title: High resolution mass spectrometry for quantitative analysis and untargeted screening of algal toxins in mussels and passive samplers.
abstract: Measurement of marine algal toxins has traditionally focussed on shellfish monitoring while, over the last decade, passive sampling has been introduced as a complementary tool for exploratory studies. Since 2011, liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been adopted as the EU reference method (No. 15/2011) for detection and quantitation of lipophilic toxins. Traditional LC-MS approaches have been based on low-resolution mass spectrometry (LRMS), however, advances in instrument platforms have led to a heightened interest in the use of high-resolution mass spectrometry (HRMS) for toxin detection. This work describes the use of HRMS in combination with passive sampling as a progressive approach to marine algal toxin surveys. Experiments focused on comparison of LRMS and HRMS for determination of a broad range of toxins in shellfish and passive samplers. Matrix effects are an important issue to address in LC-MS; therefore, this phenomenon was evaluated for mussels (Mytilus galloprovincialis) and passive samplers using LRMS (triple quadrupole) and HRMS (quadrupole time-of-flight and Orbitrap) instruments. Matrix-matched calibration solutions containing okadaic acid and dinophysistoxins, pectenotoxin, azaspiracids, yessotoxins, domoic acid, pinnatoxins, gymnodimine A and 13-desmethyl spirolide C were prepared. Similar matrix effects were observed on all instruments types. Most notably, there was ion enhancement for pectenotoxins, okadaic acid/dinophysistoxins on one hand, and ion suppression for yessotoxins on the other. Interestingly, the ion selected for quantitation of PTX2 also influenced the magnitude of matrix effects, with the sodium adduct typically exhibiting less susceptibility to matrix effects than the ammonium adduct. As expected, mussel as a biological matrix, quantitatively produced significantly more matrix effects than passive sampler extracts, irrespective of toxin. Sample dilution was demonstrated as an effective measure to reduce matrix effects for all compounds, and was found to be particularly useful for the non-targeted approach. Limits of detection and method accuracy were comparable between the systems tested, demonstrating the applicability of HRMS as an effective tool for screening and quantitative analysis. HRMS offers the advantage of untargeted analysis, meaning that datasets can be retrospectively analyzed. HRMS (full scan) chromatograms of passive samplers yielded significantly less complex data sets than mussels, and were thus more easily screened for unknowns. Consequently, we recommend the use of HRMS in combination with passive sampling for studies investigating emerging or hitherto uncharacterized toxins.
authors.affiliation: Ifremer, Laboratoire Phycotoxines, Rue de l'Ile d'Yeu, 44311 Nantes, France; LUNAM, Université de Nantes, MMS EA2160, Faculté de Pharmacie, 9 rue Bias, 44035 Nantes, France. Electronic address: Zita.Zendong@ifremer.fr.
authors.forename: Zita
authors.initials: Z
authors.lastname: Zendong
authors.affiliation: National Research Council of Canada, Biotoxin Metrology, Measurement Science and Standards, 1411 Oxford St, Halifax, Nova Scotia B3H 3Z 1, Canada.
authors.forename: Pearse
authors.initials: P
authors.lastname: McCarron
authors.affiliation: LUNAM, Université de Nantes, MMS EA2160, Faculté de Pharmacie, 9 rue Bias, 44035 Nantes, France.
authors.forename: Christine
authors.initials: C
authors.lastname: Herrenknecht
authors.affiliation: Ifremer, Laboratoire Phycotoxines, Rue de l'Ile d'Yeu, 44311 Nantes, France.
authors.forename: Manoella
authors.initials: M
authors.lastname: Sibat
authors.affiliation: Ifremer, Laboratoire Phycotoxines, Rue de l'Ile d'Yeu, 44311 Nantes, France.
authors.forename: Zouher
authors.initials: Z
authors.lastname: Amzil
authors.affiliation: Institut Parisien de Chimie Moléculaire, UMR 8232, Université Pierre et Marie Curie (Paris VI), 4 Place Jussieu, 75252 Paris, France.
authors.forename: Richard B
authors.initials: RB
authors.lastname: Cole
authors.affiliation: Ifremer, Laboratoire Phycotoxines, Rue de l'Ile d'Yeu, 44311 Nantes, France.
authors.forename: Philipp
authors.initials: P
authors.lastname: Hess
mesh_terms: D000818:Animals; D049872:Bivalvia / Q000737:chemistry*; D002853:Chromatography, Liquid / Q000379:methods*; D008387:Marine Toxins / Q000032:analysis*; D012015:Reference Standards; D012758:Shellfish / Q000032:analysis*; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D008387:Marine Toxins
keywords: Marine toxins; Matrix effects; Monitoring; Passive sampling; SPATT