Interactions between polypropylene microplastics (PP-MPs) and humic acid influenced by aging of MPs

As an emerging pollutant, microplastics (MPs) may interact with dissolved organic matter (DOM) which is prevalent in the aqueous environment. Meanwhile, the aging of MPs in the actual environment increases the uncertainty of their environmental fate. Here, the interaction mechanisms between pristine and aged polypropylene microplastics (PP-MPs) and humic acid (HA) at pH 7.0 were explored. Microstructural changes of HA were examined by fluorescence and Fourier transformation infrared (FT-IR) spectroscopy. Atomic force microscopy coupled with infrared (AFM-IR) and micro-Raman techniques were used to characterize and analyze the interacted PP-MPs. The addition of HA increased the surface roughness of both pristine and aged PP-MPs. Results of AFM-IR and Raman spectra showed that the interaction of PP-MPs with HA accelerated their surface oxidation and enhanced the characteristic signals. XPS spectra showed that the oxygen content ratio of pristine and aged PP-MPs increased by 0.95% and 1.48% after the addition of HA, respectively. PP-MPs after aging interacted more strongly with HA and there was a higher affinity between them. Two-dimensional correlation spectroscopy (2D-COS) combined with FT-IR spectra further elucidated the interaction mechanism at the molecular level. This work will help to evaluate the environmental impact of MPs in ecosystems and understand their interactions with DOM.