Decoding the oxidative digestion mechanism for polystyrene nanoplastic detection in the Great Lakes using a customizable Raman spectral processing algorithm

Despite the concerns surging around nanoplastics (NPs) regarding their prevalence and bioavailability in freshwater systems, robust detection of NPs in complex environmental matrices is hindered by the lack of standardized sample pretreatment and a mechanistic understanding of oxidative digestion. Here, we systematically investigate the interaction between hydrogen peroxide (H₂O₂) and polystyrene (PS) NPs during digestion in deionized (DI) water and four environmental matrices from in and around the Great Lakes Basin. To facilitate high-throughput analysis, we develop Pre_peak, a customizable Raman spectral processing algorithm that achieves >99% accuracy for both NP identification and interference rejection, allowing reliable NP quantification via pixel counting and systematic decoding of the oxidative digestion mechanisms. In DI water, varying H₂O₂ doses from 0 to 30% has negligible effects on the recovery and Raman signal intensity of PS NPs over 24 hours of digestion. However, morphological changes and aggregation of PS NPs are observed when the H₂O₂ dose exceeds 20%. Prolonged digestion further leads to progressive NP loss. In natural waters, the optimal dosage and digestion duration depend on matrix characteristics, including dissolved organic matter (DOM) and ion composition. This study provides mechanistic insights into NP–oxidant interactions and underscores the need for matrix-tailored digestion protocols to advance standardized NP detection in freshwater environments.