Residues of synthetic pyrethroid insecticides on horticultural crops

Foliar applications of synthetic pyrethroids were made to several crops to determine residue levels at various intervals after application. On onions, residues of cypermethrin, permethrin and fenvalerate were negligible > 0.1 mg kg^?1, 7 days after application. On lettuce, residues of fenvalerate and permethrin were 0.8 mg kg^?1. On celery, residues of fenvalerate did not decline and ranged from 0.12 to 0.25 mg kg^?1 during the 14-day period. On green bush-beans, residues of permethrin and cypermethrin did not decline during the 14-day period and ranged from 0.1 to 0.6 mg kg^?1. By day 7, residues of cyfluthrin, cypermethrin, deltamethrin, fenvalerate and permethrin on strawberries were less than the acceptable maximum tolerance of 0.1 mg kg^?1 with the exception of cypermethrin, applied at the rate of 0.14 kg a.i. ha^?1 which gave a residue of 0.14 mg kg^?1.     

Excretion and residues of the pyrethroid insecticide cypermethrin in lactating cows

Two radiolabelled forms of racemic [¹⁴C]cypermethrin (¹⁴C at the benzylic carbon or at C-1 of the cyclopropane ring) were separately administered twice daily to lactating cows in portions of the feed. The amounts dosed were equivalent to 0.2, 5 and 10 μg of cypermethrin per g of feed. The radioactivity eliminated in the milk indicated that the ingestion and elimination of radioactivity were in balance at about day 4 after the start of dosing. Urine and faeces were equally the major routes of elimination, and only a fraction of a percent of the dose appeared in the milk. The residue in the milk was unchanged cypermethrin and was found at a concentration that was proportional to the dose. At the high cypermethrin intake of 10 μg g^?1 of diet, the residue in the milk was 0.03 μg g^?1. Concentrations of residues in the tissues, measured after 7, 20 or 21 days of treatment, were low and in the order: liver>kidney>renal fat>subcutaneous fat>blood>muscle>brain. The major residue in the liver and kidney of a cow that received 10 μg of cypermethrin per g of diet was N-(3-phenoxybenzoyl)glutamic acid. Other conjugates of 3-phenoxybenzoic acid and of 3-(4-hydroxyphenoxy)benzoic acid (unidentified, with the exception of the glycine conjugate) were also present. The residue in fat (about 0.1 μg g^?1 from an intake of 10 μg g^?1 of feed) consisted mainly of cypermethrin.     

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 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.     

Residues in blackcurrants,fodder peas,spinach and potatoes treated with sublethal doses of 2,4,5-T to simulate wind drift damage

Blackcurrants, treated with 0.1 kg of 2,4,5-T ha^?1 (as esters of mixed C₄–C₆ alcohols; ‘Tormona 80’), contained 0.1 mg of 2,4,5-T residues kg^?1 in the berries at ripeness 29 days after treatment. Total residues in the berries were not reduced during growth and ripening, although the residue concentrations declined in the same period due to growth dilution. In spinach leaves from old plants, treated with 0.1 kg ha^?1, 0.05 mg of 2,4,5-T kg^?1 was found 14 days after treatment. Fodder peas showed no residues (< 0.002 mg kg^?1) at harvest 62 days after treatment with 2,4,5-T esters. After application of 0.1 kg ha^?1 on potato plants, the disappearance of 2,4,5-T was rapid during the first month, but residues were translocated into the tubers and reached a constant level of 0.02 mg kg^?1 after 1 month until harvest at 108 days after treatment. In all crops, visible effects were observed after treatment with 0.1 kg ha^?1. After the application at 0.01 kg ha^?1, phytotoxic effects were observed only in blackcurrants, but negligible residues were found in all the test crops.     

Behaviour of trifloxystrobin and tebuconazole on grapes under semi‐arid tropical climatic conditions

BACKGROUND: A mixture of trifloxystrobin and tebuconazole is excellent in controlling both powdery and downy mildew of grapes. The objective of the present work was to study the behaviour of trifloxystrobin and tebuconazole on grape berries and soil following treatment with Nativo 75 WG, a formulation containing both fungicides (trifloxystrobin 250 + tebuconazole 500 g kg^?1). This study was carried out for planned registration of this mixture for use on grapes in India. RESULTS: Initial residue deposits of trifloxystrobin and tebuconazole on grapes were below their maximum residue limit (MRL) of 0.5 and 2 mg kg^?1, respectively, when Nativo 75 WG was applied at the recommended dose of 175 g product ha^?1. The residues dissipated gradually to 0.02 and 0.05 mg kg^?1 by 30 days, and were below the quantifiable limit of 0.01 mg kg^?1 at the time of harvest (60 days after the last treatment). Trifloxystrobin and tebuconazole dissipated at a pre‐harvest interval (PHI) of 36 and 34 days, respectively, from the recommended treatment dose. The acid metabolite of trifloxystrobin, CGA 321 113, was not detected in grape berries at any point in time. Soil at harvest was free of any pesticide residues. CONCLUSION: Residue levels of both trifloxystrobin and tebuconazole were below MRLs when grapes were harvested 30 days after the last of four applications of 175 g product ha^?1 (trifloxystrobin 44 g AI ha^?1, tebuconazole 88 g AI ha^?1) under the semi‐arid tropical climatic conditions of India. Copyright © 2010 Society of Chemical Industry     

Synergised cyfluthrin and cypermethrin as grain protectants on bulk wheat

Duplicate field trials were carried out on bulk wheat in commercial silos in Queensland and New South Wales. Laboratory bioassays on samples of treated grain at intervals over 8 or 9 months storage using malathion-resistant strains of insects established that treatments were generally effective. Cyfluthrin (2 mg kg^?1) plus piperonyl butoxide (10 mg kg^?1) and cypermethrin (4 mg kg^?1) plus piperonyl butoxide (10 mg kg^?1) completely controlled two strains of Sitophilus oryzae L. Control of a third strain by the cypermethrin combination was incomplete after 11/2 months and neither controlled a multi-resistant laboratory strain. Both combinations were effective against Rhyzopertha dominica F., Tribolium castaneum Herbst and Ephestia cautella Walker. No natural infestation developed in the treated grain in any silo. Mean residues of cyfluthrin and cypermethrin after 9 months storage were 58% and 52% of the calculated application rates, respectively. Compared with overall concentrations in the wheat, residue levels were higher in bran and pollard and lower in white flour. During baking, residues decreased by up to 29%. Operators experienced respiratory irritation associated with exposure to both combinations and alternative formulations would be required for use of these materials in grain storage.     

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.     

Comparative metabolism and disposition of [14C-benzyl] cypermethrin in quail,rat and mouse

The excretion and metabolism of cis + trans-[¹⁴C-benzyl] cypermethrin has been compared in quail, rat and mouse. Radioactivity was rapidly eliminated by quail dosed orally with [¹⁴C]cypermethrin (2 mg kg^?1), as was the case in the rat and the mouse. When the birds were dosed intraperitoneally (IP) with the ¹⁴C-labelled pyrethroid, radioactivity was excreted more slowly than after oral dosing, and almost 20% of the IP dose of ¹⁴C remained in the tissues after 7 days. Both mammalian species excreted [¹⁴C]cypermethrin more rapidly than did the avian species after IP administration, and less than 6% of the dose remained in their tissues after several days. The biotransformation of the pyrethroid was more complex in the avian species (34 metabolites) than in the two mammals (some 10 metabolites in each species). In quail the predominant reactions were ester bond cleavage of cypermethrin together with either aromatic hydroxylation or amino acid conjugation of the 3-phenoxybenzyl moiety. The hydroxylated derivatives were eliminated mainly as sulphates. 3-Phenoxybenzoic acid was conjugated with a variety of amino acids including glycine, taurine, glutamic acid, serine, α-N-acetylornithine and the dipeptide glycylualine. The last two conjugations are unique to avian species. The major metabolite of cypermethrin in the rat was the sulphate conjugate of 3-(¹⁴-hydroxyphenoxy)benzoic acid, whereas in the mouse the major products were 3-phenoxybenzoic acid and its taurine conjugate. Thus, in the mammalian species where hydroxylation was maximal, amino acid conjugation was a minor metabolic route und vice versa. However, in the quail, aromatic hydroxylation and amino acid conjugation of the 3-phenoxybenzyl moiety of cypermethrin were both major reactions. The influence of the rates and sites of metabolism, and of the enzymology of amino acid conjugation, in determining this species difference are discussed. The rapid metabolism of cypermethrin to a variety of polar conjugates that are readily excreted, together with the low brain sensitivity of birds compared with mammals to its neurotoxic effects, explains the low acute toxicity of this pyrethoid to avian species.     

The bioaccumulation and biotransformation of cis,trans-cypermethrin in the rat

The disposition of the pyrethroid insecticide cypermethrin, (RS)-a-cyano-3-phenoxybenzyl (1RS)-cis, trans-3-(2,2-dichlorovinly)-2, 2-dimethylcyclopropane-carboxylate, has been studied in male and female rats following a single toxic oral dose (200mg kg⁻¹) of two radiolabelled forms ([¹⁴C-benzyl] and [¹⁴C-cyclopropyl]) of the insecticide. The bioaccumulation and elimination of ¹⁴C-benzyl-labelled cypermethrin, following repeated administration at a sub-toxic dose (2mg kg⁻¹), has also been studied in male and female rats. Although, at the toxic dose, radioactivity from the two radiolabelled forms was rapidly eliminated in urine and faeces, the increased excretion in the faeces, over that for low doses, was evidence that absorption was incomplete. The major pathways of metabolism involved cleavage of the ester bond, with subsequent hydroxylation and glucuronidation of the cyclopropyl acid moieties, together with hydroxylation and sulphation of the 3-phenoxybenzyl moiety. The absence of sex- or dose-dependent changes was reflected by the constant proportions of these metabolites found in the urine. Constant levels of radioactivity in tissues were achieved rapidly, generally within the first week of repeated administration. Elimination was rapid on the cessation of dosing, although less rapid from the fat and skin. The material in the fat was mainly the cis-isomers of cypermethrin, which were eliminated with a mean half-life of 18.2 days, compared with 3.4 days for the trans-isomers.     

The conjugation and accumulation of metabolites of cypermethrin by earthworms

When earthworms are maintained in soil containing [¹⁴C]cypermethrin they accumulate radioactive residues. These residues are not eliminated when the worms are transferred to untreated soil. The accumulated radioactive residue is a complex mixture of conjugates of two metabolites of cypermethrin (3-phenoxybenzoic acid and (1RS)-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid). One major constituent of this mixture of conjugates has been identified as N¹, N¹²-di-(3-phenoxybenzoyl)spermine. Feeding studies with quail and rats have established that the residues accumulated by the earthworms are not further bioaccumulated by earthworm predators.     

贵州地区茶叶及茶汤中氯氰菊酯残留量检测及其摄入风险分析

采用气相色谱建立了茶叶样品中氯氰菊酯残留量检测方法;通过对贵州省市售茶叶样品中氯氰菊酯的残留情况进行抽检,以了解其市售茶叶的安全性;通过田间试验制备浸泡实验用茶叶样品,设计正交实验研究了影响茶汤中氯氰菊酯浸出率的因素。结果表明,市场抽检茶叶样品中氯氰菊酯残留量平均值为0.919 mg/kg,最高残留量为1.52 mg/kg,低于茶叶中氯氰菊酯的最大残留限量(MRL)标准20 mg/kg;正交实验表明,浸泡次数和浸泡时间是影响氯氰菊酯浸出率的主要因素,茶汤中氯氰菊酯的最高浸出率为5.76%。按人均最高泡茶用量13 g/d计算,由饮茶而进入人体 的氯氰菊酯的最大量为1.5×10-2 mg/d,按氯氰菊酯每日最大允许摄入量(ADI)为0.05 mg/kg bw、 平均体重60 kg计,则其安全系数(K)为200。     

The effect of the annual use of pesticides on soil microorganisms,pesticide residues in the soil and barley yields

A study has been made of the influence of pesticides used annually on soil microorganisms and crop yields. The persistence of these pesticides in the soil was also investigated. The herbicides MCPA, glyphosate, maleic hydrazide and tri-allate, and the insecticide parathion, were applied on experimental plots on which barley was grown during the years 1973-1981. The fungicide 2-methoxyethylmercury chloride was used every year for dressing the seeds grown in pesticide-treated plots. The pesticide treatments did not affect significantly the numbers of several groups of soil microorganisms. A slight increase was, however, observed in the nitrification activity in the soil. The barley yields were on average higher on pesticide-treated plots than on controls because of successful weed control. Pesticide residues in the soil were generally very low; for example, for parathion they were below 0.02 mg kg^?1 within 11 days, and for MCPA 0.06 mg kg^?1 within 7 days. However, the glyphosate residue was 1.6 mg kg^?1 in the autumn 2 days after the treatment, and the residue settled to a level of 0.2 mg kg^?1 during the following summer. No clear dependence was observed between the residue level and the time between treatment and sampling.     

Pyrethroid residues in sediment and water samples from mesocosm and farm pond studies of simulated accidental aquatic exposure

This paper describes the residue analysis of water and hydrosoil samples taken from two separate large-scale aquatic ecotoxicology trials designed to assess the environmental fate and effects of the pyrethroids lambda-cyhalothrin and cypermethrin. Comparison of the results demonstrates the high degree of reproducibility of the chemical residue found the day after treatment using experimental mesocosms (lambda-cyhalothrin) as opposed to an in-use farm pond (cypermethrin). Both studies showed that pyrethroid residues were rapidly lost from the water column: residues of lambda-cyhalothrin were less than 2 ng litre^?1 following the final application of a cumulative seasonal exposure equivalent to twelve ?drift’? and six ?run-off’? events, each delivering a dose equivalent to that expected from a typical event under field conditions. Hydrosoil appeared to act as a sink for pyrethroid residues and, under the stringent test conditions of the mesocosm study, lambda-cyhalothrin residues reached 3.2 μg kg^?1 following the seasonal exposure described above. The cypermethrin farm-pond study illustrated the localised pattern of exposure expected under natural field conditions, with site topography and cultivation practices which represent an average ?worst case’?. Residues in hydrosoil reached a maximum level of approximately 25 μg kg^?1 in one sampling zone at one interval, and thereafter declined to a level of < 9 μg kg^?1 within four months.     

Permethrin and deltamethrin residues on lettuce

Permethrin and deltamethrin, two synthetic pyrethroid insecticides, are registered in several countries for use on lettuce. Both chemicals were applied on autumn and spring grown lettuce in the glasshouse. When applied at the normal prescribed dose rates of 25 and 12.5 g a.i. ha^?1, < 1 mg kg^?1 of either compound was found in the lettuce at harvest, even when applied only a few days before harvest. The total amount of active ingredient applied was too low to reach the 1 mg kg^?1 level when evenly applied on marketable lettuce heads weighing about 200 g each. Applying a higher dose than 25 g permethrin a.i. ha^?1 or 12.5 g deltamethrin a.i. ha^?1, or applying two applications in the 2 weeks prior to harvest, may well result in residue levels higher than the maximum residue limit of 1 mg kg^?1 for permethrin and certainly higher than the maximum residue limit of 0.2 mg kg^?1 for deltamethrin, which is more persistent.     

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.     

Residues of the algicide endothal in water,soil and rice,after paddy field applications

In order to obtain residue data from the application of the algicide endothal in Italian rice paddy fields, two experiments were carried out using a 50 g kg^?1 granular formulation in a small pond and the same granular and two liquid formulations in actual paddy fields of the Italian rice growing area. Endothal decay in the pond water was very rapid, reaching residue levels of 0·01-1·02 mg litre^?1 in two days and 0·004-0·01 mg litre^?1 at the third day. The muddy soil of the pond was free from measurable endothal residues( <0·02 mg kg^?1). In the paddy-field waters, the endothal decay was slower, with an average half-life time of 3·3 days, independently of the type of formulation. The actual residues in water after 6 days ranged from 0·3 to 1·3 mg litre^?1 according to the initial amount of product applied, and, consequently, to the initial concentration in water. Rice samples collected at the normal harvest time from the two paddy fields, treated with three different formulations, showed no endothal residue at the minimum detectable level of 0·01 mg kg^?1.     

The dietary toxicity of flocoumafen to hens: Elimination and accumulation following repeated oral administration

In a dietary toxicity study, laying hens received a diet containing the rodenticide flocoumafen at concentrations of 1.5, 5, 10 and 50 mg kg^?1 for five consecutive days. The LC₅₀ at termination following a 28-day observation period was 16.4 mg kg^?1. Livers of birds which received doses of flocoumafen between 5 and 50 mg kg^?1 had concentrations of flocoumafen (1.5 nmol g^?1) that were independent of dose. The data indicate the presence in hen liver of a saturable high-affinity flocoumafen binding site with similar characteristics and capacity to that of the quail and rat. Residues of flocoumafen in samples of breast and leg muscle were low in all exposure groups. Higher, dose-related residues were found in samples of abdominal fat and skin-associated fat and there was a clear demonstration of the transfer of dose-related residues into eggs. In a separate study in which hens were dosed with [¹⁴C]flocoumafen for five consecutive days at a daily rate of 1 and 4 mg kg^?1 body weight, the majority (68 %) of the daily radioactive dose was eliminated over the following 24 hours via excreta. Residues in liver at death or when killed accounted for < 1 % of the cumulative administered radioactivity. Residues in eggs were located primarily in the yolk with maximum concentrations 1.0 mg kg^?1 or 0.18% of the low dose; 2.1 mg kg^?1 or 0.06% of the high dose as [¹⁴C]flocoumafen equivalents were observed at 10 days after start of dosing. Some 40 % of the total activity in the yolk was unchanged flocoumafen.     

Disposition kinetics of cypermethrin and fenvalerate in black bengal lactating goats

Disposition kinetics of cypermethrin and fenvalerate were investigated in lactating black Bengal goats following single dose intravenous administration at 57 and 45 mg kg^?1 respectively. The maximum and minimum blood concentrations of cypermethrin were 18.49 (±3.17) and 0.06 (±0.002) μg ml^?1, while the corresponding values for fenvalerate were 14.58 (±2.37) and 0.04 (±0.005) μg ml^?1 respectively. Both cypermethrin and fenvalerate remained present in blood for 36 h. The mean t1/2β) and Vd_area values were 5.56 (±0.28) h and 10.38 (±2.20) litre kg^?1 for cypermethrin and 5.66 (±0.35) h and 11.31 (±2.20) litre kg^?1 respectively for fenvalerate. Both cypermethrin and fenvalerate persisted in goat milk for 36 h. The t1/2β) and AUC values of fenvalerate were 7.37 (±1.84) h and 122.38 (±11.65) μg h ml^?1 whilst the corresponding values for cypermethrin were 6.66 (±1.54) h and 99.48 (±7.81) μg h ml^?1 in milk respectively.     

Disappearance of carbosulfan residues in peaches

The disappearance kinetics of the carbamate insecticide, carbosulfan, applied at 2 kg AI ha^?1 (‘Marshal’ 250 g litre^?1 EC) in peaches was studied. Degradation took place in two consecutive stages (0–28 and 28–57 days), with half-lives of 7.4 and 17.5 days, respectively. The residues obtained 57 days after treatment did not exceed 0.2 mg kg^?1. When treatments were carried out 30, 21 and 14 days before the probable date of harvest (date of fruit maturation) with two doses (1.0 and 2.0 g formulated product litre^?1) and two volumes applied (750 and 1500 litre ha^?1), the residual levels detected were between 0.122 mg kg^?1 (30 days before harvest) and 0.4 mg kg^?1 (14 days before harvest). The major metabolite, carbofuran, was never detected above its determination limit of 0.004 mg kg^?1 throughout the whole study.