Microplastic Mass Concentrations and Distribution in German Bight Waters by Pyrolysis-Gas Chromatography-Mass Spectrometry/Thermochemolysis Reveal Potential Impact of Marine Coatings: Do Ships Leave Skid Marks?

ABSTRACT

In this first mass-related survey of microplastics (MPs, <1 mm) in the German Bight (North Sea, 2.5 m water depth), spatial load, temporal variations, and potential sources were examined. Relevant plastic types were detected using pyrolysis-gas chromatography-mass spectrometry/thermochemolysis (Py-GC/MS). This suitable method provides qualitative and trace-level polymer or polymer cluster-specific mass quantitative MP data. Neither MP concentration (2-1396 µg m-3) nor type distribution was homogeneous. Concentrations appeared to be substantially influenced by meteorological and oceanographic conditions. The coastal MP-type composition showed an overprint indicating a packaging waste-related signal. Considerably different compositions were observed in central and estuarine areas. Here, a close relation to marine (antifouling) coating particles, i.e., abrased chlorinated rubber-, acryl-styrene-, and epoxide binder-containing particles are hypothesized as the main MP source, indicating ship "skid marks". They represent a dominant, toxicologically relevant but underestimated marine-based MP share, inverting the widely cited 80% terrestrial- to 20% marine-based debris ratio for MPs. In consequence of the findings, polymer clusters attributed to the basic polymers polyethylene, polypropylene, polystyrene, poly(ethylene terephthalate), poly(vinyl chloride), poly(methyl methacrylate), and polycarbonate are proposed for Py-GC/MS MPs mass determination based on specific thermal decomposition products linked to related polymer structural units.