Comparative purification methods for determination of triadimenol residues in plant material

Two procedures are described for the determination of residues of triadimenol and compared on cereal material. After extraction, purification is carried out by Florisil column chromatography in method I and by semi-preparative High-Performance Liquid Chromatography in method II. Triadimenol residues are quantified by gas chromatography with a thermoionic detector. With method I, interference was observed but not with method II. This specific procedure has been tested on other plant materials. Recoveries in the range of 90–98% indicate that this procedure is suitable for residue analysis of this fungicide with detection limits of 0·008 mg kg^?1 in wheat grains, 0·03 mg kg^?1 in wheat straw and 0·004–0·008 mg kg^?1 in other plants. Maximum residue limits in France are: 0·1 mg kg^?1 in grain, 2·0 mg kg^?1 in straw and 1·0 mg kg^?1 in other vegetables and fruit.     

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 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     

Measurement of simazine residues in chickpeas,Cicer arietinum,by gas–liquid chromatography

A method is described for the measurement of simazine [2-chloro-4,6-bis(ethylamino)-1,3,5-triazine] residues in chickpeas (Cicer arietinum). Ground chickpea samples were extracted with dichloromethane, followed by clean-up on alumina. Gas-liquid chromatography using metribuzin [4-amino- 6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one] as internal standard with thermionic detection was used to quantify simazine residues. The limit of detection was 0.02 mg kg^?1 and the recoveries of simazine from chickpea samples (0.1–4 mg kg-1) averaged 92%.     

A rapid high-pressure liquid chromatographic method for the determination of carbaryl residues in wheat grain

Carbaryl residues in wheat grain have been determined in methanol extracts using normal-phase high-pressure liquid chromatography (h. p. l. c.) with ultraviolet detection. A single-injection, clean-up and analysis technique was used to allow more rapid analysis of samples after extraction. A detection limit of 0.1 mg kg^?1 in a 50 g sample of wheat was achieved. Recoveries of 86% at the 1 mg kg^?1 level and 90-99% at the 5 mg kg^?1 level were obtained for fortified grain samples. Methanol was found to be a superior extractant for carbaryl from wheat when compared with hexane, acetone and dichloromethane. Twelve samples containing aged carbaryl residues were analysed by the h. p. l. c. technique and by a colorimetric procedure which allowed statistical analysis of errors. For the h. p. l. c. method (excluding sampling error), a relative standard deviation of 4.4% was obtained.     

The persistence and activity of insecticide spary deposits on woven polypropylene fabric

Wettable powder formulations of the organophosphorus insecticides, fenitrothion and pirimiphos-methyl, and the pyrethroids, permethrin and deltamethrin, have been compared for persistence and activity on woven polypropylene fabric; the residues produced in maize kept under the test sheets have also been measured. The test insects were Sitophilus oryzue (L.) and Tribolium custuneum (Herbst). Permethrin at 41 and 83 mg m^?2 was completely effective for the full 12 weeks of the experiment. Deltamethrin at 6.2 and 12.5 mg m^?2 was almost equally effective but after 4 weeks the deposit was slower acting against S. oryzae. The organophosphorus compounds were effective only up to 2 weeks at 250 mg m^?2 and up to 4 weeks at 500 mg m^?2. No residues could be detected under the pyrethroids but the organophosphorus insecticides gave residues of 2–4 mg kg^?1 on a thin layer of grain. This residue was biologically effective against the test insects.     

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.     

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.     

Accumulation of endosulfan residues in fish and their predators after aerial spraying for the control of tsetse fly in Botswana

Residues of endosulfan insecticide (α- and β-isomers, and ‘endosulfan sulphate’) in fish and their predators were measured during and after operations to control tsetse fly in the Okavango Delta, Botswana. Six ultra-low-volume doses of endosulfan 35% e.c. (6–12 g a.i. ha^?1) were applied from the air in a period of 12 weeks over 2500 km². The concentration of residues found in living fish was up to 0.19 mg kg^?1 wet wt in caudal muscle, and usually < 0.8 mg kg^?1 wet wt in pooled viscera (maximum 2.8 mg kg^?1). These values returned to near-normal within 3 months after cessation of spraying, but residues were still detectable after 12 months. By comparison, fish killed by spraying contained a maximum residue level (whole-body) of 1.5 mg kg^?1 wet wt. The residue level in fish was approximately proportional to their fat content. Lean fish were more susceptible to poisoning than fat fish. The proportion of the ‘endosulfan sulphate’ metabolite in fish increased at least six times with respect to the parent isomers (α+β) during the period of spraying, but more advanced stages of metabolic breakdown were not monitored. Residue levels in fish predators (fish-eating birds and crocodiles) were similar to those in their prey, and the risk to them was consequently low.     

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

The study deals with the effect of common, annually-used pesticides on soil microorganisms, pesticide residues in soil, and carrot (Daucus carota) yields in Central Finland. Linuron residues in carrot roots were also analysed. Thiram+lindane and dimethoate were applied from 1973–1981 at the commercially recommended doses on experimental plots of carrots, linuron was applied at twice the recommended rate from 1973–1979 and at the normal rate thereafter and in addition TCA was applied in 1978. Maleic hydrazide was used in the years 1973–1976, and glyphosate after 1977. The numbers of different soil microorganisms, their activities and the pesticide residues were studied from autumn 1978 to 1981. The pesticide treatments reduced the growth of soil algae but increased the total number of microorganisms and the number of aerobic spore-forming bacteria. Linuron residues in the soil were 0.9–2.8 mg kg^?1 in the growing season and 1.2–1.7 mg kg^?1 in the autumn, 3 months after application. The residues of glyphosate in the soil were 0.7 mg kg^?1 in the autumn, 41 days after the treatment, and had declined to a level of about 0.2 mg kg^?1 by the following summer. In the pesticide-treated plots the carrot yield was only 20–60% of the yield in the hand-weeded plots. The herbicide programme controlled most of the annual weeds but not couchgrass Elymus repens and milk sow-thistle Sonchus arvensis.     

Risk posed to honeybees (Apis mellifera L,Hymenoptera) by an imidacloprid seed dressing of sunflowers

In a greenhouse metabolism study, sunflowers were seed‐treated with radiolabelled imidacloprid in a 700 g kg^?1 WS formulation (Gaucho® WS 70) at 0.7 mg AI per seed, and the nature of the resulting residues in nectar and pollen was determined. Only the parent compound and no metabolites were detected in nectar and pollen of these seed‐treated sunflower plants (limit of detection <0.001 mg kg^?1). In standard LD₅₀ laboratory tests, imidacloprid showed high oral toxicity to honeybees (Apis mellifera), with LD₅₀ values between 3.7 and 40.9 ng per bee, corresponding to a lethal food concentration between 0.14 and 1.57 mg kg^?1. The residue level of imidacloprid in nectar and pollen of seed‐treated sunflower plants in the field was negligible. Under field‐growing conditions no residues were detected (limit of detection: 0.0015 mg kg^?1) in either nectar or pollen. There were also no detectable residues in nectar and pollen of sunflowers planted as a succeeding crop in soils which previously had been cropped with imidacloprid seed‐treated plants. Chronic feeding experiments with sunflower honey fortified with 0.002, 0.005, 0.010 and 0.020 mg kg^?1 imidacloprid were conducted to assess potential long‐term adverse effects on honeybee colonies. Testing end‐points in this 39‐day feeding study were mortality, feeding activity, wax/comb production, breeding performance and colony vitality. Even at the highest test concentration, imidacloprid showed no adverse effects on the development of the exposed bee colonies. This no‐adverse‐effect concentration of 0.020 mg kg^?1 compares with a field residue level of less than 0.0015 mg kg^?1 ( = limit of detection in the field residue studies) which clearly shows that a sunflower seed dressing with imidacloprid poses no risk to honeybees. This conclusion is confirmed by observations made in more than 10 field studies and several tunnel tests. © 2001 Society of Chemical Industry     

High-pressure liquid chromatographic determination of sec-butylamine residues in potatoes

Fluorescamine, 4-phenylspiro[furan-2(3H), 1′(3′H)-isobenzofuran]-3,3′-dione, derivatives of primary aliphatic amines were separated by high-pressure liquid chromatography using a reverse-phase system with fluorescence detection. This technique was applied to the determination of residues of the fungicide sec-butylamine in potato tubers; the limit of detection was 0.36 pmol, equivalent to a residue of 0.1 mg kg^?1 in potato samples. A second amine, phenethylamine, was identified in extracts from artificially rotted potato flesh but this did not interfere with the analysis of sec-butylamine residues.     

Grain protectants for the control of malathion-resistant insects in stored sorghum

Duplicate experiments were carried out on bulk sorghum stored in South Queensland and in Central Queensland. Bioassays of treated grain, conducted during 6 months' storage, established that fenitrothion (12 mg kg^?1)+ bioresmethrin (1 mg kg^?1), and pirimiphos-methyl (4 mg kg^?1)+ carbaryl (8 mg kg^?1), controlled typical malathionresistant strains of Sitophilus oryzae (L.), Rhyzopertha dominica (F.), Tribolium castaneum (Herbst), and Ephestia cautella (Walker). Chlorpyrifos-methyl (10 mg kg^?1)+ pyrethrins (1.5 mg kg^?1)+ piperonyl butoxide (12 mg kg^?1), and fenitrothion (12 mg kg^?1)+ (1R)-phenothrin (1 mg kg^?1), also controlled the strains of S. oryzae, T. castaneum and E. cautella, but were only partly effective against R. dominica. Methacrifos (15 mg kg^?1) controlled all the tested species except E. cautella. Chemical assays established that the residues and rates of breakdown of these grain protectants on sorghum conformed to the general pattern for other cereal grains; residues from the above treatments were below the individual Maximum Residue Limits recommended by the Codex Alimentarius Commission.     

Toxico‐kinetics,recovery efficiency and microsomal changes following administration of deltamethrin to black Bengal goats

A study of the toxico‐kinetics, recovery percentage from different substrates, cytotoxicity and role of cytochrome P₄₅₀ and b₅ of liver microsome in the metabolism of deltamethrin were carried out in female black Bengal goat. The ALD₅₀ value of deltamethrin in goat by intravenous route lies between 0.2 and 0.6 mg kg^?1. Intravenous disposition kinetics using a dose of 0.2 mg kg^?1 showed that the maximum blood concentration of deltamethrin was recorded at 0.5 min, followed by rapid decline, and a minimum concentration was detected at 6 min after administration. The following values were obtained : Vd_area 0.148 (± 0.02) litre kg^?1; t_1/2 (α) 0.22 (± 0.02) min; t_1/2 (β) 2.17 (± 0.37) min; K_el 1.05 (± 0.24) min^?1; AUC 4.30(± 0.45) µg min ml^?1; Cl_B 0.05 (± 0.006) litre kg^?1 min^?1; T～B 1.93 (± 0.58); fc 0.40(± 0.05). After 10 min, liver retained the maximum residue, and heart, adrenal gland, kidney, spleen, fat and brain also held the insecticide; liver, fat, heart and spleen retained residue after 30 min, and bone, liver and fat retained residue after 60 min of intravenous administration. Oral absorption of deltamethrin was poor and inconsistent, and approximately 65% of administered dose was recovered from faeces and gastrointestinal contents. The excretion of deltamethrin through urine was meagre, and only 0.01 and 0.013% of the administered dose was recovered after 3 and 5 days of oral administration respectively. All the tissues retained the residue after 3 days; while fat, rumen, reticulum, omasum, abomasum, large and small intestine and bone retained the residue after 5 days of oral administration; and the percentage recoveries were 1.73 and 0.027 respectively. Deltamethrin reduced the level of cytochrome P₄₅₀ content of liver microsomal pellet of goat after 5 days of oral administration. Histopathological examination of liver, kidney, heart, spleen brain and lung sections of treated goats did not reveal any pathological changes. © 2001 Society of Chemical Industry     

A laboratory evaluation of the effectiveness of diflubenzuron against Dermestes maculatus De Geer and other storage insect pests

The chitin synthesis inhibitor diflubenzuron, applied as a wettable powder spray to woven polypropylene at 100–500 mg m^?2, was effective against Dermestes maculatus De Geer for at least 12 weeks. D. maculatus was unable to develop on ox hide dipped in a suspension of diflubenzuron (125 mg litre^?1), or on fishmeal dusted at 1–10 mg of active ingredient kg^?1. Diflubenzuron prevented the development of infestations of Callosobruchus maculatus (L.) on peas and of Acanthoscelides obtectus (Say) on beans dusted at 1–5 mg kg^?1. The compound was also very effective against early instar larvae of Trogoderma granarium Everts on wheat. The persistence and activity of diflubenzuron at low dosage rates against D. maculatus appear to justify larger scale trials.     

The determination of imazalil on potatoes and its use in controlling potato storage diseases

Methods are described for the extraction and analysis by gas-liquid and high-pressure liquid chromatography of the fungicide imazalil, 1-(β-allyloxy-2, 4-dishlorophenethyl) imidazole, on potatoes. Before storage, over 80% was recovered from potatoes treated with 0.01–3.0 mg imazalil kg^?1, with a detection limit of 2 μg kg^?1. Imazalil applied to potatoes at 10 g t^?1 before storage decreased the incidence of gangrene (Phoma exigua), silver scurf (Helminthosporium solani), skin spot (Polyscytalum pustulans) and black scurf (Rhizoctonia solani), and was at least as effective as thiabendazole applied at 40 g t^?1. At 1 g t^?1 it also decreased skin spot and silver scurf. Incidence of black dot (Colletotrichum coccodes) was unaffected by these fungicide treatments.     

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.     

Method for the determination of butachlor residues in water,soil and rice

A method is described for the analysis of water, soil and crops for residues of the herbicide butachlor. Residues were extracted with acetone + light petroleum distillate. The extracts were concentrated and purified on a chromatographic column containing aluminum oxide, silver–aluminum oxide and Florisil. Finally, they were quantitated by gas chromatography using an electron-capture detector. The detection limits of various samples were between 0.001 and 0.015 mg kg^?1. The average recoveries ranged from 79.4 to 104.6%.     

Build-up and subsequent decline of residues of quintozene and hexachlorobenzene in lettuce in sequential crops

The build-up and decline of quintozene and hexachlorobenzene residues in protected lettuce, resulting from one to five treatments of the soil (each of 35 g m-2) with a quintozene formulation, have been studied. Residue levels were monitored in each experimental crop during growth until harvest. Residues in the soil at harvest were also determined. Quintozene residues in the harvested lettuce were in the range < 0.02–0.80 mg kg^?1 and those of hexachlorobenzene were in the range < 0.02–0.05 mg kg^?1 (expressed on a fresh weight basis). Residue levels in the soil were 5.4–231 mg kg^?1 for quintozene, and 0.20–5.4 mg kg^?1 for hexachlorobenzene (expressed on a dry weight basis). Under the experimental conditions of the trial there was no significant build-up of quintozene or hexachlorobenzene in harvested lettuce, even after five treatments to the same site.     

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.