Quantifying UV-Driven Aging of Sub-10 µm Airborne Microplastics with High-Resolution µFTIR-ATR Imaging

Airborne microplastics (AMPs) undergo ultraviolet (UV)-driven physicochemical aging during atmospheric transport, influencing cloud processes, greenhouse-gas release, and potential respiratory health impacts. Quantifying this transformation is particularly challenging for particles smaller than 10 µm and for polymers such as polyethylene terephthalate (PET), whose intrinsic ester carbonyl band obscures newly formed acid carbonyls in conventional infrared analyses. Here, we develop a µFTIR attenuated total reflection (µFTIR-ATR) imaging method combined with a fourth-derivative oxidation index (carbonyl ratio at 1701/1716 cm−1) that resolves these overlapping bands and enables sensitive, quantitative evaluation of PET surface oxidation. The approach automates detection, identification, and oxidation analysis of particles down to ~2 µm. Laboratory UV irradiation experiments show a systematic increase in this derivative-based oxidation index with exposure dose. Application to ambient PET collected from Mt. Fuji, Tokyo, Osaka (Japan), and Siem Reap (Cambodia) reveals clear regional differences corresponding to local UV-A environments: PET from Siem Reap exhibited the highest oxidation, whereas particles from the Japanese sites showed moderate but variable aging. These results demonstrate that derivative-based µFTIR-ATR imaging provides a practical and highly sensitive tool for quantifying photo-oxidative degradation in fine AMPs and highlight the value of chemical-aging metrics for interpreting atmospheric processing and transport pathways.