Size- and Concentration-Resolved Detection of PET Microplastics in Real Water via Excitation-Emission Matrix...

The selective detection of microplastics (MPs) in aquatic environments is hindered by particle size diversity and matrix-induced interferences. This study reports an excitation-emission matrix (EEM) fluorescence sensing platform using polyamide-derived carbon quantum dots (PACQDs; 0.5-2.6 nm) for the size- and concentration-resolved detection of polyethylene terephthalate MPs (PETMPs). PACQDs exhibited a pronounced fluorescence "turn-off" response upon PETMP interaction, governed by particle size (10-149 μm) and loading (4-8 g L^-1). Small PETMPs (10 μm) followed linear Stern-Volmer behavior, achieving a detection limit of 1.67 mg L^-1 in deionized water. Conversely, larger particles induced non-linear optical effects, including scattering-driven enhancement and inner-filter effects. Multivariate analysis using PCA and PARAFAC resolved three distinct components associated with surface-state quenching, scattering-mediated redistribution, and surface area-driven binding. Component-specific scores confirmed that PACQDs are most sensitive to small PETMPs, while larger particles primarily introduce optical interference. Selectivity tests showed distinct discrimination of PETMPs over polyamide and polypropylene. In tap water, significant matrix effects were corrected via matrix-matched calibration, achieving recoveries within 80-120%. This study establishes EEM-based multivariate fluorescence as a mechanism-informed strategy for PETMP sensing, highlighting the robust applicability of PACQDs for monitoring small PETMPs in real-world water matrices.