A protocol based on solid phase microextraction-gas chromatography-tandem mass spectrometry for the monitoring of parabens and bisphenols in human saliva

The herein presented work aims to the development of an easy method for the quantitative determination of parabens and bisphenols in human salivabased on the use of methyl chloroformate as a derivatizing agent, followed by solid-phase microextraction (SPME) and gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS) analysis with selected reaction monitoring (SRM). Using multivariate analysis, two derivatization strategies were compared and optimized, demonstrating that the use of methyl chloroformate led to better sensitivity than the classical derivatization by acetic anhydride. Good performance in the sorption process of the derivatized target analytes was obtained using the most recent commercialized overcoated fiber (PDMS/DVB/ PDMS). The validation procedure of the final protocol led to satisfactory results in terms of linearity, limit of quantitation, accuracy, and precision. All parabens were quantified from 10 ng/L using the developed method, except for methylparaben, which was quantified from 100 ng/L along with all bisphenols. Intra-and inter-day accuracy and intra-and inter-day precision can be considered satisfactory for all analytes (values between 73% and 118%), except for the inter-day accuracy of BPF. Quite good results also in terms of matrix effect were obtained for the target compounds (range 71% to 118%, RSD% less than 13.6%), except for BPA at the middle concentration and MeP at the lowest concentration. The greenness of the method was evaluated and the results indicated that our approach is more eco-friendly than previously published methods. Based on its characteristics, the presented method can be considered a suitable approach to determine parabens and bisphenols in routine analysis for biomonitoring purposes.

Automated summary

The present study aimed to develop a simple method for quantitatively determining parabens and bisphenols in human saliva using methyl chloroformate as a derivatizing agent, followed by SPME and GC-QqQ-MS analysis with SRM. Two derivatization strategies were compared and optimized using multivariate analysis, and it was found that the use of methyl chloroformate provided better sensitivity than the classical acetic anhydride derivatization. The performance of the derivatized analytes' sorption process was good using the overcoated fiber (PDMS/DVB/PDMS). The method showed satisfactory results in terms of linearity, limit of quantitation, accuracy, and precision for all parabens and bisphenols, making it a suitable approach for routine biomonitoring purposes.