Fourier transform infrared (FTIR) is a spectroscopy technique widely used to identify organic materials. It has recently gained popularity in microplastic (MP) pollution research to determine the chemical composition of unknown plastic fragments. However, it could also be used to evaluate the degree of ageing of MPs collected from the environment. In this context, the principal aim of our research has been to qualitatively evaluate the natural weathering of environmental MPs collected in an Italian freshwater body (the Ofanto River) using ATR-FTIR technology. Furthermore, we compared environmental particles to weathered artificial MPs under controlled light and temperature conditions and to unaltered pristine materials to assess the results. FTIR spectra were acquired using a Nicolet Summit FTIR (ThermoFisher Scientific) equipped with an Everest ATR with a diamond Crystal plate and a DTGS KBr detector (wavenumber range 4000–500 cm⁻¹, 32 scans per spectrum, spectral resolution of 4 cm⁻¹). The degree of ageing was assessed using three different indexes known to be related to changes in MPs: Carbonyl Index (CI), Hydroxyl Index (HI), and Carbon-Oxygen Index (COI). The overall results showed that the regions reflecting changes (hydroxyl groups, peaks from 3100 to 3700 cm⁻¹, alkenes or carbon double bonds, 1600 and 1680 cm⁻¹, and carbonyl groups, 1690 and 1810 cm⁻¹) appeared significantly modified in artificial and natural weathered particles compared to the pristine materials. The indexes calculated for polymers degraded under the artificial photo and thermo ageing conditions displayed a general tendency to increase with the time in contact with irradiation time. Particular enhancements of CI of PS fragment and PE pellet, HI of PE and PS fragments and PE pellet, and COI of PS fragment were observed. Otherwise, the following incubation of the same particles at a constant temperature of 45 °C did not further affect the chemical composition of the particles. Moreover, new unique peaks were also observed in the freshwater particles, almost all in the fingerprint region (1500–500 cm⁻¹). Differences in CI, HI, and COI were evidenced among the different morphological MP shapes. On the one hand, the CI calculated for the environmental PE pellets showed values ranging from 0.05 to 0.26 with a mean value of 0.17 ± 0.10. Most samples (57%) presented a CI with values between 0.16 and 0.30. On the other hand, fragments presented slicer modifications in the carbonyl region with CI values lower than pellets (0.05 ± 0.05). This index helps evaluate the degradation of PE MPs by UV light, increasing with enhancing residence time in the environment. Conversely, fragments showed greater values of HI (5.90 ± 2.57) and COI (1.04 ± 0.48) than pellets, as well as lines, which presented the maximum value of HI (11.51). HI is attributed to the bond vibrations of hydroxyl, carboxyl, or phenol groups. In contrast, COI is frequently attributed to the vibrations of C_O bonds found in carbohydrates, alkanes, secondary alcohols, and ketones. In conclusion, our results showed characteristics spectra acquired from environmental particles compared to pristine and artificial aged ones. The interpretation of our main results emphasizes the need to conduct ecotoxicological experimental studies using naturally weathered particles due to the unicity of their properties, which are more helpful for understanding microplastic pollution effects.

Microplastics have recently been stated as being remarkable contaminants of all environmental matrices. The lack of consistent and standardised methods and protocols used to evaluate and quantify microplastics present in riverine systems made a comparison among different studies a critical issue. Based on literature research and the practical expertise of the authors, this work presents a complete collection and analysis of procedures concerning the monitoring of microplastics in riverine environments, focusing on their sampling and analytical protocols to identify, quantify, and characterise them. Further details regarding the advantages and disadvantages of each analytical technique described, such as general recommendations and suggestions, are provided to give practical support for analytical procedures. In particular, microplastics studies consist firstly of their sampling from the aquatic compartment (aqueous and solid phase). Based on the goal of the research, specific devices can be used to collect particles from different matrices. It follows their quantification after extraction from the environmental matrix, adopting different protocols to isolate microplastics from a large amount of organic matter present in a riverine system. In the end, additional qualitative analyses (e.g., RAMAN and FTIR spectroscopy, GC-MS) are required to identify the chemical composition of particles for a better image regarding the abundance of polymer types, their origin, or other information related to manufacturing processes.

Although several sample preparation methods for analyzing microplastics (MPs) in environmental matrices have been implemented in recent years, important uncertainties and criticalities in the approaches adopted still persist. Preliminary purification of samples, based on oxidative digestion, is an important phase to isolate microplastics from the environmental matrix; it should guarantee both efficacy and minimal damage to the particles. In this context, our study aims to evaluate Fenton’s reaction digestion pre-treatment used to isolate and extract microplastics from environmental matrices. We evaluated the particle recovery efficiency and the impact of the oxidation method on the integrity of the MPs subjected to digestion considering different particles’ polymeric composition, size, and morphology. For this purpose, two laboratory experiments were set up: the first one to evaluate the efficacy of various digestion protocols in the MPs extraction from a complex matrix, and the second one to assess the possible harm of different treatments, differing in temperatures and volume reagents used, on virgin and aged MPs. Morphological, physicochemical, and dimensional changes were verified by Scanning Electron Microscope (SEM) and Fourier Transformed Infrared (FTIR) spectroscopy. The findings of the first experiment showed the greatest difference in recovery rates especially for polyvinyl chloride and polyethylene terephthalate particles, indicating the role of temperature and the kind of polymer as the major factors influencing MPs extraction. In the second experiment, the SEM analysis revealed morphological and particle size alterations of various entities, in particular for the particles treated at 75 °C and with major evident alterations of aged MPs to virgin ones. In conclusion, this study highlights how several factors, including temperature and polymer, influence the integrity of the particles altering the quality of the final data.

This research activity, conducted in collaboration with the Aero-Naval Operations Department of the Guardia di Finanza of Bari as part of the Special Commissioner for urgent measures of reclamation, environmental improvements and redevelopment of Taranto’s measurement, is based on the use of a high-resolution airborne sensor, mounted on board a helicopter to identify and map all in operation and abandoned mussel farming in the first and second inlet of Mar Piccolo. In addition, factors able to compromise the environmental status of the Mar Piccolo ecosystem were also evaluated. The methodological workflow developed lets extract significant individual frames from the captured video tracks, improves images by applying five image processing algorithms, georeferences the individual frames based on flight data, and implements the processed data in a thematic Geographical Information System. All mussel farms, in operation and derelict, all partially submerged and/or water-coated invisible to navigation poles and other elements such as illegal fishing nets and marine litter on the seabed up to about 2 m deep, have been identified and mapped. The creation of an instant, high-precision cartographic representation made it possible to identify the anthropogenic pressures on the Mar Piccolo of Taranto and the necessary actions for better management of the area.