Effect of Aging on Physicochemical Properties and Size Distribution of PET Microplastic: Influence on Adsorption of Diclofenac and Toxicity Assessment

Microplastics (MPs) are detected in the water, sediments, as well as biota, mainly as a consequence of the degradation of plastic products/waste under environmental conditions. Due to their potentially harmful effects on ecosystems and organisms, MPs are regarded as emerging pollutants. The highly problematic aspect of MPs is their interaction with organic and inorganic pollutants; MPs can act as vectors for their further transport in the environment. The objective of this study was to investigate the effects of ageing on the changes in physicochemical properties and size distribution of polyethylene terephthalate (PET), as well as to investigate the adsorption capacity of pristine and aged PET MPs, using pharmaceutical diclofenac (DCF) as a model organic pollutant. An ecotoxicity assessment of such samples was performed. Characterization of the PET samples (bottles and films) was carried out to detect the thermooxidative aging effects. The influence of the temperature and MP dosage on the extent of adsorption of DCF was elucidated by employing an empirical modeling approach using the response surface methodology (RSM). Aquatic toxicity was investigated by examining the green microalgae Pseudokirchneriella subcapitata. It was found that the thermooxidative ageing process resulted in mild surface changes in PET MPs, which were reflected in changes in hydrophobicity, the amount of amorphous phase, and the particle size distribution. The fractions of the particle size distribution in the range 100–500 μm for aged PET are higher due to the increase in amorphous phase. The proposed mechanisms of interactions between DCF and PET MPs are hydrophobic and π–π interactions as well as hydrogen bonding. RSM revealed that the adsorption favors low temperatures and low dosages of MP. The combination of MPs and DCF exhibited higher toxicity than the individual components.