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...

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Main Authors: Albergamo, Vittorio, Wohlleben, Wendel, Plata, Desirée L
Other Authors: Massachusetts Institute of Technology. Department of Civil and Environmental Engineering
Format: Article
Language:English
Published: Royal Society of Chemistry (RSC) 2023
Online Access:https://hdl.handle.net/1721.1/148452
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author Albergamo, Vittorio
Wohlleben, Wendel
Plata, Desirée L
author2 Massachusetts Institute of Technology. Department of Civil and Environmental Engineering
author_facet Massachusetts Institute of Technology. Department of Civil and Environmental Engineering
Albergamo, Vittorio
Wohlleben, Wendel
Plata, Desirée L
author_sort Albergamo, Vittorio
collection MIT
description 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° N latitude. The particles were characterized using ATRFTIR 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.
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spelling mit-1721.1/1484522023-03-10T03:16:43Z Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals Albergamo, Vittorio Wohlleben, Wendel Plata, Desirée L Massachusetts Institute of Technology. Department of Civil and Environmental Engineering 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° N latitude. The particles were characterized using ATRFTIR 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. 2023-03-09T19:41:10Z 2023-03-09T19:41:10Z 2023-01-24 2023-03-09T19:19:31Z Article http://purl.org/eprint/type/JournalArticle https://hdl.handle.net/1721.1/148452 Albergamo, Vittorio, Wohlleben, Wendel and Plata, Desirée L. 2023. "Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals." Environmental Science: Processes & Impacts. en 10.1039/d2em00415a Environmental Science: Processes & Impacts Creative Commons Attribution NonCommercial License 3.0 https://creativecommons.org/licenses/by-nc/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry (RSC)
spellingShingle Albergamo, Vittorio
Wohlleben, Wendel
Plata, Desirée L
Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals
title Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals
title_full Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals
title_fullStr Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals
title_full_unstemmed Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals
title_short Photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals
title_sort photochemical weathering of polyurethane microplastics produced complex and dynamic mixtures of dissolved organic chemicals
url https://hdl.handle.net/1721.1/148452
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AT wohllebenwendel photochemicalweatheringofpolyurethanemicroplasticsproducedcomplexanddynamicmixturesofdissolvedorganicchemicals
AT platadesireel photochemicalweatheringofpolyurethanemicroplasticsproducedcomplexanddynamicmixturesofdissolvedorganicchemicals