A new rapid and sensitive analytical method using negative ion chemical ionization-gas chromatography-mass spectrometry in selective ion monitoring mode has been developed for the determination of residues of different synthetic pyrethroid insecticides, allethrin, bifenthrin, cypermethrin, cyphonothrin, cyfluthrin, lambda-cyhalothrin, deltamethrin, fenvalerate, fenpropathrin, permethrin, prallethrin, and trans-fluthrin, in whole blood. The residues of pyrethroid molecules were extracted from the whole blood using a hexane and acetone (8:2, v/v) solvent mixture without separating the serum. The method was found sensitive to detect the residues of pyrethroids up to the level 0.2 pg/mL. Experiments conducted with the whole blood samples at the fortification level 1-100 pg/mL showed 91-103% recovery, whereas blood serum samples collected after the fortification of pyrethroids in whole blood showed 36-54% recovery. Recovery experiments conducted by direct fortification of pyrethroids in blood serum samples showed 96-108%. The applications of the analytical method was tested by analyzing 73 human blood samples collected from the population exposed continuously to different pyrethroid-based formulations. None of the blood samples showed residues of pyrethroids. The results were also confirmed by the detection of the appropriate amounts in a number of these samples, which had subsequently been spiked with known quantity of pyrethroids.
To our knowledge, this is the first report of DNA adduct accumulation in patients with ED. Increased DNA adduct accumulation correlated with the severity of the disease, and they lie in parallel with diminished antioxidant capacity observed in patients with ED. Based on the observations from our present work and our earlier studies, we reiterate that oxidative stress is involved in the disease process. Hence we believe antioxidant vitamin E and C supplementation might be beneficial to patients with ED.
A new sensitive analytical procedure has been developed for the determination of residues of endosulfan in human blood samples. The method involves the extraction of residues of endosulfan from blood samples by the addition of 60% sulfuric acid at 10 degrees C, liquid/liquid partitioning by using hexane and acetone mixture (9:1) and quantification by using GC-ECD. Residues of endosulfan in blood samples were quantified as the sum of alpha-endosulfan, beta-endosulfan, endosulfan sulfate and endosulfandiol. The influence of temperature during the extraction has been studied. Recovery experiments were conducted over the concentration range 1.0-50 ng ml(-1) and the relative standard deviation calculated. The method was found to be sufficiently sensitive to quantify the residue of total endosulfan up to the 1.0 ng ml(-1) level. The recovery was 92% with a calculated relative standard deviation of 1.96%. Conversion of endosulfan to endosulfandiol is found to be less than 0.5% under the defined conditions. The method was applied to the analysis of residue contents of endosulfan and its metabolites in blood samples collected from the exposed population. The data obtained has been confirmed by GC-MS-EI in selective ion monitoring (SIM) mode.
A new analytical procedure based on solid-phase microextraction (SPME) has been developed for the determination of residues of eight selected herbicides: trifluralin, butachlor, pretilachlor, metolachlor, atrazine, acetochlor, alachlor, and fluroxypyr-meptyl, in ground water samples. Carbowax divinylbenzene was used for SPME of the herbicides. Quantification was done at equilibrium. Various parameters, such as, effect of pH, ionic strength, humic acid content and exposure time of fiber, were investigated to find the extraction efficiency. The linearity was determined. The method was found suitable for the determination of residues of herbicides at concentration levels from 5 to 20 ng L-1. The relative standard deviation of the detection limits were calculated. The humic acid content was found to interfere more significantly in the determination of residues. An ionic chloride strength, in terms of sodium chloride, of up to 10% did not have any significant impact on the determination. Furthermore, there was an enhanced sensitivity of detection up to pH 3.0. The method was applied to the analysis of the residue contents of the pesticides under investigation in real ground water samples collected from susceptible places. The results when compared with the standard methods published in the literature showed no significant deviation in their quantification and the values were comparable.
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