Complementary analytical strategies based on ICP-TQ-MS were used for the detection and characterization of selenium-containing nanoparticles in selenized yeast.

No abstract

Laboratory algal cultures exposed to selenate were shown to produce and release selenomethionine, selenomethionine oxide, and several other organic selenium metabolites. Released discrete organic selenium species accounted for 1.6-13.1% of the selenium remaining in the media after culture death, with 1.3-6.1% of the added selenate recovered as organic metabolites. Analysis of water from an industrially impacted river collected immediately after the death of massive annual algal blooms showed that no selenomethionine or selenomethionine oxide was present. However, other discrete organic selenium species, including a cyclic oxidation product of selenomethionine, were observed, indicating the previous presence of selenomethionine. Industrial biological treatment systems designed for remediation of selenium-contaminated waters were shown to increase both the concentration of organic selenium species in the effluent, relative to influent water, and the fraction of organic selenium to up to 8.7% of the total selenium in the effluent, from less than 1.1% in the influent. Production and emission of selenomethionine, selenomethionine oxide, and other discrete organic selenium species were observed. These findings are discussed in the context of potentially increased selenium bioavailability caused by microbial activity in aquatic environments and biological treatment systems, despite overall reductions in total selenium concentration.

A new anion-exchange chromatographic separation method was used for the simultaneous speciation analysis of selenoamino acids and the more ubiquitous inorganic selenium oxyanions, selenite and selenate. For quantification, this separation was coupled to inductively coupled plasma-mass spectrometry to achieve an instrumental detection limit of 5 ng Se L(-1) for all species. This chromatographic method was also coupled to electrospray tandem mass spectrometry to observe the negative ion mode fragmentation of selenomethionine and one of its oxidation products. Low detection limits were achieved, which were similar to those obtained using inductively coupled plasma-mass spectrometry. An extensive preconcentration and cleanup procedure using cation-exchange solid-phase extraction was developed for the identification and quantification of trace levels of selenomethionine in environmental samples. Preconcentration factors of up to five were observed for selenomethionine, which in addition to the removal of high concentrations of sulphate and chloride from industrial process waters, allowed for an unambiguous analysis that would have been impossible otherwise. Following these methods, selenomethionine was identified at an original concentration of 3.2 ng Se L(-1) in samples of effluent collected at a coal-fired power plant's biological remediation site. It is the first time that this species has been identified in the environment, outside of a biological entity. Additionally, oxidation products of selenomethionine were identified in river water and laboratory algal culture samples. High-resolution mass spectrometry was employed to postulate the chemical structures of these species.

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.