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Quantification of organic contaminants in urban stormwater by isotope dilution and liquid chromatography-tandem mass spectrometry

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Abstract

Pollutants transported in urban stormwater runoff induce pervasive water quality degradation in receiving waters. To accurately characterize stormwater quality and treatment system performance across the range of possible contaminant characteristics, comprehensive multi-residue analytical methods are necessary. Here, we developed a solid-phase extraction (SPE) and high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method to quantify representative stormwater-derived organic contaminants across multiple chemical classes, including vehicle-related chemicals, corrosion inhibitors, industrial chemicals, pesticides, pharmaceuticals and personal care products, and antioxidants. Extraction conditions, isotope-labeled internal standards, and LC-MS/MS parameters were optimized to enhance recovery, minimize matrix effects, and maximize selectivity and sensitivity. The developed method was sensitive (method quantification limits < 10 ng/L for > 80% of selected analytes) and accurate (mean relative recoveries in the range of 70–130%, with relative standard deviations < 25% for 77% of the analytes) for most of the analytes. The method was used to analyze samples collected from nine urban watersheds during a storm event; 62% of the 39 analytes were detected at least once at concentrations up to 540 ng/L (1,3-diphenylguanidine). Spatial trends in detection and concentration were observed for vehicle-related and industrial chemicals that correlated with vehicle traffic. Total concentrations of pesticides suggested that residential uses could be more important sources than agriculture. This study illustrates the pervasive occurrence of a wide variety of stormwater-derived chemicals in urban receiving waters and highlights the need to better understand their environmental fate and ecological implications.

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Acknowledgments

The research group at the Center for Urban Waters and the University of Washington (Tacoma and Seattle campuses) is greatly appreciated for helping with the experiments, data analysis, and manuscript writing. We thank Agilent for their excellent technical advice.

Funding

This work was partially supported by the Environmental Protection Agency (EPA grant no. 01J18101) and the University of Washington (Tacoma/Seattle). Fan Hou received scholarship support from the Chinese Scholarship Council for her visit to the Department of Civil and Environmental Engineering (UW-Seattle) as a joint Ph.D. student.

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Authors and Affiliations

  1. Department of Civil and Environmental Engineering, University of Washington, 306 More Hall, Seattle, WA, 98195, USA

    Fan Hou, Alex D. Gipe, Haoqi Zhao & Edward P. Kolodziej

  2. Center for Urban Waters, 326 East D Street, Tacoma, WA, 98421, USA

    Fan Hou, Zhenyu Tian, Katherine T. Peter, Christopher Wu, Alex D. Gipe, Haoqi Zhao & Edward P. Kolodziej

  3. Department of Applied Chemistry, College of Science, China Agricultural University, Beijing, 100193, China

    Fan Hou & Fengmao Liu

  4. Interdisciplinary Arts and Sciences, University of Washington Tacoma, Tacoma, WA, 98421, USA

    Zhenyu Tian, Katherine T. Peter, Christopher Wu, Ernesto A. Alegria & Edward P. Kolodziej

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  1. Fan Hou
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  2. Zhenyu Tian
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  3. Katherine T. Peter
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  4. Christopher Wu
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Correspondence to Edward P. Kolodziej.

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Hou, F., Tian, Z., Peter, K.T. et al. Quantification of organic contaminants in urban stormwater by isotope dilution and liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 411, 7791–7806 (2019). https://doi.org/10.1007/s00216-019-02177-3

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