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Environmental analysis of alcohol ethoxylates and nonylphenol ethoxylate metabolites by ultra-performance liquid chromatography–tandem mass spectrometry

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Abstract

Surfactants and their metabolites can be found in aquatic environments at relatively high concentrations compared with other micropollutants due in part to the exceptionally large volumes produced every year. We have focused our attention here on the most widely used nonionic surfactants, alcohol ethoxylates (AEOs), and on nonylphenol ethoxylate (NPEO) degradation products (short-chain nonylphenol ethoxylates, NP1-3EO, nonylphenol, NP, and nonylphenol ethoxycarboxylates, NP1-2EC), which are endocrine-disrupting compounds. Our main objective in this work was to develop a methodology aimed at the extraction, isolation, and improved analysis of these analytes in environmental samples at trace levels. Extraction recoveries of target compounds were determined for sediment samples after ultrasonic extraction and purification using HLB or C18 solid-phase extraction minicolumns. Recovery percentages were usually between 61 and 102% but were lower for longer AEO ethoxymers. Identification and quantification of target compounds was carried out using a novel ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC–MS-MS) approach, a combination that provides higher sensitivity and faster analysis than prior methods using conventional high-performance liquid chromatography–mass spectrometry. Limits of detection were usually below 0.5 ng/g, being higher for monoethoxylate species (>5 ng/g) because of poor ionization. The method was used for analyzing surface sediment samples collected at Jamaica Bay (NY) in 2008. The highest values (28,500 ng/g for NP, 4,200 ng/g for NP1-3EO, 22,400 ng/g for NP1-2EC, and 1,500 ng/g for AEOs) were found in a sampling station from a restricted water circulation area that is heavily impacted by wastewater discharges.

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Acknowledgments

This work was carried out within the project BADEPAS (ref. 221686), funded by the Marie Curie FP7 program, and with the help of two postdoctoral fellowships under Spanish Ministry of Education and Science (MEC)–Fulbright and Marie Curie FP7 programs. Additional support was provided from the National Fish and Wildlife Foundation (Project 2005-0333-012).

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Authors and Affiliations

  1. Departamento de Química Física, Facultad de Ciencias del Mar y Ambientales, Universidad de Cádiz, Campus Río San Pedro s/n, 11510, Puerto Real, Cádiz, Spain

    Pablo A. Lara-Martín & Eduardo González-Mazo

  2. School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, NY, 11794-5000, USA

    Pablo A. Lara-Martín & Bruce J. Brownawell

Authors
  1. Pablo A. Lara-Martín
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  2. Eduardo González-Mazo
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  3. Bruce J. Brownawell
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Correspondence to Pablo A. Lara-Martín.

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Published in the special issue Mass Spectrometry in Spain with guest editors José Miguel Vadillo and Damìa Barcelo.

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Lara-Martín, P.A., González-Mazo, E. & Brownawell, B.J. Environmental analysis of alcohol ethoxylates and nonylphenol ethoxylate metabolites by ultra-performance liquid chromatography–tandem mass spectrometry. Anal Bioanal Chem 402, 2359–2368 (2012). https://doi.org/10.1007/s00216-011-5449-6

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  • DOI: https://doi.org/10.1007/s00216-011-5449-6

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