Enzymatic Synthesis and Structural Modeling of Bio-Based Oligoesters as an Approach for the Fast Screening of Marine Biodegradation and Ecotoxicity.

Given the widespread use of esters and polyesters in products like cosmetics, fishing nets, lubricants and adhesives, whose specific application(s) may cause their dispersion in open environments, there is a critical need for stringent eco-design criteria based on biodegradability and ecotoxicity evidence. Our approach integrates experimental and computational methods based on short oligomers, offering a screening tool for the rapid identification of sustainable monomers and oligomers, with a special focus on bio-based alternates. We provide insights into the relationships between the chemical structure and properties of bio-based oligomers in terms of biodegradability in marine environments and toxicity in benchmark organisms. The experimental results reveal that the considered aromatic monomers (terephthalic acid and 2,5-furandicarboxylic acid) accumulate under the tested conditions (OECD 306), although some slight biodegradation is observable when the inoculum derives from sites affected by industrial and urban pollution, which suggests that ecosystems adapt to non-natural chemical pollutants. While clean seas are more susceptible to toxic chemical buildup, biotic catalytic activities offer promise for plastic pollution mitigation. Without prejudice to the fact that biodegradability inherently signifies a desirable trait in plastic products, nor that it automatically grants them a sustainable "license", this study is intended to facilitate the rational design of new polymers and materials on the basis of specific uses and applications.

Robinia pseudoacacia L. (Black Locust) Leaflets as Biomonitors of Airborne Microplastics.

Here we investigate the suitability of Robinia pseudoacacia L. (black locust) leaflets as a novel biomonitor of airborne microplastics (MPs) including tyre wear particles (TWPs). Leaflets were collected from rural roadside locations (ROs, n = 5) and urban parks (UPs, n = 5) in Siena, Italy. MPs were removed by washing, identified by stereomicroscope, and analysed for polymer type by Fourier transform infrared spectroscopy. Daily MP deposition was estimated from leaf area. The mass magnetic susceptibility and the bioaccumulation of traffic-related potentially toxic elements (PTEs) were also analysed. The total number of MPs at ROs was significantly higher at 2962, dominated by TWPs, compared with 193 in UPs, where TWPs were not found. In contrast, total microfibres were significantly higher in UPs compared with ROs (185 vs. 86). Daily MP deposition was estimated to range from 4.2 to 5.1 MPs/m2/d across UPs and 29.9-457.6 MPs/m2/d across ROs. The polymer types at ROs were dominated by rubber (80%) from TWPs, followed by 15% polyamide (PA) and 5% polysulfone (PES), while in UPs the proportion of PES (44%) was higher than PA (22%) and polyacrylonitrile (11%). The mean mass magnetic susceptibility, a proxy of the bioaccumulation of traffic-related metallic particles, was higher at ROs (0.62 ± 0.01 10-8 m3/kg) than at UPs (-0.50 ± 0.03 10-8 m3/kg). The content of PTEs was similar across sites, except for significantly higher concentrations of Sb, a tracer of vehicle brake wear, at ROs (0.308 ± 0.008 µg/g) compared with UPs (0.054 ± 0.006 µg/g). Our results suggest that the waxy leaflets and easy determination of surface area make Robinia an effective biomonitor for airborne MPs including TWPs.