Fate and transport of forever chemicals in the aquatic environment: Partitioning and biotransformation of mixtures of Per- and Polyfluoroalkyl Substances (PFAS) from different point sources and resulting concentrations in biota

ISBN 978-82-326-5853-4 (printed ver.) ISBN 978-82-326-5392-8 (electronic ver.) ISSN 1503-8181 (printed ver.) ISSN 2703-8084 (online ver.)

Doctoral theses at NTNU, 2021:89

Håkon Austad Langberg

Fate and transport of forever chemicals in the aquatic

environment

Partitioning and biotransformation of mixtures of Per- and Polyfluoroalkyl Substances (PFAS) from different point

sources and resulting concentrations in biota

Doctor al thesis

Doctoral theses at NTNU, 2021:89Håkon Austad Langberg NTNU Norwegian University of Science and Technology Thesis for the Degree of Philosophiae Doctor Faculty of Natural Sciences Department of Biology

Håkon Austad Langberg

Fate and transport of forever chemicals in the aquatic

environment

Partitioning and biotransformation of mixtures of Per- and Polyfluoroalkyl Substances (PFAS) from different point sources and resulting concentrations in biota

Thesis for the Degree of Philosophiae Doctor Trondheim, March 2021

Norwegian University of Science and Technology Faculty of Natural Sciences

Department of Biology

NTNU

Norwegian University of Science and Technology Thesis for the Degree of Philosophiae Doctor Faculty of Natural Sciences

Department of Biology

© Håkon Austad Langberg

ISBN 978-82-326-5853-4 (printed ver.) ISBN 978-82-326-5392-8 (electronic ver.) ISSN 1503-8181 (printed ver.)

ISSN 2703-8084 (online ver.) Doctoral theses at NTNU, 2021:89 Printed by NTNU Grafisk senter

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ACKNOWLEDGEMENTS

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KEY TERMS AND PHRASES

PFAS

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PFAS mixture

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Hot spots and point sources

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Environmental fractionation

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Source tracking and fingerprinting

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LIST OF TABLES

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LIST OF PAPERS

7KLVWKHVLVFRQVLVWVRIILYHSDSHUV

3DSHU, /DQJEHUJ+$+DOH6(%UHHGYHOG*'-HQVVHQ%0DQG-DUWXQ 0 µPFAS fingerprints in fish from Norwegian freshwater bodies subject to different source inputs¶6XEPLWWHGWR(QYLURQPHQWDO6FLHQFH 7HFKQRORJ\

3DSHU,, /DQJEHUJ+$$US+3%UHHGYHOG*'6OLQGH*$*U¡QQLQJ +0+¡LV WHUc-DUWXQ05XQGEHUJHW7-HQVVHQ%0DQG+DOH 6(µPaper product production identified as the main source of per- and polyfluoroalkyl substances (PFAS) in a Norwegian lake:

source and historic emission tracking¶ (QYLURQPHQWDO 3ROOXWLRQ KWWSVGRLRUJMHQYSRO

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µFluorinated Precursor Compounds in Sediments as a Source of Perfluorinated Alkyl Acids (PFAA) to Biota¶ (QYLURQPHQWDO

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3DSHU,9 /DQJEHUJ + $ %UHHGYHOG * ' *U¡QQLQJ + 0 .YHQQnV 0 -HQVVHQ % 0 DQG +DOH 6 ( µBioaccumulation of Fluorotelomer Sulfonates and Perfluoroalkyl Acids in Marine Organisms Living in Aqueous Film-Forming Foam Impacted Waters¶ (QYLURQPHQWDO 6FLHQFH 7HFKQRORJ\ SS ± GRLDFVHVWE

3DSHU9 $OL$0/DQJEHUJ+$+DOH6(.DOOHQERUQ5+DUW]:) 0RUWHQVHQ c. &LHVLHOVNL 7 0 0F'RQRXJK & $ +DUW] : -HQVVHQ % 0 DQG %UHHGYHOG * ' µThe fate of poly- and perfluoroalkyl substances in a marine food web influenced by land- based sources in the Norwegian Arctic¶6XEPLWWHGWR(QYLURQPHQWDO 6FLHQFH3URFHVVHV ,PSDFWV

Declaration of contribution:

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INTRODUCTION

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Time Period Event References

1920 The first PFAS, perfluoroacetic acid, was synthesized Krafft and Riess (2015b) and references therein 1926 The first perfluoroalkane, carbon tetrafluoride, was

isolated

Krafft and Riess (2015b) and references therein 1938 The serendipitous discovery of

poly(tetrafluoroethylene) (PFTE, (e.g. Teflon))

Krafft and Riess (2015b); Lemal (2004) and references therein 1940s

The first applications of fluorocarbon chemistry: The Manhattan Project required extremely inert materials for the separation of uranium isotopes

Lemal (2004) and references therein

1947 Large scale PFCA production began using electrochemical fluorination (ECF).

Prevedouros et al.

(2006); Dorrance et al.

(2017) and references therein

1949-2000 Large scale manufacture of PFOSF based products (including PFOS) using ECF.

Paul et al. (2009);

Dorrance et al. (2017) and references therein 1960s-1970s PFCA based AFFF were produced Prevedouros et al.

(2006) 1960s The first teflon frying pan, "The Happy Pan" reached

the market

The New York Times (1986)

1970s-2002 AFFF based on POSF were produced and largely replaced PFCA based AFFF

Prevedouros et al.

(2006); Dorrance et al.

(2017) and references therein

1970s

High concentrations of organic fluorine were detected in the blood of workers at a perfluorochemical production factory

Krafft and Riess (2015b) and references therein

1970s Large scale PFAS production using telomerization

Prevedouros et al.

(2006) and references therein

Late 1970s- present

Fluorotelomer based AFFF were produced. They were used to a large extent after the PFOS phase-out in the early 2000s.

Prevedouros et al.

(2006); Dorrance et al.

(2017) and references therein

1974 POSF based PFAS introduced in paper products Olsen et al. (2005) 1995 Fluorotelomer based PFAS commercialized for use in

paper products Lee and Mabury (2011)

2000-2002

3M voluntarily phase-out PFOA and PFOS and other POSF related products due to concerns about toxicological and environmental impacts.

Dorrance et al. (2017) and references therein 2002 PFOS is no longer produced in the United States. Dorrance et al. (2017)

and references therein

Time Period Event References

2002

DuPont took over large scale PFOA production. As DuPont used telomerization, this became the dominate production technique for PFOA production.

Dorrance et al. (2017) and references therein

2000s Asian PFAS production increases, leading to a shift in global emission pathways

Krafft and Riess (2015a) and references therein

2006-2015

Eight global companies, including DuPont, stopped the production of PFOA and related PFAS and their precursors. Many PFAS based products were reformulated to contain PFAS with alternative chemistries

Dorrance et al. (2017) and references therein

2007 PFOS based AFFF is phased-out in Norway. Replaced by fluorotelomer based AFFF

Norwegian Government (2006)

2009 PFOS including its salts and POSF are included in the Stockholm convention

UNEP - The Stockholm Convention (2019)

2012-2015 All PFAS based firefighting foams are phased out in Norway

The Norwegian Defence Estates Agency, personal

communication, C.E.

Amundsen, June 2016

2013

PFOS and its derivatives are included as a priority hazardous substance under the EU Water Framework Directive. Annual average value Environmental Quality Standard (AA-EQS) values of 0.65 ng L^-1 and 0.13 ng L^-1 were set for PFOS in inland surface waters and in seawater, respectively. An EQS of 9.1 μg kg^-1 was set for PFOS in biota

Directive 2013/39/EU (2013)

2019 PFOA including its salts and precursors are included in the Stockholm convention

United Nations Environment Programme - The Stockholm Convention (2019)

2019

HFPO-DA (tradename GenX) its salts and its acyl halides, are identified as substances of very high concern by the European Union under the regulation Registration, Evaluation, Authorisation and

Restriction of Chemicals (REACH)

Perfluorobutane sulfonic acid (PFBS) and its salts are identified as substances of very high concern under REACH

(European Chemicals Agency, 2019a, 2019b)

2020

The European Food Safety Authority (EFSA) set a safety threshold for tolerable weekly intake (TWI) of PFOA, PFOS, perfluorononanoic acid (PFNA), and perfluorohexanesulfonic acid (PFHxS) of 4.4 nanograms per kilogram of body weight per week

European Food Safety Authority (2020);

Schrenk et al. (2020)

PFAS in the environment: sources, fate and transport Sources of PFAS to the environment

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