Simultaneous determination of aromatic and chlorinated compounds in urine of exposed workers by dynamic headspace and gas chromatography coupled to mass spectrometry (dHS-GC-MS)

Abstract

Mixed exposure to chemical products is a topical issue for occupational health and often includes exposure to volatile organic compounds (VOCs). As very few methods are available for evaluating these mixed exposures, the aim of this work was to develop a simple biomonitoring method to assess simultaneous occupational exposures to chlorinated and aromatic VOCs by analyzing the unmetabolized fraction of the VOCs in the urine of workers. Volatile organic compounds were analyzed using dynamic headspace gas chromatography coupled to mass spectrometry (dHS-GC-MS), and 11 unmetabolized urinary VOCs were measured into headspace phase, without any time-consuming pretreatment. Simultaneously, a standardized collection protocol was designed to avoid VOC losses or the contamination of urinary samples. The calibration samples were real urines, spiked with known amounts of the VOC mixtures studied. Test investigations were performed on potentially exposed workers in three factories in order to assess the effectiveness of both the collection protocol and analytical method. A satisfactory level of sensitivity was achieved, with limits of quantification (LOQ) between 10 and 15 ng/L obtained for all VOCs (except for styrene at 50 ng/L). Calibration curves were linear in the 0-20 μg/L range tested, with R² correlation coefficients of 0.991 to 0.998. At the lowest concentration tested (0.08 μg/L), within-day precision varied from 2.1 to 5.5% and between-day precision ranged from 2.7 to 8.5%. Sample stability at -20 °C required that urinary samples be analyzed within 3 months. Even though the urinary concentrations of VOCs used in the plants were mostly quite low, significant differences between post-shift and pre-shift were observed. In conclusion, a fast, sensitive, specific and easy-to-use method has been developed for extracting VOCs from human urine using dHS-GC-MS. The method described has proven to be reliable for assessing current occupational exposure to chlorinated and aromatic VOCs in France.

Keywords: BTEX; Biomonitoring; Chlorinated compounds; Dynamic headspace; Occupational exposure; Urine.