Nodularin in feathers and liver of eiders (Somateria mollissima) caught from the western Gulf of Finland in June–September 2005

Nodularins are cyanobacterial hepatotoxins, which may cause intoxication at very low exposure levels. The nodularin-producing cyanobacterium Nodularia spumigena usually forms massive blooms in much of the Baltic Sea during the summer season. Breast feathers and liver samples from common eider (Somateria mollissima) were analysed for nodularins by liquid chromatography–mass spectrometry (LC–MS) and enzyme-linked immunosorbent assay (ELISA). Fifteen eiders from the western Gulf of Finland were caught by hunters between June and September 2005. Blue mussels (Mytilus edulis), a dietary component of the birds, were also obtained by diving near the same marine area and time as the collection of the ducks. Eider breast feathers contained 6–52 μg nodularin-R (Nod-R)/kg dry weight (dw) by ELISA, and 8–43 μg Nod-R/kg dw by LC–MS. No Nodularia filaments were adhered to feather samples according to light microscopy assessment. Liver samples from the same individuals contained Nod-R between 3 and 48 μg/kg dw by LC–MS. Mussel samples from the area contained Nod-R at concentrations of 12–80 μg/kg dw by LC–MS. Analysis of bird feathers offers a facile and non-invasive means of assessing the exposure of birds to nodularins.     

LC–ESI-Q-TOF-MS for faster and accurate determination of microcystins and nodularins in serum

Microcystins (MC) and nodularins (Nod) are cyclic peptide hepatotoxins and tumour promoters produced by cyanobacteria. This study deals with liquid chromatography–mass spectrometry (LC–MS) analyses of 9 major cyanobacterial peptide toxins, starting with a comparison of six small particle size reversed-phase HPLC columns, from which one, Phenomenex Synergi Hydro-RP, was chosen for further chromatography with accurate mass MS studies in a complex biological fluid, serum. The instrumentation used for the serum sample analysis included a Bruker micrO-TOF-Q-MS coupled to an Agilent 1200RR LC system. Total analysis run time per sample was 8.5 min. The Q-TOF-MS instrument was operated on auto MS–MS mode to obtain fragment ions (such as the characteristic fragment m/z 135 from Adda amino acid residue) for toxin identification purposes. Detected mass errors in serum samples were in the range of from 0.3 mDa to 9.1 mDa. The narrow mass window (±20 mDa) for mass chromatograms used in quantitation gave benefits by background noise reduction. We conclude that a LC–ESI-Q-TOF-MS instrumentation is a powerful tool for identification and quantitation of cyanobacterial peptide toxins in a biological matrix.