < 0.05 1.29 30 n.a. n.a. n.a. 0.62 / 1.66 * 32 n.a. n.a. n.a. 0.31 / 0.52 * 34 n.a. n.a. n.a. 0.19 / 0.25 * 36 n.a. n.a. n.a. 0.19 / 0.14 * 38 n.a. n.a. n.a. 0.22 / 0.10 * 40 n.a. n.a. n.a. 0.19 / 0.15 *

478 Etofenprox

Day Group (Dose level) Control (0 mg/cow/day)



200× 50 ppm (1000 mg/cow/day)

42 < 0.05 n.a. n.a. 0.10 / 0.09 * n.a. not analysed * results of two individual animals on withdrawal part of the study

Residues of etofenprox were all below the LOQ (0.05 mg/kg) in liver, kidney and skeletal

muscle from cows in the 1× and 3× dose groups. Residues in peritoneal fat were up to 0.54 mg/kg (1×) and 1.89 mg/kg (3×) and in subcutaneous fat were up to 0.28 mg/kg (1×) and 0.5 mg/kg (3×).

In the 200× dose group, residues were detected in all of the analysed tissues, up to 14.3 mg/kg in peritoneal fat, 3.54 mg/kg in subcutaneous fat, 1.16 mg/kg in kidney, 0.63 mg/kg in liver and 0.35 mg/kg in skeletal muscle and were also measurable in all tissues (except liver) at the end of the 14-day withdrawal period.

Table 66 Residues of etofenprox in cow tissues

Dose group Dose level [mg/cow/day]

Cow-No.

Etofenprox residues (mg/kg) Liver Kidney Skeletal muscle Peritoneal fat Subcutaneous

fat

Control 0 1 3

< 0.05 < 0.05

< 0.05 < 0.05

< 0.05 < 0.05

< 0.05 < 0.05

< 0.05 < 0.05

1× (0.5 ppm) 10 4 5 6

< 0.05 < 0.05 < 0.05

< 0.05 < 0.05 < 0.05

< 0.05 < 0.05 < 0.05

0.41 0.21 0.54

0.08 0.12 0.28

3× (1.5 ppm) 30 7 8 9

< 0.05 < 0.05 < 0.05

0.05 < 0.05 < 0.05

< 0.05 < 0.05 < 0.05

1.89 0.84 0.98

0.18 0.07 0.50

200× (50 ppm) 1000 10 11 12

0.36 0.25 0.63

1.16 0.62 0.08

0.10 0.08 0.35

14.3 1.77 13.4

3.07 1.02 3.54

200× (50 ppm) 1000 13 14

0.05 < 0.05

0.23 0.23

0.05 0.05

4.15 11.8

0.33 3.01

NATIONAL RESIDUE DEFINITIONS

The meeting was provided with information on the etofenprox residue definitions adopted in a number of countries. These are summarised in the following table.

Table 67 National residue definitions for etofenprox

Country Commodities Residue definition (dietary intake)

Residue definition (MRL compliance)

Australia (APVMA) plant and animal commodities etofenprox etofenprox Brazil plant and animal commodities etofenprox etofenprox European Union plant commodities etofenprox + α-CO etofenprox + α-CO

animal commodities etofenprox etofenprox Japan plant and animal commodities etofenprox etofenprox Korea plant commodities etofenprox etofenprox USA plant etofenprox etofenprox

Etofenprox 479

APPRAISAL

Etofenprox, a pyrethroid-like insecticide, active through contact or ingestion, is effective against a range of agricultural and horticultural insect pests and is also used as an indoor non-food crack and crevice insecticide, a spot treatment for pets, and as an outdoor (fog) treatment to control a variety of flying and crawling insect pests.

Residue and analytical aspects of etofenprox were evaluated by the JMPR in 1993 and the compound was listed in the Periodic Re-Evaluation Program at the Forty-second Session of the CCPR for periodic review by the 2011 JMPR. The most recent toxicological review was in 1993 when an ADI of 0–0.03 mg/kg bw was established for etofenprox. Specifications for etofenprox technical material, emulsifiable concentrate, wettable powder and emulsion (oil-in-water) have been published by FAO in July 2007 (http://www.fao.org/ag/AGP/AGPP/Pesticid/Specs/docs/Pdf/new/Etofenprox07.pdf).

Authorisations exist for the agricultural uses of etofenprox (EC and SC formulations) in Italy, Germany, Brazil and Japan with use in rice in USA being a granular formulation for aerial application.

The manufacturer submitted studies on metabolism, analytical methods, supervised field trials, processing, freezer storage stability, environmental fate in soil and rotational crop residues.

Etofenprox, (2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether) is virtually insoluble in water (23 µg/L), stable to hydrolysis, of low volatility (8.1 × 10-7 Pa at 25 °C), has a log POW of 6.9 and is soluble (> 600 g/L) in hexane, dichloromethane, acetone, ethyl acetate, xylene and toluene.

Etofenprox (MTI-500)

The following abbreviations are used for the metabolites discussed below:

α-CO 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzoate

4’-OH 2-(4-ethoxyphenyl)-2-methylpropyl 3-(4-hydroxyphenoxy) benzyl ether

m-PB-acid 3-phenoxybenzoic acid

4’-OH-PB-acid 3-(4-hydroxyphenoxy) benzoic acid

m-PB-alc 3-phenoxybenzyl alcohol

EPMP 2-(4-ethoxyphenyl)-2-methylpropionic acid

DE 3-phenoxybenzyl 2-(4-hydroxyphenyl)-2-methylpropyl ether (desethyl-etofenprox)

DP 3-hydroxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether

PENA 2-(4-ethoxyphenyl)-2-methylpropyl alcohol

Metabolites identified in italics are common to other pyrethroids

Animal metabolism

The Meeting received etofenprox metabolism studies on animals (rats, lactating goats and laying hens).

O

CH3CH2O C CH3

CH3

CH2O CH2

http://www.fao.org/ag/AGP/AGPP/Pesticid/Specs/docs/Pdf/new/Etofenprox07.pdf

480 Etofenprox

In rats, dosed with a 1:1 mixture of [α-14C-benzyl] and [2-14C-propyl], absorbtion was rapid, but incomplete, with residues in plasma reaching a maximum in 3-5 hours. Distribution and depletion from tissues was rapid except for fat (estimated DT50 5–8.5 days). About 3% AR remained in the carcase after 7 days. No unchanged etofenprox was found in urine but it was a major component in faeces, most likely due to unabsorbed material. Cleavage of the parent molecule did not appear to be a significant metabolic process, although a number of radiolabelled entities were not identified. Desethyl-etofenprox (DE) occurred at 19.5–25.1% of the dose and etofenprox hydroxylated in the 4΄ position of the phenoxybenzyl moiety (4’-OH) occurred at 7.2–13.8% of the dose. Other primary metabolic steps involved oxidation of carbons on either side of the ether linkage, one of which (α-CO) is a major metabolite in plants, soil and in photo-degradation studies.

Lactating goats were orally dosed twice daily for 7 days with an encapsulated 1:1 mixture of [α-14C-benzyl] and [2-14C-propyl] labelled etofenprox in acetone at dietary equivalents of 1.5 ppm or 13.5 ppm per day. At the end of the 7-day dosing period, the goats were sacrificed 21 hours after the last administration.

Most of the applied radioactivity (about 78–84%) was excreted via faeces and urine. Transfer to milk was low (less than 0.8% of the applied dose), mostly (47–68%) in the milk fat and with residues reaching a plateau after 3–4 days. About 2–3% of the applied radioactivity was found in fat with 0.5-0.66% in muscle and 0.1–0.2% in liver.

Etofenprox (parent) was the predominant residue in milk and edible tissues, making up 93–97% TRR in milk, muscle and fat, and 33–38% TRR in liver and kidney. The highest residue level was found in fat (0.72 mg/kg for the high dose).

Other metabolites found at low levels were EPMB and m-PB-acid (each at about 0.04 mg/kg in kidney) m-PB-alc/PENA (0.05 mg/kg in liver) and DE (0.02 mg/kg in liver). The α-CO metabolite was not detectable, but is likely to occur as a transitory intermediate leading to the formation of PENA and m-PB-acid.

Laying hens (5 hens per dose group) were dosed each morning for 14 days with a 1:1 mixture of [α-14C-benzyl] and [2-14C-propyl] labelled etofenprox at dietary equivalents of 0.9 ppm or 9.6 ppm. At the end of the 14-day dosing period, the hens were sacrificed about 24 hours after the last administration. Eggs were collected prior to dosing and during administration twice daily (just before dosing and 5 to 8 hours later).

Excretion of residues was high (83–92% of applied radioactivity). Very little radioactivity was present in eggs (0.6% AR, more than 80% present in the yolk). Edible tissues and organs contained 2.2 to 2.7% AR, mostly in fat.

Etofenprox was the only significant residue, making up about 80% TRR in egg yolk, 69 to 93% TRR in muscle, fat and skin and 15–30% TRR in liver. The remaining extractable radioactivity consisted of unidentified metabolites, except for the DE metabolite which was present at about 0.03 mg/kg (less than 0.08 mg/kg after acid hydrolysis).

In summary, about 80–90% of the applied radioactivity was excreted in lactating goats and laying hens dosed with less than 1% being found in milk and eggs and less than 4% present in edible tissues. The predominant residue in milk, eggs and edible tissues was the parent etofenprox, present at less than 0.1 mg/kg in all tissues except fat (0.7–1.6 mg/kg), up to about 0.7 mg/kg egg yolk and about 0.3 mg/kg in milk, with five identified metabolites present at low levels (up to 0.07 mg/kg).

The proposed metabolic pathways involve desethylation of the ethoxyphenyl group to form the DE metabolite, hydroxylation of the phenoxy ring (to form the 4’-OH metabolite), the formation of the α-CO by oxidation of the benzyl methylene group (in goats) and and the loss of the phenoxy group to form the DP metabolite (in hens). Cleavage of these primary metabolites produces the EPMP, m-PB-acid, PENA, m-PB-alc, OH-P-alc and 4’-OH-PB-acid which subsequently become conjugated.

Etofenprox 481

Plant metabolism

The Meeting received plant metabolism studies on grapes, lettuce, winter rape and rice following foliar applications of a 1:1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox and on rice following a pre-harvest soil application.

For grapes treated at rates equivalent to 0.3 kg ai/ha (50 g ai/hL) and 3.0 kg ai/ha (500 g ai/hL) as foliar sprays, mature grape bunches were sampled either 28 or 14 days after treatment and washed with water and then ethanol to determine the surface radioactivity. The washed bunches were then separated into stems and grapes with the grapes being homogenised and the juice separated from pulp, skin and pips by centrifugation.

Total residues in grape bunches from the 0.3 kg ai/ha treatments were about 5 mg/kg parent equivalents (14 day PHI) and about 2.5 mg/kg parent equivalents after 28 days. The majority of the radioactive residues were found in the surface washes, 82% TRR after 14 days and decreasing to 60–75% TRR after 28 days. The radioactivity remaining in washed grapes increased from about 12–23% TRR (14 DAT) to 20–23% TRR (28 DAT).

Etofenprox was the major residue in grapes, making up 85–87% TRR, with only low levels of other metabolites being found. The only metabolite found at levels greater than 5% TRR was α-CO, present at levels up to 6.5% TRR.

Eight days after foliar treatment of lettuce plants with etofenprox at 0.18 kg/ha (normal dose) or 1.8 kg ai/ha (high dose), the total radioactive residues were 2.4 mg/kg eq and 19.2 mg/kg eq, respectively. About half the radioactive residue was found in the surface washes of the plants.

The major radioactive residue in lettuce was etofenprox, making up about 90% TRR with α-CO being the only significant metabolite found, at up to 3% TRR.

In foliar-treated paddy rice treated 21 days before harvest with rates equivalent to 0.2 kg ai/ha or 2.0 kg ai/ha, total radioactive residues in brown rice at harvest were about 0.08 mg/kg and 1.1 mg/kg parent equivalents respectively, with levels in chaff and straw being about 4–5 mg/kg (low rate) and 38–51 mg/kg (high rate).

Etofenprox was the predominant residue, making up about 53–76% TRR in whole grain, chaff and brown rice and 49–55% TRR in straw. The metabolite α-CO was found at up to 16% TRR in whole rice, 12% TRR in brown rice, 15% TRR in chaff and 22% TRR in straw.

In paddy rice treated 35 days before harvest with soil treatments of 0.45 kg ai/ha or 2.0 kg ai/ha and re-flooded to simulate paddy field conditions, TRRs at harvest were less than 0.04 mg/kg (low rate) and about 0.1 mg/kg parent equivalents (high rate) in brown rice, with the respective levels in straw being about 0.18 mg/kg and 0.62 mg/kg.

Etofenprox was a significant residue in straw (11–44% TRR), a minor residue in whole grain and was not detected in brown rice. Other metabolites, including α-CO, m-PBAcid and PENA, and conjugates of m-PBAcid, PENA, and 4’-OH-PBAcid, were found at low levels (about 0.002–0.02 in whole grain, brown rice and chaff and < 0.2 mg/kg in straw). Unextracted radioactivity was characterized as carbohydrates, proteins, and lignin, indicating that the majority of the radioactivity in soil-treated rice, resulted from the reincorporation of the radiolabel into natural products.

When winter rape was sprayed with radiolabelled etofenprox at flowering (at the equivalent of 0.12 kg ai/ha or 1.2 kg ai/ha), radioactivity present in mature plants harvested 8 weeks after treatment did not exceed 0.1 and 3.5 mg/kg eq respectively and was found mostly in foliage. In seeds (not directly exposed to the spray), residues did not exceed 0.02 (low rate) or 0.14 mg/kg (high rate).

The predominant residue was etofenprox (up to 62% TRR in seeds) with the α-CO metabolite present at up to 5% TRR in foliage and seeds. Minor metabolites found in seeds, including m-PB-Acid and m-PB-alc, individually did not exceed 0.004 mg/kg.

In summary, plant metabolism studies conducted in four diverse crops (grapes, lettuce, winter rape and rice) showed similar profiles and when applied as a foliar treatment, etofenprox is the major

482 Etofenprox

residue, accounting for more than 85% TRR in grapes and lettuce and more than 50% in rice and winter rape. The α-CO metabolite is generally present at less than 10% TRR (12–16% TRR in rice grain and 15–22% TRR in rice chaff and straw).

The proposed metabolic pathway in plants involves an initial oxidation of the benzylic carbon to form the α-CO metabolite, the hydrolysis of ester links to yield the DE and DP metabolites and an aromatic hydroxylation leading to the 4’-OH metabolite. Further metabolism occurs by the cleavage of the first generation metabolites at the oxygen bond, resulting in the formation of m-PB-acid, m-PB-alcohol, EPMP and PENA.

Environmental fate

The Meeting received information the environmental fate and behaviour of etofenprox, including hydrolytic stability, photolysis, behaviour in water/sediment systems and metabolism in rotational crops. A 1:1 mixture of [α-14C-benzyl]-etofenprox and [2-14C-propyl]-etofenprox was used in these studies.

Etofenprox is stable to hydrolysis and is rapidly degraded under simulated sunlight in both buffer solution at pH 7 (DT50 4.7 days) and natural pond water (DT50 7.9 days). The predominant metabolite found at the end of the 15-day study period was α-CO (38-64% applied radioactivity). The α-CO metabolite is stable to hydrolysis at pH 4 and 7 and slowly degraded at pH 9 (calculated DT50 of about 43 days).

In water/sediment systems, etofenprox degrades relatively quickly, with DT50 values of 1-10 days in the water phases and 6-20 days in the entire systems. One major degradation product, the 4’-OH metabolite, was detected in sediment at levels of up to 12–21% AR. DT50 values for this 4’-OH metabolite in water/sediment systems ranged from of 22–57 days.

The Meeting concluded that the residues of etofenprox are not likely to persist in the environment.

Residues in succeeding crops

In rotational crop metabolism studies involving lettuce, carrots and spring barley grown in a silt loam soil treated with 14C-etofenprox and aged for about 4 weeks showed only a very small uptake of radioactivity. The highest concentrations were in barley straw (0.07 mg/kg parent equivalents), in barley grain and lettuce (each at about 0.02 mg/kg parent equivalents). Only very low amounts of the radioactive residues could be extracted, even using aggressive extraction techniques (suggesting that the C14 may have entered the carbon pool in the plant) and no further identification of the residue was conducted. Based on these results, significant residues of etofenprox and the α-CO metabolite are not expected in rotational crops.

Analytical methods

Several analytical methods have been reported for the analysis of etofenprox and its α-CO metabolite. The principle of most methods involves extraction steps using organic solvents (predominantly acetone), liquid/liquid partition (commonly hexane), and column chromatographic clean-up (alumina, silica gel, Florisil) and analysis by GC/ECD, GC/MS, HPLC or LC-MS/MS.

The methods have been validated for range of plant and animal substrates with LOQs of 0.01 mg/kg and based on the results of validation studies and the concurrent recovery rates achieved in the supervised field trials, the available analytical methods are considered suitable for determining residues of etofenprox and its α-CO metabolite.

Insufficient information was available to conclude whether etofenprox can be analysed with commonly used multiresidue methods.

Etofenprox 483

Stability of pesticide residues in stored analytical samples

In frozen storage stability studies with a range of representative substrates with a with a high water content (apples, cabbage, peaches), a high starch content (rice grain), a high oil content (rape seed) and a high acid content (grapes), residues of etofenprox and its α-CO metabolite were stable for at least 24 months (rice for 7 months) when samples were stored at -20 °C. Sample storage intervals in the supervised field trials were within these storage intervals.

No information was available on the stability of animal matrices under frozen storage. The Meeting noted that in the hen metabolism study, separate radiolabelled liver samples analysed 12 months apart showed no significant change in the relative TLC profiles. Sample storage intervals in the animal metabolism studies were 3–4 months and 1–2 months in the animal feeding studies.

Residue definition

In livestock metabolism studies (goats, hens), the parent compound is the predominant residue in milk, eggs and edible tissues, with the α-CO metabolite not being found. Only low levels (< 0.05%TRR) of other metabolites (EPMP, m-PB-Acid, m-PB-alc/PENA and DE) occurred in liver and kidney.

The Meeting recommended that for animal commodities, the residue definition for both MRL enforcement and dietary intake estimation should be etofenprox.

Based on the ratio of residues in fat and muscle observed in the livestock metabolism and feeding studies (about 50:1) and supported by the log Kow of 6.9, the Meeting concluded that etofenprox residues are fat-soluble.

In plants, the metabolism studies on grapes, lettuce, oilseed rape and rice indicate that the predominant residue following foliar applications of etofenprox is the parent compound.

The only significant residue in plants is the α-CO metabolite, generally present at levels of less than 10% TRR in grapes, lettuce and rape seed and up to about 12% TRR in brown rice. In supervised trials on pome fruit, stone fruit and grapes, residues of the α-CO metabolite averaged between 14% and 19% of the etofenprox residues in fruit from trials matching GAP.

The Meeting recommended that for plant commodities, the residue definition for MRL enforcement should be etofenprox.

Based on the results of the plant metabolism studies and noting that the NOAEL for α-CO metabolite is about 2.5 times higher than that for etofenprox, the Meeting agreed that although the α-CO metabolite was present in some treated commodities (pome fruit, stone fruit, grapes) at levels averaging 14–19% of the etofenprox residues in samples taken at GAP, this metabolite need not be included in the residue definition for plant commodities for dietary intake estimation.

The Meeting therefore recommended that for plant commodities, the residue definition for dietary intake estimation should be etofenprox.

Analytical methods exist to measure etofenprox residues in animal and plant matrices.

Definition of the residue (for estimation of dietary intake and for compliance with MRL) – plant and animal commodities: etofenprox

The residue is fat soluble

Supervised trials

The meeting received supervised trial data for foliar applications of etofenprox (EC and SC formulations) on a range of fruit, vegetable, cereal, pulse and oilseed crops and for granular broadcast applications to paddy rice. These trials were conducted mainly in Europe, Brazil, USA (rice) and Japan (rice).

The OECD MRL calculator was used as a tool to assist in the estimation of maximum residue levels from the selected residue data set obtained from the supervised residue trials. As a first step, the

484 Etofenprox

Meeting reviewed the trial conditions and other relevant factors related to each data set to arrive at a best estimate of the maximum residue level, using expert judgement. Then the OECD calculator was employed. If the statistical calculation spreadsheet suggested a different value from that recommended by the Meeting, a brief explanation of the deviation was supplied.

Oranges

Residue data were provided to the Meeting from trials in Brazil on oranges.

The GAP for use on citrus fruit in Brazil is for 2 applications of up to 0.0025 kg ai/hL, applying about 8 litres of spray mix per tree, and with a PHI of 7 days. No trials matching GAP were available

Apple

Residue data were provided to the Meeting from trials in Brazil (no GAP) and Southern Europe on apples.

The GAP for use on apples and pears in Italy is for foliar sprays of up to 0.014 kg ai/hL, applying about 1500 L/ha, and with a PHI 7 days.

In trials from Italy, Spain and France matching this GAP, residues of etofenprox in apples were: 0.1, 0.12, 0.13, 0.18, 0.2, 0.22, 0.25, 0.26 and 0.34 mg/kg (n = 9).

The Meeting estimated an STMR of 0.2 mg/kg, an HR of 0.34 mg/kg and recommended a maximum residue level of 0.6 mg/kg for etofenprox in apples, agreed to extrapolate these recommendations to pears and to withdraw the previous recommendation of 1.0 mg/kg for pome fruits.

Peach

Residue data were provided to the Meeting from trials in Brazil (no GAP) and Southern Europe on peaches.

The GAP for use on stone fruit (apricot, cherry, peach, plum) in Italy is for foliar sprays of up to 0.014 kg ai/hL, applying about 1500 L/ha, and with a PHI 7 days.

In trials from Italy, Spain and France matching this GAP, residues of etofenprox in peaches were: 0.01, 0.08, 0.08, 0.1, 0.12, 0.14, 0.18, 0.18, 0.2, 0.21, 0.23 and 0.37 mg/kg (n = 12).

The Meeting estimated an STMR of 0.16 mg/kg, an HR of 0.37 mg/kg and recommended a maximum residue level of 0.6 mg/kg for etofenprox in peaches and agreed to extrapolate these recommendations to nectarines.

Grapes

Residue data were provided to the Meeting from trials in Europe on grapes.

The GAP for use on grapes in Italy is for foliar sprays of up to 0.028 kg ai/hL, with a PHI 14 days.

No trials matching this GAP were available, but in trials in southern Europe (Italy, Spain and France), involving spray concentrations of 0.015 kg ai/hL (0.15 kg ai/ha) and a PHI of 14 days, residues of etofenprox in grapes were: 0.25, 0.29, 0.35, 0.38, 0.39, 0.39, 0.53, 0.63, 0.96 and 1.4 mg/kg (n = 10).

The Meeting agreed that the results from these trials could be proportionally adjusted to match the Italian GAP. When scaled to the Italian GAP of 0.028 kg ai/hL (by multiplying by 1.87), etofenprox residues in grapes were: 0.47, 0.54, 0.65, 0.71, 0.73, 0.73, 0.99, 1.2, 1.8 and 2.6 mg/kg (n = 10).

The Meeting recommended an STMR of 0.73 mg/kg, an HR of 2.6 mg/kg and recommended a maximum residue level of 4 mg/kg for etofenprox in grapes.

Etofenprox 485

Cabbages, Head

Residue data were provided to the Meeting from trials in Southern Europe on cabbages (without wrapper leaves).

The GAP for use on cabbages in Italy is for foliar sprays of up to 0.014 kg ai/hL, applying 700–1500 L/ha and with a PHI of 7 days but no trials matching this GAP were available.

Tomatoes

Residue data were provided to the Meeting from trials in Brazil on tomatoes.

The GAP for use in Brazil is for foliar sprays of up to 0.02 kg ai/hL, applying about 300 L/ha and with a PHI of 7 days.

In trials matching this GAP, residues of etofenprox were < 0.01 and < 0.01 mg/kg.

The Meeting agreed the data were not sufficient to estimate an MRL for etofenprox in tomatoes.

Beans (dry)

Residue data were provided to the Meeting from trials in Brazil on dry beans.

The GAP for use in Brazil on beans is for foliar sprays of up to 0.15 kg ai/ha, applying about 300–400 L/ha and with a PHI of 3 days.

In trials matching this GAP, residues of etofenprox in beans (without pods) were: < 0.01, < 0.01, < 0.01, < 0.05, < 0.05, < 0.05 and < 0.05 mg/kg (n = 7).

The Meeting recommended an STMR of 0.05 mg/kg and recommended a maximum residue level of 0.05 mg/kg for etofenprox in beans (dry).

Potato

The results of three residue trials in Brazil were provided to the Meeting, but GAP for the use of etofenprox on potatoes was not available.

The Meeting agreed the data were not sufficient to estimate an MRL for etofenprox in potatoes and withdrew the previous recommendation of 0.01 * mg/kg for potatoes.

Soya bean (dry)

Residue data were provided to the Meeting from trials in Brazil on soya beans.

The GAP for use on soya beans in Brazil is for foliar sprays of up to 0.15 kg ai/ha, applying about 100-250 L/ha and with a PHI of 15 days

In trials matching this GAP, residues of etofenprox on soya bean seeds were: < 0.01, < 0.05 and < 0.05 mg/kg.

The Meeting agreed the data were not sufficient to estimate an MRL for etofenprox in soya bean (dry)

Wheat

Residue data were provided to the Meeting from trials in Brazil on wheat.

The GAP for use on wheat in Brazil is for foliar sprays of up to 0.03 kg ai/ha in about 100 L/ha, and with a PHI of 16 days.

In one trial matching the GAP application rate (0.03 kg ai/ha) and with a PHI of 3 days, etofenprox residues in wheat grain were < 0.01 mg/kg.

The Meeting agreed the data were not sufficient to estimate an MRL for etofenprox in wheat.

486 Etofenprox

Maize

Residue data were provided to the Meeting from trials in Brazil on maize.

The GAP for use on maize in Brazil is for foliar sprays of up to 0.03 kg ai/ha in 300–400 L/ha, and with a PHI of 3 days.

In trials matching this GAP, etofenprox residues in maize kernels were: < 0.01, < 0.05, < 0.05, < 0.05, < 0.05 and < 0.05 mg/kg (n = 6).

Two additional trials involving application rates 1.5 × GAP also reported etofenprox residues of < 0.01 mg/kg (2)

The Meeting estimated an STMR of 0.05 mg/kg, an HR of 0.05 mg/kg and recommended a maximum residue level of 0.05 * mg/kg in maize.

Rice

Residue data were provided to the Meeting from trials in Brazil (no GAP), Japan and USA on rice.

GAP in Japan is for use as a foliar spray, with up to 3 applications of 0.02 kg ai/hL and a 21 day PHI but no trials matching this GAP were available.

GAP in USA is as a granular broadcast application to paddy rice, applying up to 0.3 kg ai/ha, 1–7 days after flooding and with a PHI of 60 days.

In trials in USA matching the GAP of the USA, residues of etofenprox in whole rice grain were: < 0.01, < 0.01, < 0.01, < 0.01, < 0.01, < 0.01 and < 0.01 mg/kg. In two further trials in USA, involving exaggerated (5×) rates of 1.5 kg ai/ha, residues in whole rice grain were also < 0.01 and < 0.01 mg/kg.

The Meeting estimated an STMR of 0.0 mg/kg and an HR of 0.0 mg/kg and recommended a maximum residue level of 0.01 * mg/kg for etofenprox in rice.

Coffee

Six trials from Brazil on coffee were provided to the meeting, but information on GAP for use on coffee in Brazil was not available.

Cotton seed

Residue data were provided to the Meeting from trials in Brazil on cotton.

GAP in Brazil is for foliar sprays of up to 0.3 kg ai/ha in 300-400 litres water/ha and with a PHI of 15 days.

In trials matching this GAP, etofenprox residues were: < 0.01, < 0.05, < 0.05 and < 0.05 mg/kg.

The Meeting agreed the data were not sufficient to estimate an MRL for etofenprox in cotton seed.

Oil seed rape

Residue data were provided to the Meeting from trials in Northern Europe on oil seed rape.

The GAP for use in Germany is for up to 2 foliar sprays up to the start of flowering, applying up to 0.058 kg ai/ha in about 200 L/ha.

In trials from Germany and UK matching this GAP, etofenprox residues were: < 0.01, < 0.01, < 0.01, < 0.01, < 0.01, < 0.01, < 0.01 and < 0.01 mg/kg.

The Meeting estimated an STMR of 0.01 mg/kg and an HR of 0.01 mg/kg and recommended a maximum residue level of 0.01 * mg/kg for etofenprox on oil seed rape.

Etofenprox 487

Animal feeds

Rice straw

In trials from USA matching the USA GAP (0.3 kg ai/ha, 1–7 days after flooding, PHI 60 days), etofenprox residues in rice straw were: < 0.01, < 0.01, < 0.01, < 0.01, 0.01 and 0.025 mg/kg.

The Meeting estimated a median residue of 0.01 mg/kg, a highest residue of 0.025 mg/kg and recommended a maximum residue level of 0.05 mg/kg for etofenprox on rice straw.

Fate of residues during processing

The effect of processing on the nature of residues was investigated in buffer solutions under a range of hydrolysis conditions. Etofenprox was shown to be stable under these conditions.

Processing studies reflecting household or commercial practices were provided for rape seeds, grapes, peaches and apples. Estimated processing factors and calculated STMR-Ps for commodities considered at this meeting are summarised below.

Summary of selected processing factors and STMR-Ps for etofenprox


STMR (mg/kg)

HR (mg/kg)

Processed commodity

Calculated processing factors a Processing factor

STMR-P (mg/kg)

HR-P (mg/kg)

Grape 0.73 2.6 Juice b < 0.05, < 0.04, < 0.03, < 0.01, 0.007

< 0.03 (median) 0.022

Wine b < 0.05, < 0.04, < 0.03 < 0.04 (median 0.029

Raisins 2.5, 1.6 2.1 (mean) 1.53 5.46

Apples 0.2 0.34 Puree 0.32, 0.29, < 0.09 0.305 c 0.061

Juice < 0.09, < 0.06, 0.045 < 0.06 (median) 0.012

Canned apples < 0.09 < 0.09 0.018

Press cake (wet pomace)

3.6, 2.2, 2.2 2.7 (mean) 0.53

Dry pomace 13 13 2.6

Peach 0.16 0.37 Juice < 0.32, < 0.05, < 0.04 < 0.05 (median) 0.008

purée 1.7, 0.67, 0.32 0.67 (median) 0.107

Canned peaches < 0.11 < 0.11 0.018

a Ratio of the total residue in the processed item/total residue in the RAC (if above the LOQ). b Residues < 0.01 in all samples. c Best estimate (mean of the two highest values)

The Meeting noted that the HR for etofenprox in grapes was 2.6 mg/kg and based on the mean processing factor of 2.1, the calculated highest residue in raisins is 5.5 mg/kg and the Meeting recommended a maximum residue level of 8 mg/kg for dried grapes (raisins).

Residues in animal commodities

Farm animal dietary burden

The Meeting estimated the dietary burden of etofenprox in farm animals on the basis of the diets listed in Annex 6 of the 2009 JMPR Report (OECD Feedstuffs Derived from Field Crops) and the STMR or

488 Etofenprox

highest residue levels estimated for etofenprox (parent only) at the present Meeting. Dietary burden calculations are provided in Annex 6 of the 2011 JMPR Report and are summarised below.

Animal dietary burden for etofenprox, ppm of dry matter diet Maximum Dietary Burden Mean Dietary Burden

Beef cattle 0.277 a 0.267 b Dairy cattle 0.136 c 0.132 d Poultry broiler 0.0 0.0 Poultry layer 0.0 0.0

a Used for calculating HRs and estimating maximum residue levels for mammalian tissues, based on highest residue in individual animals in relevant dose groups b Used for calculating STMRs for mammalian tissues, based on mean residues in relevant dose groups c Used for calculating highest residues in milk, based on mean residues in relevant dose groups d Used for calculating the STMR for milk, based on mean residues in relevant dose groups

Farm animal feeding studies

The Meeting received information on the residue levels arising in animal tissues and milk when dairy cows were dosed with etofenprox for 28–30 days at 10, 30 and 1000 mg ai/cow/day (equivalent to about 0.5 ppm, 1.5 ppm and 50 ppm in the diet).

In milk, etofenprox residues were at or below the LOQ (0.05 mg/kg) in the 1× and 3× dose groups and in the 200× dose group, residues of 0.66 mg/l were detected on day 2 of the dosing period, increasing to a maximum of 2.11 mg/l. Over the withdrawal period, residues declined rapidly during the first 5-6 days with a slower decline over the last 7–8 days.

In liver, kidney and skeletal muscle, residues of etofenprox were all below the LOQ (0.05 mg/kg) from cows in the 1× and 3× dose groups. In the 200× dose group, residues were detected in all of the analysed tissues, up to 1.16 mg/kg in kidney, 0.63 mg/kg in liver and 0.35 mg/kg in skeletal muscle and were also measurable in all tissues (except liver) at the end of the 14-day withdrawal period.

Residues in peritoneal fat were up to 0.54 mg/kg (1×) and 1.89 mg/kg (3×) and in subcutaneous fat were up to 0.28 mg/kg (1×) and 0.5 mg/kg (3×). In the 200× dose group, residues were up to 14.3 mg/kg in peritoneal fat and 3.54 mg/kg in subcutaneous fat and were also measurable at the end of the 14-day withdrawal period.

Animal commodity maximum residue levels

Cattle

For MRL estimation, the high residues in the tissues were calculated by extrapolating the maximum dietary burden (0.277 ppm) from the 0.5 ppm feeding level in the dairy cow feeding study and using the highest tissue concentrations from individual animals within those feeding groups.

The STMR values for the tissues were calculated by extrapolating the mean dietary burden (0.267 ppm) from the 0.5 ppm feeding level in the dairy cow feeding study and using the mean tissue concentrations from those feeding groups.

For milk MRL estimation, the high residues in the milk were calculated by extrapolating the maximum dietary burden for dairy cattle (0.136 ppm) from the 0.5 ppm feeding levels in the dairy cow feeding study and using the mean milk concentrations from those feeding groups.

The STMR value for milk was calculated by extrapolating the mean dietary burden for dairy cattle (0.132 ppm) from the 0.5 ppm feeding levels in the dairy cow feeding study and using the mean milk concentrations from those feeding groups.

Etofenprox 489

Feed level (ppm) for milk

residues

Residues (mg/kg) in

milk

Feed level (ppm) for

tissue residues

Etofenprox residues (mg/kg) in: Muscle Liver Kidney Fat c

MRL beef or dairy cattle Feeding study a 0.5 < 0.05 0.5 < 0.05 < 0.05 < 0.05 0.54

Dietary burden and residue estimate 0.136 < 0.014 0.277 < 0.028 < 0.028 < 0.028 0.3 STMR beef or dairy cattle Feeding study b 0.5 < 0.05 0.5 < 0.05 < 0.05 < 0.05 0.39

Dietary burden and residue estimate 0.132 < 0.013 0.267 < 0.027 < 0.027 < 0.027 0.208 a Highest residues for tissues and mean residues for milk b Mean residues for tissues and for milk c Peritoneal fat

Maximum residues of etofenprox in cattle tissues are: 0.3 mg/kg in fat and < 0.03 mg/kg in muscle, liver and kidney. The mean residue for milk is < 0.014 mg/kg.

The Meeting estimated maximum residue levels of 0.5 mg/kg (fat) for etofenprox in meat (from mammals other than marine mammals), 0.05 mg/kg for edible offal (mammalian) and 0.02 mg/kg for milks.

Estimated HRs for dietary intake estimation for etofenprox are 0.3 mg/kg for mammalian fat and 0.03 mg/kg for mammalian muscle, liver and kidney.

Estimated STMRs for dietary intake estimation for etofenprox are 0.21 mg/kg for mammalian fat, 0.03 mg/kg for muscle, liver and kidney and 0.013 mg/kg for milks.

Poultry

None of the animal feed commodities considered by the Meeting contributed to the dietary burden for poultry layers or broilers.

The Meeting estimated maximum residue levels of 0.01 (*) mg/kg for etofenprox in poultry meat, fat, offal and eggs and the estimated HRs and STMRs for dietary intake estimation are 0.0 mg/kg for poultry meat, fat, offal and eggs.

RECOMMENDATIONS

On the basis of the data from supervised trials the Meeting concluded that the residue levels listed below are suitable for establishing maximum residue limits and for IEDI assessment.

Definition of the residue for plant and animal commodities (for compliance with MRL and estimation of dietary intake): etofenprox.

The residue is fat soluble.

Commodity MRL Recommendation mg/kg

STMR or HR

CCN Name New Prev STMR-P FP 0226 Apple 0.6 0.2 0.34 VD 0071 Beans (dry) 0.05 0.05 DF 5263 Dried grapes (currants, raisins, sultanas) 8 1.5 5.5 MO 0105 Edible offal (mammalian) 0.05 0.03 liver

0.03 kidney 0.03 liver 0.03 kidney

PE 0112 Eggs 0.01 (*) 0.0 0.0 FB 0269 Grape 4 0.73 2.6 GC 0645 Maize 0.05 (*) 0.05 0.05

490 Etofenprox

Commodity MRL Recommendation mg/kg

STMR or HR

CCN Name New Prev STMR-P MM 0095 Meat (from mammals other than marine

mammals) 0.5 (fat) 0.03 muscle

0.21 fat 0.03 muscle 0.3 fat

ML 0106 Milks 0.02 0.013 FS 0245 Nectarine 0.6 0.16 0.37 FS 0247 Peach 0.6 0.16 0.37 FP 0230 Pears 0.6 0.2 0.34 FP 0009 Pome fruits W 1 VR 0589 Potato W 0.01 (*) PM 0110 Poultry meat 0.01 (*) 0.0 0.0 PO 0111 Poultry, Edible offal of 0.01 (*) 0.0 0.0 SO 0495 Rape seed 0.01 (*) 0.01 0.01 GC 0649 Rice 0.01 (*) 0.0 0.0 AS 0469 Rice straw and fodder, dry 0.05 0.01 0.025 JF 0226 Apple juice 0.012 AB 1230 Apple pomace (wet) 0.53 Apple purée 0.05 Canned apples 0.018 Canned peaches 0.018 JF 0269 Grape juice 0.029 Peach juice 0.008 Wine 0.029

DIETARY RISK ASSESSMENT

Long-term intake

The International Estimated Daily Intake (IEDI) for etofenprox was calculated for the food commodities for which STMRs or HRs were estimated and for which consumption data were available. The results are shown in Annex 3 of the 2011 JMPR Report.

The International Estimated Daily Intakes of etofenprox for the 13 GEMS/Food regional diets, based on estimated STMRs were 1–3% of the maximum ADI of 0.03 mg/kg bw (See Annex 3 of the 2011 JMPR Report). The Meeting concluded that the long-term intake of residues of etofenprox from uses that have been considered by the JMPR is unlikely to present a public health concern.

Short-term intake

The International Estimated Short-term Intake (IESTI) for etofenprox was calculated for the food commodities for which STMRs or HRs were estimated and for which consumption data were available (see Annex 4 of the 2011 JMPR Report).

For etofenprox the IESTI varied from 0–10% of the ARfD (1 mg/kg bw) for the diets submitted in 2011. The Meeting concluded that the short-term intake of residues of etofenprox from uses considered by the Meeting is unlikely to present a public health concern.

REFERENCES Reference Principal Author Year Title, Report reference 21024 McCorquodale

GY 2002 Physico-chemical testing with [14C]-Alpha-CO: partition coefficient. Inveresk

Research, Report No. 21024. Inveresk Research, Report No. 21024. Mitsui Chemicals Agro, Inc. GLP, unpublished

Etofenprox 491

Reference Principal Author Year Title, Report reference 21386 McCorquodale G

Y 2002 Physico-chemical testing with [14C]-Alpha-CO: water solubility. Inveresk Research,

Report No: 21386. Inveresk Research, Report No: 21386. Mitsui Chemicals Agro, Inc. GLP, unpublished

21993 Clayton MA 2003 Hydrolytic stability of [14C]-alpha-CO in buffered aqueous solution. Inveresk Research, Report No. 21993. Inveresk Research, Report No. 21993. Mitsui Chemicals Agro, Inc. GLP, unpublished

200102 Mitsui 2001 Analysis of etofenprox and α-CO in crops.(GC/MS method) Ver.200102. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. Not specified. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. Not specified. Mitsui Chemicals Agro, Inc. Unpublished

692728 Tognucci A 1998 Determination of the relative density of etofenprox. RCC Ltd, Report No. 692728. RCC Ltd, Report No. 692728. Mitsui Chemicals Agro, Inc. GLP, unpublished

692730 Tognucci A 1998 Determination of the boiling point / boiling range of etofenprox. RCC Ltd, Report No: 692730. RCC Ltd, Report No: 692730. Mitsui Chemicals Agro, Inc. GLP, unpublished

692741 Schmiedel U 1998 Expert statement on the dissociation of MTI-500 (etofenprox) in water. RCC Ltd, Report No. 692741. RCC Ltd, Report No. 692741. Mitsui Chemicals Agro, Inc. Unpublished

692752 Tognucci A 1998 Determination of the solubility of etofenprox in organic solvents. RCC Ltd, Report No. 692752. RCC Ltd, Report No. 692752. Mitsui Chemicals Agro, Inc. GLP, unpublished

692763 Tognucci A 1998 Determination of the partition coefficient (N-octanol / water) of etofenprox and amendment dated October 13, 1999. RCC Ltd, Report No. 692763. RCC Ltd, Report No. 692763. Mitsui Chemicals Agro, Inc. GLP, unpublished

718830 Tognucci A 1999 Determination of the melting point / melting range of etofenprox. RCC Ltd, Report No. 718830. RCC Ltd, Report No. 718830. Mitsui Chemicals Agro, Inc. GLP, unpublished

731158 van der Gaauw A 2001 14C-etofenprox: hydrolysis at three different pH values. RCC Ltd, Report No. 731158. RCC Ltd, Report No. 731158. Mitsui Chemicals Agro, Inc. GLP, unpublished

751803 Tognucci A 2000 Determination of the vapour pressure of etofenprox. RCC Ltd, Report No. 751803. RCC Ltd, Report No. 751803. Mitsui Chemicals Agro, Inc. GLP, unpublished

755515 Kunz C 2000 Determination of the water solubility of 14C-etofenprox at three pH values and amendment dated October 04, 2000. RCC Ltd, Report No. 755515. RCC Ltd, Report No. 755515. Mitsui Chemicals Agro, Inc. GLP, unpublished

755526 van der Gaauw A 2003 Aqueous photolysis of [14C]-etofenprox under laboratory conditions and determination of quantum yield. RCC Ltd, Report No. 755526. RCC Ltd, Report No. 755526. Mitsui Chemicals Agro, Inc. GLP, unpublished

784168 Völkel W 2002 14C-MTI-500: plant metabolism in grapes. RCC Ltd, Report No. 784168. RCC Ltd, Report No. 784168. Mitsui Chemicals Agro, Inc. GLP, unpublished

784170 Völkel W 2002 14C-MTI-500: plant metabolism in rape. RCC Ltd, Report No. 784170. RCC Ltd, Report No. 784170. Mitsui Chemicals Agro, Inc. GLP, unpublished

789377 Wolf S 2003 Validation of the residue analytical method for MTI-500 and α-CO in cucumber. RCC Ltd, Report No. 789377. RCC Ltd, Report No. 789377. Mitsui Chemicals Agro, Inc. GLP, unpublished

789390 Wolf S 2001 Validation of the residue analytical method for MTI-500 and α-CO in oil seed rape. RCC Ltd, Report No. 789390. RCC Ltd, Report No. 789390. Mitsui Chemicals Agro, Inc. GLP, unpublished

789401 Wolf S 2002 Validation of the residues analytical method for MTI-500 and α-CO in grape (bunches). RCC Ltd, Report No. 789401. RCC Ltd, Report No. 789401. Mitsui Chemicals Agro, Inc. GLP, unpublished

791245 Wolf S 2003 Development and validation of the residue analytical method for MTI-500 and α-CO in meat (ruminant and chicken), milk, fat (ruminant) and egg. RCC Ltd, Report No. 791245. RCC Ltd, Report No. 791245. Mitsui Chemicals Agro, Inc. GLP, unpublished

799233 Burri R 2002 [14C]-MTI-500: adsorption, distribution, metabolism and excretion after repeated oral administration to lactating goats. RCC Ltd, Report No. 799233. RCC Ltd, Report No. 799233. Mitsui Chemicals Agro, Inc. GLP, unpublished

799244 Burri R 2003 [14C]-MTI-500: absorption, distribution, metabolism and excretion after repeated oral administration to laying hens. RCC Ltd, Report No. 799244. RCC Ltd, Report No. 799244. Mitsui Chemicals Agro, Inc. GLP, unpublished

802888 Wolf S 2003 MTI-500: storage stability in oil seed rape (RAC seeds). RCC Ltd, Report No. 802888. RCC Ltd, Report No. 802888. Mitsui Chemicals Agro, Inc. GLP,

492 Etofenprox

Reference Principal Author Year Title, Report reference unpublished

807017 Wais A 2002 Determination of residues of MTI-500 and its metabolite α-CO in/on winter rape following treatment with MTI-500 30% EC from two field trials (harvest trials) in Germany; 2001, includes trials A/GE/I/02/28, A/GE/I/02/29. RCC Ltd, Report No. 807017. RCC Ltd, Report No. 807017. Mitsui Chemicals Agro, Inc. GLP, unpublished

807028 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on winter rape (RAC Seeds) following treatment with MTI-500 30% EC from two field trials (harvest trial) in UK; 2001, includes trials A/UK/I/02/26, A/UK/I/02/27. RCC Ltd, Report No. 807028. RCC Ltd, Report No. 807028. Mitsui Chemicals Agro, Inc. GLP, unpublished

810900 Wolf S 2003 Alpha-CO: storage stability in oil seed rape (RAC seeds). RCC Ltd, Report No. 810900. RCC Ltd, Report No. 810900. Mitsui Chemicals Agro, Inc. GLP, unpublished

814588 Wolf S 2002 Validation of the residue analytical method for MTI-500 and a-CO in cabbage. RCC Ltd, Report No. 814588. RCC Ltd, Report No. 814588. Mitsui Chemicals Agro, Inc. GLP, unpublished

815084 Mamouni A 2002 14C-MTI-500: plant metabolism in lettuce. RCC Ltd, Report No. 815084. RCC Ltd, Report No. 815084. Mitsui Chemicals Agro, Inc. GLP, unpublished

820326 Wais A 2002 Determination of residues of MTI-500 and its metabolite α-CO in/on cabbage (RAC heads) following treatment with MTI-500 30% EC from two field trials (one harvest trial and one residue decline study) in Spain; 2001, includes trials A/SP/I/01/47, A/SP/I/01/48. RCC Ltd, Report No. 820326. RCC Ltd, Report No. 820326. Mitsui Chemicals Agro, Inc. GLP, unpublished

820337 Wais A 2002 Determination of residues of MTI-500 and its metabolite α-CO in/on head cabbage (RAC heads) following treatment with MTI-500 30% EC from two field trials (one harvest trial and one residue decline study) in Italy; 2001, includes trials A/IT/I/01/45, A/IT/I/01/46. RCC Ltd, Report No. 820337. RCC Ltd, Report No. 820337. Mitsui Chemicals Agro, Inc. GLP, unpublished

820348 Wais A 2002 Determination of residues of MTI-500 and its metabolite α-CO in/on grapes (RAC grapes) following treatment with MTI-500 30% EC from two field trials (one harvest trial and one residue decline study) in Spain; 2001, includes trials A/SP/I/01/43 and A/SP/I/01/44. RCC Ltd, Report No. 820348. RCC Ltd, Report No. 820348. Mitsui Chemicals Agro, Inc. GLP, unpublished

820350 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on grapes (RAC grapes) following treatment with MTI-500 30% EC from two field trials in Italy; 2001–first amendment dated October 01, 2003, includes trials A/IT01/41 and A/IT01/42. RCC Ltd, Report No. 820350. RCC Ltd, Report No. 820350. Mitsui Chemicals Agro, Inc. GLP, unpublished

843535 Wolf S 2005 Etofenprox (MTI-500) and α-CO: storage stability in grape (bunches). RCC Ltd, Report No. 843535. RCC Ltd, Report No. 843535. Mitsui Chemicals Agro, Inc. GLP, unpublished

843536 Wolf S 2005 Etofenprox (MTI-500) and α-CO: storage stability in cabbage. RCC Ltd, Report No. 843536. RCC Ltd, Report No. 843536. Mitsui Chemicals Agro, Inc. GLP, unpublished

843554 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on head cabbage (RAC heads) following treatment with MTI-500 30%EC from two field trials (one harvest trial and one residue decline study) in Italy; 2002, includes trials A/IT/I/02/41, A/SP/I/02/42. RCC Ltd, Report No. 843554. RCC Ltd, Report No. 843554. Mitsui Chemicals Agro, Inc. GLP, unpublished

843555 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on head cabbage (RAC heads) following treatment with MTI-500 30%EC from two fields trials (one harvest trial and one residue decline study) in Spain; 2002, includes trials A/SP/I/02/39, A/SP/I/02/40. RCC Ltd, Report No. 843555. RCC Ltd, Report No. 843555. Mitsui Chemicals Agro, Inc. GLP, unpublished

843556 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on winter rape (RAC seeds) following treatment with MTI-500 30%EC from two field trials (harvest trials) in Germany; 2002 , includes trials A/GE/I/02/31, A/GE/I/02/32. RCC Ltd, Report No. 843556. RCC Ltd, Report No. 843556. Mitsui Chemicals Agro, Inc. GLP, unpublished

Etofenprox 493

Reference Principal Author Year Title, Report reference 843557 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on winter rape

(RAC seeds) following treatment with MTI-500 30%EC from two field trials (harvest trials) in the UK; 2002, includes trials A/UK/I/02/33, A/UK/I/02/34. RCC Ltd, Report No. 843557. RCC Ltd, Report No. 843557. Mitsui Chemicals Agro, Inc. GLP, unpublished

843558 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on grapes (RAC grapes) following treatment with MTI-500 30%EC from two fields trials (one harvest trial and one residue decline study) in Southern France; 2002, includes trials A/SF/I/02/37 and A/SF/I/02/38. RCC Ltd, Report No. 843558. RCC Ltd, Report No. 843558. Mitsui Chemicals Agro, Inc. GLP, unpublished

843559 Wais A 2003 Determination of residues of MTI-500 and its metabolite α-CO in/on grapes (RAC grapes) following treatment with MTI-500 30%EC from two fields trials (one harvest trial and one residue decline study) in Italy; 2002, includes trials A/IT/I/02/35 and A/IT/I/02/36. RCC Ltd, Report No. 843559. RCC Ltd, Report No. 843559. Mitsui Chemicals Agro, Inc. GLP, unpublished

843640 Diehl M 2003 Confined accumulation of 14C-MTI-500 in rotational crops. RCC Ltd, Report No. 843640. RCC Ltd, Report No. 843640. Mitsui Chemicals Agro, Inc. GLP, unpublished

848642 Wais A 2004 Determination of residues of MTI-500 and its metabolite α-CO in/on peach (RAC fruits) following treatment with MTI-500 30%EC from one field trial (residue decline study) in Spain; 2003. RCC Ltd, Report No. 848642. RCC Ltd, Report No. 848642. Mitsui Chemicals Agro, Inc. GLP, unpublished

848643 Wais A 2004 Determination of residues of MTI-500 and its metabolite α-CO in/on apple (RAC fruits) following treatment with MTI-500 30% EC from four field trials (two harvest trials and two residue decline studies) in Spain; 2003, includes trials A/SP/I/03/52, A/SP/I/03/53, A/SP/I/03/54, A/SP/I/03/55. RCC Ltd, Report No. 848643. RCC Ltd, Report No. 848643. Mitsui Chemicals Agro, Inc. GLP, unpublished

013194-1 Panthani A 2002 Metabolism of [14C]MTI-500 in rice (soil treatment and postemergence spray treatment). Ricerca, LLC, Report No. 013194-1. Ricerca, LLC, Report No. 013194-1. Mitsui Chemicals Agro, Inc. GLP, unpublished

019820-1 Cassidy P 2006 Independent laboratory validation of an LC-MS/MS method for determination of residues of etofenprox and a-CO in rice grain and rice straw. Ricerca Biosciences; Study No.: 019820-1. Ricerca Biosciences; Study No.: 019820-1. Mitsui Chemicals Agro, Inc. GLP, unpublished

04-alpha-08 Kratz T 2005 Determination of the residues of MTI-500 and its metabolite α-CO in/on grapes (RAC grapes) following treatment with Trebon 30 EC from three field trials (two harvest trials and one residue decline study) in Northern France; 2004- first amendment dated February 17, 2005, includes trials S04LKRALPHGG58 and S04LKRALPHTD62. Landis Kane Consulting, Report No. 04ALPHA08. Landis Kane Consulting, Report No. 04ALPHA08. Mitsui Chemicals Agro, Inc. GLP, unpublished

05-alpha-19 Kratz T 2006 Determination of residues of MTI-500 and its metabolite α-CO in/on peaches (RAC) and on processed samples following two applications of Trebon 30 EC from two field trials (one harvest and one residue decline) in Southern France; 2005 .- first amendment dated July 20, 2007, includes trials X05 170 519FR02 and X05 170 519FR01. Landis Kane Consulting, Report No. 05ALPHA19. Landis Kane Consulting, Report No. 05ALPHA19. Mitsui Chemicals Agro, Inc. GLP, unpublished

05-alpha-20 Kratz T 2006 Determination of residues of MTI-500 and its metabolite α-CO in/on apples (RAC) and on processed samples following two applications of Trebon 30 EC from one field trial (harvest study) in Southern France; 2005- first amendment dated July 20, 2007. Landis Kane Consulting, Report No. 05ALPHA20. Landis Kane Consulting, Report No. 05ALPHA20. Mitsui Chemicals Agro, Inc. GLP, unpublished

05-alpha-21 Kratz T 2006 Determination of residues of MTI-500 and its metabolite α-CO in/on grapes (RAC) and on processed samples following two applications of Trebon 30 EC from three field trials (two harvest and one residue decline) in Northern France; 2005–first amendment dated July 20, 2007, includes trials A5115AN1, A5115AL1, A5115CT1. Landis Kane Consulting, Report No. 05ALPHA21. Landis Kane Consulting, Report No. 05ALPHA21. Mitsui Chemicals Agro, Inc. GLP, unpublished

494 Etofenprox

Reference Principal Author Year Title, Report reference 05-alpha-22 Kratz T 2006 Determination of residues of MTI-500 and its metabolite α-CO in/on grapes (RAC

grapes) following two applications of trebon 30 EC from two field trials (one harvest and one residue decline) in Germany; 2005–first amendment dated July 20, 2007, includes trials A5116GE1, A5166HA1. Landis Kane Consulting, Report No. 05ALPHA22. Landis Kane Consulting, Report No. 05ALPHA22. Mitsui Chemicals Agro, Inc. GLP, unpublished

06-alpha-74 Mirbach M 2006 Etofenprox: comments on the physical state. Landis Kane Consulting, Report No. 06-alpha-74. Landis Kane Consulting, Report No. 06-alpha-74. Mitsui Chemicals Agro, Inc. Unpublished

116/99 Pastor Ciscato CH 1999 Analysis of Corn after Application of Trebon 100SC (etofenprox). INSTITUTO BIOLOGICO. Report No. 116/99, Study No. 122 aS/99. . INSTITUTO BIOLOGICO. Report No. 116/99, Study No. 122 aS/99. . SIPCAM ISAGRO BRASIL S.A Unpublished

117/99 Pastor Ciscato CH 1999 Analysis report: Trebon 100SC residues (etofenprox) in/on soybean. INSTITUTO BIOLOGICO. Report No. 117/99, Study No. 123 aS/99. INSTITUTO BIOLOGICO. Report No. 117/99, Study No. 123 aS/99. SIPCAM ISAGRO BRASIL S.A Unpublished

118/99 Pastor Ciscato CH 1999 Analysis report: Trebon 100SC residues (etofenprox) in/on bean. INSTITUTO BIOLOGICO. Report No. 118/99, Study No. 124 aS/99. INSTITUTO BIOLOGICO. Report No. 118/99, Study No. 124 aS/99. SIPCAM ISAGRO BRASIL S.A Unpublished

119/99 Pastor Ciscato CH 1999 Analysis report: Trebon 100SC residues (etofenprox) in/on tomato–revised report dated October 19, 1999. INSTITUTO BIOLOGICO. Report No. 119/99, Study No. 125 aS/99. INSTITUTO BIOLOGICO. Report No. 119/99, Study No. 125 aS/99. SIPCAM ISAGRO BRASIL S.A Unpublished

120/99 Pastor Ciscato CH 1999 Analysis report: Trebon 100SC residues (etofenprox) in/on tomato–revised report dated October 19, 1999. INSTITUTO BIOLOGICO. Report No. 120/99, Study No. 126 aS/99. INSTITUTO BIOLOGICO. Report No. 120/99, Study No. 126 aS/99. SIPCAM ISAGRO BRASIL S.A Unpublished

122/99 Pastor Ciscato CH 1999 Analysis Report: Trebon 300 CE Residues (etofenprox) in/on soybean. INSTITUTO BIOLÓGICO. Report No. 122/99, Study No. R/99/RS143/Plantec. INSTITUTO BIOLÓGICO. Report No. 122/99, Study No. R/99/RS143/Plantec. SIPCAM ISAGRO BRASIL S.A Unpublished

132/87587 Roberts NL 1987 Residues of etofenprox in the milk and tissues of dairy cows. Huntingdon Research Centre Ltd., Huntingdon, Cambridgeshire, PE18 6ES, England, Report No. MTC 132/87587. Huntingdon Research Centre Ltd., Huntingdon, Cambridgeshire, PE18 6ES, England, Report No. MTC 132/87587. Mitsui Chemicals Agro, Inc. GLP, unpublished

200104B Mitsui 2001 Analysis of etofenprox and α-CO in meat (beef) (GC/MS method) Ver.200104. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. not specified. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. not specified. Mitsui Chemicals Agro, Inc. Unpublished

200104E Mitsui 2001 Analysis of etofenprox and α-CO in eggs (GC/MS method) Ver.200104. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. not specified. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. not specified. Mitsui Chemicals Agro, Inc. Unpublished

200104M Mitsui 2001 Analysis of etofenprox and α-CO in milk (GC/MS method) Ver.200104. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. not specified. Mitsui Chemicals, Inc. Life Science Laboratory, Report No. not specified. Mitsui Chemicals Agro, Inc. Unpublished

2144/96 Casadei de Baptista G

1996 Analysis of pesticide residues Trebon 300CE in corn. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. 2144/96. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. 2144/96. SIPCAM ISAGRO BRASIL S.A Unpublished

2273/97 Casadei de Baptista G

1997 Analysis of Trebon 300CE residues in bean. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. 2273/97. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. 2273/97. SIPCAM ISAGRO BRASIL S.A Unpublished

236C-136 Nixon W 2006 Analytical method validation for the determination of etofenprox and a-CO in rice and rice straw. Wildlife International, Ltd., Report No. 236C-136. Wildlife International, Ltd., Report No. 236C-136. Mitsui Chemicals Agro, Inc. GLP, unpublished

236C-138 MacGregor JA 2006 Freezer storage stability for etofenprox and α-CO in rice and rice straw. Wildlife International Ltd., Report No 236C-138. Wildlife International Ltd., Report No 236C-138. Mitsui Chemicals Agro, Inc. GLP, unpublished

Etofenprox 495

Reference Principal Author Year Title, Report reference 236C-146 Martin K & Nixon

W 2007 Assessment of multi-residue methodology as presented in the Pesticide Analytical

Manual (PAM), Volume 1, for the determination of etofenprox and α-CO in rice. Wildlife International Ltd., Report No 236C-146. Mitsui Chemicals Agro, Inc. GLP, unpublished

32/99 Pastor Ciscato CH 1999 Analysis of beans after the application of Trebon 100SC (etofenprox). INSTITUTO BIOLOGICO. Study No. 32/99. INSTITUTO BIOLOGICO. Study No. 32/99. SIPCAM ISAGRO BRASIL S.A Unpublished

33/99 Pastor Ciscato CH 1999 Analysis of Corn after Application of Trebon 100SC (etofenprox). INSTITUTO BIOLOGICO. Study No. 33/99. INSTITUTO BIOLOGICO. Study No. 33/99. SIPCAM ISAGRO BRASIL S.A Unpublished

34/99 Pastor Ciscato CH 1999 Analysis of soybean after application of Trebon 100SC (etofenprox). INSTITUTO BIOLOGICO. Study No. 34/99. INSTITUTO BIOLOGICO. Study No. 34/99. SIPCAM ISAGRO BRASIL S.A Unpublished

43406A027 Hummel R 2006 Raw agricultural commodity (RAC) residue evaluation of etofenprox applied to rice. Landis International, Inc., Report No. 43406A027. Landis International, Inc., Report No. 43406A027. Mitsui Chemicals Agro, Inc. GLP, unpublished

43406A028 Hummel R 2007 Raw agricultural commodity (RAC) residue evaluation of etofenprox applied to rice. Landis International, Inc., Report No. 43406A028. Landis International, Inc., Report No. 43406A028. Mitsui Chemicals Agro, Inc. GLP, unpublished

43406A029 Hummel R 2007 Processed commodity (PC) residue evaluation of etofenprox applied to rice. Landis International, Inc., Report No. 43406A029. Landis International, Inc., Report No. 43406A029. Mitsui Chemicals Agro, Inc. GLP, unpublished

692-G Class T 2003 Etofenprox: independent laboratory validation of analytical methods used for the determination of residues of etofenprox in plant materials. PTRL Europe GmbH, Report No. P 692 G. PTRL Europe GmbH, Report No. P 692 G. Mitsui Chemicals Agro, Inc. GLP, unpublished

A-32-02-01 Dubey L 2003 Method validation for the determination of etofenprox (MTI-500) and α-CO in apples. Battelle, Report No. A-32-02-01. Battelle, Report No. A-32-02-01. Mitsui Chemicals Agro, Inc. GLP, unpublished

A-32-02-02 Dubey L 2003 Method validation for the determination of etofenprox (MTI-500) and α-CO in peaches. Battelle, Report No. A-32-02-02. Battelle, Report No. A-32-02-02. Mitsui Chemicals Agro, Inc. GLP, unpublished

A-32-02-03 Dubey L 2005 Freezer storage stability of etofenprox (MTI-500) and metabolite α-CO in apples and peaches. Battelle, Report No. A-32-02-03. Battelle, Report No. A-32-02-03. Mitsui Chemicals Agro, Inc. GLP, unpublished

A39598 Adam D 2006 14C-Etofenprox and alpha-CO: hydrolysis study to investigate the nature of the residue after food processing. RCC Ltd, Report No. A39598. RCC Ltd, Report No. A39598. Mitsui Chemicals Agro, Inc. GLP, unpublished

D2142 Lewis CJ 2001 (14C)-MTI-500: degradation and retention in water-sediment systems and amendment dated July 22, 2002. Covance Laboratories Ltd., Report No. CLE 719/6-D2142. Covance Laboratories Ltd., Report No. CLE 719/6-D2142. Mitsui Chemicals Agro, Inc. GLP, unpublished

D2149 Lewis CJ 2002 (14C)-MTI-500: recovery of radioactivity, isolation and analysis of a degradation product from a water-sediment system. Covance Laboratories Ltd., Report No. CLE 719/14-D2149. Covance Laboratories Ltd., Report No. CLE 719/14-D2149. Mitsui Chemicals Agro, Inc. GLP, unpublished

ET1/PC Soler Gil-Mascarell JR

2002 Generation of peach specimens, suitable for residue analysis etofenprox following two applications of Trebon 30 (etofenprox 30% = 280 g/l EC), includes trials ET1/PC/S-01 and ET1/PC/S-02. SIPCAM Inagra S.A., Report No. ET1/PC. SIPCAM Inagra S.A., Report No. ET1/PC. Mitsui Chemicals Agro, Inc. GLP, unpublished

ET1/PC-p Domenichini P 2002 Processing studies with peach fruits following two applications of Trebon 30 (etofenprox 30% = 280 g/L EC) under field conditions (Spain 2001) (follow up study). SIPCAM Inagra S.A., Report No. ET1/PC-p. SIPCAM Inagra S.A., Report No. ET1/PC-p. Mitsui Chemicals Agro, Inc. GLP, unpublished

ET2/PC Soler Gil-Mascarell JR

2003 Generation of peach specimens, suitable for residue analysis of etofenprox following two applications of Trebon 30 (etofenprox 30% = 280 g/l EC), includes trials ET2/PC/S-01 and ET2/PC/S-02. SIPCAM Inagra S.A., Report No. ET2/PC. SIPCAM Inagra S.A., Report No. ET2/PC. Mitsui Chemicals Agro, Inc. GLP, unpublished

496 Etofenprox

Reference Principal Author Year Title, Report reference ET4 Domenichini P 2002 Generation of wine grape bunch samples, suitable for residue analysis following

application of etofenprox 280 g/L EC and for processed commodity of wine grape, include trials ET4/I/01VI and ET4/I/02VI. SIPCAM, Report No. ET4. SIPCAM, Report No. ET4. SIPCAM S.p.A. GLP, unpublished

ET4/I/01VIp Domenichini P 2002 Processing studies with grape bunches following two application of etofenprox 280 g/L EC under field conditions. SIPCAM, Report No. ET4/I/01VIp. SIPCAM, Report No. ET4/I/01VIp. SIPCAM S.p.A. GLP, unpublished

ET4/I/03/Sp Domenichini P 2002 Processing studies with peach fruits following two applications of etofenprox 280 g/L EC under field conditions (Italy 2001) (follow-up studies). SIPCAM S.p.A., Report No. ET4/I/03/Sp. SIPCAM S.p.A., Report No. ET4/I/03/Sp. Mitsui Chemicals Agro, Inc. GLP, unpublished

ET4/SIP Domenichini P 2002 Generation of peach fruit samples, suitable for residue analysis following application of etofenprox 280g/l EC and for processed commodity of peach, includes trials ET4/I/03PS and ET4/I/04PS. SIPCAM S.p.A., Report No. ET4 SIP. SIPCAM S.p.A., Report No. ET4 SIP. Mitsui Chemicals Agro, Inc. GLP, unpublished

ET5/ME Domenichini P 2003 Determination of the magnitude and residue of etofenprox 280 g/L EC in apple fruits and amendment dated September 19, 2003, includes trials ET5/I/10ME, ET5/I/11ME, ET5/I/12ME, ET5/I/13ME. SIPCAM S.p.A., Report No. ET5/ME. SIPCAM S.p.A., Report No. ET5/ME. Mitsui Chemicals Agro, Inc. GLP, unpublished

ET5/PS Domenichini P 2003 Determination of the magnitude and residue of etofenprox 280 g/L EC in peach fruits, includes trials ET5/I/07PS, ET5/I/08PS and ET5/I/09PS. SIPCAM S.p.A., Report No. ET5/PS. SIPCAM S.p.A., Report No. ET5/PS. Mitsui Chemicals Agro, Inc. GLP, unpublished

MT-25 Komoto N 1989 Crop Residue Analysis Report for etofenprox on paddy rice. Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 25, . Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 25, . Mitsui Chemicals Agro, Inc. Unpublished

MT-39 Komoto N 1992 Crop residue analysis report for etofenprox on paddy rice. Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 39, . Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 39, . Mitsui Chemicals Agro, Inc. Unpublished

MT-49 Ishikawa K 1993 Crop residue analysis report for etofenprox on paddy rice. Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 49, . Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 49, . Mitsui Chemicals Agro, Inc. Unpublished

MT-61 Ishikawa K 1996 Crop residue analysis report for etofenprox on paddy rice. Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 61, . Mitsui Toatsu Chemicals, Inc. Life Science Laboratory, Report No. 61, . Mitsui Chemicals Agro, Inc. Unpublished

P/B 701-G Class T 2003 Etofenprox: independent laboratory validation of an analytical method used for the determination of residues of etofenprox in foodstuffs of animal origin. PTRL Europe, Report No: P/B 701 G. PTRL Europe, Report No: P/B 701 G. Mitsui Chemicals Agro, Inc. GLP, unpublished

RS135 Pastor Ciscato CH 1999 Analysis report: Trebon 300CE residues (etofenprox) in/on Cotton. INSTITUTO BIOLOGICO. Report No. 125/99 Study No. R/99/RS135/Plantec. . INSTITUTO BIOLOGICO. Report No. 125/99 Study No. R/99/RS135/Plantec. . SIPCAM ISAGRO BRASIL S.A Unpublished

RS140 Pastor Ciscato CH 1999 Analysis Report: Trebon 300 CE Residues (etofenprox) in/on potato; 1999. INSTITUTO BIOLÓGICO, Report No. R/99/RS140/Plantec. INSTITUTO BIOLÓGICO, Report No. R/99/RS140/Plantec. SIPCAM ISAGRO BRASIL S.A Unpublished

RS141 Pastor Ciscato CH 1999 Analysis Report: Trebon 300 CE Residues (etofenprox) in/on tomato. INSTITUTO BIOLÓGICO. Report No. 124/99, Study No. R/99/RS141/Plantec. INSTITUTO BIOLÓGICO. Report No. 124/99, Study No. R/99/RS141/Plantec. SIPCAM ISAGRO BRASIL S.A Unpublished

RS142 Pastor Ciscato CH 1999 Analysis Report: Trebon 300 CE Residues (etofenprox) in/oncorn. INSTITUTO BIOLÓGICO. Report No. 121/99, Study No. R/99/RS142/Plantec. INSTITUTO BIOLÓGICO. Report No. 121/99, Study No. R/99/RS142/Plantec. SIPCAM ISAGRO BRASIL S.A Unpublished

RS144 Pastor Ciscato CH 1999 Analysis report: Trebon 300CE residues (etofenprox) in/on bean. INSTITUTO BIOLOGICO. Report No. 123/99, Study No. R/99/RS144/Plantec. . INSTITUTO BIOLOGICO. Report No. 123/99, Study No. R/99/RS144/Plantec. . SIPCAM ISAGRO BRASIL S.A Unpublished

Etofenprox 497

Reference Principal Author Year Title, Report reference RS145 Pastor Ciscato CH 1999 Analysis Report: Trebon 300 CE Residues (etofenprox) in/on wheat. INSTITUTO

BIOLÓGICO. Report No. 136/99, Study No. R/99/RS145/Plantec. INSTITUTO BIOLÓGICO. Report No. 136/99, Study No. R/99/RS145/Plantec. SIPCAM ISAGRO BRASIL S.A Unpublished

RS152 Pastor Ciscato CH 1999 Analysis Report: Trebon 100SC Residues (etofenprox) in/on cotton. INSTITUTO BIOLOGICO. Report No. 138/99, Study No. R/99/RS152/Plantec. INSTITUTO BIOLOGICO. Report No. 138/99, Study No. R/99/RS152/Plantec. SIPCAM ISAGRO BRASIL S.A Unpublished

RS153 Pastor Ciscato CH 1999 Analysis Report: Trebon 100SC Residues (etofenprox) in/on cotton. INSTITUTO BIOLOGICO. Report No. 137/99, Study No. R/99/RS153/Plantec. INSTITUTO BIOLOGICO. Report No. 137/99, Study No. R/99/RS153/Plantec. SIPCAM ISAGRO BRASIL S.A Unpublished

RS389 Casadei de Baptista G

2001 Determination of Trebon 100SC residues in/on orange. Laboratory of Pesticide Residue. Study No. R/00/RS389/PLANTEC/ IRACEMÁPOLIS-SP. Laboratory of Pesticide Residue. Study No. R/00/RS389/PLANTEC/ IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRAZIL S.A. Unpublished


2001 Determination of Trebon 100SC residues in/on orange. Laboratory of Pesticide Residue. Study No. R/00/RS390/PLANTEC/ ENGENHERIO COELHO-SP. Laboratory of Pesticide Residue. Study No. R/00/RS390/PLANTEC/ ENGENHERIO COELHO-SP. SIPCAM ISAGRO BRASIL S.A. Unpublished


2001 Determination of Trebon 100SC residues in/on orange. Laboratory of Pesticide Residue. Study No. R/00/RS391/PLANTEC/ COSMOPÓLIS-SP. Laboratory of Pesticide Residue. Study No. R/00/RS391/PLANTEC/ COSMOPÓLIS-SP. SIPCAM ISAGRO BRASIL S.A. Unpublished


2002 Determination of Trebon 100SC residues in/on coffee. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS427/PLANTEC. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS427/PLANTEC. SIPCAM ISAGRO BRASIL S.A Unpublished


2003 Determination of Trebon 100SC residues in/on coffee. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS428/PLANTEC. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS428/PLANTEC. SIPCAM ISAGRO BRASIL S.A Unpublished


2003 Determination of Trebon 100SCresidues in/on coffee–revised report dated January 23, 2003. University of Sao Paulo, School of Agricultural “Luiz De Queiroz” Study No. R/99/RS429/PLANTEC. University of Sao Paulo, School of Agricultural “Luiz De Queiroz” Study No. R/99/RS429/PLANTEC. SIPCAM ISAGRO BRASIL S.A Unpublished


2002 Determination of Trebon 100SC residues in/on bean. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS533/PLANTEC/ IRACEMÁPOLIS-SP. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS533/PLANTEC/ IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished

RS534B Casadei de Baptista G

2003 Determination of Trebon 100SC residues in/on soybean. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/99/RS534/PLANTEC/ IRACEMÁPOLIS-SP. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/99/RS534/PLANTEC/ IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2002 Determination of Trebon 100SC residues in/on corn. Laboratory of Pesticide Residue. Study No. R/04/RS535/PLANTEC/ IRACEMÁPOLIS-SP. Laboratory of Pesticide Residue. Study No. R/04/RS535/PLANTEC/ IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2003 Determination of Trebon 100SC residues in/on cotton. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS536/PLANTEC/IRACEMÁPOLIS-SP. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS536/PLANTEC/IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2003 Determination of Trebon 100SC residues in/on cotton. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS536B/PLANTEC/JAIBA-MG. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/99/RS536B/PLANTEC/JAIBA-MG. SIPCAM ISAGRO BRASIL S.A Unpublished

498 Etofenprox

Reference Principal Author Year Title, Report reference RS538 Pimentel Trevizan

LR 2003 Technical report on Trebon 300CE in/on potato; 2003. Laboratory of Pesticide

Residue. Report No. R/99/RS538/PLANTEC/IRACEMÁPOLIS-SP. Laboratory of Pesticide Residue. Report No. R/99/RS538/PLANTEC/IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2003 Determination of Trebon 100SC residues in/on soybean. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/99/RS534B/PLANTEC/GENTIL-RS. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/99/RS534B/PLANTEC/GENTIL-RS. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on bean. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/723/PL/IRACEMÁPOLIS-SP. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/723/PL/IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on bean. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/724/PL/VARGEM GRANDE DO SUL-SP. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/724/PL/VARGEM GRANDE DO SUL-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on bean. CHATEAUBRIAND-PR. Study No. R/04/725/PL/ASSIS . CHATEAUBRIAND-PR. Study No. R/04/725/PL/ASSIS . SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on soybean. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/04/726/PL/ IRACEMÁPOLIS-SP. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/04/726/PL/ IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on soybean. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/04/727/PL/ ASSIS CHATEAUBRIAND-PR. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/04/727/PL/ ASSIS CHATEAUBRIAND-PR. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on soybean. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/04/728/PL/GENTIL-RS. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Study No. R/04/728/PL/GENTIL-RS. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on corn. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/729/PL/ IRACEMÁPOLIS-SP. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/729/PL/ IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on corn. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/730/PL/ASSIS CHATEAUBRIAND-PR. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/730/PL/ASSIS CHATEAUBRIAND-PR. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on corn. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/730/PL/GENTIL-RS. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/730/PL/GENTIL-RS. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on cotton. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/732/PL/IRACEMÁPOLIS-SP. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/732/PL/IRACEMÁPOLIS-SP. SIPCAM ISAGRO BRASIL S.A Unpublished


2004 Determination of Trebon 100SC residues in/on cotton. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/733/PL/ASSISCHATEAUBRIAND-PR. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/733/PL/ASSISCHATEAUBRIAND-PR. SIPCAM ISAGRO BRASIL S.A Unpublished

Etofenprox 499

Reference Principal Author Year Title, Report reference RS734 Casadei de

Baptista G 2004 Determination of Trebon 100SC residues in/on cotton. University of Sao Paulo,

School of Agricultural “Luiz De Queiroz”. Study No. R/04/734/PL/JAIBA-MG. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. R/04/734/PL/JAIBA-MG. SIPCAM ISAGRO BRASIL S.A Unpublished

RS919 Loiola ECD 2006 Determination of etofenprox residues in/on peach fruit, after application of Trebon 100SC. PLANTEC Planejamento e Tecnologia Agrícola Ltda. Study No. R/05/RS919/PL. PLANTEC Planejamento e Tecnologia Agrícola Ltda. Study No. R/05/RS919/PL. SIPCAM ISAGRO BRASIL S.A Unpublished



RS922 Matallo MB 2006 Determination of etofenprox residues in/on rice grain, after the application of Trebon 100SC. INSTITUTO BIOLOGICO. Study No. R/05/RS922/PL. . INSTITUTO BIOLOGICO. Study No. R/05/RS922/PL. . SIPCAM ISAGRO BRASIL S.A Unpublished



RS925 Matallo MB 2006 Determination of etofenprox residues in/on apple fruit, after the application of Trebon 100SC. INSTITUTO BIOLÓGICO. Study No. R/05/RS925/PL. INSTITUTO BIOLÓGICO. Study No. R/05/RS925/PL. SIPCAM ISAGRO BRASIL S.A Unpublished



RS928 Matallo MB 2006 Determination of etofenprox residues in/on coffee grain, after the application of Trebon 100SC. INSTITUTO BIOLOGICO. Study No. R/05/RS928/PL. INSTITUTO BIOLOGICO. Study No. R/05/RS928/PL. SIPCAM ISAGRO BRASIL S.A Unpublished



SIP1314 Freschi G 2002 Residue analysis of etofenprox and its metabolite alfa-CO in peaches (whole fruit) and on processed samples (jam, juice and puree). SIPCAM S.p.A., Report No. SIP314. SIPCAM S.p.A., Report No. SIP314. Mitsui Chemicals Agro, Inc. GLP, unpublished

SIP1326 Domenichini P 2002 Residue analysis of etofenprox and its metabolite alfa-CO in peaches (whole fruit), jam, juice and pureee. SIPCAM S.p.A., Report No. SIP1326. SIPCAM S.p.A., Report No. SIP1326. Mitsui Chemicals Agro, Inc. GLP, unpublished

SIP1327 Domenichini P 2002 Residue analysis of etofenprox and its metabolites alfa-CO in wine grape (bunches), juice, young wine and bottled wine. SIPCAM, Report No. SIP1327. SIPCAM, Report No. SIP1327. SIPCAM S.p.A. GLP, unpublished

500 Etofenprox

Reference Principal Author Year Title, Report reference SIP1354 Freschi G 2003 Validation of the method for residue analysis of etofenprox and alpha-CO in apple

samples (whole fruit). SIPCAM S.p.A, Report No. SIP1354. SIPCAM S.p.A, Report No. SIP1354. Mitsui Chemicals Agro, Inc. GLP, unpublished

SIP1355 Freschi G 2003 Validation of the method for residues analysis of etofenprox and alpha-CO in peach samples (whole fruit). SIPCAM S.p.A, Report No. SIP1355. SIPCAM S.p.A, Report No. SIP1355. Mitsui Chemicals Agro, Inc. GLP, unpublished

SIP1395 Freschi G 2003 Residue analysis of etofenprox and its metabolite α-CO in peach fruit samples. SIPCAM S.p.A., Report No. SIP1395. SIPCAM S.p.A., Report No. SIP1395. Mitsui Chemicals Agro, Inc. GLP, unpublished

USP-1991-T Casadei de Baptista G

1991 Analysis of Pesticide Residue. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Report No. not specified. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Report No. not specified. SIPCAM ISAGRO BRASIL S.A Unpublished

USP-1991-W

Casadei de Baptista G

1991 Analysis of pesticide residue. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. not specified. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. not specified. SIPCAM ISAGRO BRASIL S.A Unpublished

USP-1994-P Casadei de Baptista G

1994 Analysis of Pesticide Residue. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. not specified. University of Sao Paulo, School of Agricultural “Luiz De Queiroz”. Study No. not specified. SIPCAM ISAGRO BRASIL S.A Unpublished

USP-1995-S Casadei de Baptista G

1995 Analysis of Pesticide Residue. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Report No. not specified. University of Sao Paolo, School of Agriculture “Luiz de Queiroz”. Report No. not specified. SIPCAM ISAGRO BRASIL S.A Unpublished

ETOFENPROX (184)...CAS number 80844-07-1 CIPAC number 471 Molecular mass: 376.47 g/mol Molecular...

Documents

Transcript of ETOFENPROX (184)...CAS number 80844-07-1 CIPAC number 471 Molecular mass: 376.47 g/mol Molecular...