Raman spectra and surface changes of microplastics weathered under natural environments

Raman spectroscopy can be used to effectively analyze submicron- to microsized microplastics, but Raman spectra of weathered microplastics commonly show deviations from those of unweathered microplastics and are often affected by fluorescence. However, studies of weathering-induced surface changes in microplastics have been limited to laboratory simulations. To systematically study Raman spectra and surface changes of microplastics weathered under natural environments, we collected microplastics from sediments around waste plastics processing and recycling industries in Laizhou City, Shandong Province, East China. Raman spectra of weathered microplastics differ greatly from standard spectra of unweathered plastic material. Peaks in the Raman spectra of weathered microplastics are weakened and even invisible. A preliminary Raman database of weathered microplastics (RDWP) including 124 Raman spectra of weathered microplastics was built to accurately identify microplastics in natural environments, and it is open to all users. FTIR spectroscopy revealed the presence of oxygen-containing functional groups and CC bonds related to oxidation and chain scission. SEM showed that weathered microplastics had rough surfaces and that PP was more easily fractured than PE. Complementary C and O elemental maps suggested that the O/C ratio is a potential indicator of oxidation degree. EDS revealed titanium on PET and PVC surfaces, which is related to titanium dioxide typically used as a light-blocking aid. Our data document that Raman spectroscopy has great potential in the identification of naturally weathered microplastics and that combined spectral and elemental analyses can be useful in deciphering the degradation processes of microplastics under natural conditions. CAPSULE: Raman spectra of weathered microplastics differ greatly from standard spectra. A Raman database of weathered microplastics is established. Surface changes of weathered microplastics were systematically studied.