Determination of sugarbeet herbicides in soil samples by hplc

Determination of sugarbeet herbicides such as chloridazon, metamitron and phenmedipham in soil samples is described. After extraction with acetone, pesticides were determined by HPLC on an RP-18 column using methanol/water as mobile phase. Average recoveries were 82% for chloridazon, 93% for metamitron and 77% for phenmedipham. Quantification limits were 3·5 μg kg^?1 for chloridazon, 6·3 μg kg^?1 for metamitron and 3·6 μg kg^?1 for phenmedipham.     

Simultaneous determination of benzimidazole fungicides by HPLC on apples,pears and their pulps

The simultaneous HPLC determination of carbendazim, thiabendazole and thiophanate-methyl in apples, pears and their pulps is described. The method is based on a clean-up procedure carried out on an Extrelut 20 cartridge followed by HPLC analysis on a Diol column using hexune+isopropanol as mobile phase. Average recoveries of 83.8% for carbendazim, 82.9% for thiabendazole and 68.8% for thiophanate-methyl on apple matrix were obtained; recoveries on pear matrix were in the same range. Detection limits with UV detection at 285 nm of 100 ng ml^?1 for carbendazim, 140 ng ml^?1 for thiabendazole and 500 ng ml^?1 for thiophanate-methyl were achieved.     

The HPLC determination of residues of maleic hydrazide in cloves of garlic bulbs following foliar application

A method was developed for the extraction and HPLC analysis of the plant growth regulator maleic hydrazide (MH) from garlic bulbs. Recovery of MH from fortified garlic tissue was 75.8(±6.1)% at the 1 and 2 mg kg^?1 fortification levels. MH residues were determined by HPLC in cloves of garlic bulbs following treatment at three sites in southern Ontario with foliar applications at 3.75 kg ha^?1. MH residues in the cloves were in the order of 3 mg kg^?1 at two sites, and 11 mg kg^?1 at the third side.     

HPLC determination of fenoxaprop and fenoxaprop-ethyl in different soils

This paper describes a method for the determination of fenoxaprop ethyl and fenoxaprop residues in four soil types using two extraction procedures: extraction with 0.1 M hydrochloric acid/methanol, partitioning with dichloromethane and extraction with ethyl acetate. The extracts were purified on florisil or alumina cartridge. The analyses were performed by reverse phase HPLC with UV detection at 280 nm. The best results in terms of recovery, clean-up efficiency and independence of soil characteristics were obtained with the combination ethyl acetate extraction alumina clean-up. Under these conditions, the recoveries were higher than 70 % and the detection limit was 0.02 mg kg^?1 soil.     

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 determination of coumaphos residues in honey by HPTLC with in-situ fluorimetry

An HPTLC method for determining fluorimetrically the residues of coumaphos in honey samples is described. The active ingredient is solid phase extracted with a C-18 disposable column and determined densitometrically on HPTLC pre-coated silica plates. The method does not require additional clean-up steps, is extremely quick and can easily be adapted to routine determinations of a large number of samples. The determination limit is 0-01 mg kg^?1 and recoveries are above 87%.     

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%.     

Acaricide toxicity and resistance in larvae of different strains of Tetranychus urticae and Panonychus ulmi (Acari: Tetranychidae)

The toxicities of eight structurally different acaricidal compounds to six‐legged larvae (first motile stage) of three laboratory strains of the two‐spotted spider mite, Tetranychus urticae, and the European red mite, Panonychus ulmi, were evaluated following spray application. The larvae of five field‐derived strains of T urticae originating from France, Italy, Brazil, California and Florida were also tested for their susceptibilities to discriminating concentrations of several acaricides resulting in 95% mortality when applied to the organophosphate‐resistant laboratory reference strain WI. The spray bioassay used was robust and gave repeatable results with a wide range of acaricidal compounds, irrespective of their mode of action (ovo‐larvicides or primarily acting on motile life stages). Compounds tested were abamectin, azocyclotin, chlorpyrifos, clofentezine, deltamethrin, fenpyroximate, hexythiazox and pyridaben. Larvae of one of the laboratory strains of T urticae, AK, originally collected in Japan in 1996 and maintained without further selection pressure, exhibited 2000‐ and >4000‐fold resistance to the mitochondrial electron transport inhibitors pyridaben and fenpyroximate, respectively. Another strain of T urticae, AU, obtained from Australia and maintained in the laboratory under selection with hexythiazox and clofentezine since 1987 showed >770‐ and >1000‐fold resistance to clofentezine and hexythiazox, respectively. The same resistance pattern was observed against larvae of a laboratory strain of P ulmi, CE, also selected with hexythiazox. Larvae of one of the field‐derived strains of T urticae, BR, showed a lower susceptibility to a number of compounds, whilst the others were susceptible to all compounds except the organophosphates. © 2001 Society of Chemical Industry     

Fenitrothion plus (1R)-phenothrin,and pirimiphos-methyl plus carbaryl,as grain protectant combinations for 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 9 months, using malathion-resistant strains of insects, established that treatments were generally effective. Fenitrothion (12 mg kg^?1)+ (1R)-phenothrin (2 mg kg^?1) was more effective than pirimiphos-methyl (6 mg kg^?1) + carbaryl (10 mg kg^?1) against Sitophilus oryzae (L.) and Ephestia cautella (Walker); the order of effectiveness was reversed for S. granarius (L.). Against Rhyzopertha dominica (F.), Tribolium castaneum (Herbst), T. confusum Jackquelin du Val and Oryzaephilus surinamensis (L.), both treatments effectively prevented the production of progeny. The order of persistence was pirimiphos-methyl> (1R)-phenothrin>carbaryl or fenitrothion. During processing from wheat to white bread, residues were reduced by 98% for carbaryl, >44% for (1R)-phenothrin, 98% for fenitrothion and 85% for pirimiphosmethyl.     

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%.     

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     

Solid-phase extraction and gas chromatographic determination flumethrin residues in honey

A gas chromatographic method to determine flumethrin (‘Bayvarol’) in honey samples is described. The method consists of solid-phase extraction with RP C-18 cartridges, clean-up if required on silica cartridges, and quantitation of the active ingredient with an electron capture detector using deltamethrin as internal standard. Compared to previous methods it is very rapid, and a number of samples can be prepared simultaneously. The minimum detectable quantity is 0·005 mg kg^?1 and mean recoveries are of the order of 95%.     

Chlorpyrifos-methyl plus bioresmethrin; Methacrifos; Pirimiphos-methyl plus bioresmethrin; and synergised bioresmethrin as grain protectants for wheat

Field trials with various pesticide combinations were carried out on bulk wheat in commercial silos in Queensland, South Australia and Western Australia. Laboratory bioassays on samples of treated grain at intervals over 8 months using malathion-susceptible and malathion-resistant strains established the following orders of efficacy: against Sitophilus oryzae (L.), chlorpyrifos-methyl 10 mg kg^?1 + bioresmethrin 1 mg kg^?1 = methacrifos 15 mg kg^?1 in aerated storage > pirimiphos-methyl 4 or 6 mg kg^?1 + bioresmethrin 1 mg kg^?1 = bioresmethrin 4 mg kg^?1 + piperonyl butoxide 16 mg kg^?1; against Rhyzopertha dominica (F.), bioresmethrin 4 mg kg^?1 + piperonyl butoxide 16 mg kg^?1 > methacrifos 15 mg kg^?1 > chlorpyrifos-methyl 10 mg kg^?1 + bioresmethrin 1 mg kg^?1 = pirimiphos-methyl 4 or 6 mg kg^?1 + bioresmethrin 1 mg kg^?1. All treatments completely prevented production of progeny in Sitophilus granarius (L.), Tribolium castaneum (Herbst), T. confusum Jackquelin du Val and Oryzaephilus surinamensis (L.). The biological efficacy of methacrifos was greater and the rate of degradation lower in aerated than in non-aerated storage. Residue levels of all compounds were determined chemically and were below proposed international residue levels to be considered by the Codex Alimentarius Commission.     

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.     

Organophosphorothioates and synergised synthetic pyrethroids as grain protectants on bulk wheat

Organophosphorothioates and synergised synthetic pyrethroids were used in duplicate field trials carried out on bulk wheat in commercial silos in Queensland and New South Wales. Laboratory bioassays using malathion-resistant strains of insects were carried out on samples of treated grain at intervals over 9 months. These established that all treatments were generally effective. Deltamethrin (2 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1), fenitrothion (12 mg kg^?1)+ fenvalerate (1 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1), fenitrothion (12 mg kg^?1)+ phenothrin (2 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1) and pirimiphos-methyl (4 mg kg^?1)+ permethrin (1 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1) controlled common field strains of Sitophilus oryzae (L.) and Rhyzopertha dominica (F.). Against a highly resistant strain of S. oryzae, deltamethrin (2 mg kg^?1)+ piperonyl butoxide (8 mg kg^?1) was superior to the remaining treatments. All treatment combinations completely prevented progeny production in Tribolium castaneum (Herbst), T. confusum Jacquelin du Val and in Ephestia cautella (Walker). Residues of deltamethrin, fenvalerate, permethrin and phenothrin were determined and shown to be highly persistent on stored wheat. During milling, residues accumulated in the bran fractions and were reduced in white flour. They were not significantly reduced during baking.     

A bioassay for determining simazine in water using aquatic flowering plants (Ceratophyllum oryzetorum,Ranunculus trichophyllus and Alisma plantago-aquatica)

A simple and rapid bioassay for the measurement of simazine in water using aquatic flowering plants (Ceratophyllum oryzetorum Kom., Ranunculus trichophyllus Chaix. and Alisma plantago-aquatica L.) is reported in this paper. It is based on the effect of simazine on the amount of oxygen produced by photosynthesis which is measured directly using a Clark-type oxygen electrode. This method is rapid, sensitive, and capable of measuring a simazine concentration of 0.02 mg litre^?1 within 10 min of treatment. The precision of this method was examined with spiked river water by comparing the results obtained with HPLC. Mean recoveries of simazine measured by bioassay using C. oryzetorum were 96 to 100% which were comparable to those (98 to 100%) obtained with C18 column extraction and HPLC measurement. The results obtained by the two methods showed excellent agreement. Maintenance of stock cultures of the plants and the bioassay procedure itself were much simpler and more easily conducted than methods using algae.     

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.     

Disposal of concentrated solutions of diazinon using organic absorption and chemical and microbial degradation

Peat moss has been found to be an effective ‘organic matrix’ for the absorption and degradation of diazinon in experimental disposal pits. High concentrations of diazinon sorbed onto nutrient-enriched commercial grade peat moss were rapidly degraded. Pits treated with diazinon concentrations ranging from 4000 to 32000 mg kg^?1 contained less than 1 to 7 mg kg^?1 after 18 weeks. Initially, degradation probably was due to hydrolysis resulting from the effects of heat, moisture, low pH and some microbial activity. Further degradation of the hydrolysis product, IMHP, was most likely due to microbial activity. The results obtained suggest that a managed degradation pit, containing a nutrient-enriched organic matrix (peat moss), might provide a useful means for absorbing and neutralizing waste pesticide formulations because the materials used in this system are readily available and the system may be regenerative so that it can be used repeatedly.     

Persistence of carbendazim in field-grown soybeans following application of thiophanate-methyl fungicide

Carbendazim was quantified spectrophotometrically in leaves, petioles, stems and pods from upper and lower halves of entire soybean plants following one or two foliar applications of thiophanate-methyl fungicide (1.1 kg ha^?1 a.i.). Following the first application, the highest carbendazim concentrations occurred 1-4 days post-application and declined thereafter to undetectable (?0.12 mg kg^?1) or barely detectable levels by day 26. The highest concentrations were in the leaves where carbendazim levels exceeded 3.5 mg kg^?1 on day 4 and remained above 1.0 mg kg^?1 until day 19. Concentrations in petioles and upper pods were initially in excess of 1.0 mg kg^?1 and remained above 0.5 mg kg^?1 for 12 days. In lower pods and in stems, concentrations were very low and often not detectable. Typically, concentrations were higher in samples from the upper half of the plant than in those from the lower half. A second application on day 18 resulted in carbendazim concentrations similar to those immediately after the first application; however, concentrations declined rapidly coincidentally with a period of rain. This decline may have been facilitated by poor fungicide uptake due to senescence of the plants.     

Combinations of pirimiphos-methyl and carbaryl for stored grain protection

In laboratory experiments, whole wheat was treated with pirimiphos-methyl or carbaryl or combinations of these two insecticides; the treated grain was then adjusted to a 12% moisture content and stored at 25°C for bioassay at various intervals over a period of 39 weeks. Pirimiphos-methyl at 5.1 mg kg^?1 effectively controlled Sitophilus granarius (L.) and Tribolium confusum Jacquelin du Val but was ineffective against Rhyzopertha dominica (F.) CRD 118, a strain showing malathion resistance. Conversely, carbaryl at 6.5 mg kg^?1 (but not at 3.1 mg kg^?1) was effective against R. dominica, but ineffective against the other two species. A combination of pirimiphosmethyl + carbaryl, at 1.8 + 5.1 mg kg^?1, controlled S. granarius and R dominica but not T. confusum, whilst a 4.2 + 3.4 mg kg^?1 combination was relatively more effective against T. confusum but less so against R. dominica. In a separate experiment, whole wheat was treated with carbaryl at 2.5, 5.0 and 7.5 mg kg^?1 (nominal rates). Samples were stored and, at various times after the treatments, were bioassayed with R. dominica CRD 2, at 20, 25, 30 and 35°C. The results were comparable with those for the CRD 118 strain, but efficacy was reduced at higher temperatures. The combination of pirimiphos-methyl at 4–5 mg kg^?1 and carbaryl at 5–6 mg kg^?1 is suggested as a potentially useful grain protectant where R. dominica is a problem and long term storage is required. These results are discussed in relation to the protection of stored grain in Australia.