Direct rapid analysis of multiple PPCPs in municipal wastewater using ultrahigh performance liquid chromatography–tandem mass spectrometry without SPE pre-concentration

Ultrahigh performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) was utilized to develop a rapid, sensitive and reliable method without solid phase extraction (SPE) pre-concentration for trace analysis of 11 pharmaceuticals and personal care products (PPCPs) in influent and effluent from municipal wastewater treatment plants (WWTPs). This method not only shortened the analysis time but also reduced analysis cost significantly by omitting SPE process and avoiding the consumption of SPE cartridge. Detection parameters for UHPLC–MS/MS analysis were optimized, including sample pH, eluent, mobile phase (solvent and additive), column temperature, and flow rate. Under the optimal conditions, all analytes were well separated and detected within 8.0 min by UHPLC–MS/MS. The method quantification limits (MQLs) for the 11 PPCPs ranged from 0.040 to 88 ng L−1 and from 0.030 to 90 ng L−1 for influent and effluent, respectively. The matrix effect was systematically investigated and quantified for different types of samples. The analysis of influent and effluent samples of two WWTPs in Hong Kong revealed the presence of 11 PPCPs, including acyclovir, benzophenone-3, benzylparaben, carbamazepine, ethylparaben, fluconazole, fluoxetine, methylparaben, metronidazole, propylparaben, and ranitidine. Their concentrations ranged from 9.1 to 1810 ng L−1 in influent and from 6.5 to 823 ng L−1 in effluent samples collected from Hong Kong WWTPs.

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► Signal enhancements of 11 PPCPs were observed for non-SPE pre-concentrated samples.
► MTnon-SPE shortened analysis time, reduced analysis cost, and was more accurate.
► Good chromatographic separation of 11 PPCPs was achieved within 8.0 min.
► Method quantification limits of 11 PPCPs were as low as 0.030–90 ng L−1.
► Concentrations of 11 PPCPs were 6.5–1810 ng L−1 in Hong Kong municipal wastewater.