Pyrethroid residues in milk and blood of dairy cows following single topical applications

The presence of the pyrethroid insecticides flumethrin, deltamethrin, cypermethrin and cyhalothrin in milk and blood of 10 cows was determined after single dermal applications of recommended doses. Milk and blood samples were collected every 7 days over a 35 d period and analyzed by high performance liquid chromatography. The highest residues in milk were found on day 28 for flumethrin and day 1 for deltamethrin, cypermethrin and cyhalothrin, while in blood the highest concentrations were present on day 28 for flumethrin and deltamethrin, the first day for cypermethrin, and day 14 for cyhalothrin.

Gas Chromatographic Determination of Cyprodinil, Fludioxonil, Pyrimethanil, and Tebuconazole in Grapes, Must, and Wine

A rapid and simple gas chromatographic method for determinating cyprodinil, fludioxonil, pyrimethanil, and tebuconazole in grapes, must, and wine is described. An on-line microextraction method was used with a one-step extraction-partition procedure. Nitrogen-phosphorus and mass spectrometric detectors were used, because of their low sensitivity and high selectivity. Because of high selectivity of detector, no cleanup was necessary and the extract was concentrated 5 times. Recoveries from fortified grapes, must, and wine ranged from 93 to 110%. Limits of determination were 0.05 mg/kg for cyprodinil and pyrimethanil and 0.10 mg/kg for fludioxonil and tebuconazole.

Developmental and behavioral effects of postnatal amitraz exposure in rats

The effects of postnatal amitraz exposure on physical and behavioral parameters were studied in Wistar rats, whose lactating dams received the pesticide (10 mg/Kg) orally on days 1, 4, 7, 10, 13, 16 and 19 of lactation; control dams received distilled water (1 ml/kg) on the same days. A total of 18 different litters (9 of them control and 9 experimental) born after a 21- day gestation were used. The results showed that the median effective time (ET50) for fur development, eye opening, testis descent and onset of the startle response were increased in rats postnatally exposed to amitraz (2.7, 15.1, 21.6 and 15.3 days, respectively) compared to those of the control pups (1.8, 14.0, 19.9 and 12.9 days, respectively). The ages of incisor eruption, total unfolding of the external ears, vaginal and ear opening and the time taken to perform the grasping hindlimb reflex were not affected by amitraz exposure. Pups from dams treated with amitraz during lactation took more time (in seconds) to perform the surface righting reflex on postnatal days (PND) 3 (25.0 ±2.0), 4 (12.3 ± 1.2) and 5 (8.7 ± 0.9) in relation to controls (10.6 ± 1.2; 4.5 ± 0.6 and 3.4 ± 0.4, respectively); the climbing response was not changed by amitraz. Postnatal amitraz exposure increased spontaneous motor activity of male and female pups in the open-field on PND 16 (140± 11)and 17(124± 12), and 16 (104±9), 17 (137 ± 9) and 18 (106 ± 8), respectively. Data on spontaneous motor activity of the control male and female pups were 59 ± 11 and 69 ± 10 for days 16 and 17 and 49 ± 9, 48 ± 7 and 56 ± 7 for days 16, 17 and 18, respectively. Some qualitative differences were also observed in spontaneous motor behavior; thus, raising the head, shoulder and pelvis matured one or two days later in the amitraz- treated offspring. Postnatal amitraz exposure did not change locomotion and rearing frequencies or immobility time in the open-field on PND 30, 60 and 90. The present findings indicate that postnatal exposure to amitraz caused transient developmental and behavioral changes in the exposed offspring and suggest that further investigation of the potential health risk of amitraz exposure to developing human and animal offsprings may be warranted.

HPLC determination of flumethrin, deltamethrin, cypermethrin, and cyhalothrin residues in the milk and blood of lactating dairy cows

A procedure to determine residue concentrations of synthetic pyrethroid insecticides (flumethrin, deltamethrin, cypermethrin and cyhalothrin) in the milk and blood of lactating dairy cows was developed. Extraction was performed with acetonitrile, n-hexane partitioning, and silica gel column cleanup with n-hexane and diethyl ether. Analysis was carried out by high- performance liquid chromatography and ultraviolet detection. Recovery of the four pyrethroids averaged 78 to 91% with a minimum detectable concentration of 0.001 mg/kg. The method was reproducible and sensitive.

Efficiency of safety measures applied to a manual knapsack sprayer for paraquat application to Maize (Zea mays L.)

The objectives of the present study were to evaluate the safety of mixer/loaders and applicators of paraquat to maize crop by knapsack sprayers and to determine the efficacy of safety measures applied to the sprayers. Potential dermal exposure (PDE) was evaluated in 22 worker body parts. The Cu2+ cation of a copper-based fungicide was used as tracer in the spray solution. Sanitary pads and cotton gloves were used to collect the pesticide solution on the sampled body parts. It was observed that paraquat application in front of the applicator's body (0.5 and 1.0 m lance) is unsafe because PDE was 1,979.8 ml/day (for 0.5 m lance) and 1,290.4 ml/day (for 1.0 m lance) and needs 50-80% and 37-69% control of PDE respectively. Control can be achieved by the use of protective garment on the legs and feet only, which received 92-93% of the PDE. Switching the spray nozzle to the back of the operator reduced the PDE by 98% and was sufficient to make working conditions safe, while maintaining the efficiency of application and making the work lighter and more comfortable. Mixer/loaders received 86% of the PDE to the hands and the work condition was safe (MOS > 1), however impermeable gloves could be used as a further safety measure.

Determination of 2,4-D and dicamba in food crops by MEKC

The determination of 2,4-D (2,4-dichlorophenoxyacetic acid) and Dicamba (2-methoxy-3,6-dichlorobenzoic acid) residues in sugar cane, rice and corn was performed by a supercritical fluid extraction (SFE) method using CO2/acetone as extraction mix and an SFE apparatus developed in our laboratory. The extracts were cleaned up after extraction by both liquid- liquid partition and a Florisil column. Micellar electrokinetic capillary chromatography (MEKC) coupled with ultraviolet on-column detection was used for the analysis of these pesticides. The detection limits were improved by the preparation of a special detection cell with an increased pathlength that gave detection limits of ca. 0.6 pg for 2,4-D and Dicamba. Our results demonstrated that capillary electrophoresis can be a powerful new analytical tool for pesticide residue analysis.

Toxicity of synthetic piperonyl compounds to leaf-cutting ants and their symbiotic fungus

The development of Leucoagaricus gongylophorus, the fungus cultured by the leaf-cutting ant Atta sexdens was inhibited in vitro by synthetic compounds containing the piperonyl group. In addition, worker ants that were fed daily on an artificial diet to which these compounds were added had a higher mortality rate than the controls. The inhibition of the fungal growth increased with the size of the carbon side chain ranging from C1 through C8 and decreasing thereafter. 1-(3,4-Methylenedioxybenzyloxy)octane (compound 5) was the most active compound and inhibited the fungal development by 80% at a concentration of 15 μg m1-1. With worker ants the toxic effects started with compound 5 and increased with the number of carbons in the side chain. Thus, for the same concentration (100 μg m1-1) the mortality rates observed after 8 days of diet ingestion were 82%, 66% and 42%, for 1-(3,4-methylenedioxybenzyloxy)decane, 1-(3,4-methylenedioxybenzyloxy)dodecane and compound 5, respectively, whereas with commercial piperonyl butoxide the mortality was 68%. The latter compound, which is known as a synergist insecticide, was as inhibitory to the symbiotic fungus as the synthetic compound 5. The possibility of controlling these insects in the future using compounds that can target simultaneously both organisms is discussed. © 2001 Society of Chemical Industry.