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Fluorine mass balance in wildlife and consumer products: How much organofluorine are we missing?
Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.ORCID iD: 0000-0002-3409-4389
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Per- and polyfluoroalkyl substances (PFASs) are a class of anthropogenic pollutants. Many PFASs are highly persistent and have been linked to adverse effects in humans. According to latest estimates, there are more than 4700 PFASs in global commerce, which poses immense challenges for environmental monitoring. This thesis aims at the development, validation and application of total fluorine (TF) and extractable organic fluorine (EOF) methods to consumer products and wildlife in order to estimate the fraction of unidentified organic fluorine in these samples via fluorine mass balance calculations.

Fluoropolymer-coated food packaging materials and reference materials were used in paper I to validate and compare the performance of three different TF methods. Combustion ion chromatography (CIC), particle-induced gamma ray emission spectroscopy (PIGE) and instrumental neutron activation analysis (INAA) revealed excellent analytical agreement and precision under most circumstances. PIGE and INAA had the advantage of being non-destructive, while CIC was favored due to low detection limits. Fluorine mass balance experiments indicated large amounts of unidentified EOF and non-extractable fluorine. Paper II investigated the occurrence of PFASs, EOF and TF in cosmetic products from the Swedish market. In addition to extremely high concentrations (up to 470 µg/g) of polyfluoroalkyl phosphate diesters (diPAPs; perfluoroalkyl acid (PFAA) precursors), unintentionally-added PFAAs were found in a number of products, together with large amounts of unidentified organic fluorine. Human exposure estimates for perfluorooctanoate (PFOA) using the latest dermal uptake coefficients revealed that PFAA exposure via cosmetics may be significant. Paper III evaluated time trends of PFASs, EOF and TF in Baltic cod (Gadus morhua) from 1981 to 2013. Increasing trends were observed for the predominant PFAS perfluorooctane sulfonate (PFOS), as well as for C9-C12 perfluoroalkyl carboxylic acids (PFCAs) at rates of up to 7.7% per year. Declining concentrations were detected for the PFOS precursor perfluorooctane sulfonamide (FOSA), the EOF and its fraction not accounted for by target PFASs, while TF did not show any significant trends. The increasing concentrations of PFAAs despite their production phase-out could be attributed to either direct exposure of cod to legacy PFAAs or to indirect exposure via PFAA-precursor metabolism. Furthermore, negative correlations of certain PFASs with liver somatic index and body length were observed, which play an important role in the under-standing of toxicological effects of PFASs on wildlife. Paper IV studied the distribution of PFASs, EOF and TF in tissues from a Greenland killer whale (Orcinus orca). The sum of target PFAS concentrations was highest in liver (339 ng/g) and lowest in blubber (9.4 ng/g), consistent with other tissue distribution studies in marine mammals. In contrast, TF and EOF concentrations were highest in blubber (1315 and 229 ng/g, respectively), suggesting the presence of high concentrations of one or more presently unidentified fluorinated compounds. With the help of high resolution mass spectrometry-based suspect screening, several PFAS homologue series and individual PFASs not included in target analysis were detected.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University , 2019. , p. 24
Keywords [en]
PFASs, PFOS, fluorine mass balance, organofluorine, EOF, TF, wildlife, consumer products, combustion ion chromatography, high resolution mass spectrometry, suspect screening
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
URN: urn:nbn:se:su:diva-167449ISBN: 978-91-7797-596-0 (print)ISBN: 978-91-7797-597-7 (electronic)OAI: oai:DiVA.org:su-167449DiVA, id: diva2:1300861
Public defence
2019-05-17, Nordenskiöldsalen, Geovetenskapens hus, Svante Arrhenius väg 12, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Manuscript.

Available from: 2019-04-24 Created: 2019-03-29 Last updated: 2019-04-25Bibliographically approved
List of papers
1. Total Fluorine Measurements in Food Packaging: How Do Current Methods Perform?
Open this publication in new window or tab >>Total Fluorine Measurements in Food Packaging: How Do Current Methods Perform?
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2019 (English)In: Environmental Science and Technology Letters, E-ISSN 2328-8930, Vol. 6, no 2, p. 73-78Article in journal (Refereed) Published
Abstract [en]

Per- and polyfluoroalkyl substances (PFASs) represent a class of more than 4000 compounds. Their large number and structural diversity pose a considerable challenge to analytical chemists. Measurement of total fluorine in environmental samples and consumer products is therefore critical for rapidly screening for PFASs and for assessing the fraction of unexplained fluorine(i.e., fluorine mass balance). Here we compare three emerging analytical techniques for total fluorine determination: combustion ion chromatography (CIC), particle-induced gamma-ray emission spectroscopy (PIGE), and instrumental neutron activation analysis (INAA). Application of each method to a certified reference material (CRM), spiked filters, and representative food packaging samples revealed good accuracy and precision. INAA and PIGE had the advantage of being nondestructive, while CIC displayed the lowest detection limits. Inconsistencies between the methods arose due to the high aluminum content in the CRM, which precluded its analysis by INAA, and sample heterogeneity (i.e., coating on the surface of the material), which resulted in higher values from the surface measurement technique PIGE compared to the values from the bulk volume techniques INAA and CIC. Comparing CIC-based extractable organic fluorine to target PFAS measurements of food packaging samples by liquid chromatography-tandem mass spectrometry revealed large amounts of unidentified organic fluorine not captured by compound-specific analysis.

National Category
Earth and Related Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-166559 (URN)10.1021/acs.estlett.8b00700 (DOI)000458937300004 ()
Available from: 2019-03-04 Created: 2019-03-04 Last updated: 2019-03-29Bibliographically approved
2. Per- and polyfluoroalkyl substances and fluorine mass balance in cosmetic products from the Swedish market: implications for environmental emissions and human exposure
Open this publication in new window or tab >>Per- and polyfluoroalkyl substances and fluorine mass balance in cosmetic products from the Swedish market: implications for environmental emissions and human exposure
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2018 (English)In: Environmental Science: Processes & Impacts, ISSN 2050-7887, E-ISSN 2050-7895, Vol. 20, no 12, p. 1680-1690Article in journal (Refereed) Published
Abstract [en]

Per- and polyfluoroalkyl substances (PFASs) are a diverse class of >4700 chemicals used in commercial products and industrial processes. Concerns surrounding PFASs are principally due to their widespread occurrence in humans and the environment and links to adverse health effects. One of the lesser known uses for PFASs is in cosmetic products (CPs) which come into contact with the skin (e.g. hair products, powders, sunblocks, etc.). In the present work, thirty-one CPs from five product categories (cream, foundation, pencil, powder and shaving foam) were analyzed for 39 PFASs by liquid chromatography-tandem mass spectrometry, as well as extractable organic fluorine (EOF) and total fluorine (TF) by combustion ion chromatography (CIC). This multi-platform approach enabled determination of the fraction of fluorine accounted for by known PFASs (i.e. fluorine mass balance). Foundations and powders contained 25 different PFASs with the most frequently detected being perfluorinated carboxylic acids (perfluoroheptanoic acid and perfluorohexanoic acid) and polyfluoroalkyl phosphate esters (PAPs). sigma(14)PAP concentrations up to 470 g g(-1) were measured in products listing mixtures of PAPs as an ingredient. For all samples, sigma(39)PFAS concentrations only explained a small fraction of the EOF and TF, pointing to the presence of unknown organic and/or inorganic fluorinated substances, including polymers. While creams, pencil and shaving foams did not contain measurable concentrations of any of the 39 PFASs targeted here, CIC revealed high to moderate TF content. Overall, these data highlight the need for further investigations into the occurrence of PFASs in CPs and their importance with regards to human and environmental exposure.

National Category
Earth and Related Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-163573 (URN)10.1039/c8em00368h (DOI)000453014000004 ()30427048 (PubMedID)
Available from: 2019-01-14 Created: 2019-01-14 Last updated: 2019-03-29Bibliographically approved
3. Temporal trends (1981-2013) of per- and polyfluoroalkyl substances and unidentified organofluorine in Baltic cod
Open this publication in new window or tab >>Temporal trends (1981-2013) of per- and polyfluoroalkyl substances and unidentified organofluorine in Baltic cod
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(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-167447 (URN)
Funder
Swedish Research Council Formas
Available from: 2019-03-29 Created: 2019-03-29 Last updated: 2019-03-29Bibliographically approved
4. High Concentrations of Unidentified Extractable Organofluorine observed in Blubber from a Greenland Killer Whale (Orcinus orca)
Open this publication in new window or tab >>High Concentrations of Unidentified Extractable Organofluorine observed in Blubber from a Greenland Killer Whale (Orcinus orca)
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(English)Manuscript (preprint) (Other academic)
National Category
Environmental Sciences
Research subject
Applied Environmental Science
Identifiers
urn:nbn:se:su:diva-167448 (URN)
Available from: 2019-03-29 Created: 2019-03-29 Last updated: 2019-04-01Bibliographically approved

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