Interplay between extracellular polymeric substances (EPS) from a marine diatom and model nanoplastic through eco-corona formation.

The occurrence of nanoplastics in oceans' surface waters is no more a hypothesis and it could severely affect marine organisms from different trophic levels. Nanoscale particles interaction with dissolved natural organic matter (NOM) significantly influence their behaviour and consequently bioavailability and toxicity to marine species. Extracellular polymeric substances (EPS) are among the main components of the NOM pool in seawater yet have been so far little investigated for their effect in altering the physical-chemical properties of nanosized objects. Here we employed EPS from marine diatom Phaeodactylum tricornutum to study the evolution of an eco-corona formation upon incubation with 60 nm carboxylated polystyrene nanoparticles (PS-COOH NPs), as proxy for nanoplastics in seawater. EPS significantly reduced PS-COOH NPs aggregation rate compared to biomolecule free natural seawater (NSW) and caused the formation of complexes constituted by both carbohydrate and protein components. Size Exclusion Chromatography (SEC) revealed four main distinct groups of peaks, spanning from high (>100 kDa) to low molecular weight (20 kDa) molecules, characterized by a high chemical heterogeneity. The lowering of the chromatographic signals detected after EPS incubation with PS-COOH NPs, mainly in the eluates at high molecular weight, suggests that an important fraction of EPS remained adsorbed on PS-COOH NPs. In agreement, SDS-PAGE analysis of proteins adsorbed on PS-COOH showed the occurrence of an eco-corona formed by proteins in the range of molecular weight 30-100 kDa. No toxicity to diatoms was observed upon PS-COOH exposure (72 h, 1-100 mg L) even by adding a further source of exogenous EPS during exposure. Moreover, the addition of EPS reduced ROS production, even when cells were incubated with PS-COOH NPs at 10 and 50 mg L, suggesting an antioxidant scavenging activity of EPS.