Abstract
The degradation of two β-blockers (atenolol and propranolol) and one β-receptor agonist (salbutamol) during water chlorination was investigated by liquid chromatography–mass spectrometry (LC-MS). An accurate-mass quadrupole time-of-flight system (QTOF) was used to follow the time course of the pharmaceuticals and also used in the identification of the by-products. The degradation kinetics of these drugs was investigated at different concentrations of chlorine, bromide and sample pH by means of a Box–Behnken experimental design. Depending on these factors, dissipation half-lives varied in the ranges 68–145 h for atenolol, 1.3–33 min for salbutamol and 42–8362 min for propranolol. Normally, an increase in chlorine dosage and pH resulted in faster degradation of these pharmaceuticals. Moreover, the presence of bromide in water samples also resulted in a faster transformation of atenolol at low chlorine doses. The use of an accurate-mass high-resolution LC-QTOF-MS system permitted the identification of a total of 14 by-products. The transformation pathway of β-blockers/agonists consisted mainly of halogenations, hydroxylations and dealkylations. Also, many of these by-products are stable, depending on the chlorination operational parameters employed.
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Acknowledgements
This work was funded by Ministerio de Ciencia e Innovación and FEDER funds, project no.: CTQ2009-08377 and CTQ2010-18927. J.B.Q. and R.R. also acknowledge Ministerio de Ciencia e Innovación for their contracts (Ramón y Cajal research program).
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Published in the special issue Young Investigators in Analytical and Bioanalytical Science with guest editors S. Daunert, J. Bettmer, T. Hasegawa, Q. Wang and Y. Wei.
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Quintana, J.B., Rodil, R. & Cela, R. Reaction of β-blockers and β-agonist pharmaceuticals with aqueous chlorine. Investigation of kinetics and by-products by liquid chromatography quadrupole time-of-flight mass spectrometry. Anal Bioanal Chem 403, 2385–2395 (2012). https://doi.org/10.1007/s00216-011-5707-7
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DOI: https://doi.org/10.1007/s00216-011-5707-7