Chemical stability of CdSe quantum dots in seawater and their effects on a marine microalga.

With the increasing use of nanotechnologies, it is expected that nanomaterials end up in natural aquatic systems, from freshwater to the sea. In this work we studied the chemical behaviour of water-soluble CdSe QDs in seawater and their effects on the marine diatom Phaeodactylum tricornutum, as a model of a biological receptor in the marine environment. We evaluated QD toxicity in terms of growth rate inhibition, oxidative stress and ROS accumulation. In addition, we used the synthesis of phytochelatins (PCs) as a biomarker of the presence of free Cd(2+) ions released from QDs. The optical and chemical characterization demonstrated the propensity of QDs to aggregate after dispersion in raw seawater. In addition, bare CdSe QDs, lacking the ZnS shell, underwent a salinity-dependent degradation process. Short-term exposure experiments showed that the ease of degradation of QDs in seawater correlated with the synthesis of PCs in P. tricornutum cells. Long-term exposure experiments, carried out with the most stable CdSe/ZnS QDs, showed that algae accumulated Cd, but synthesized negligible amounts of PCs. Since the production of PCs is a specific signal of the presence of bioavailable metal ions, our findings suggest that QDs, associated to P. tricornutum cells, did not release PC-inducing metal species. Our data also showed a gradual decrease in algal growth rate at concentrations of QDs higher than 0.5nM. Measurements of the activity of the antioxidant enzymes showed that superoxide dismutase (SOD) and catalase (CAT) activities were increased by exposure to [QDs]≥0.5 nM, whereas ascorbate peroxidase (APX) and glutathione reductase (GR) activities were not significantly affected. The increase in SOD and CAT activity can be considered a symptom of oxidative stress induced by an enhanced production of ROS. This hypothesis was confirmed by the concomitant increase in the intracellular ROS concentration.