Abstract
An improved selectivity method for the simultaneous determination of four benzotriazoles (benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, and 5,6-dimethyl-1H-benzotriazole) and six benzothiazoles (benzothiazole, 2-hydroxybenzothiazole, 2-benzothiazolamine, mercaptobenzothiazole, 2-methylbenzothiazole, and 2-methylthiobenzothiazole) in aqueous matrices has been developed. Under optimal conditions, analytes are concentrated using a MAX solid-phase extraction (SPE) cartridge, based on divinylbenzene-N-vinylpyrrolidone functionalized with quaternary amine groups, which allows reversed-phase interactions in combination with ionic exchange. Selected compounds are recovered with methanol–acetone 7:3 (v/v) whereas acidic interferences remained attached to the sorbent, and as determined by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), LOQs for surface, urban and industrial wastewater are in the range of 0.002–0.29 ng/mL. Figures of merit of the method revealed good precision (RSD% <12%), linearity (R 2 > 0.99) and accuracy (%R = 80–100%) for surface waters and effluents allowing direct external standard quantification. For more complex samples, such as urban and industrial raw wastewater, either the standard addition method or pseudo-external standard calibration using matrix matched standards are recommended. Analysis of different real samples, surface, urban wastewater and, for the first time, metal industry wastewater, reflected concentrations up to 310 ng/mL. The methylbenzotriazole isomers ratio was also determined.
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Acknowledgments
This study has been supported by Spanish Government, Ministry of Education and Science (project CTQ2009-08377), Xunta de Galicia (project PGIDIT08MDS008CT) and FEDER funds. I. Carpinteiro and M. Ramil thank the Spanish Ministry of Science and Innovation and Xunta de Galicia for their FPU and I. Parga Pondal contracts, respectively.
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Carpinteiro, I., Abuin, B., Ramil, M. et al. Simultaneous determination of benzotriazole and benzothiazole derivatives in aqueous matrices by mixed-mode solid-phase extraction followed by liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 402, 2471–2478 (2012). https://doi.org/10.1007/s00216-012-5718-z
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DOI: https://doi.org/10.1007/s00216-012-5718-z