Microplastics and microfibers contamination in the Arno River (Central Italy): Impact from urban areas and contribution to the Mediterranean Sea

Fluvial ecosystems are among the main drivers of microparticles (MPC) in the form of both synthetic polymers (i.e. microplastics; MPs) and natural-based textile fibers (MFTEX) to the seas. A wide dimensional range of MPC (5 to 5000 μm, hereafter MPCTOT) were investigated for the first time in the Arno River waters, one of the principal rivers of Central Italy, crossing a highly anthropized landscape. Fluxes of MPCTOT discharging to the Mediterranean Sea, one the most polluted Sea worldwide, were estimated as well. A specific sampling and analytical protocol was set up to distinguish between microplastics (MPs) and natural-based textile fibers (MFTEX) contribution for MPC larger than 60 μm (MPC>60), and investigate MPC smaller than 60 μm (MPC<60) as well. Results suggest extreme MPCTOT contamination all along the river (up to 6 × 10^4 particles/L), strongly driven by MPC<60, which account for >99 % of total particles found and whose abundance increases inversely with particle size. The MPC>60 fraction (<0.5 % of MPCTOT) highlighted a predominance (76 % of the total) of MFTEX and synthetic polymers microfibers (e.g., PET) suggesting strong contributions from laundry effluents. Specifically, MFTEX represent around 70 % of all MPC>60. The metropolitan area of Florence was identified as an MPCTOT hotspot as a consequence of the intense urbanization and possibly of over-tourism phenomenon affecting the city. The Arno River discharges approximately 4.6 ×10^15 MPCTOT annually to the Mediterranean Sea. Fluxes are highly dependent on the seasonality, with a MPCTOT delivery of 2.4 ×10^13 particles/day and 1.2 ×10^12 particles/day during wet and dry season, respectively. The total mass of discharged MPCTOT is estimated at about 29 tons/year (t/y); the MPC>60 fraction amounts to about 8 t/y, and MFTEX to about 1 t/y.