Seasonal monitoring of dissolved and particulate algal biotoxins in the northern Salish Sea using high performance liquid chromatography and tandem mass spectrometry.

Harmful algae are present in the coastal waters of British Columbia, Canada yet little is known about the spatial and temporal distributions of the biotoxins produced by these organisms. We describe a method for profiling dissolved and particulate algal biotoxins in sea water including those associated with amnesic, paralytic, and diarrhetic shellfish poisoning (ASP, PSP and DSP). Surface sea water was filtered and biotoxins recovered from filters and filtrate using solvent extraction and solid phase extraction, respectively. Extracts were analyzed by high-performance liquid chromatography and tandem mass spectrometry using hydrophilic interaction liquid chromatography for ASP and PSP toxins and reversed-phased liquid chromatography for DSP and other lipophilic toxins. The method was applied to samples collected in the northern Salish Sea in April, June and October 2022. Highest total concentrations of domoic acid and saxitoxin were found above a shallow sill in the eastern Juan de Fuca Strait whereas those of dinophysistoxin 1, pectenotoxin 2, yessotoxin, and PSP toxins C1 and C2 were measured near the southern end of Malaspina Strait. These maximum concentrations were observed in June when surface salinity was lowest, temperature highest, and harmful algae most abundant, as reflected in the relative high proportion of particulate biotoxins. In contrast, the high proportion of dissolved biotoxins observed in April when temperature and algal abundance were relatively low suggests that certain biotoxins may persist in surface waters and that the risk of biotoxin exposure does not necessarily correlate with the abundance of harmful algae.