Microplastics (MPs) quantification in benthic marine sediments is typically performed by time-consuming and moderately accurate mechanical separation and microscopy detection. In this paper we describe the results of our innovative Polymer Identification and Specific Analysis (PISA) of microplastic total mass, previously tested on either less complex sandy beach sediment or less demanding (because of the high MPs content) wastewater treatment plant sludges, applied to the analysis of benthic sediments from a sublittoral area north-west of Leghorn (Tuscany, Italy). Samples were collected from two shallow sites characterized by coarse debris in a mixed seabed of Posidonia oceanica, and by a very fine silty-organogenic sediment, respectively. After sieving at <2 mm the sediment was sequentially extracted with selective organic solvents and the two polymer classes polystyrene (PS) and polyolefins (PE and PP) were quantified by pyrolysis-GC/MS. A contamination in the 8-65 ppm range by PS could be accurately detected. Acid hydrolysis on the extracted residue to achieve total depolymerization of all natural and synthetic polyamides, tagging of all aminated species in the hydrolyzate with a fluorophore, and reversed-phase HPLC (RP-HPLC) analysis, allowed to quantify within the 137-1523 ppm range the individual mass of contaminating Nylon 6 and Nylon 6,6, based on the detected amounts of the respective monomeric amines 6-aminohexanoic acid (AHA) and hexanediamine (HMDA). Finally, alkaline hydrolysis of the residue from acid hydrolysis followed by RP-HPLC analysis of the purified hydrolysate showed contamination by polyethylene terephthalate (PET) in the 12.1-2.7 ppm range, based on the content of its comonomer, terephthalic acid.

Up to 13 million tons of plastic waste are estimated to enter the oceans every year. A generally accepted picture based on an increasing number of environmental studies suggests that the largest fraction of it consists or is rapidly degraded into microplastics (MPs). Most of the analytical studies focused on MPs are based on the detection and identification of the polymers. On the other hand, plastic debris in the environment undergo chemical (mainly photoxidative) and physical degradation processes leading not only to fragmentation but also to the formation of leachable, soluble and/or volatile degradation products that are released in the environment. The formation of such low molecular weight species is generally neglected in the studies on MPs even if these compounds, released in the environment from the plastics debris, may pose even higher risks for the environment and for the biota than the MPs particles themselves, risks that are far from being understood and assessed. In this study we performed the analysis of reference MPs - polymer micropowders obtained by grinding a set of five polymer types down to final size in the 857-509 μm range, namely high- and low-density polyethylene (HDPE and LDPE, respectively), polystyrene (PS), polypropylene (PP), and polyethylene terephthalate (PET). The reference MPs were artificially aged in a Solar-Box and their degradation products were analyzed to investigate their degradation processes. In particular, a systematic and thorough characterization of the aged (photo-oxidized) MPs and of their low molecular weight and/or highly oxidized fraction extractable in polar organic solvents was performed. For this purpose, the artificially aged MPs were subjected to selective extraction with organic solvent that are non-solvents for the virgin polymers, targeting selective recovery of the low molecular weight fractions generated during the artificial aging. Analysis of both the extractable fractions and the residues was carried out by a multi-technique approach combining evolved gas analysis-mass spectrometry (EGA-MS) and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). Up to 18 wt% of newly extractable, low molecular weight fraction was recovered from the photo-aged MPs, depending on the polymer type. The results highlight the need for more extensive studies about the potential harmfulness of the oxidation products (molecular and oxidized oligomeric species) that may leach out from plastic debris during their permanence in the environment.