Production and release of selenocyanate by different green freshwater algae in environmental and laboratory samples

In a previous study, selenocyanate was tentatively identified as a biotransformation product when green algae were exposed to environmentally relevant concentrations of selenate. In this follow-up study, we confirm conclusively the presence of selenocyanate in Chlorella vulgaris culture medium by electrospray mass spectrometry, based on selenium's known isotopic pattern. We also demonstrate that the observed phenomenon extends to other green algae (Chlorella kesslerii and Scenedesmus obliquus) and at least one species of blue-green algae (Synechococcus leopoliensis). Further laboratory experiments show that selenocyanate production by algae is enhanced by addition of nitrate, which appears to serve as a source of cyanide produced in the algae. Ultimately, this biotransformation process was confirmed in field experiments where trace amounts of selenocyanate (0.215 ± 0.010 ppb) were observed in a eutrophic, selenium-impacted river with massive algal blooms, which consisted of filamentous green algae (Cladophora genus) and blue-green algae (Anabaena genus). Selenocyanate abundance was low despite elevated selenium concentrations, apparently due to suppression of selenate uptake by sulfate, and insufficient nitrogen concentrations. Finally, trace levels of several other unidentified selenium-containing compounds were observed in these river water samples; preliminary suggestions for their identities include thioselenate and small organic Se species.