Determination of organophosphorus pesticide residues in human tissues by capillary gas chromatography–negative chemical ionization mass spectrometry analysis

Abstract

We describe an analytical method that allows the determination of organophosphorus pesticides (OPs) in different human tissues. It involves an extraction procedure with ethanol–ethyl acetate, followed by gel permeation chromatography clean-up step and analysis by capillary gas chromatography–negative chemical ionization mass spectrometry in the selected ion monitoring mode. The method was tested for 37 OPs and the recoveries obtained vary between 60 and 106% with standard deviations ranging between ±2 and ±10. These values are independent of the analyzed tissue. Peak area repeatability as RSD for some OPs was ≤4.8% while a good linear relationship in the range 1.0–500 pg μl −1 with r 2≥0.9878 was obtained. The limit of detection for the 37 OPs falls between 0.01 and 0.09 ng g −1 with an RSD≤9.5%. The analytical set up in this paper has been used to analyze different samples of human tissues (liver, healthy kidney, cancer kidney and adipose tissue) of 24 patients. The number of the identified OPs in the tissue samples is different (max. 20) according to the sample while their concentration ranges between the limit of detection and 28.0 ng g −1. The highest concentrations have been determined in liver samples without any pathology (0.4–28.0 ng g −1) while the lowest concentrations have been determined in healthy kidney samples (0.01–1.50 ng g −1). In the cancer kidney samples OP concentrations vary between 0.03 and 4.6 ng g −1: these concentrations are more elevated than those determined in healthy kidney samples. The comparison between the concentration of OPs determined in the healthy part, when possible, and those determined in the cancer part of the same kidney sample are very interesting: in fact, in the latter the OP concentration is generally 1–2-times higher than that in the former, an index of lower enzymatic activity in the cancer tissue.