Excretion and residues of the pyrethroid insecticide cypermethrin in laying hens

Laying hens were treated daily for 14 days with oral doses of [¹⁴C-phenoxy]cypermethrin (1.52 mg day^?1, 0-7 mg kg^?1) formulated on a small quantity of diet. Radioactivity in the eggs reached a plateau value of 0.05 μg equivalents g^?1 8 days after the start of dosing. Most of the residue was found in the yolk and was a mixture of cypermethrin and material which was closely associated with neutral lipids and phosphatidyl cholines. Four and a half hours after the last dose, the birds were killed and selected tissues were taken for analysis. The highest residue was found in the liver. This was composed of cypermethrin and a mixture of very polar metabolites which were not hydrolysed to significant amounts of 3-phenoxybenzoic acid or its 4-hydroxy derivative.     

Residues of zeta‐cypermethrin in bovine tissues and milk following pour‐on and spray application

The depletion of zeta‐cypermethrin residues in bovine tissues and milk was studied. Beef cattle were treated three times at 3‐week intervals with 1 ml 10 kg^?1 body weight of a 25 g litre^?1 or 50 g litre^?1 pour‐on formulation (2.5 and 5.0 mg zeta‐cypermethrin kg^?1 body weight) or 100 mg kg^?1 spray to simulate a likely worst‐case treatment regime. Friesian and Jersey dairy cows were treated once with 2.5 mg zeta‐cypermethrin kg^?1 in a pour‐on formulation. Muscle, liver and kidney residue concentrations were generally less than the limit of detection (LOD = 0.01 mg kg^?1). Residues in renal‐fat and back‐fat samples from animals treated with 2.5 mg kg^?1 all exceeded the limit of quantitation (LOQ = 0.05 mg kg^?1), peaking at 10 days after treatment. Only two of five kidney fat samples were above the LOQ after 34 days, but none of the back‐fat samples exceeded the LOQ at 28 days after treatment. Following spray treatments, fat residues were detectable in some animals but were below the LOQ at all sampling intervals. Zeta‐cypermethrin was quantifiable (LOQ = 0.01 mg kg^?1) in only one whole‐milk sample from the Friesian cows (0.015 mg kg^?1, 2 days after treatment). In whole milk from Jersey cows, the mean concentration of zeta‐cypermethrin peaked 1 day after treatment, at 0.015 mg kg^?1, and the highest individual sample concentration was 0.025 mg kg^?1 at 3 days after treatment. Residues in milk were not quantifiable beginning 4 days after treatment. The mean concentrations of zeta‐cypermethrin in milk fat from Friesian and Jersey cows peaked two days after treatment at 0.197 mg kg^?1 and 0.377 mg kg^?1, respectively, and the highest individual sample concentrations were 2 days after treatment at 0.47 mg kg^?1 and 0.98 mg kg^?1, respectively. © 2001 Society of Chemical Industry     

The fate of the rodenticide flocoumafen in the rat: Retention and elimination of a single oral dose

A single oral dose of 0.14 mg kg^?1 of [¹⁴C] flocoumafen to rat, which gave a transient, non-lethal, effect, was rapidly absorbed, radioactivity appearing in the blood maximally at 4 h and falling to half maximum value by 8 h. The maximum effect on prothrombin time was at 24 h and the value returned to normal by 48 h. Elimination of radioactivity was very slow, with less than 0.5% of the dose in the urine up to 7 days after dosing, and 23-26% in the faeces (more than half of which appeared in the first 24 h). Most of the administered radioactivity (74-76%) was retained 7 days after dosing. Approximately half of the dose was in the liver; it was eliminated with a halflife of 220 days. At 48 h after dosing, most of the hepatic radioactivity comprised unchanged flocoumafen. Treatments of flocoumafen-dosed rats with warfarin or with cytochrome P450-inducing doses of phenobarbitone were without effect on the hepatic residue of flocoumafen.     

A barn owl feeding study with [14c]flocoumafen-dosed mice: Validation of a non-invasive method of monitoring exposure of barn owls to anticoagulant rodenticides in their prey

A study was carried out to assess the feasibility of monitoring the exposure of barn owls (Tyto alba) to an anticoagulant rodenticide, flocoumafen, by analysis of residues in regurgitated pellets following consumption of flocoumafen-contaminated mice. Mice were fed on a diet containing [¹⁴C]flocoumafen, equivalent to 12 mg kg^?1, and killed 24 h later. A single [¹⁴C]flocoumafen-contaminated mouse was fed to each of four captive barn owls, equivalent to 0·11-0·23 mg kg^?1 per bird, followed on seven successive days by control diet (i.e. undosed mice). The [¹⁴C]flocoumafen dose was eliminated by the owls over the eight-day period in pellets (44%, range 35–55%) and faeces (18%, range 11–21%), with the highest residues being observed in samples from the first 24-h period. Further detailed analysis of the pellets confirmed that flocoumafen residues in the first-day pellets represented 15% (range 8–26%) of the original flocoumafen residues ingested by the barn owls. Calculations based on these data and typical flocoumafen residues in live captured rodents (following baiting) confirm that pellet residue analysis is a sensitive and appropriate method for the non-invasive monitoring of exposure of barn owls to flocoumafen. There were no symptoms of anticoagulant poisoning in any of the birds; two of the birds were successfully paired the next season and produced fledgelings.     

The toxicity of three second-generation rodenticides to Barn Owls

The toxicity of three second-generation rodenticides to Barn Owls (Tyto alba Scop.) has been investigated. Brodifacoum, difenacoum and flocoumafen were separately fed to owls over a period of 15 days via rodenticide-fed mice to simulate the potential route of exposure in the wild. The owls survived a cumulative dose of each rodenticide of at least 1.9 mg kg^?1 owl body weight over 15 days. This is equivalent to the consumption of two 25 g mice with a rodenticide residue of 1 mg kg^?1 each day for 15 days. Residue analysis confirmed that the liver is the organ which retains the largest residue of ingested rodenticide.     

Herbicide residues in waste waters from ricefields

The herbicides bentazone, 2,4-D, MCPA, propanil, molinate, and tiocarbazil, and the insecticide phenthoate, were applied to ricefields in Sardinia at rates equivalent to maximum aqueous concentrations of 0.4-2.8 mg kg^?1, assuming the water to be 20 cm deep. Their concentrations in water were measured by high-performance liquid chromatography. Residues in 162 water samples, collected from 16 ricefields 1, 4, 7, 10, 12, 18, 21 and 120 days after the last spraying, were all below the limit of determination (0.03 mg kg^?1). Residues in 40 water samples taken from five drainage canals were also less than 0.03 mg kg^?1.     

Uptake of phorate by lettuce

Following experimental and commercial applications to soil of a granular formulalation of phorate (O,O-diethyl S-ethylthiomethyl phosphorodithioate), residues in the soil and in lettuce were determined by gas-liquid chromatography. When applied by the bow-wave method as a continuous logarithmically-changing dose ranging from approximately 0.9 to 16.0 kg a.i. ha^?1, the proportional rate of oxidation in soil of phorate sulphoxide to phorate sulphone was inversely related to dose. Ten weeks after application, total phorate residues in the soil had declined by about 35% at all dose levels. Residues in mature lettuce, from the 1-5 kg ha^?1 dose-range, comprised the parent and oxygen analogue sulphoxides and sulphones; the relative proportions of the individual metabolites were independent of dose. Over this dose-range, total residue concentrations in the crop became proportionally slightly greater with increasing dose. When single doses of 1.1, 2.0 or 2.2 kg a.i. ha^?1 were applied at drilling, the total residue concentrations in the lettuce declined from 5 mg kg^?1 in seedlings from some treatments to <0.05 mg kg^?1 at harvest. In plants raised in peat blocks containing 10 or 20 mg a.i. per block, however, residues in seedlings totalled 45-47 mg kg^?1 and declined to only 0.7 mg kg^?1 at harvest. It was concluded that bowwave applications of phorate when field-sowing lettuce were unlikely to lead to unacceptable residues in the harvested crop, but that residues in lettuce raised in phorate-treated peat blocks may be unacceptably high.     

Gamma-HCH in rape seedlings grown from treated seeds

Rape seedlings grown from seeds treated with a gamma-HCH seed dressing at a dose rate of 15.7 g kg^?1 had a maximum gamma-HCH concentration of 380 mg kg^?1 in seedlings collected 1 day after emergence. The mean gamma-HCH concentration in the seedlings decreased to 2.6 and to 0.9 mg kg^?1 by 7 and 15 days after emergence, respectively. Gamma-HCH was chemically detected in true leaves, at concentrations up to 1.9 mg kg^?1, indicating translocation of gamma-HCH in young plants.     

Distribution and depletion of [14C]resmethrin isomers administered orally to laying hens

The cis and trans isomers of the synthetic pyrethroid resmethrin, labelled with radiocarbon in either the alcohol or acid moiety, were individually administered orally to White Leghorn laying hens at a dosage of 10 mg kg^?1. With each isomer and label position, greater than 90% of the radiocarbon was eliminated in the excreta within 24 h after the treatment. Radiocarbon residues in the egg white and yolk fractions were low, with peak levels observed 1 and 4-5 days after treatment in white and yolk, respectively. In birds sacrificed 12 h after treatment, radiocarbon residues in tissues were low; the highest levels were found in the liver and kidney.     

Residues of methomyl in strawberries,tomatoes and cucumbers

An accurate and rapid high performance liquid chromatography method was developed to monitor residues of methomyl in plant extracts. The rate of disappearance of foliage-applied methomyl from strawberries, tomatoes and cucumbers was studied. Residues reached levels of 0.55, 0.2 and 0.6 mg kg^?1 seven days after methomyl had been applied to strawberries, tomatoes and cucumbers, respectively. Results also showed that rinsing treated fruits with tap water removed considerable amounts of methomyl. Samples of strawberries, tomatoes and cucumbers were collected from local markets at Ismailia, and checked for methomyl residues. Residues in 12.5% of tomato and 25% of strawberry samples were above 0.2 mg kg^?1.     

Influence of block and cell size,growing medium and insecticide dose on the behaviour and uptake of phorate by lettuce and uptake of carbofuran and chlorfenvinphos by calabrese

Phorate residues in peat blocks and lettuce were determined following incorporation of the insecticide into different block and ‘Speedling’ cell sizes. Between-block variability was influenced little by block size. Phorate oxidation was most extensive in the largest blocks containing the smallest dose. Total residue concentrations in the lettuce declined from the time of planting to harvest, although accumulation of insecticide continued and was related more to dose than to block or cell size. Residues in the lettuce at harvest exceeded the proposed maximum limit of 0.2 mg kg^?1 in some treatments. Residues at planting comprised mainly the parent sulphoxide and sulphone, but by harvest, the oxygen analogue sulphoxide and sulphone predominated. Lettuce weight was not influenced by dose but was related directly to block size. Carbofuran and chlorfenvinphos residues were determined in calabrese sown into two sizes of blocks. At planting time, carbofuran residue concentrations were 100 times greater than those of chlorfenvinphos but residues of both insecticides in the mature heads were < 0.01 mg kg^?1. Seedling weights in both sowings declined with increasing concentrations of the insecticides. It was concluded that manipulations of block size and the dose of insecticide need to be evaluated for individual insecticide/crop combinations to exploit the technique fully.     

Residues of Mecoprop in Post-emergence-Treated Wheat and Oat

The dissipation of mecoprop in wheat (Triticum aestivum L.) and oat (Avena sativa L.) was monitored over a growing season following post-emergence application of the dimethylamine salt of mecoprop to each crop at 1·1 kg ha^?1. Residues of mecoprop, as its methyl ester, were determined gas chromatographically using electrolytic conductivity detection. Initial residues in wheat (119 (±20) mg kg^?1) and oat (95·3 (± 10·0) mg kg^?1) on the day of application (four-leaf stage of wheat and four- to five-leaf stage of oat) decreased to 0·1 to 0·2 mg kg^?1, respectively, within six weeks. Residues were non-detectable in the mature seed of both crops. Recoveries of mecoprop were in the order of 90% from the green tissue and seed of both crops fortified at 0·05 mg kg^?1.     

The determination of the herbicide dinoseb in lentils

Residues of the herbicide dinoseb were determined gas chromatographically in lentils which had been treated at two locations in Saskatchewan with post-emergence applications of dinoseb at 1.4 and 1.7 kg ha^?1. Herbicide residues, determined at selected times after application, were not detected at the limit of detection of the analytical method (0.05 mg kg^?1) in either the seed and straw at maturity, or in the green foliage six to eight weeks after application. Recoveries of dinoseb were 76% from fortified green foliage at the 0.1 mg kg^?1 level, and 64% from fortified seed at the 0.05 mg kg^?1 level.     

Repellent action of permethrin,cypermethrin and resmethrin against black flies (Simulium spp.) attacking cattle

Permethrin, cypermethrin, and resmethrin were tested under field conditions as repellents to protect cattle from black flies (Simulium spp.). The chemicals were applied topically to the entire body surface of steers. Ethanolic solutions of technical permethrin, at doses of 1, 2, 4 and 6 mg a. i. kg^?1 of body weight, effectively repelled black flies by preventing at least 70% of the flies present from taking a blood meal for up to 8 days, and for at least 11 days at a dose of 12 mg a. i. kg^?1. Aqueous mixtures of a 20% permethrin emulsifiable concentrate (e. c.), at doses of 1, 2 and 6 mg a. i. kg^?1, effectivelyrepelled black flies for 2, 10 and 11 days, respectively. Aready-to-use 5% permethrin dust, at doses of 1, 2, and 4 mg a. i. kg^?1, effectively repelled black flies for 4, 5 and 8 days, respectively. Ethanolic solutions of technical cypermethrin, at doses of 1 and 2 mg a. i. kg^?1, repelled black flies for 3 and 4 days, respectively. Aqueous mixtures of a 40% cypermethrin e. c., at doses of 2 and 4 mg a. i. kg^?1, repelled black flies for at least 5 days. Ethanolic solutions of technical resmethrin, at doses of 2 and 6 mg a. i. kg^?1, repelled black flies for 1 and 2 days, respectively.     

The metabolism of tefluthrin in the goat

A goat was dosed orally with [¹⁴C]tefluthrin, twice daily for 4 days, at a rate equivalent to 10.9 mg kg^?1 in its diet. Within 16 h of the final dose, 70.1% of the dose had been excreted (urine 41.4%, faeces 28.7%). Extensive metabolism occurred in the goat by ester cleavage and oxidation at a variety of positions on the molecule. Low radioactive residues were detected in the milk (0.076 mg kg^?1), fat (0.076 mg kg^?1) and muscle (0.016 mg kg^?1), with tefluthrin as the largest individual component of the residue (milk 66.5%, fat 76.7%, muscle 34.2%). Higher residues were present in the kidney (0.3 mg kg^?1) and liver (1.0 mg kg^?1) and only a small percentage of this residue was due to tefluthrin (kidney 3.4%, liver 6.1%). The remainder of the residue in the kidney and liver was a complex mixture of metabolites. Most of the kidney metabolites were identified, but a high proportion of the liver residue was due to six unidentified polar compounds.     

Dissipation of cyproconazole and quinalphos on/in grapes

The persistence of cyproconazole and quinalphos on/in grapes was investigated when both compounds were applied to vines at the locally recommended application frequencies and rates and at double these rates, using commercially available formulations. Residues of cyproconazole applied at recommended and double the recommended rates of application in/on grapes immediately after the last application were 0-049 (±0.034) and 0.077 (±0.008) mg kg^?1, respectively, reduced to 0.011 (±0.003) and 0.018 (±0.010) mg kg^?1 respectively seven days after the last application. The corresponding residue levels of quinalphos immediately following the last application were 1.42 (±0.10) and 3.36 (±0.07) mg kg^?1, reduced to 0.043 (±0.002) and 0.072 (±0.028) mg kg^?1 respectively 21 days after the last application. Cyproconazole, being systemic, is rapidly absorbed by the grape tissues and its residues dissipate with a half-life of three to four days, while quinalphos, being non-systemic, dissipates faster with a half-life of two or three days. The residues of both pesticides were analysed by a GLC-NPD system.     

Residues of carbofuran and 2,3-dihydro-3-hydroxy- 2,2-dimethylbenzofuran-7-yl methylcarbamate in the mushroom,agaricus bisporus,cultivated in casing soils treated with the insecticide

Residues of carbofuran ( 1 ) and 2,3-dihydro-3-hydroxy-2,2-dimethylbenzofuran-7-yl methylcarbamate ( 2 ) in and on mushrooms, cultivated on casing soils containing added carbofuran granular insecticide, were determined. The quantitative estimations in cleaned mushroom extracts were done on thin-layer plates using a cholinesterase inhibition method. Samples were analysed, which had been harvested at different times from cultures, to which different amounts of carbofuran were added. Residues in washed and unwashed mushroom samples were compared. Residues did not exceed 0.5 mg (carbofuran) kg^?1 and 0.25 mg (compound 2 ) kg^?1 for fresh unwashed mushrooms grown on casing soil treated with carbofuran granules 1 g (a.i.) m^?2.     

Acaricides and their residues in Spanish commercial beeswax

BACKGROUND: The purpose of this work was to determine residues of acaricides in recycled Spanish beeswax. RESULTS: Chlorfenvinphos, fluvalinate, amitraz, bromopropylate, acrinathrin, flumethrin, coumaphos, chlorpyrifos, chlordimeform, endosulfan and malathion residues were determined by GC‐µECD/NPD/MS detection. Owing to the extreme instability of amitraz, this analyte was transformed into the stable end‐metabolite 2,4‐dimethylaniline, later derivatised with heptafluorobutyric anhydride and determined by GC‐µECD/MS. Recoveries from spiked samples ranged from 86 to 108%, while quantification limits varied from 0.10 to 0.30 mg kg^?1 using GC‐µECD/NPD, and from 12 to 85 µg kg^?1 by GC‐MSD. Of a total of 197 samples analysed, only eight samples (4%) were free of residues of chlorfenvinphos (0.019–10.6 mg kg^?1), fluvalinate was present in 93.6% of samples analysed (0.027 –88.7 mg kg^?1), while coumaphos was confirmed in only five of the 134 samples analysed at concentrations of less than 195 µg kg^?1. The remaining acaricides were identified with different levels of incidence at concentrations from 12 to 231 µg kg^?1. CONCLUSIONS: Residues of acaricides were found in an extensive number of beeswax samples. The contamination with chlorfenvinphos and tau‐fluvalinate was very relevant, particularly as chlorfenvinphos is not legally authorised for use in beekeeping. The possible impacts of the main acaricides detected on larval and adult honey bees are discussed. Copyright © 2010 Society of Chemical Industry     

Fenbutatin oxide,fate in soil after extensive commercial use in Italy and Spain

The long-term fate of the acaricide, fenbutatin oxide, in soil has been investigated. Residues of the compound and its two principal metabolites have been determined in soil samples obtained from citrus orchards in Italy and Spain where the product had been applied commercially over a period of 6–10 years. The average fenbutatin oxide content in the upper 0–15 cm soil layer ranged from ? 1 mg kg^?1 to 5 mg kg^?1 in sites receiving single and double applications per year. The residues were located primarily (> 95%) in the top 0–30 cm layer and there was virtually no movement of the compound through the soil to lower depths. Below 0.5 m depths, the sites contained average concentrations of ? 0.01 mg kg^?1, the limit of determination. No significant build-up of residues was observed and the data indicate an approximate half-life in soil of just less than one year. Residues of the two metabolites, dihydroxy-bis(2-methyl-2-phenylpropyl)stan-nane and 2-methyl-2-phenylpropyl stannonic acid, were on average 11% and 16% of the fenbutatin oxide concentration, respectively. As with fenbutatin oxide, there was no significant movement through the soil to lower levels.     

Gamma-HCH in eggs and poultry arising from exposure to thermal vaporisers

Levels of gamma-HCH have been determined in poultry tissue and eggs taken from poultry houses in which thermal vaporisers were operated. During continuous operation for 14 months, residue levels of gamma-HCH in both substrates were related closely to changing levels of insecticide in the vaporiser; up to 46 mg kg^?1 (on a fat basis) was found in tissue and up to 4.0 mg kg^?1 (on a whole liquid basis) in eggs. Where the vaporisers were operated discontinuously, maximum levels were 6.7 mg kg^?1 in tissue and 0.53 mg kg^?1 in eggs.