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Analytical and Bioanalytical Chemistry

, Volume 400, Issue 2, pp 577–585 | Cite as

Screening for multiple classes of marine biotoxins by liquid chromatography–high-resolution mass spectrometry

  • Pearl Blay
  • Joseph P. M. Hui
  • James Chang
  • Jeremy E. MelansonEmail author
Original Paper

Abstract

Marine biotoxins pose a significant food safety risk when bioaccumulated in shellfish, and adequate testing for biotoxins in shellfish is required to ensure public safety and long-term viability of commercial shellfish markets. This report describes the use of a benchtop Orbitrap system for liquid chromatography–mass spectrometry (LC-MS) screening of multiple classes of biotoxins commonly found in shellfish. Lipophilic toxins such as dinophysistoxins, pectenotoxins, and azaspiracids were separated by reversed phase LC in less than 7 min prior to MS data acquisition at 2 Hz with alternating positive and negative scans. This approach resulted in mass accuracy for analytes detected in positive mode (gymnodimine, 13-desmethyl spirolide C, pectenotoxin-2, and azaspiracid-1, -2, and -3) of less than 1 ppm, while those analytes detected in negative mode (yessotoxin, okadaic acid, and dinophysistoxin-1 and -2) exhibited mass errors between 2 and 4 ppm. Hydrophilic toxins such as domoic acid, saxitoxin, and gonyautoxins were separated by hydrophilic interaction LC (HILIC) in less than 4 min, and MS data was collected at 1 Hz in positive mode, yielding mass accuracy of less than 1 ppm error at a resolving power of 100,000 for the analytes studied (m/z 300–500). Data were processed by extracting 5 ppm mass windows centered around the calculated masses of the analytes. Limits of detection (LOD) for the lipophilic toxins ranged from 0.041 to 0.10 μg/L (parts per billion) for the positive ions, 1.6–5.1 μg/L for those detected in negative mode, while the domoic acid and paralytic shellfish toxins yielded LODs ranging from 3.4 to 14 μg/L. Toxins were detected in mussel tissue extracts free of interference in all cases.

Keywords

Marine biotoxins Paralytic shellfish toxins High-resolution mass spectrometry Accurate mass screening LC-MS HILIC 

Notes

Acknowledgements

The authors wish to thank Dr. Pearse McCarron for reviewing this manuscript and for providing extracts of the reference material containing lipophilic toxins. Loan of the Exactive™ mass spectrometer from Thermo Fisher Scientific is also gratefully acknowledged. This is NRC publication number 51791.

Supplementary material

216_2011_4772_MOESM1_ESM.pdf (320 kb)
ESM 1 (PDF 320 kb)

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Copyright information

© Crown copyright in right of Canada 2011

Authors and Affiliations

  • Pearl Blay
    • 1
  • Joseph P. M. Hui
    • 1
  • James Chang
    • 2
  • Jeremy E. Melanson
    • 1
    Email author
  1. 1.National Research Council of Canada, Institute for Marine BiosciencesHalifaxCanada
  2. 2.Thermo Fisher ScientificSan JoseUSA

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