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Trace Analysis of 61 Emerging Br-, Cl-, and I-DBPs: New Methods to Achieve Part-Per-Trillion Quantification in Drinking Water
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    Trace Analysis of 61 Emerging Br-, Cl-, and I-DBPs: New Methods to Achieve Part-Per-Trillion Quantification in Drinking Water
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    • Amy A. Cuthbertson
      Amy A. Cuthbertson
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
    • Hannah K. Liberatore
      Hannah K. Liberatore
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
    • Susana Y. Kimura
      Susana Y. Kimura
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
      Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta T2N 1N4, Canada
    • Joshua M. Allen
      Joshua M. Allen
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
    • Alena V. Bensussan
      Alena V. Bensussan
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
    • Susan D. Richardson*
      Susan D. Richardson
      Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
      *Phone: 803-777-6932. Fax: 803-777-9521. E-mail: [email protected]
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    Analytical Chemistry

    Cite this: Anal. Chem. 2020, 92, 4, 3058–3068
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    https://doi.org/10.1021/acs.analchem.9b04377
    Published January 17, 2020
    Copyright © 2020 American Chemical Society

    Abstract

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    Disinfection byproducts (DBPs) are a ubiquitous source of chemical exposure in drinking water and have been associated with serious health impacts in human epidemiologic studies. While toxicology studies have pinpointed DBPs with the greatest toxic potency, analytical methods have been lacking for quantifying complete classes of most toxic DBPs at sufficiently low quantification limits (ng/L). This new method reports the parts-per-trillion quantification for 61 toxicologically significant DBPs from 7 different chemical classes, including unregulated iodinated haloacetic acids (HAAs) and trihalomethanes (THMs), haloacetaldehydes, haloketones, haloacetonitriles, halonitromethanes, and haloacetamides, in addition to regulated HAAs and THMs. The final optimized method uses salt-assisted liquid–liquid extraction in a single extraction method for a wide range of DBPs, producing the lowest method detection limits to-date for many compounds, including highly toxic iodinated, brominated, and nitrogen-containing DBPs. Extracts were divided for the analysis of the HAAs (including iodinated HAAs) by diazomethane derivatization and analysis using a GC-triple quadrupole mass spectrometer with multiple reaction monitoring, resulting in higher signal-to-noise ratios, greater selectivity, and improved detection of these compounds. The remaining DBPs were analyzed using a GC-single quadrupole mass spectrometer with selected ion monitoring, utilizing a multimode inlet allowed for lower injection temperatures to allow the analysis of thermally labile DBPs. Finally, the use of a specialty-phase GC column (Restek Rtx-200) significantly improved peak shapes, which improved separations and lowered detection limits. Method detection limits for most DBPs were between 15 and 100 ng/L, and relative standard deviations in tap water samples were mostly between 0.2 and 30%. DBP concentrations in real samples ranged from 40 to 17 760 ng/L for this study.

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.analchem.9b04377.

    • Additional data and tables including a comparison of previous methods and data for each drinking water plant with relative standard deviations (PDF)

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    Cited By

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    This article is cited by 61 publications.

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    Analytical Chemistry

    Cite this: Anal. Chem. 2020, 92, 4, 3058–3068
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.analchem.9b04377
    Published January 17, 2020
    Copyright © 2020 American Chemical Society

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