Effect of Exposure Concentration and Growth Conditions on the Association of Cerium Oxide Nanoparticles with Green Algae

The increasing release of engineered nanoparticles (NPs) into aquatic ecosystems makes it crucial to understand the interactions of NPs with aquatic organisms, such as algae. In this study, the association of CeO₂ NPs with unicellular algae (Raphidocelis subcapitata) and changes to the cellular elemental profile were investigated using three exposure concentrations (1, 50, and 1000 µg CeO₂/L) at two different algal growth conditions-exponential and inhibited growth (1% glutaraldehyde). After a 24 h-exposure, algal suspensions were settled by gravity and CeO₂-NP/algae association was analyzed by single-cell inductively coupled plasma quadrupole mass spectrometry (sc-ICP-QMS) and ICP time-of-flight MS (sc-ICP-TOFMS). Concurrent detection of the cellular fingerprint with cerium indicated NP association with algae (adsorption/uptake) and changes in the cellular elemental profiles. Less than 5% of cells were associated with NPs when exposed to 1 µg/L. For 50 µg/L exposures in growing and inhibited cell treatments, 4% and 16% of cells were associated with CeO₂ NPs, respectively. ICP-TOFMS analysis made it possible to exclude cellular exudates associated with CeO₂ NPs due to the cellular fingerprint. Growing and inhibited cells had different elemental profile changes following exposure to CeO₂ NPs-e.g., growing cells had higher Mg and lower P contents independent of CeO₂ concentration compared to inhibited cells.