Rapid determination of polyether marine toxins using liquid chromatography-multiple tandem mass spectrometry

• Published in: Journal of Chromatography A Vol. 1056; no. 1-2; pp. 77 - 82
• Main Authors: Puente, P.F, Saez, M.J.F, Hamilton, B, Lehane, M, Ramstad, H, Furey, A, James, K.J
• Format: Journal Article Conference Proceeding
• Language: English
• Published: Amsterdam Elsevier 12.11.2004
• Subjects: Analytical chemistry; bioaccumulation; Biological and medical sciences; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, High Pressure Liquid - methods; Dinophysis acuta; dinophysistoxins; Exact sciences and technology; food contamination; Food toxicology; liquid chromatography; Luminescence; Marine Toxins - analysis; mass spectrometry; Mass Spectrometry - methods; Medical sciences; mussels; Mytilus; okadaic acid; Other chromatographic methods; pectenotoxins; phycotoxins; phytoplankton; Reproducibility of Results; Toxicology; Trace analysis; Chemical analysis; Ether; Mussel; Mytilus edulis; Coupled method; Liquid chromatography; Pectenotoxins; Dinophysistoxins; Marine environment; Toxin; Diarrhetic shellfish poisoning; Plankton; Bivalvia; Mass spectrometry MS/MS; Okadaic acid; Phytoplankton; Ionophore; Invertebrata; Mollusca
• ISSN: 0021-9673
• DOI: 10.1016/s0021-9673(04)01197-5

The diarrhetic shellfish poisoning (DSP) toxins, okadaic acid (OA), dinophysistoxins (DTX); pectenotoxin-2 (PTX2) and pectenotoxin-2 seco acids, were determined in marine phytoplankton, Dinophysis acuta, and mussels (Mytilus edulis) collected along the southwest coast of Ireland. Liquid chromatography-multiple tandem mass spectrometry (LC-MS/MS) was employed for the simultaneous determination of a series of marine toxins with large polarity differences. Separation of five DSP toxins was achieved on a C18 column (Luna-2, 150 mm x 2.1 mm, 5 microm) using an acetonitrile-water gradient with ammonium acetate as an eluent modifier. Electrospray ionisation (ESI) in negative mode, was used to generate the molecule related ion, [M-H]-, for each toxin. To develop a multiple reaction monitoring (MRM) method, fragmentation studies were performed to determine the optimum precursor-product ion combinations: OA (803/255), DTX2 (803/255), DTX1 (817/255), PTX2SAs (875/137) and PTX2 (857/137). This highly sensitive method had detection limits better than 1 pg (on-column). Linear calibrations were obtained for shellfish extracts that were spiked with toxins, OA, 0.007-1.00 microg/ml (r2 = 0.9993, N = 3) and DTX2, 0.054-8.5 microg/ml (r2 = 0.9992, N = 3). Good reproducibility data were also achieved with %RSD values (N = 3) ranging from 3.15% (0.56 microg DTX2/ml) to 5.71% (0.14 microg DTX2/ml), for shellfish extracts. The method was sufficiently sensitive to permit the determination of DSP toxins in small numbers of picked phytoplankton cells (N = 12-40). In one sample of D. acuta the average toxin composition per cell was: OA (7.0 pg), DTX2 (11 pg) and PTX2 (7.2 pg).