Quantitative assessment of interactions of hydrophilic organic contaminants with microplastics in natural water environment

The interaction between microplastics (MPs) and hydrophilic organic contaminants (HOCs) in natural water environment has recently raised great public attentions due to the potential toxicity to humans. However, the quantitative assessment is less studied. In this study, the interaction between ciprofloxacin (CIP) and ofloxacin (OFL) (two important HOCs) and virgin and aged polystyrene (PS) was investigated. The aged PS showed higher adsorption rate and capacity than the virgin PS, due to its larger surface area and more O-containing groups. The pH-dependent adsorption of CIP was higher than OFL on both virgin and aged PS; the maximum adsorption for both HOCs occurred at pH 5. The sequential orders of functional groups for the adsorption were discovered according to the study by the 2D correlation Fourier transform infrared spectroscopy. Several mechanisms existed for the interaction: (1) at 3.0 < pH < 5.0, the electrostatic attraction (EA) was inhibited while H-bond (HB) was dominant, accounting for > 60% of the total uptake; (2) at 5.0 < pH < 8.0, the contribution of EA increased to around 50-60% while HB decreased to 30-40%; (3) at 8.0 < pH < 10.0, EA, HB and π-π conjugation caused 30-40%, 25-40% and 20-45% of the total uptake, respectively; (4) at 10.0 < pH < 12.0, π-π conjugation accounted for 90-100%. Notably, higher adsorption of CIP was mainly attributed to the presence of secondary amino groups and its higher pKa value, correspondingly leading to the additional ordinary HB and negative charge-assisted HB, and EA interactions with PS. This study further provides clear evidences on the risk of MPs and HOCs on humans and aqueous living organisms.