Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals

Sunlight exposure can naturally mitigate microplastics pollution in the surface ocean, however it results in emissions of dissolved organic carbon (DOC) whose characteristics and fate remain largely unknown. In this work, we investigated the effects of solar radiation on polyether (TPU_Ether) and polyester (TPU_Ester) thermoplastic polyurethane, and on a thermoset polyurethane (PU_Hardened). The microplastics were irradiated with simulated solar light with a UV dose of 350 MJ m(-2), which corresponds to roughly 15 months outdoor exposure at 31 degrees N latitude. The particles were characterized using ATR-FTIR and elemental analysis. The DOC released to the aqueous phase was quantified by total organic carbon analysis and characterized by nontarget liquid chromatography coupled to high-resolution mass spectrometry. Polyurethane microplastics were degraded following mechanisms reconcilable with UV photo-oxidation. The carbon mass fraction released to the aqueous phase was 8.5 +/- 0.5%, 3.7 +/- 0.2%, and 2.8 +/- 0.2% for TPU_Ether, TPU_Ester, and PU_Hardened, respectively. The corresponding DOC release rates, expressed as mg carbon per UV dose were 0.023, 0.013, and 0.010 mg MJ(-1) for TPU_Ether, TPU_Ester and PU_Hardened, respectively. Roughly three thousand unique by-products were released from photo-weathered TPUs, whereas 540 were detected in the DOC of PU_Hardened. This carbon pool was highly complex and dynamic in terms of physicochemical properties and susceptibility to further photodegradation after dissolution from the particles. Our results show that plastics photodegradation in the ocean requires chemical assessment of the DOC emissions in addition to the analysis of aged microplastics and that polymer chemistry influences the chain scission products.

Automated summary

Sunlight exposure can reduce microplastics pollution in the surface ocean, but it also leads to the release of dissolved organic carbon (DOC) with unknown characteristics and fate. This study investigated the effects of solar radiation on different types of polyurethane microplastics and their release of DOC. The results showed that polyurethane microplastics were degraded by UV photo-oxidation, and the released DOC varied among different types of polyurethane. Chemical assessment of DOC emissions and analysis of aged microplastics are both necessary to understand plastic photodegradation in the ocean.