Identification of polymer types and additives in marine microplastic particles using pyrolysis-GC/MS and scanning electron microscopy

Abstract

Any assessment of plastic contamination in the marine environment requires knowledge of the polymer type and the additive content of microplastics. Sequential pyrolysis-gas chromatography coupled to mass spectrometry (Pyr-GC/MS) was applied to simultaneously identify polymer types of microplastic particles and associated organic plastic additives (OPAs). In addition, a scanning electron microscope equipped with an energy-dispersive X-ray microanalyser was used to identify the inorganic plastic additives (IPAs) contained in these particles. A total of ten particles, which were optically identified as potentially being plastics, were extracted from two sediment samples collected from Norderney, a North Sea island, by density separation in sodium chloride. The weights of these blue, white and transparent fragments varied between 10 and 350 μg. Polymer types were identified by comparing the resulting pyrograms with those obtained from the pyrolysis of selected standard polymers. The particles consisted of polyethylene (PE), polypropylene, polystyrene, polyamide, chlorinated PE and chlorosulfonated PE. The polymers contained diethylhexyl phthalate, dibutyl phthalate, diethyl phthalate, diisobutyl phthalate, dimethyl phthalate, benzaldehyde and 2,4-di-tert-butylphenol. Sequential Py-GC/MS was found to be an appropriate tool for identifying marine microplastics for polymer types and OPAs. The IPAs identified were titanium dioxide nanoparticles (TiO₂-NPs), barium, sulphur and zinc. When polymer–TiO₂ composites are degraded in the marine environment, TiO₂-NPs are probably released. Thus, marine microplastics may act as a TiO₂-NP source, which has not yet been considered.