Determination of residues of endosulfan in human blood by a negative ion chemical ionization gas chromatographic/mass spectrometric method: impact of long‐term aerial spray exposure

A new and sensitive analytical method using negative ion chemical ionization gas chromatography/mass spectrometry in selective ion monitoring (SIM) mode has been developed for the determination of residues of endosulfan in the human blood. The residues of endosulfan are extracted from whole blood samples without separating the serum by the addition of 60% sulfuric acid at 10 degrees C followed by partition with hexane + acetone (9 + 1 by volume). The total endosulfan is quantified as the sum of alpha-endosulfan, beta-endosulfan and endosulfan sulfate in SIM mode. The mass-fragment ions used for this purpose that are monitored for in SIM mode include endosulfan diol: 95, 169, 214, 313, alpha-endosulfan: 99, 242, 270, 406, beta-endosulfan: 99, 242, 270, 406, and endosulfan sulfate: 97, 353, 386. Recovery experiments were conducted at the concentration range 1.0-100 pg ml(-1). Results showed 112-98% recovery of total endosulfan from the whole blood samples. The relative standard deviation was 1.49-2.68%. The method was found to be highly sensitive in quantifying endosulfan residues down to the 0.1 pg ml(-1) level. Conversion of endosulfan to endosulfan diol was found to be less than 0.1% under the conditions used. The results were compared with published data. The applications of the analytical method for the determination of endosulfan residues in real samples was tested by analyzing 106 human blood samples collected from a population living in Padre village, Kasargode District, Kerala, India, where aerial spraying of endosulfan has been a common agricultural practice over the years. The results showed that none of the blood samples contained residues of endosulfan (alpha-endosulfan 4 beta-endosulfan + endosulfan sulfate) or endosulfan diol. The results were confirmed by the detection of the appropriate amounts in a number of these samples which had subsequently been spiked with endosulfan.