Surface characteristics and adsorption properties of polypropylene microplastics by ultraviolet irradiation and natural aging

The vast application and deep integration of plastic commodity with our human lives raise a great concern about the ubiquitous microplastics (MPs) in nature, yet the environmental behavior of MPs remain unclear. As a main type and candidate of MPs, pristine polypropylene MPs (PP-MP-Pris), as well as the influence of ultraviolet (UV) irradiation on the degree of aging and surface characteristics, were characterized quantitatively by Fourier infrared spectroscopy, scanning electron microscopy, contact angle meter, automatic specific surface area and pore analyzer and laser particle analyzer, with natural aged PP-MPs (PP-MP-Age) as comparison. The carbonyl index (CI) of UV aged PP-MPs (PP-MP-U) was increased with extension of exposure time, while biofilm with abundant functional groups and the maximum CI value were the characteristics of PP-MP-Age. Moreover, the adsorption capacity of PP-MP-U for crystal violet (CV) was increased and reached the maximum after 30 days, while that of PP-MP-Age was weakened, probably due to the enhanced hydrophilicity and the shedding of calcium carbonate (CaCO) during the natural aging process, which was demonstrated by hydrochloric acid treatment, indicating the vital involvement of CaCO. Moreover, the better fitting to PSO kinetics and Freundlich isotherm models indicated that the multilayered and non-homogeneous surface adsorption was acted as the rate-controlling step. Furthermore, the positive values of ΔG, ΔH and ΔS indicated that the adsorption was a non-spontaneous, endothermic process with increased degree of the freedom on the interface of PP-MPs and CV solution. The presence of divalent salts inhibited CV adsorption, demonstrating that electrostatic attraction played a major role in CV capture. The hydrophobic interaction, micropore filling, hydrogen bonding, and π - π conjugation were possible involved. This study is of great significance for better understanding the complex pollution of MPs and its potential environmental risks in the future.