Silvia Serranti, Giuseppe Bonifazi, Pietro Cocozza, Paola Cucuzza, Roberta Palmieri, Margherita Benzi, Marco Lezzi, Cristina Mazziotti, Elena Riccardi, Elena Barbieri, Irene Ingrando, F. Moroni
In this study, hyperspectral imaging (HSI) was systematically compared with Fourier-transform infrared spectroscopy (FTIR/micro-FTIR) for microplastic (MP) polymer identification using environmental samples collected during a 12-month monitoring campaign at six stations along 300 km of the Po River (Italy), following the Marine Strategy Framework Directive (MSFD, 2008/56/EC) guidelines adapted to freshwater environments. In total, 11,828 MP particles (330 μm-5 mm) were collected and analyzed to assess MP abundance, morphology, color and polymer composition. Across the monitored sites and sampling period, MP concentrations ranged from 0.03 to 12.7 n°/m 3 , generally lower than values reported for other major world rivers. Fragments and foam dominated the MP categories (56% and 24%, respectively), and white was the dominant color (57%), while PE, PP and EPS were the most abundant polymers (44.9%, 28.8% and 22.5%, respectively). The particle-by-particle comparison between HSI in the short-wave infrared range (1000-2500 nm) and FTIR or micro-FTIR, depending on particle size, yielded an overall polymer identification agreement exceeding 99%. HSI significantly improved analytical efficiency, requiring only 8 min for classification of 100 particles compared to 300-500 min using FTIR/micro-FTIR spectroscopy. Black MP particles (8.2% of the total) were systematically excluded from HSI analysis and characterized exclusively by FTIR/micro-FTIR. The results support the proposal of a new analytical protocol using HSI as the primary tool for polymer classification, with FTIR/micro-FTIR reserved for black or unclassified particles, enabling faster, scalable and reliable MP monitoring.