Assessment of the grain protectants chlorpyrifos-methyl plus bioresmethrin,fenitrothion plus (1R)-phenothrin,methacrifos and pirimiphos-methyl plus carbaryl under practical conditions in Australia

Methacrifos (22.5 g t^?1) and the three protectant combinations chlorpyrifos-methyl (10 g t^?1) plus bioresmethrin (1 g t^?1), fenitrothion (12 g t^?1) plus (1R)-phenothrin (2 g t^?1) and pirimiphos-methyl (4 g t^?1) plus carbaryl (8 g t^?1) were each applied to grain that was stored in at least 15 silos. Grain temperature and levels of protectant were regularly monitored, and samples from 12 storages using each treatment were taken for laboratory assays against Rhyzopertha dominica and Tribolium castaneum. Grain condition did not deteriorate during storage. Grain remained free of insects in 60 of the 63 storages treated; partial failure in the other 3 storages was attributed to low or irregular levels of protectant. The mean and range of residue values of all protectants were recorded as a function of time and the mean observed values corresponded to predicted values. In laboratory bioassay, the order of effectiveness against T. castaneum was methacrifos > chlorpyrifos-methyl plus bioresmethrin > fenitrothion plus (1R)-phenothrin = pirimiphos-methyl plus carbaryl. The order of effectiveness against R. dominica was carbaryl plus pirimiphos-methyl = (1R)-phenothrin plus fenitrothion > methacrifos > bioresmethrin plus chlorpyrifos-methyl.     

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.     

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.     

Responses of Corcyra cephalonica (Stainton) to pirimiphos-methyl, spinosad, and combinations of pirimiphos-methyl and synergized pyrethrins

Field control failures with pirimiphos-methyl against the rice moth, Corcyra cephalonica (Stainton), in Weslaco, Texas, USA, led us to investigate the susceptibility of this particular strain to pirimiphos-methyl, spinosad, pyrethrins synergized with piperonyl butoxide, and pirimiphos-methyl combined with synergized pyrethrins. In laboratory bioassays, 50 eggs of C cephalonica were exposed to untreated and insecticide-treated corn and sunflower seeds to determine larval survival after 21 days, egg-to-adult emergence after 49 days, and larval damage to seeds at both exposure periods. Pirimiphos-methyl at both 4 and 8 mg kg(-1) did not prevent larval survival or egg-to-adult emergence of C cephalonica on either corn or sunflower seeds, and seed damage was evident at both rates. The C cephalonica strain was highly susceptible to spinosad at 0.5 and 1 mg kg(-1). At both spinosad rates, reduction in larval survival, egg-to-adult emergence, and seed damage relative to the control treatment was > or = 93% on both corn and sunflower seeds. Pirimiphos-methyl and spinosad were generally more effective against C cephalonica on corn than sunflower seeds. The C cephalonica strain was completely controlled on corn treated with 1.5 mg kg(-1) of pyrethrins synergized with 15 mg kg(-1) of piperonyl butoxide. Many larvae survived and became adults on corn treated with synergized pyrethrins at < or = 0.75 mg kg(-1). Corn treated with pirimiphos-methyl at 4, 6 or 8 mg kg(-1) in combination with 0.38 to 1.5 mg kg(-1) of synergized pyrethrins reduced larval survival by > or = 95%, egg-to-adult emergence by > or = 97%, and seed damage by > or = 94%. Our results suggest that the C cephalonica strain can be controlled on corn by combining pirimiphos-methyl with synergized pyrethrins or with synergized pyrethrins at the labeled rate. Although spinosad is not currently labeled for use on stored corn and sunflower seeds, it appears to be effective against C cephalonica on both commodities at very low rates.     

The fate and insecticidal activity of pirimiphos-methyl in stored wheat grain

The degradation of [¹⁴C]pirimiphos-methyl was investigated on a 1-kg bulk of grain stored in the laboratory at 15°C for 28 weeks. Breakdown of pirimiphos-methyl was slow, leaving 77% of the applied dose unchanged at the end of the experiment. The major degradation product was the hydroxypyrimidine (up to 12.5% of the applied dose) with the remainder of the residue (up to 12.1%) remaining within the grain tissues after solvent extraction. The efficacy of the treatment was assessed in a parallel experiment by bioassay of a 5-kg bulk of grain dosed with unlabelled pirimiphos-methyl. 100% Mortality of an organophosphateresistant strain of Oryzaephilus surinamensis L. was maintained throughout the experiment whereas some survival of an organophosphate-resistant strain of Tribolium castanewm (Herbst) occurred after 12 weeks of storage. This increased to give a 20% survival rate at the end of the experiment.     

An assessment of chlorpyrifos-methyl,etrimfos, fenitrothion and pirimiphos-methyl as grain protectants

Trials were carried out over two consecutive years to compare the efficacy of chlorpyrifos-methyl, etrimfos, fenitrothion and pirimiphos-methyl against susceptible and organophosphorus-resistant strains of Tribolium castaneum Herbst, Sitophilus granarius L. and Oryzaephilus surinamensis L., gamma-HCH-resistant strains of Acarus siro L. and Glycyphagus destructor Schrank, and a susceptible strain of Tyrophagus longior Ger-vais. Pirimiphos-methyl was not evaluated against the three mite species as data on the efficacy of this material had previously been published. Etrimfos and pirimiphos-methyl were also tested against a susceptible and an organophosphorus-resistant strain of Sitophilus oryzae L. Each pesticide was applied to two separate 20-tonne batches of English wheat and stored under ambient conditions for 36 weeks. The efficacy of the pesticides was assessed regularly over the storage period using established bioassay techniques. However, chlorpyrifos-methyl and fenitrothion were assessed against susceptible and resistant strains of S. granarius for 32 weeks only. Each of the four pesticides produced >95% mortality of the susceptible strain of all insect species tested for the entire duration of the trial with the exception of fenitrothion, when survival of T. castaneum increased after 32 weeks. Only fenitrothion failed to give 100% mortality of the resistant strain of S. granarius throughout the trial, but even so, the mortality was always >95%. Chlorpyrifos-methyl, etrimfos and pirimiphos-methyl gave much better control of the resistant T. castaneum than fenitrothion, and etrimfos gave slightly better control of resistant O. surinamensis than pirimiphos-methyl which was in turn better than chlorpyrifos-methyl at 36 weeks. Both etrimfos and pirimiphos-methyl gave 100% mortality of the susceptible and resistant strains of S. oryzae. None of the pesticides maintained 100% kill of A. siro throughout the trial and fenitrothion failed to achieve this level of mortality after only 4 weeks. Etrimfos produced 100% mortality of the other two mites species tested throughout the trial, whereas both chlorpyrifos-methyl and fenitrothion achieved this level of mortality for 32 weeks.     

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.     

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.     

A collaborative study of residues on wheat of chlorpyrifos-methyl,fenitrothion, malathion,methacrifos and pirimiphos-methyl. 1. Method development

The accuracy and reproducibility of analytical methods for the assay of five organophosphorus grain protectants have been investigated by a coordinated test programme. Results were assessed using data from field applications of chlorpyrifos-methyl, fenitrothion, malathion, methacrifos and pirimofos-methyl at commercial silos in New South Wales and Queensland. A satisfactory analytical procedure is recommended following an extended series of tests.     

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.     

Toxicity of calciferol,warfarin and their combinations to Rattus norvegicus (albino) and R. rattus

The response of Rattus norvegicus and R. rattus to calciferol, warfarin and a combination of these compounds was tested. Both species succumbed to the recommended bait concentrations of calciferol (1000 mg/kg) and warfarin (250 mg/kg) when tested individually. However, R. rattus was more susceptible to lower concentrations of calciferol (500 and 750 mg/kg) as compared to R. norvegicus, which was sensitive to lower concentrations of warfarin (12.5 and 25 mg/kg bait). Addition of calciferol at different concentrations did not affect the toxicity of warfarin against R. norvegicus. However, with R. rattus calciferol (250–350 mg/kg) or warfarin (50 mg/kg bait), which individually produced partial mortality, in combination produced a complete kill besides accelerating death. Combination of higher dosages of calciferol with warfarin (1000 + 250 mg/kg bait) tested against both species showed no advantages, resulting in neither lower bait consumption nor speedier death, though individually the components gave complete kills.     

Efficacy of current and potential grain protectant insecticides against a fenitrothion-resistant strain of the sawtoothed grain beetle,Oryzaephilus surinamemis L

The responses of a highly fenitrothion-resistant and a susceptible strain of Oryzaephilus surinamensis L. from Australia were measured against a range of alternative grain protectants using impregnated-paper and treated-grain assays. The R-strain was also highly resistant to carbaryl, moderately resistant to malathion and pirimiphos-methyl and showed low-level resistance to methacrifos, chlorpyrifos-methyl, bioresmethrin, permethrin, cyfluthrin, cypermethrin and dichlorvos. There was marginal resistance to deltamethrin. Methoprene, to which there was no resistance, was the most effective material at suppressing progeny production of the resistant strain. At current commercial application rates chlorpyrifos-methyl was the only compound of those tested that would completely control both adults and larvae of resistant O. surinamensis for a storage period of nine months. Overall, the homogeneity of response of both strains to insecticides using the treated-grain assay was as good as the response from impregnated-paper assays. The latter also tended to exaggerate resistance factors compared to the treated-grain assays.     

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.     

Enantioselective catalysis for agrochemicals: synthetic routes to (S)-metolachlor, (R)-metalaxyl and (αS,3R)-clozylacon

The application of enantioselective catalytic methods for the technical preparation of chiral agrochemicals is illustrated for three active ingredients of the acylanilide type. The key step for the technical synthesis of the herbicide (S)-metolachlor is the enantioselective hydrogenation of an imine intermediate using a novel iridium ferrocenyldiphosphine catalyst with an unprecedented high activity and 80% ee. (R)-metalaxyl and (αS,3R)-clozylacon were synthesized via the enantioselective hydrogenation of corre-sponding enamide precursors with Rh and Ru/binap catalysts with >95% and 99% enantiomeric purity, respectively. © 1998 Society of Chemical Industry     

cis-Jasmone treatment induces resistance in wheat plants against the grain aphid,Sitobion avenae (Fabricius) (Homoptera: Aphididae)

cis-Jasmone is a plant volatile known to have roles as an insect semiochemical and in inducing plant defence. It was evaluated in laboratory and field trials for control of cereal aphids. In an olfactometer bioassay cis-jasmone was repellent to alatae of the grain aphid, Sitobion avenae (Fabricius) (Homoptera: Aphididae). Moreover, wheat, Triticum aestivum (L), seedlings sprayed with formulated cis-jasmone 24 h previously were less susceptible to attack by S. avenae than control plants. In field simulator studies, significantly fewer alate S. avenae settled on cis-jasmone-treated plants over a 24-h period. In addition, the intrinsic rate of population increase, r(m), of S. avenae apterae was reduced on cis-jasmone treated seedlings. In a series of small-plot experiments conducted over four years, cis-jasmone applications reduced cereal aphid populations infesting wheat in the field.     

Structure-activity relationships of 1,2,3-benzothiadiazoles as synergists for carbaryl against the house fly (Musca domestica)

Fifty six 1,2,3-benzothiadiazoles and related compounds were evaluated as carbaryl synergists against the house fly (Musca domestica). Many of these were excellent synergists, the most active being those containing various combinations of halogen, alkyl, or alkoxy substituents in the 5- and/or 6-positions of the ring.Regression analysis on the data from 14 compounds for which substituents constants were available established that synergistic activity can be satisfactorily described by equations in terms of the hydrophobic bonding constant (π) and the homolytic free radical constant (σ ·).The results with compounds related to the 1,2,3-benzothiadiazoles suggest that synergistic activity is associated primarily with the diazosulfide moiety.     

Effects of sharp eyespot (Rhizoctonia cerealis) on yield and grain quality of winter wheat

Sharp eyespot caused by Rhizoctonia cerealis was assessed in four winter wheat crops surveyed at four locations in north-central Poland in 2006?C2009. At the four locations symptoms developed on 41.9?C67.7?% of shoots of all plants (average of 4?years) and on 49?C73.5?% of shoots of diseased plants (average of 4?years). Slight (category 1) disease was most frequent, occurring on 24.4?C41.3?% of shoots (range 14.8?C51.3?%); moderate (category 2) disease was less frequent, occurring on 16.9?C25.5?% of shoots (range 8.9?C32.4?%); severe (category 3) disease was least frequent, occurring on 3.2?C7.1?% (range 0?C22.0?%) of shoots. Sharp eyespot affected wheat growth and yield, and grain quality. Disease, especially in the severe category, was associated with significant decreases in plant and ear dry weights, number of grains per ear, grain dry weight per ear and thousand-grain weight, and with increases in grain protein and wet gluten contents, Hagberg falling number and sedimentation value. There was an association between occurrence of sharp eyespot in stems and colonization of grain by fungi. Alternaria alternata and E. nigrum were the most common species.     

Soil-borne spores as a source of inoculum for wheat bunt (Tilletia caries)

Wheat bunt ( Tilletia caries ) has previously been controlled in the UK by routine seed treatment with organomercury. Recent examples are presented of unusual levels of infection due to soil-borne inoculum. The recent infections may be due to unusually dry weather, favouring the survival of spores in the soil, or to the presence of a more persistent strain of T. caries.     

Spectrophotometric determination of ferric dimethyldithiocarbamate (ferbam) in formulations,grain and apples using 1, 10-phenanthroline

A procedure has been developed for the determination of ferbam (ferric dimethyldithiocarbamate) by converting it into ferbam-phenanthroline complex, which is dissolved in acetone + water (1 + 1 by volume), and the absorbance measured at 490 nm against a reagent blank. Beer's law is obeyed over the concentration range 0–8–20-0 mg litre^?1 in the final solution. The method is sensitive, selective and can be used for the direct determination of ferbam in commercial samples, in mixtures with various other dithiocarbamates (ziram, zineb, maneb, etc.) and from grains (rice and wheat) and apples. The limit of determination from foodstuffs is 0–4 mg kg^?1.     

小麦叶片营养物质与抗麦长管蚜的相关性分析

为了阐明小麦叶片营养物质与小麦抗蚜性之间的关系,观察了麦长管蚜Sitobion avenae(F.)在不同小麦品种上的选择趋性,测定其相对日均体重增长率,并采用Branford法和高效液相色谱技术分别测定了不同品种小麦叶片总蛋白、韧皮部中游离氨基酸以及可溶性糖的含量。结果表明,麦长管蚜显著趋向于铭贤169、西农889与西农1376;在铭贤169、西农889和西农1376上的成蚜相对日均体重增长率显著大于中四-有芒、小偃22;西农889叶片的总蛋白含量最高,为2 822.04μg/mL,小偃22叶片韧皮部的可溶性糖含量最高,铭贤169和西农889叶片韧皮部的游离氨基酸总含量相对较高,分别为1 424.3、1 301.1 nmol·L~(-1)·g~(-1)DW;各游离氨基酸在相对抗蚜品种中四-有芒和小偃22中的绝对含量与其抗蚜性无相关性。研究表明,中四-有芒、小偃22对麦长管蚜具有较强的抗性,植物营养在小麦抗蚜性中起到一定作用。