High salinity promotes the photoaging of polystyrene microplastics with humic acid in seawater

The photoaging of microplastics (MPs) accumulated in the sea can be influenced by humic acid (HA). However, the role of salinity cannot be ignored, as it may potentially disrupt the interaction between MPs and HA, thereby altering the photoaging of MPs. Herein, this study investigated how salinity influences the effect of humic acid (HA, derived from lignite) on the photoaging of polystyrene microplastics (PS MPs) in artificial and natural seawater. The results revealed that HA promoted the photoaging of PS MPs under both low (5 PSU) and high salinity (35 PSU) in light conditions (L), reflected in the formation of fragments, the production of oxygen-containing functional groups (OH, CO, and OCO), and the increase in hydrophilicity of PS MPs. Furthermore, high salinity promoted the photoaging of PS MPs with HA more significantly, as evidenced by the similar indicators and the order of oxygen/carbon atom ratio (O/C): L-HA-High (0.15) > L-HA-Low (0.10) > Unaged (0.02). Interestingly, due to the reduction of electrostatic repulsion, the adsorption of HA on photoaged PS MPs in natural and artificial high salinity seawater was 1.77 mg/g and 0.39 mg/g, respectively, which was significantly higher than those PS MPs photoaged in the low salinity seawater. Furthermore, the electron spin resonance (ESR) results confirmed that more hydroxyl radicals (OH) were generated after adsorbing HA under high salinity conditions, thus promoting the fragmentation and oxidation of PS MPs. Overall, our findings highlight the crucial role of salinity in influencing the photoaging of MPs with HA and help to assess the marine risk of MPs accurately.