Using chiral liquid chromatography quadrupole time-of-flight mass spectrometry for the analysis of pharmaceuticals and illicit drugs in surface and wastewater at the enantiomeric level

• Published in: Journal of Chromatography A Vol. 1249; pp. 115 - 129
• Main Authors: Bagnall, J.P., Evans, S.E., Wort, M.T., Lubben, A.T., Kasprzyk-Hordern, B.
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 03-08-2012
• Subjects: amphetamine; beta-adrenergic antagonists; cellulose 1,4-beta-cellobiosidase; Chiral; Enantiomer; enantiomers; Illicit drug; illicit drugs; liquid chromatography; mass spectrometry; Mass Spectrometry - methods; Pharmaceutical; Pharmaceutical Preparations - analysis; propranolol; Reference Standards; River water; sewage; sewage effluent; Stereoisomerism; vancomycin; Wastewater; Water Pollutants, Chemical - analysis; Pharmaceutical; Wastewater; Illicit drug; River water; Chiral; Enantiomer
• ISSN: 0021-9673; 1873-3778
• DOI: 10.1016/j.chroma.2012.06.012

► Here two chiral LC–QTOF-MS methods are detailed for the analysis of pharmaceuticals and illicit drugs. ► Methods are suitable for resolving and quantifying chiral compounds in river and wastewater. ► Chiral compounds quantified in environment samples were confirmed using MS/MS confirmation. ► Differences in EF between compounds in sewage and river water were evident.
This paper presents and compares for the first time two chiral LC–QTOF-MS methodologies (utilising CBH and Chirobiotic V columns with cellobiohydrolase and vancomycin as chiral selectors) for the quantification of amphetamine, methamphetamine, MDA (methylenedioxyamphetamine), MDMA (methylenedioxymethamphetamine), propranolol, atenolol, metoprolol, fluoxetine and venlafaxine in river water and sewage effluent. The lowest MDLs (0.3–5.0ngL−1 and 1.3–15.1ngL−1 for river water and sewage effluent respectively) were observed using the chiral column Chirobiotic V. This is with the exception of methamphetamine and MDMA which had lower MDLs using the CBH column. However, the CBH column resulted in better resolution of enantiomers (Rs=2.5 for amphetamine compared with Rs=1.2 with Chirobiotic V). Method recovery rates were typically >80% for both methodologies. Pharmaceuticals and illicit drugs detected and quantified in environmental samples were successfully identified using MS/MS confirmation. In sewage effluent, the total beta-blocker concentrations of propranolol, atenolol and metoprolol were on average 77.0, 1091.0 and 3.6ngL−1 thus having EFs (Enantiomeric Fractions) of 0.43, 0.55 and 0.54 respectively. In river water, total propranolol and atenolol was quantified on average at <10.0ngL−1. Differences in EF between sewage and river water matrices were evident: venlafaxine was observed with respective EF of 0.43±0.02 and 0.58±0.02.