A colorimetric method for the determination of eight carbamate insecticide residues

A simple, quick and reliable method is described for the colorimetric estimation of residues of eight carbamate insecticides. The method is applicable to carbamates which on hydrolysis yield phenols with free para-positions suitable for coupling with a diazo reagent to yield coloured solutions. Optimum conditions for the development and measurement of the colour are described. Analytical data including graphs and some results from mud-bricks and cloth are presented to show the wide applicability of the method.     

A gas-liquid chromatographic method for determining imazalil residues in citrus fruit

An electron capture gas-liquid chromatographic method is described for the analysis of the fungicide imazalil,^a 1-(β-allyloxy-2, 4-dichlorophenethyl)imidazole, in citrus fruit. Recoveries were 80–95% from citrus fruit fortified at 0.50–2.0 mg/kg, with a limit of detection of 0.01 mg/kg.     

Sex-related response to organophosphorus and carbamate insecticides in adult Oriental fruit moth, Grapholita molesta

During the development of a resistance-monitoring bioassay that uses males as the life-stage tested, the relationship of adult female and male susceptibility of Grapholita molesta to different classes of insecticides was investigated. Preliminary results indicated that more males survived diagnostic doses of azinphos-methyl than females. Additional research revealed that, although the body mass of adult male G molesta was only 69% of that of female moths (5.67 and 8.20 mg, respectively), their LC50 values were 2.6, 4.1 and 10.3 times higher than those of females for azinphosmethyl, malathion and parathion-methyl, respectively. However, female G molesta moths were more tolerant to methomyl than were male moths. There was no indication that this sex-related response occurred in G molesta larvae. The results presented here raise concerns regarding the use of pheromone traps for determining whether insecticide treatments are required and as part of resistance monitoring programs.     

The gas-liquid chromatographic determination of prothoate and the corresponding phosphorothioate residues in fruit

The fruit was macerated in acetone and the extract cleaned up by liquid-liquid partition. Prothoate and its phosphorothioate were determined by gas-liquid chromatography with thermionic detection. Recoveries were 78-100 % at 0.05 mg/ kg for apples, grapes, peaches and oranges and did not critically depend on the stage of ripeness of the fruit.     

Evaluation of endosulfan residues in vegetables grown in greenhouses

The reduction in residue levels of endosulfan with time after treatment of tomatoes, green beans, peppers and cucumbers grown in different types of commercial greenhouses (flat- and asymmetric-roof greenhouses) in Almería (Spain) was investigated. A study of the major and minor degradation products of endosulfan in peppers and cucumbers (endosulfan-sulfate, -ether and -lactone) was carried out using gas chromatography-tandem mass spectrometry (GC-MS/MS). To establish the influence of environmental conditions on the degradation of endosulfan, several field trials have been carried out in which crops were sprayed at different rates (full, half- and quarter- of those rates recommended) during two seasons (spring and winter). For statistical purposes, the disappearance of endosulfan with time was considered to follow a pseudo-first-order reaction. Analysis of variance (ANOVA) has been applied to the results obtained. Half-lives of residue disappearance were 4.03-4.68 days in green beans, 4.03-4.20 days in tomatoes, 8.22 days in peppers and 7.97 days in cucumbers. Half-lives in spring were shorter than in the winter season. The application rate and the type of greenhouse did not influence the half-lives.     

Routine methods for analysis of organophosphorus and carbamate insecticides in soil and ryegrass

The organophosphate insecticides dichlorvos, trichlorphon and isofenphos have been extracted from soil and ryegrass by blending with acetone+ benzene (19+1, v/v) and charcoal. After filtering, water and waxes were precipitated from the extract at ? 78°. The extracts were analysed for insecticide by gas chromatography using alkali flameionisation detection. Trichlorphon was converted to the acetate by on-column acetylation. Recoveries ranged from 73 to 93% for levels of insecticide from 0.1 to 10mg/kg. The carbamate insecticides methomyl and carbofuran plus the metabolite 2,3-dihydro-3-hydroxy-2,2-dimethylbenzofuran-7-yl methylcarbamate have been extracted from soil and ryegrass samples by shaking with acidified ammonium acetate. Following filtration and neutralisation, the aqueous phase was extracted with dichloromethane. The carbamates in the extracts were determined by gas chromatography using on-column trans-esterification to methyl methylcarbamate. Recoveries ranged from 79 to 97% for levels of insecticide from 0.1 to 10 mg/kg.     

The metabolism of the carbamate insecticide bendiocarb in the rat and in man

The metabolism of the carbamate insecticide bendiocarb (2,2-dimethylbenzo-1, 3-dioxol-4-yl methylcarbamate) has been investigated in male and female rats and in a male human volunteer using radiolabelled material. The compound was rapidly and extensively absorbed and completely metabolised following oral administration. In man, absorption was complete, >99% of the dose being excreted in the urine within 22 h. In the rat, > 86% of the radiolabel was excreted in the urine within the first 24 h. Faecal excretion from the rat was minor (3–8% of dose) and a small amount of the compound (1–3%) was metabolised and excreted as [¹⁴C]carbon dioxide. The major metabolic pathway in both species involved cleavage of the carbamate ester group to yield the phenol,2,2-dimethylbenzo-1, 3-dioxol-4-ol (I). This metabolite, occurring as sulphate and glucuronide conjugates, accounted for more than 95% of the dose excreted by the human volunteer. In man, small amounts of conjugates of 2, 2-dimethylbenzo-1, 3-dioxol-4-yl N-(hydroxymethyl)carbamate (II) were also found in early samples. In the rat, the metabolism was more complex with the formation of small amounts of conjugates of II and several minor metabolites, thought to be ring-hydroxylated derivatives of bendiocarb and I.     

Osmoregulatory function in ducks following ingestion of the organophosphorus insecticide fenthion

Salt gland function and osmoregulation in aquatic birds drinking hyperosmotic water has been suggested to be impaired by organophosphorus insecticides. To test this hypothesis, adult black ducks (Anas rubripes) were provided various regimens of fresh or salt (1.5% NaCl) water before, during, and after ingestion of mash containing 21 ppm fenthion. Ducks were bled by jugular venipuncture after 1, 7, and 12 days of treatment, and were then killed. Brain and salt gland acetylcholinesterase activities were substantially inhibited (44–61% and 14–36%) by fenthion. However, salt gland weight and Na⁺-K⁺-ATPase activity, and plasma Na⁺, Cl^?, and osmolality, were uniformly elevated in all groups receiving salt water including those ingesting fenthion. In a second study, salt gland Na⁺-K⁺-ATPase activity in mallards (A. platyrhynchos) was not affected after in vitro incubation with either fenthion oxon at concentrations ranging from 0.04 to 400 μM, but was reduced in the presence of 40 and 400 μM DDE (positive control). These findings suggest than environmentally realistic concentrations of organophosphorus insecticides do not markedly affect osmoregulatory function in adult black ducks.     

2-Trichloromethylbenzimidazole,a new selective chromogenic reagent for detection of some heteroaromatic pesticides on thin-layer chromatographic plates

A highly selective method for the detection of several pesticides containing a heteroaromatic ring in the molecule (e.g. nicotine, pyrifenox or prochloraz) on thin-layer chromatographic (TLC) plates is described. The necessary detection condition is the presence in the ring of at least one tertiary nitrogen atom without substitutents on the two adjacent carbon atoms and, in the case of azoles, the protection of a secondary NH group by an alkyl or acyl group. The detection is realized by spraying the developed chromatogram with an acetone solution of 2-trichloromethylbenzimidazole and subsequently heating at 100-150°C in a drier. The detection limit is 20 ng to 10 μg depending on the detected compound. Some pesticide formulations may be analyzed using this method.     

A method for the estimation of 1,2-dibromoethane in vegetables

Residues of 1,2-dibromoethane (EDB) were readily estimated in treated vegetables down to levels of 0.2 mg/kg. Clean-up was effected by steam distillation into a toluene trap. This was followed by X-ray fluorescence determination of the collected EDB in the toluene. Good recoveries of added EDB were obtained at 0.5, 2, 5 and 20 mg/kg in cucumbers, pumpkins and zucchinis.     

A small-scale method for the determination of pyrethroid insecticide residues in crops and soils

A small-scale method for the determination of pyrethroid insecticide residues in crops and soils is described. Compared with the conventional methods, the overall analysis time is reduced by approximately 60% and solvent usage is reduced by approximately 80% using this approach. Results obtained on a range of crops using the small-scale and conventional methods were in good agreement, and a repeatability study showed that the small-scale approach is unbiased and gives good precision. To date, linseed, tobacco, cotton foliage, cotton seed, wheat grain, sorghum, savoy, cauliflower, cabbage, cucumber, apple, peach, blackcurrant, gooseberry, raspberry and soil samples have been analysed using the method. Good recoveries were obtained with all these matrices.     

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.     

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.     

出口蔬菜病虫害防治及农残控制

本文对出口蔬菜田间病虫害及防治控制、田间环境、产品农残进行了调查与分析,提出了前茬作物的农药控制,田间病虫害防治中农药的合理使用以及生产加工过程中的批次管理等出口蔬菜生产过程中3个关键点,并提出了具体控制措施.     

A multiresidue analytical method for determining organochlorine,organophosphorus, dinitrophenyl and carbamate pesticides in apples

A multiresidue analytical method for the simultaneous extraction of organochlorine, organophosphorus, dinitrophenyl and carbamate pesticides from apples is presented. Extraction is performed with a mixture of toluene and hexane. After clean-up on a Florisil column, and in some cases conversion to derivatives, quantitative determination is performed by electron-capture gas chromatography. Qualitative verification is performed by thin-layer chromatography or gas chromatography-mass spectrometry.     

Rapid in vitro screening assay for immunotoxic effects of organophosphorus and carbamate insecticides on the generation of cytotoxic T-lymphocyte responses

There has been an increasing need for rapid and easily interpreted techniques for the screening of possible immunotoxicants. Besides the obvious detrimental effects of exposure to immunosuppressive agents, the modulation of the immune system which results from exposure to these toxicants may be a sensitive index to the toxicologic effects of such agents. Other researchers have proposed assays to screen the effect of in vitro treatment with immunotoxicants on mitogenic and humoral immune responses. In this report, we have described an in vitro technique for screening the effect of immunotoxicants, in the presence and absence of a NADPH fortified liver postmitochondrial supernatant (S-9) from Arochlor 1254-treated rat, on another aspect of the mammalian immune system, the generation of a T-cell-mediated cytolytic (CTL) response. This enzyme system altered the effect of organophosphorus compounds on the generation of a CTL response. Malathion and fenitrothion were no longer suppressive following this pretreatment; however, ethyl and methyl parathion and fenthion were only partially detoxified. In contrast, the S-9 enzyme system did not alter the effect of carbamate pesticides, carbaryl and carbofuran, on the generation of CTL responses. This report describes the effects of these seven organophosphorus and carbamate pesticides on the generation of the CTL response. In addition, some of the in vivo data published on the immunomodulatory effects of these compounds were collated from the literature and a correlation between in vitro and in vivo studies was discussed.     

Gas-liquid chromatographic method for perfluidone residues in rice grains and husks

A gas-liquid chromatographic method using electron-capture detection is described for the determination of perfluidone residues in rice grains and husks. The procedure consists of extraction, purification on an anion-exchange resin, methylation and further clean-up (if necessary) by adsorption on “Florisil”. The recoveries from fortified rice grains and husks were respectively 73.5–98% and 77–104% in the range 0.01–0.50 mg/kg. Sensitivity permits detection of perfluidone at 0.005 mg/kg level.