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Identification and determination of the dechlorination products of Dechlorane 602 in Great Lakes fish and Arctic beluga whales by gas chromatography–high resolution mass spectrometry

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Abstract

During the course of our studies of in-use chlorinated flame retardants, such as Dechlorane Plus® and Dechloranes 602 and 604, blubber of beluga whales from the Canadian Arctic and lake trout and whitefish from the North American Great Lakes were found to contain two novel dechlorination products of Dechlorane 602 (Dec602). The structures of these compounds were characterized by experiments performed using both gas chromatography–high resolution mass spectrometry and Fourier transform mass spectrometry with a prepared technical mixture of monohydro and dihydroDec602 derivatives. These Dec602 derivatives are analogous to the well-known monohydro and dihydro photochemical degradation products of Mirex. The ratio of the two monohydroDec602 diastereomers varied between Lake Ontario fish and those from the upper lakes, but only one isomer was found in Arctic beluga, indicating that one isomer is either more stable or more bioaccumulative. Dechlorane Plus®, Dec603, and Dec 604 were not detected in Arctic beluga, but Dec602 and its monohydroDec602 derivative were measured in approximately equal concentrations, ranging from 25 to 300 pg/g lipid. In Great Lakes fish, concentrations of the monohydroDec602 derivatives were also close to those of Dec602, ranging from 2 to 67 ng/g lipid and were greatest in Lake Ontario. This study reports on the first measurements of dechlorane-related compounds in Arctic biota and the first detection of monohydroDec602 degradation products and their accumulation in biota.

Dechlorane 602 and its dechlorination product are detected in Great Lakes fish and Arctic beluga

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Acknowledgments

We thank Liad Haimovici (Ministry of Environment), Kerri Pleskach, and Bruno Rosenberg (Fisheries & Oceans) for preparing the beluga samples for analysis and Xianming Zhang (University of Toronto) for estimating chemical properties. L. Shen and K. Jobst gratefully acknowledge financial support provided in part through the Canada-Ontario Agreement respecting the Great Lakes program. KJJ thanks the Natural Sciences and Engineering Research Council of Canada (NSERC) for a Visiting Fellowship.

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Authors and Affiliations

  1. Department of Chemistry, Brock University, 500 Glenridge Avenue, St. Catharines, ON, L2S 3A1, Canada

    Li Shen & Ian D. Brindle

  2. Ontario Ministry of the Environment, 125 Resources Road, Toronto, ON, M9P 3V6, Canada

    Li Shen, Karl J. Jobst, Paul A. Helm & Eric J. Reiner

  3. Environment Canada, 867 Lakeshore Road, Burlington, ON, L7R 4A6, Canada

    Karl J. Jobst, Sean Backus & Chris H. Marvin

  4. Department of Chemistry, University of Toronto, Toronto, ON, M5S 3H6, Canada

    Eric J. Reiner

  5. Wellington Laboratories Inc., Guelph, ON, N1G 3M5, Canada

    Robert McCrindle

  6. Arctic Aquatic Research Division, Fisheries and Oceans Canada, Freshwater Institute, 501 University Crescent, Winnipeg, MB, R3T 2N6, Canada

    Gregg T. Tomy

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  1. Li Shen
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  2. Karl J. Jobst
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  7. Sean Backus
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  8. Ian D. Brindle
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  9. Chris H. Marvin
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Correspondence to Eric J. Reiner.

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Published in the topical collection Emerging Contaminants in Biota with guest editors Yolanda Picó and Damià Barceló.

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Shen, L., Jobst, K.J., Helm, P.A. et al. Identification and determination of the dechlorination products of Dechlorane 602 in Great Lakes fish and Arctic beluga whales by gas chromatography–high resolution mass spectrometry. Anal Bioanal Chem 404, 2737–2748 (2012). https://doi.org/10.1007/s00216-012-6164-7

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  • DOI: https://doi.org/10.1007/s00216-012-6164-7

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