The behaviour of residues of flamprop-isopropyl and its breakdown products in barley

Residue data are reported for flamprop-isopropyl ( I ) in barley grain and straw samples following applications of the herbicide to crops grown in eight countries. The samples were analysed for I and its hydrolysis product N-benzoyl-N-(3-chloro-4-fluorophenyl)-DL -alanine ( II ). Following recommended applications (normally 1 kg ha^?1 at Feekes scale G-I/J), residues of I and II in the grain were low (90% were <0.02 mg kg^?1 for I , 86% were <0.06 mg kg^?1 for II , levels which were essentially the limits of determination). Residues in straw were higher and more variable, but again 63 and 77% of samples were below 1 mg kg^?1 for I and II , respectively.     

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.     

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.     

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 sensitive method for the determination of residues of N,N'-Bis(1,3,4-thiadiazol-2-yl)methanediamine in rice

A sensitive method for the isolation, clean-up and thin-layer chromatographic semi-quantitative determination of residues of N,N'-bis(1,3,4-thiadiazol-2-yl)methanediamine ( II ) in rice is reported. The residue from II in rice was found to be its degradation product 1,3,4-thiadiazol-2-ylamine ( I ). The mean recovery by this method was 85%, and the lowest limit of determination was 0.01 mg kg^?f. Using this proposed technique, the residues of I and II in various field-treated rice samples were studied.     

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.     

Metabolism of [3H]triforine in barley grown in the field: The unbound radioactive residue

Barley was sown and grown normally in an experimental field. At the growth stage J,

1 Growth stage J: during the stem extension stage; second node of stem formed and next-to-last leaf just visible.

the aerial part of the plants was sprayed with an aqueous emulsion of a mixture of triforine and [³H]triforine (uniformly labelled in the piperazine ring) using the recommended dose rate of about 240g triforine ha^?1. The barley was harvested when ripe and the straw and grain were analysed separately. The total radioactivity concentration was 20 times higher in straw than in grain. In straw and grain, 12 and 25% respectively of the total incorporated radioactivity in each of these tissues was methanol soluble. The composition of the methanol-soluble radioactive residue was investigated and was shown to contain triforine and its metabolites which were free and unbound in barley straw and grain. No radioactive piperazine was observed, in spite of the high detection sensitivity for radioactivity. The concentrations of triforine and its identified metabolites in straw and grain respectively (mg kg^?1, relative to the fresh weight of tissue) were: triforine, 0.034 and 0.0018; N-[(2,2,2-trichloro-1-(piperazin-1-yl)ethyl]formamide), 0.009 and 0.0006; iminodiacetic acid, 0.021 and 0.001; glycine, 0.043 and 0.0033. Other radioactive water-soluble and very polar, unidentified compounds were observed, corresponding to advanced metabolic products of triforine.     

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.     

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.     

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.     

Extensive pilot use of the grain protectant combinations,fenitrothion plus bioresmethrin and pirimiphos-methyl plus bioresmethrin

Each of the combinations, bioresmethrin (1 mg kg^?1) plus pirimiphos-methyl(6 mg kg^?1) or fenitrothion (12 mg kg^?1), was applied in 1976 to grain in 21 commercial storages. Grain condition and protectant residues were regularly monitored. Three storages became infested with Rhizopertha dominica (F.), but all storages remained free of other insect species. In two of the three infested storages, application of protectant was uneven, and the third became infested only after 8 months of storage. Despite some variations in recovered residues between sites, the mean residue levels were accurately described by predictive models. Falls in temperature during storage varied considerably, and were related to factors other than climate and bin size. There was a marked effect by aeration with ambient cold air on both the grain temperature and the rate of loss of residues. Results of collaborative studies on the determination of residues indicate a need for regular check programmes of analysis, and confirm previous conclusions that residues of fenitrothion and pirimiphos-methyl can be accurately and conventionally determined.     

Fusarium graminearum and Fusarium pseudograminearum caused the 2010 head blight epidemics in Australia

Wheat crops in southeast Queensland (Qld) and northern New South Wales (NSW) were infected with fusarium head blight (FHB)‐like symptoms during the 2010–11 wheat growing season. Wheat crops in this region were surveyed at soft dough or early maturity stage to determine the distribution, severity, aetiology and toxigenicity of FHB. FHB was widespread on bread wheat and durum, and Fusarium graminearum and/or F. pseudograminearum were diagnosed from 42 of the 44 sites using species‐specific PCR primers directly on spikelets or from monoconidial cultures obtained from spikelets. Stem base browning due to crown rot (CR) was also evident in some samples from both states. The overall FHB and CR severity was higher for NSW than Qld. Deoxynivalenol (DON) concentration of immature grains was more than 1 mg kg^?1 in samples from 11 Qld and 14 NSW sites, but only 13 of 498 mature grain samples sourced from the affected areas had more than 1 mg kg^?1 DON. DON concentration in straw also exceeded 1 mg kg^?1 in eight Qld and all but one NSW sites but this was not linked to DON concentration of immature grains. The proportion of spikelets with positive diagnosis for F. graminearum and/or F. pseudograminearum and weather‐related factors influenced DON levels in immature grains. The average monthly rainfall for August–November during crop anthesis and maturation exceeded the long‐term monthly average by 10–150%. Weather played a critical role in FHB epidemics for Qld sites but this was not apparent for the NSW sites, as weather was generally favourable at all sites.     

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.     

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.     

Insecticidal efficacy of fipronil against four stored‐product insect pests: influence of commodity,dose, exposure interval,relative humidity and temperature

BACKROUND: Fipronil is an insecticidal pyrazole that is commonly used as an insecticide in field crops, urban pesticide and veterinary medicine, but there are no reports of its evaluation against stored‐product insects. Three series of laboratory bioassays were conducted to assess fipronil as a potential grain protectant against adults of Sitophilus oryzae (L.), Tribolium confusum Jacquelin du Val, Rhyzopertha dominica (F.) and Prostephanus truncatus (Horn). Factors such as dose (0.01, 0.1, 1 and 10 mg fipronil kg^?1 grain), exposure interval (24 h, 48 h, 7 days and 14 days), temperature (20, 25 and 30 °C), relative humidity (RH; 55 and 65%) and commodity (wheat, maize, barley and paddy rice) were evaluated with regard to their impact on the insecticidal activity of fipronil. Progeny production was assessed after 64 days of exposure. RESULTS: At doses of < 1 mg fipronil kg^?1 grain, efficacy of fipronil was enhanced by an increase in temperature from 20 to 25 °C against S. oryzae or R. dominica for exposures of > 48 h and against T. confusum or P. truncatus for exposures of > 24 h. A further increase in temperature from 25 to 30 °C, although it enhanced efficacy at doses of < 1 mg fipronil kg^?1 grain against S. oryzae at all exposure intervals and against T. confusum after 7 days of exposure, it was negatively associated with efficacy against R. dominica or P. truncatus for exposures of > 24 h. By contrast, increase in RH did not have a significant impact on efficacy of fipronil. Although the performance of fipronil among the tested commodities was species dependent, this substance appeared to be less effective in paddy rice than in barley, maize and wheat. Regardless of the treated commodity, progeny production of all the tested species was almost suppressed with doses higher than 0.1 mg fipronil kg^?1 grain. CONCLUSIONS: Fipronil appeared to be a very effective alternative to the existing substances in stored‐grain protection at doses equal to or higher than 1 mg fipronil kg^?1 grain, and thus these doses require further evaluation in terms of safety for the consumer and residues on stored products. Copyright © 2010 Society of Chemical Industry     

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     

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     

Organophosphorus insecticide residues in virgin Greek olive oil, 1988–1990

Organophosphorus insecticide residues have been monitored for two years in virgin olive oil after dimethoate and fenthion treatments to control the olive fruit fly. No dimethoate residues were detected in any of the samples. For the first and second years, 50% and 21%, respectively, of the samples contained no detectable fenthion residues, while 4% and 6%, respectively had residue concentrations exceeding the Codex Alimentarious Maximum Residue Limit (1 mg kg^?1). The mean concentration was 0·236 mg kg^?1 oil and the estimated daily intake of fenthion 0·0002 mg kg^?1 body weight (Acceptable Daily Intake 0·001 mg kg^?1 body weight). The parent compound was the most important residue in fresh samples, while aged samples contained a higher amount of the metabolite fenthion sulfoxide. The contribution of the oxygen analogues (P= 0 metabolites) of fenthion to the total residue concentration was<5% in most cases.     

The determination of residues of 2,4-D in post-emergence-treated triticale

A gas chromatographic method, using electrolytic conductivity detection, is presented for the determination of 2,4-0 as its methyl ester in triticale (X Triticosecale Wittmack). The method was used to monitor the dissipation of 2,4-0 residues in triticale over a growing season at two sites following post-emergence application of the dimethylamine salt of 2,4-D at 0.56 kkg ha^?1. Initial residues, in the order of30 mg kg^?1. on the day afer application (3- to 4-leaf stage of the crop), decreased to non-detectable levels in the mature straw and seed. Recoveries of 2,4-D were greater than 90% fiom green tissue fortified at 0.1 mg k^?1., and in the order of 75% from seed fortified at 0.05 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.