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Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in an aquatic ecosystem [Elektronische Ressource] : distribution and fate / Anna Maria Becker

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111 pages
University of Bayreuth Chair of Environmental Chemistry and Ecotoxicology Perfluorooctanoic Acid (PFOA) and Perfluorooctane Sulfonate (PFOS) in an Aquatic Ecosystem - Distribution and Fate Dissertation Faculty of Biology, Chemistry and Geosciences University of Bayreuth Anna Maria Becker Bayreuth, 2008 Die vorliegende Arbeit wurde in der Zeit vom 15.11.2004 bis 30.06.2008 in der Forschungs-stelle Umweltchemie und Ökotoxikologie unter der Betreuung von Herrn Prof. Hartmut Frank angefertigt. Vollständiger Abdruck der, von der Fakultät für Biologie, Chemie und Geowissenschaften der Universität Bayreuth genehmigten Dissertation zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.). Promotionsgesuch eingerichtet am: 02.10.2008 Tag des wissenschaftilichen Kolloquiums: 03.12.2008 Prüfungsausschuss: Prof. Hartmut Frank (1. Gutachter) Prof. Stefan Peiffer (2. Gutachter) Prof. Cornelius Zetzsch (Vorsitz) Prof. Helmut Alt Prof. Karlheinz Seifert For Alex Acknowledgements I would like to thank Prof. Dr. Hartmut Frank for giving me the opportunity to work at the Chair of Environmental Chemistry and Ecotoxicology with such a challenging and exciting topic as perfluorinated surfactants. His guidance and stimulating remarks were of great help through the whole project. Special thanks are directed to Dr.
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University of Bayreuth
Chair of Environmental Chemistry and Ecotoxicology











Perfluorooctanoic Acid (PFOA) and Perfluorooctane Sulfonate (PFOS)
in an Aquatic Ecosystem - Distribution and Fate




Dissertation
Faculty of Biology, Chemistry and Geosciences
University of Bayreuth







Anna Maria Becker






Bayreuth, 2008
Die vorliegende Arbeit wurde in der Zeit vom 15.11.2004 bis 30.06.2008 in der Forschungs-
stelle Umweltchemie und Ökotoxikologie unter der Betreuung von Herrn Prof. Hartmut Frank
angefertigt.

Vollständiger Abdruck der, von der Fakultät für Biologie, Chemie und Geowissenschaften der
Universität Bayreuth genehmigten Dissertation zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften (Dr. rer. nat.).









Promotionsgesuch eingerichtet am: 02.10.2008
Tag des wissenschaftilichen Kolloquiums: 03.12.2008

Prüfungsausschuss:
Prof. Hartmut Frank (1. Gutachter)
Prof. Stefan Peiffer (2. Gutachter)
Prof. Cornelius Zetzsch (Vorsitz)
Prof. Helmut Alt
Prof. Karlheinz Seifert


















For Alex Acknowledgements
I would like to thank Prof. Dr. Hartmut Frank for giving me the opportunity to work at the
Chair of Environmental Chemistry and Ecotoxicology with such a challenging and exciting
topic as perfluorinated surfactants. His guidance and stimulating remarks were of great help
through the whole project.
Special thanks are directed to Dr. Silke Gerstmann for her engagement, support and scientific
discussions. She helped me realise what I am capable of and made sure I never forget it.
I am very grateful to Dr. Radomir Čabala for his assistance and tips related to the instrument.
I am thankful to Benjamin Schmidt for his active support in the laboratory and during sam-
pling campaigns.
Many thanks to Irmgard Lauterbach, Dr. Kamila Jakubowska- Świtaj, Dr. Franziska Knabe,
Monika Weckert, Joanna Znaleziona, Magdalena Suchan, Katja Bäuml, Michael Heyers,
Stefan Will, Agnes Bednorz and other colleagues from the Chair of Environmental Chemistry
and Ecotoxicology for their support and good working atmosphere.
Financial support of the Bayerische Forschungsstiftung is acknowledged.
I would like to express my gratitude to Dr. Klupp and the employees of the Bavarian Fishery
Association and of the waste water treatment plant of Bayreuth for their cooperation.
Last but not least I could not forget to thank my husband and parents for their constant sup-
port and belief in me.
Table of Content
Table of Content

Table of Content ...................................................................................................................... I
List of Publications and Author’s Contribution................................................................ III
List of Abbreviations..............................................................................................................V
List of Tables........................................................................................................................VII
List of Figures .................................................................................................................... VIII
Summary ............................................................................................................................... IX
Zusammenfassung ................................................................................................................ XI
1 Introduction .....................................................................................................................1
1.1 Perfluorinated Surfactants (PFSs) – Background, Production and Use ........................1
1.2 Physico-Chemical Properties of PFOA and PFOS........................................................3
1.3 Sources of PFOA and PFOS in the Environment..........................................................4
1.4 Environmental Concentrations of PFOA and PFOS .....................................................4
1.4.1 Air and Precipitation...............................................................................................5
1.4.2 Aquatic Samples ......................................................................................................6
1.4.3 Solid Matrices..........................................................................................................8
1.4.4 Biota ......................................................................................................................10
1.4.4.1 Concentrations in Biological Samples.........................................................10
1.4.4.2 Temporal Trends .........................................................................................13
1.4.5 Humans..................................................................................................................14
1.5 Toxicity........................................................................................................................16
1.5.1 Bioaccumulation and Biomagnification Potential ................................................16
1.5.2 Ecotoxicity .............................................................................................................18
1.5.3 Human Toxicity and Health Risk Assessment........................................................19
1.6 Analytical Methods for PFOA and PFOS Determination ...........................................21
1.6.1 Historical Analytical Methods...............................................................................21
1.6.2 Analysis of Air Samples .........................................................................................22
1.6.3 Analysis of Aqueous Samples ................................................................................23
1.6.4 Analysis of Solid Matrices .....................................................................................24
1.6.5 Analysis of Biota and Human Samples..................................................................25
2 Aim of the Work ............................................................................................................27
I Table of Content
3 Optimised Analytical Procedures ................................................................................28
3.1 Sample Preparation Procedures...................................................................................28
3.1.1 River and Waste Water..........................................................................................28
3.1.2 Sludge and Sediment..............................................................................................28
3.1.3 Fish ........................................................................................................................29
3.2 HPLC-ESI-MS/MS......................................................................................................29
3.3 Quantification ..............................................................................................................29
3.4 Sampling Campaigns...................................................................................................30
3.4.1 River Water, Waste Water and Sludge ..................................................................30
3.4.2 Sediment ................................................................................................................30
3.4.3 Fish30
4 Results and Discussion ..................................................................................................32
4.1 Optimisation of Analytical Protocols ..........................................................................32
4.2 River, Waste Water and Sludge...................................................................................33
4.2.1 River waters...........................................................................................................33
4.2.2 Liquid and solid wastes .........................................................................................34
4.3 Sediments ....................................................................................................................35
4.4 Fish ..............................................................................................................................36
5 Conclusions and Recommendations ............................................................................38
6 Publication I ...................................................................................................................40
7 Publication II .................................................................................................................45
8 Publication III................................................................................................................52
9 Publication IV63
10 Publication V..................................................................................................................66
Bibliography....................................................................................................................... XIII
Ehrenwörtliche Erklärung .............................................................................................XXXI

II List of Publications and Author’s Contribution
List of Publications and Author’s Contribution

The following cumulative doctoral thesis “Perfluorooctanoic Acid (PFOA) and Perfluorooc-
tane Sulfonate (PFOS) in an Aquatic Ecosystem - Distribution and Fate” is based on the sci-
entific publications listed below. Three of them are published and two others have been sub-
mitted for publication. Author’s contribution to each of them is given below.

Publication I
Weremiuk, A.M., Gerstmann, S., Frank, H. 2006. Quantitative Determination of Perfluori-
nated Surfactants in Water by LC-ESI-MS/MS. J. Sep. Sci. 29, 2251 – 2255.
Own contribution: idea (50 %), field work (80 %), laboratory work and data evaluation
(70 %), writing (70 %).

Publication II
Becker, A.M., Gerstmann, S., Frank, H. 2008. Perfluorooctane Surfactants in Waste Waters,
the Major Source of River Pollution. Chemosphere, 72, 115-121.
Own contribution: idea (70 %), field work (80 %), laboratory work and data evaluation
(85 %), writing (70 %).

Publication III
Becker, A.M., Suchan, M., Gerstmann, S., Frank, H. 2008. Perfluorooctanoic Acid and Per-
fluorooctane Sulfonate Released from a Waste Water Treatment Plant in Bavaria, Germany.
Submitted for publication to Environ. Sci. Poll. Res..
Own contribution: idea (90 %), field and laboratory work (30 %), data evaluation (50 %),
writing (80 %).
III List of Publications and Author’s Contribution
Publication IV
Becker, A.M., Gerstmann, S., Frank, H. 2008. Perfluorooctanoic Acid and Perfluorooctane
Sulfonate in the Sediment of the Roter Main River, Bayreuth. Environ. Poll. In Press.
Own contribution: idea (80 %), field work (70 %), laboratory work and data evaluation
(90 %), writing (80 %).

Publication V
Becker, A.M., Gerstmann, S., Frank, H. 2008. Perfluorooctanoic Acid and Perfluorooctane
Sulfonate in Two Fish Species Collected from the Roter Main River, Bayreuth, Germany.
Submitted to Bull. Environ. Contam. Toxicol.
Own contribution: idea (80 %), field work (20 %), laboratory work and data evaluation
(90 %), writing (80 %).
IV List of Abbreviations
List of Abbreviations

APPI-MS – atmospheric pressure photoionisation mass spectrometry
API – atmospheric pressure chemical ionisation
ASE – accelerated solvent extraction
BLfU – Bayerischer Landesamt für Umwelt, Bavarian State Office for Environment
dw – dry weight
EFC – electrochemical fluorination
ESI-MS/MS – electrospray ionisation coupled to tandem mass spectrometry detection
FTOHs – fluorotelomer alcohols
GC-ECD – gas chromatography coupled with electron capture detection
GFF – glass fibre filter
HPLC – high performance liquid chromatography
LC – liquid chromatography
LC-MS – liquid chromatography coupled to mass spectrometry
LOD – limit of detection
LOQ – limit of quantification
MeOH – methanol
na – not analysed
nd – not detected
NMR – nuclear magnetic resonance
NY – New York State
OECD – Organisation for Economic Co-Operation and Development
PFOA – perfluorooctanoic acid/ perfluorooctanoate
PFOS – perfluorooctane sulfonate
PFCs – perfluorocarboxylates
PFSs – perfluorinated surfactants
PFE – pressurised fluid extraction
POSF – perfluorooctanesulfonyl fluoride
PTFE – polytetrafluoroethylen
SPE – solid phase extraction
SPME – solid phase microextraction
TOF – time-of-flight
TOC – total organic carbon
V List of Abbreviations
UK – United Kingdom
USA – United States of America
ww – wet weight
WWTP – waste water treatment plant

VI