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Emissions of per- and polyfluoroalkyl substances (PFAS) by fluoropolymer production plants
Stockholm University, Faculty of Science, Department of Environmental Science.ORCID iD: 0000-0001-5605-5201
2025 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Per- and polyfluoroalkyl substances (PFAS) are synthetic chemicals of environmental and human health concern due to their persistence, potential toxicities, and potential to bioaccumulate. Fluoropolymers, a subset of polymeric PFAS, consist of a carbon backbone that is fully or partially fluorinated. This structure confers unique properties such as chemical and thermal resistance, as well as hydrophobicity and lipophobicity and has led to diverse industrial and consumer applications of fluoropolymers. As such, these materials are positioned as a significant component of the global fluorochemical industry and economy.

However, fluoropolymer production has raised concerns due to the use, formation, and emission of various non-polymeric PFAS. In response, industry has sought to mitigate its impacts by introducing alternative PFAS, implementing emission abatement technologies, and modifying production processes.

This thesis aimed to determine and characterize PFAS emissions from fluoropolymer production plants (FPPs) in Europe and China by gaining a holistic understanding of production processes to identify sources and emission pathways. Emissions were captured through emission data collection (Paper I) and environmental sampling near FPPs (Papers II-IV) and further characterized through an emission inventory (Paper I), targeted analyses, suspect screening (Papers II-IV), and atmospheric dispersion modelling (Papers II and IV). Differences in management of PFAS emissions by FPPs between China and Europe were investigated by comparing measured atmospheric concentrations and assessing the implications for human exposure.

Results indicated that despite recent emission reduction efforts in the UK and the Netherlands, FPPs remain point sources of various PFAS, including introduced alternatives (Papers I-III). Perfluorooctanoic acid (PFOA), which was listed in the Stockholm Convention on Persistent Organic Pollutants in 2019, was still in use and emitted in large quantities during the sampling period in China in 2019 (Paper IV). Other identified emissions included monomeric PFAS, by-products from monomer production and polymerization, and PFAS used in fluoropolymer processing (Paper I). Furthermore, due to the persistence of PFAS, historical emissions have turned some production sites into contamination hotspots (Paper III).

Atmospheric dispersion modelling (Papers II and IV) showed that part of the atmospheric PFAS emissions could be subject to long-range atmospheric transport and contribute to PFAS loads in remote locations. Thus, PFAS emissions by FPPs not only influenced the local environment, but possibly had global impacts. Measured median concentrations of atmospheric PFAS (Papers II-IV) exceeded guidance values for exposure through inhalation 30 km from the FPP in China. Before the implementation of emission abatement systems, a similar situation could have existed in the Netherlands and the UK, due to emissions of PFOA and its replacements.

Overall, this thesis underscored the need for a broader scope in future research and regulatory efforts, extending beyond specific well-known PFAS to encompass other PFAS emissions by FPPs. Additionally, addressing geographical disparities in PFAS management is crucial for effective global solutions.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science, Stockholm University , 2025. , p. 41
Keywords [en]
PFAS, fluoropolymer production, emissions, environmental sampling, emission inventory, liquid chromatography, high-resolution mass spectrometry, atmospheric dispersion modelling, human exposure
National Category
Environmental Sciences
Research subject
Environmental Sciences
Identifiers
URN: urn:nbn:se:su:diva-239353ISBN: 978-91-8107-116-0 (print)ISBN: 978-91-8107-117-7 (electronic)OAI: oai:DiVA.org:su-239353DiVA, id: diva2:1936674
Public defence
2025-03-28, Högbomsalen, Geovetenskapens Hus, Svante Arrhenius väg 14, 13:30 (English)
Opponent
Supervisors
Available from: 2025-03-05 Created: 2025-02-11 Last updated: 2025-02-24Bibliographically approved
List of papers
1. Emission inventory of PFASs and other fluorinated organic substances for the fluoropolymer production industry in Europe
Open this publication in new window or tab >>Emission inventory of PFASs and other fluorinated organic substances for the fluoropolymer production industry in Europe
2024 (English)In: Environmental Science: Processes & Impacts, ISSN 2050-7887, E-ISSN 2050-7895, Vol. 26, no 2, p. 269-287Article in journal (Refereed) Published
Abstract [en]

Fluoropolymers are a group of fluorinated polymers within the broad class of substances known as per- and polyfluoroalkyl substances (PFASs). During their production, a wide array of additional fluorinated organic substances (many PFASs and some not defined as PFASs) are used, formed and emitted to air and water. This study aims to assess, and make an inventory of, all emissions of PFASs and other fluorinated organic substances by the fluoropolymer production industry in Europe using available emission databases and permits. Air emissions of the fluorinated gases (i.e., chlorofluorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons and perfluorocarbons (CFCs, H(C)FCs and PFCs)) by this industry have reportedly decreased between 2007 and 2021 from roughly 500 to 150 tonnes per year. Emissions of fluorosurfactants to air and water have also been reduced significantly. However, large uncertainties remain regarding the emissions of substances that are neither fluorinated gases nor fluorosurfactants but are classified as PFASs, such as polymerization by-products, chain transfer agents and fluorinated solvents. The available data indicate that the release of these substances is not decreasing but remains relatively stable. As this inventory probably underestimates emissions, further research, improved data availability and more harmonized reporting of emissions are necessary to obtain more accurate emission data for these substances. Nevertheless, based on the available data, it is clear that the emissions from fluoropolymer production plants to air and water are still significant and that the production of fluoropolymers continues to introduce persistent substances to the environment. This study assesses the environmental impact of the fluoropolymer industry in Europe by making an inventory of their emissions of PFASs and other fluorinated organic substances.

National Category
Environmental Sciences
Identifiers
urn:nbn:se:su:diva-226558 (URN)10.1039/d3em00426k (DOI)001143523300001 ()38231136 (PubMedID)2-s2.0-85182909999 (Scopus ID)
Available from: 2024-02-14 Created: 2024-02-14 Last updated: 2025-02-11Bibliographically approved
2. HFPO-DA and other PFAS in air downwind of a fluoropolymer production plant in the Netherlands: measurements and modeling
Open this publication in new window or tab >>HFPO-DA and other PFAS in air downwind of a fluoropolymer production plant in the Netherlands: measurements and modeling
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences
Identifiers
urn:nbn:se:su:diva-239349 (URN)
Available from: 2025-02-10 Created: 2025-02-10 Last updated: 2025-02-11
3. Perfluoro(2-ethoxy-2-fluoroethoxy)-acetic acid (EEA) and other target and suspect PFAS in the vicinity of a fluoropolymer production plant
Open this publication in new window or tab >>Perfluoro(2-ethoxy-2-fluoroethoxy)-acetic acid (EEA) and other target and suspect PFAS in the vicinity of a fluoropolymer production plant
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(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences
Identifiers
urn:nbn:se:su:diva-239350 (URN)
Available from: 2025-02-10 Created: 2025-02-10 Last updated: 2025-02-11
4. Emission of perfluoroalkyl acids and perfluoroalkyl ether carboxylic acids to the atmosphere from a fluorochemical industrial park in China
Open this publication in new window or tab >>Emission of perfluoroalkyl acids and perfluoroalkyl ether carboxylic acids to the atmosphere from a fluorochemical industrial park in China
Show others...
(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences
Identifiers
urn:nbn:se:su:diva-239352 (URN)
Available from: 2025-02-10 Created: 2025-02-10 Last updated: 2025-02-11

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