Profiles and levels of fatty acid esters of okadaic acid group toxins and pectenotoxins during toxin depuration. Part II: Blue mussels (Mytilus edulis) and flat oyster (Ostrea edulis)

Bivalve molluscs accumulate toxins of the okadaic acid (OA) and pectenotoxin (PTX) groups, which are frequently found in Dinophysis spp. Transformation of the OA-group toxins into fatty acid ester derivatives (often designated DTX3) is common in many bivalve species but the degree to which these toxins are transformed vary between species, and is also depending on the parent toxin involved. In this paper, detailed profiles and levels of fatty acid esters of OA, DTX1, DTX2 and PTX2 SA were studied in blue mussels (Mytilus edulis) and European flat oysters (Ostrea edulis), collected during a bloom of Dinophysis spp. and after 3 and 6 weeks of depuration. Analysis of samples by HPLC-MS/MS and HPLC-MS2 revealed some differences in identity and abundance of fatty acid moieties of the OA-group esters between species, but the 16:0 fatty acid esters dominated in both oysters and mussels, which is in accordance with the free fatty acid profiles in these species. A wider range of FM SA-esters were detected compared to esters of the CA-group toxins in both mussels and oysters, and in oysters, both 14:0, 18:4 and 20:5 fatty acid side chains were more common than 16:0. OA-group toxins were esterified to a larger degree in oysters (83-93%) compared to mussels (21-41%), and in mussels a higher proportion of OA was esterified compared to DTX1 and DTX2. Contrary to what was observed for CA-group toxins, PTX2 SA was esterified to a larger degree in mussels (81%) compared to oysters (64%). Calculations of depuration rates for all individual esters of each parent compound showed that the esters of DTX1 depurated significantly slower from both mussels and oysters compared to esters of OA, DTX2 and PTX2 SA, but overall the deputation rates of esters of both toxin group were highly similar for both species. This indicated that differences in depuration rates are not causing the large species-specific differences in levels and profiles of these toxins. Instead, the results for the CA-group toxins suggested that a higher rate of esterification in oysters is the main factor causing the observed differences in the proportion of esters to free toxin. For FM SA, large differences in ester profiles and a higher proportion of esters of PTX2 SA in mussels compared to oysters suggested differential assimilation and metabolic rate processes for the PTXs compared to OA-group toxins between these species. Hence, although produced by the same Dinophysis species, conclusions about the dynamics of one toxin group based on results from the other group should be avoided in future studies. (C) 2008 Elsevier Ltd. All rights reserved.