Effect of surface waxes on the persistence of chlorpyrifos-methyl in apples, strawberries and grapefruits

The effects of the cuticle and epicuticular waxes of grapefruit, strawberry and apple on the photodegradation and penetration of chlorpyrifos-methyl were studied. Photodegradation experiments were conducted by exposing the insecticide to the light of a xenon lamp in the presence of a film of wax extracted from the fruit surface. The half-life of chlorpyrifos-methyl irradiated in absence of waxes was 9.6 min. The half-lives of pesticide irradiated in the presence of wax extracts of apple, grapefruit and strawberry were 83, 34 and 26 min, respectively. In penetration studies, fruit with and without wax layers were treated with an aqueous suspension of pesticide. The penetration of the pesticide from the cuticle to the pulp was measured after 24 h. Samples without wax contained a higher total amount of insecticide than those with wax. No pesticide was detected in samples of apple and grapefruit pulp. Residues were detected in all fractions of strawberry. The waxes and cuticle appear to have some effect on the photodegradation and penetration of chlorpyrifos-methyl in fruit samples.     

Impact of resistance on the efficacy of binary combinations of spinosad, chlorpyrifos-methyl and s-methoprene against five stored-grain beetles

Laboratory experiments were conducted to determine the efficacy of spinosad (a biopesticide), chlorpyrifos-methyl (an organophosphorus compound (OP)) and s-methoprene (a juvenile hormone analogue) applied alone and in binary combinations against five stored-grain beetles in wheat. There were three strains of Rhyzopertha dominica, and one strain each of Sitophilus oryzae, Tribolium castaneum, Oryzaephilus surinamensis and Cryptolestes ferrugineus. These strains were chosen to represent a range of possible resistant genotypes, exhibiting resistance to organophosphates, pyrethroids or methoprene. Treatments were applied at rates that are registered or likely to be registered in Australia. Adults were exposed to freshly treated wheat for 2 weeks, and the effects of treatments on mortality and reproduction were determined. No single protectant or protectant combination controlled all insect strains, based on the criterion of >99% reduction in the number of live F₁ adults relative to the control. The most effective combinations were spinosad at 1 mg kg⁻¹+chlorpyrifos-methyl at 10 mg kg⁻¹ which controlled all strains except for OP-resistant O. surinamensis, and chlorpyrifos-methyl at 10 mg kg⁻¹+s-methoprene at 0.6 mg kg⁻¹ which controlled all strains except for methoprene-resistant R. dominica. The results of this study demonstrate the difficulty in Australia, and potentially other countries which use protectants, of finding protectant treatments to control a broad range of pest species in the face of resistance development.     

Effect of grain storage and processing on chlorpyrifos-methyl and pirimiphos-methyl residues in post-harvest-treated wheat with regard to baby food safety requirements

A study was undertaken to assess the effects of storage intervals and of milling procedures on the dissipation of chlorpyrifos-methyl and pirimiphos-methyl residues in post-harvest-treated wheat grain and to obtain scientific data on the compliance of the processed products with safety requirements concerning baby foods. The insecticide formulations were applied on stored wheat at recommended rates (20 ml t^-1). The initial concentration levels in whole grain were determined in samples taken 1 h after treatment. The dissipation of residues and their distribution in different fractions of the milled grain were studied after various storage intervals, from 7 to 270 days after treatment. Samples of treated grain were milled in a fractionating laboratory mill and eight fractions — bran, semolina, three types of groats and three types of flour — were collected and analysed for pesticide residues. The residues were determined by an analytical method based on acetone extraction, graphitized carbon clean-up and GC-ECD, respectively, and GC-NPD determination of residues. The limits of determination of both pesticides were 0.005 mg kg^-1, which is high enough for enforcement of the European Commission Directive that established a maximum residue level of 0.01 mg kg^-1 for any pesticide in cereal-based baby food. The results showed that the pesticides chlorpyrifos-methyl and pirimiphos-methyl applied post-harvest on wheat as grain protectants were distinguished by relatively low rates of degradation in the grain under practical storage conditions. Milling did not significantly reduce the bulk of the chemicals but resulted in the distribution of residues in various processed products. The main part of the insecticides deposited on the grain remained in the bran and partly in semolina fractions. After 270 days of treatment, the residues of chlorpyrifos-methyl were within the range 0.8-2.1 mg kg^-1 and of pirimiphos-methyl — between 0.6 and 3.7 mg kg^-1 in the various types of flour.     

Degradation of organophosphorus pesticides in wheat during cookie processing

For investigating carryover of some organophosphorus pesticide residues in the cereal food chain from grain to consumer, a study was set up on wheat bran, flour and cookies, with and without bran. Special emphasis was given to malathion and chlorpyrifos-methyl residues in cookies for better protection of consumers. Pesticide-free wheat was placed in a small-scale model of a commercial storage vessel and treated with these pesticides. The residue levels of insecticides were determined in wheat, as well as in bran, flour and cookies produced from stored wheat at various time intervals during storage. A multiresidue analysis was performed using GC–NPD and GC–MS. Malathion and chlorpyrifos-methyl residue levels were higher than the maximum residue limits (MRLs) in wheat after 240 days of storage. MRLs established by the EC for malathion and chlorpyrifos-methyl in wheat are 8 and 3 mg kg⁻¹, respectively. The residue levels of insecticides in flour samples also exceeded the MRL (2 mg kg⁻¹ for both insecticides). Eight months of storage were not effective for reducing the residues in wheat to the levels below MRLs. Although, considerable amounts of the insecticides remained in the bran and flour, the cookie processing significantly reduced the concentrations in general. Chlorpyrifos-methyl was more persistent than was malathion and comparatively less degradation occurred during milling and cookie processing due to its physicochemical properties.