Possible overestimation of bisphenol analogues in municipal wastewater analyzed with GC-MS

This work for the first time showed that sulfated BPA could be directly analyzed as BPA with GC-MS after the derivatization with N,O-bis-(trimethylsilyl) trifluoroacetamide (BSTFA)+1% trimethylchlorosilane (TMCS), i.e. the deconjugation step was not necessary. This was because sulfated BPA indeed could be simultaneously deconjugated and derivatized to BPA derivative during derivatization, suggesting that any co-elution of BPA and sulfated BPA during sample extraction led to BPA overestimation in the GC-MS method with BSTFA +1% TMCS as the derivative reagent. Using BPA 4,4'-disulfates (BPA diS) as the pure standard, the co-elution phenomena of sulfated BPA was confirmed with two widely used elution solvents (i.e. methanol and ethyl acetate) or their mixed solutions with different ratios, which further suggested if only sulfated BPA existed in any wastewater sample, BPA was likely over-determined. To further confirm this finding, both influent and effluent samples collected from a local municipal wastewater treatment plant were analyzed, which clearly showed the overestimation of BPA in the two wastewaters due to co-existence of sulfated BPA in the wastewater samples. In addition to BPA, the results also showed the overestimation of other nine bisphenol analogues. As sulfated micropollutants including estrogens, androgens, phytoestrogens, etc., have been widely found in municipal wastewater, the overestimating phenomenon observed in this study may also be extended to determination of other micropollutants, which should be addressed in future.