Determination of persistent organochlorine pollutants in human serum by combining liquid-liquid extraction and solid-phase extraction with gas chromatography-tandem mass spectrometry

Abstract

Persistent organochlorine pollutants (POCPs) are a group of “forever chemicals” that are ubiquitous in the environment and pose adverse health effects to humans. However, the lack of sensitive and widely applicable analytical method for internal POCPs exposure assessment puts limits on the researches of health risk evaluations. Therefore, we developed a method for the measurement of 43 POCPs in human serum using gas chromatography-tandem mass spectrometry (GC-MS/MS). Serum samples were treated with methanol and acid to precipitate protein and remove lipids, respectively. 13C-labeled analogue was spiked and liquid-liquid extraction (LLE) was performed to extract target analytes by hexane and methyl tert-butyl ether. The extract was purified by solid-phase extraction (SPE) and eluted with dichloromethane. The eluate was concentrated under nitrogen stream and reconstituted with toluene. Samples were analyzed by GC-MS/MS operated in electron impact (EI) and multiple reaction monitoring (MRM) mode. Calibration curves of all target analytes showed favorable linearity within the concentration range of 0.008 to 10 μg/L for different POCPs, with regression coefficients above 0.991. The method detection limits and limits of quantification ranged from 0.005 to 0.10 μg/L and 0.017 to 0.34 μg/L, respectively. The recoveries and precision of all analytes at 3 different spike levels were in the range of 65.3 % to 121.8 % and 1.8 % to 13.9 %, respectively. The matrix effects (ME) ranged from 74.9 % to 125.6 %. The results of measuring quality control samples from the National Institute of Standards and Technology (NIST) were with relative deviations of less than 30 %. With an optimized sample preparation procedure, the proposed method has successfully achieved in improving extraction efficiency and reducing ME. It was applied in the simultaneous determination of POCPs in a small volume of human serum in China National Human Biomonitoring.