New Insights For The Fragmentation Of Plastics Into Microplastics In The Ocean

Pollution of the ocean by plastic litter has become a major environmental problem resulting from its accumulation in terrestrial and marine environments. When mismanaged, plastics enter the aquatic environment where they undergo degradation and fragmentation into microplastics that are now ubiquitous in all aquatic compartments. In addition to the fact that microplastics are impossible to remove from the marine environment, they are even more damaging than the macro waste. Various studies have shown that microplastics are ingested by many types of marine organisms leading to adverse effects at several levels of the food chain and of the marine ecosystems. It is also suspected that microplastics, that constitute a new habitat for micro-organisms, are vectors for potentially pathogenic bacteria.The fate of polymers in the aquatic environment depends both on abiotic phenomena (UV, mechanical stress), and on biotic ones, due to the colonization of plastics by marine micro-organisms (bacteria, phytoplankton, fungi, etc.). A primary step for bio-degradation is the constitution of a biofilm and reduction of the polymer chain length via exo-enzymes produced by bacteria from the biofilm. Once polymer chains are short enough, they can be assimilated by bacteria. While abiotic phenomena lead to the damage and fragmentation of a polymer by oxidation and hydrolysis mechanisms, creation of structural defects and fracture propagation, it is generally admitted that only biotic phenomena will result into the complete bio-degradation of a polymer, i.e. its conversion into biomass, water and CO2. In the marine environment, many questions remain about the relative kinetics of abiotic and biotic degradation and their respective impact in terms of fragmentation. For instance, several papers have recently reported that the size distribution of particles collected in the ocean between 5mm and a few hundreds of microns, does not seem to correspond to a single-kinetic fragmentation process.The erosion patterns of semi-crystalline polymers have been extensively studied in laboratory under enzymatic or bacterial conditions and various degradation patterns have been observed whose occurrence is mainly linked to the difference in the erosion kinetics between crystalline and amorphous regions. To date, there are much less studies addressing how the evolution of these surface patterns will in turn influence the erosion process, lead to fracture and potential fragments generation.In order to study the enzymatic erosion process, we used the well-known model system PDLLA/proteinase K. Being specifically interested in the role of heterogeneities at the scale of a few nanometers to a few micrometers, we used a polymer of a given chemical composition (PDLLA, 1.7% of D-mer, Mn = 95 kg/mol, polydispersity index I=1.63) and monitored its morphology through its change in crystallinity ratio, everything else remaining constant.Three types of samples were studied: 100% amorphous (A), semi-crystalline with 5% (SC5) and 35% (SC35) crystallinity.The samples morphologies were characterized through DSC, polarized optical microscopy (POM) and SEM. Enzymatic erosion kinetics were measured through weight loss experiments for the 3 polymers and the erosion patterns were observed over time through atomic force microscopy (AFM) and SEM. In order to interpret the results, we combined a simple two-phase geometric erosion model with the well-known Michaelis-Menten model for enzymatic kinetics. Our geometric erosion model is based on the evolution of the erosion front with time induced by the erosion rate difference between crystalline and amorphous regions. This new model accounts very well for the experimental results. Moreover, we observed a morphology-dependent release of fragments, which the model is also able to predict. In particular, one observes the release of spherulites as long as they are smaller than a critical size determined in the model. Some important consequences relevant for the understanding of the formation of micro-plastics in the ocean can be drawn from these experiments.