Abstract
A new anion-exchange chromatographic separation method was used for the simultaneous speciation analysis of selenoamino acids and the more ubiquitous inorganic selenium oxyanions, selenite and selenate. For quantification, this separation was coupled to inductively coupled plasma-mass spectrometry to achieve an instrumental detection limit of 5 ng Se L−1 for all species. This chromatographic method was also coupled to electrospray tandem mass spectrometry to observe the negative ion mode fragmentation of selenomethionine and one of its oxidation products. Low detection limits were achieved, which were similar to those obtained using inductively coupled plasma-mass spectrometry. An extensive preconcentration and cleanup procedure using cation-exchange solid-phase extraction was developed for the identification and quantification of trace levels of selenomethionine in environmental samples. Preconcentration factors of up to five were observed for selenomethionine, which in addition to the removal of high concentrations of sulphate and chloride from industrial process waters, allowed for an unambiguous analysis that would have been impossible otherwise. Following these methods, selenomethionine was identified at an original concentration of 3.2 ng Se L−1 in samples of effluent collected at a coal-fired power plant’s biological remediation site. It is the first time that this species has been identified in the environment, outside of a biological entity. Additionally, oxidation products of selenomethionine were identified in river water and laboratory algal culture samples. High-resolution mass spectrometry was employed to postulate the chemical structures of these species.
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Acknowledgments
We thank Jacqueline London, Naomi Stock, Michael Doran, Dorothy Howard-Gill, and Sarah D’Amario for their assistance in the lab, and Robert Trahan for acting as a guide along the Porcupine River. We also thank Katherine Kellersberger at Bruker Corporation for her assistance with high-resolution mass spectrometric analysis. Financial support was provided by Air and Waste Management Association (Ontario Chapter), Queen Elizabeth II Graduate Scholarship in Science and Technology, and National Science and Engineering Research Council (NSERC) of Canada CGS grants to KL, and an NSERC Discovery grant to DW. We are also grateful to the Electric Power Research Institute (Paul Chu) for funding part of the work at the coal-fired power plant biotreatment sites and the personnel at these power plants for assisting us with on-site logistics
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LeBlanc, K.L., Ruzicka, J. & Wallschläger, D. Identification of trace levels of selenomethionine and related organic selenium species in high-ionic-strength waters. Anal Bioanal Chem 408, 1033–1042 (2016). https://doi.org/10.1007/s00216-015-9124-1
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DOI: https://doi.org/10.1007/s00216-015-9124-1