title: Screening for multiple classes of marine biotoxins by liquid chromatography-high-resolution mass spectrometry.
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.
authors.affiliation: National Research Council of Canada, Institute for Marine Biosciences, 1411 Oxford Street, Halifax, NS B3H 3Z1, Canada.
authors.forename: Pearl
authors.initials: P
authors.lastname: Blay
authors.forename: Joseph P M
authors.initials: JP
authors.lastname: Hui
authors.forename: James
authors.initials: J
authors.lastname: Chang
authors.forename: Jeremy E
authors.initials: JE
authors.lastname: Melanson
mesh_terms: D000818:Animals; D049872:Bivalvia / Q000737:chemistry; D002853:Chromatography, Liquid / Q000379:methods*; D008387:Marine Toxins / Q000032:analysis*; D013058:Mass Spectrometry / Q000379:methods*; D012623:Seawater / Q000032:analysis; D012758:Shellfish / Q000032:analysis; D014874:Water Pollutants, Chemical / Q000032:analysis*
chemical_list: D008387:Marine Toxins; D014874:Water Pollutants, Chemical