Atmospheric distribution and seasonality of airborne polyfluorinated compounds [Elektronische Ressource] : spatial and temporal concentration variations from ship-and land-based measurements in Northern Germany, the Atlantic Ocean, and Polar regions / vorgelegt von Annekatrin Dreyer

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Atmospheric Distribution and Seasonality of Airborne Polyfluorinated Compounds Spatial and Temporal Concentration Variations from Ship- and Land-Based Measurements in Northern Germany, the Atlantic Ocean, and Polar Regions Dissertation zur Erlangung des Grades Doktor der Naturwissenschaften (Dr. rer. nat.) an der Fakultät Biologie/Chemie/Geowissenschaften der Universität Bayreuth vorgelegt von Annekatrin Dreyer geb. am 05.02.1980 in Wismar Bayreuth, Mai 2009 Die Arbeiten zur vorliegenden Dissertation wurden in der Zeit von April 2006 bis Mai 2009 in der Abteilung Umweltchemie des Instituts für Küstenforschung am GKSS Forschungszentrum durchgeführt. Vollständiger Abdruck der von der Fakultät für Chemie/Biologie/Geowissenschaften der Universität Bayreuth genehmigten Dissertation zur Erlangung des Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.). Tag der Einreichung: 19.05.2009 Tag des wissenschaftlichen Kolloquiums: 10.12.2009 Prüfungsausschuss: Prof. Dr. Thomas Foken (Vorsitzender) Hartmut Frank (1. Gutachter) Prof. Dr. Ralf Ebinghaus (2. Prof. Dr. Cornelius Zetzsch PD Dr. Bruno Glaser We had the experience but missed the meaning, And approach to the meaning restores the experience in a different form T. S. Eliot TABLE OF CONTENTS Table of Contents ....
Publié le : jeudi 1 janvier 2009
Lecture(s) : 26
Source : OPUS.UB.UNI-BAYREUTH.DE/VOLLTEXTE/2010/652/PDF/DISS_DREYER.PDF
Nombre de pages : 254
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Atmospheric Distribution and Seasonality
of Airborne Polyfluorinated Compounds

Spatial and Temporal Concentration Variations from Ship-
and Land-Based Measurements in Northern Germany,
the Atlantic Ocean, and Polar Regions






Dissertation zur Erlangung des Grades
Doktor der Naturwissenschaften
(Dr. rer. nat.)
an der Fakultät Biologie/Chemie/Geowissenschaften
der Universität Bayreuth


vorgelegt von

Annekatrin Dreyer
geb. am 05.02.1980 in Wismar


Bayreuth, Mai 2009




Die Arbeiten zur vorliegenden Dissertation wurden in der Zeit von April 2006 bis Mai 2009
in der Abteilung Umweltchemie des Instituts für Küstenforschung am GKSS
Forschungszentrum durchgeführt.



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








Tag der Einreichung: 19.05.2009

Tag des wissenschaftlichen Kolloquiums: 10.12.2009



Prüfungsausschuss:

Prof. Dr. Thomas Foken (Vorsitzender) Hartmut Frank (1. Gutachter)
Prof. Dr. Ralf Ebinghaus (2.
Prof. Dr. Cornelius Zetzsch
PD Dr. Bruno Glaser





























We had the experience but missed the meaning,
And approach to the meaning restores the experience in a different form
T. S. Eliot


TABLE OF CONTENTS

Table of Contents
............................................................................................................................... i
List of Figures ................................................................................................................................... iv
List of Tables ................................................................................................................................... vii
Abbreviations .................................................................................................................................... x
Summary ......................................................................................................................................... xiii
Zusammenfassung .......................................................................................................................... xvi

Extended Summary .............................................................................................................. 1
1. Introduction .............................................................................................................................. 3
1.1. Rationale ........................................................................................................................................ 3
1.2. Background .................................................................................................................................... 4
1.3. Environmental Concerns ................................................................................................................ 8
1.3.1. Persistence .................................................................................................................................. 8
1.3.2. Bioaccumulation ......................................................................................................................... 9
1.3.3. Toxicity .................................................................................................................................... 10
1.3.4. Long-Range Transport .............................................................................................................. 12
1.4. Atmospheric Chemistry of Polyfluorinated Compounds ............................................................. 17
1.5. Research Objectives ..................................................................................................................... 18
2. Experimental ........................................................................................................................... 20
2.1. Sampling ...................................................................................................................................... 20
2.2. Extraction ..................................................................................................................................... 22
2.3. Instrumental Analysis & Quantification ...................................................................................... 24
2.4. Quality Assurance & Quality Control .......................................................................................... 25
2.5. Air Mass Back Trajectories .......................................................................................................... 25
3. Results & Discussion .............................................................................................................. 26
3.1. Synopsis of PFC Concentrations in Ambient Air ........................................................................ 26
3.2. Temporal Concentration Variations of Polyfluorinated Compounds in Ambient Air .................. 27
3.3. Spatial Concentration Distribution of Polyfluorinated Compounds in Ambient Air ................... 29
3.4. Influence of Air Mass Origin on Concentrations of Polyfluorinated Compounds ....................... 31
3.5. Atmospheric Residence Times ..................................................................................................... 33
3.6. Where Did They Come From? – A Discussion About Sources of Atmospheric Polyfluorinated
Compounds .................................................................................................................................. 34
4. Conclusion ............................................................................................................................... 37
References ........................................................................................................................................ 39
Contributions to the Included Studies .......................................................................................... 53

Cumulative Study ................................................................................................................ 55
Study 1
An Optimized Method Avoiding Solvent-Induced Response Enhancement in the Analysis
of Volatile and Semi-Volatile Polyfluorinated Alkylated Compounds Using Gas
Chromatography-Mass Spectrometry ..................................................................................... 57
i
TABLE OF CONTENTS

Abstract ............................................................................................................................................ 59
Keywords ......................................................................................................................................... 59
1. Introduction ............................................................................................................................ 59
2. Experimental ........................................................................................................................... 61
2.1. Chemicals ..................................................................................................................................... 61
2.2. Sample Preparation ...................................................................................................................... 62
2.3. Instrumental Analysis & Quantification ...................................................................................... 63
2.4. Quality Assurance & Quality Control .......................................................................................... 64
3. Results & Discussion .............................................................................................................. 65
3.1. Recovery Experiments on Solvents ............................................................................................. 65
3.2. Extraction Experiments ................................................................................................................ 69
Acknowledgements ......................................................................................................................... 72
References ........................................................................................................................................ 72
Supporting Information ................................................................................................................. 75
Study 2
Annual Time Series of Air Concentrations of Polyfluorinated Compounds ........................ 91
Abstract ............................................................................................................................................ 93
1. Introduction ............................................................................................................................ 93
2. Experimental ........................................................................................................................... 96
2.1. Sampling & Sample Analysis ...................................................................................................... 96
2.2. Blanks .......................................................................................................................................... 98
2.3. Trajectory Analysis ...................................................................................................................... 98
2.4. Statistical Analysis ....................................................................................................................... 99
3. Results & Discussion .............................................................................................................. 99
3.1. Concentrations & Proportions of Polyfluorinated Compounds .................................................... 99
3.2. Air Mass Origin ......................................................................................................................... 103
3.3. Intra-Annual Variations ............................................................................................................. 105
3.4. Correlation Analyses .................................................................................................................. 107
Acknowledgements ....................................................................................................................... 108
References ...................................................................................................................................... 109
Supporting Information ............................................................................................................... 113
Study 3
Polyfluorinated Compounds in Ambient Air from Ship- and Land-Based Measurements
in Northern Germany ............................................................................................................ 133
Abstract .......................................................................................................................................... 135
Keywords ....................................................................................................................................... 136
1. Introduction .......................................................................................................................... 136
2. Experimental ......................................................................................................................... 138
2.1. Chemicals ................................................................................................................................... 138
2.2. Sampling ......................................................................................................................
2.3. Sample Preparation .................................................................................................................... 139
2.4. Instrumental Analysis & Quantification .................................................................................... 140
2.5. Quality Assurance & Quality Control ........................................................................................ 141
2.6. Air Mass Trajectories ................................................................................................................. 142
ii
TABLE OF CONTENTS

2.7. Statistical Analysis ..................................................................................................................... 142
3. Results ................................................................................................................................... 143
3.1. Concentrations of Polyfluorinated Compounds ......................................................................... 143
3.2. Composition of Polyfluorinated Compounds ............................................................................. 143
3.3. Correlation Analysis .................................................................................................................. 148
4. Discussion .............................................................................................................................. 148
Acknowledgements ....................................................................................................................... 152
References ...................................................................................................................................... 152
Supporting Information ............................................................................................................... 157
Study 4
Polyfluorinated Compounds in the Atmosphere of the Atlantic and Southern Ocean:
Evidence for a Global Distribution ....................................................................................... 171
Abstract .......................................................................................................................................... 173
1. Introduction .......................................................................................................................... 174
2. Experimental ......................................................................................................................... 175
2.1. Chemicals ................................................................................................................................... 175
2.2. Sampling .................................................................................................................................... 176
2.3. Sample Preparation & Instrumental Analysis ............................................................................ 178
2.4. Blanks ........................................................................................................................................ 178
2.5. Trajectory Analysis .................................................................................................................... 179
2.6. Statistical Analysis ..................................................................................................................... 179
2.7. Atmospheric Residence Times ................................................................................................... 179
3. Results & Discussion ............................................................................................................ 180
3.1. Concentrations of Polyfluorinated Compounds ......................................................................... 180
3.2. Composition of Polyfluorinated Compounds ............................................................................. 181
3.3. Correlation Analyses ............. 183
3.4. Spatial Distribution .................................................................................................................... 183
3.5. Atmospheric Residence Times ..... 188
Acknowledgements ....................................................................................................................... 189
References ...................................................................................................................................... 189
Supporting Information ............................................................................................................... 195

Acknowledgements ................................................................................................................ 225
Erklärung ............................................................................................................................... 229
iii
LIST OF FIGURES

List of Figures

Figure I: Summary of the most important reactions occurring during the atmospheric degradation
of volatile polyfluorinated compounds in air. ............................................................................. 17
Figure II: Overview about sampling campaigns discussed in this thesis. ................................................... 21
Figure III: Average recovery rates of polyfluorinated compounds after the evaporation of 50 mL
solvent. ....................................................................................................................................... 23
Figure IV: Box-Whisker plots of gas-phase concentrations of fluorotelomer alcohols, fluorotelomer
acrylates, perfluoralkyl sulfonamides, and perfluoralkysulfonamido ethanols from studies
2-4 summarized for selected regions. .......................................................................................... 27
Figure V: Gas-phase concentrations of 8:2 fluorotelomer alcohol at Barsbüttel and GKSS over the
14 months sampling period. ........................................................................................................ 28
Figure VI: Spatial distribution of 8:2 fluorotelomer alcohol gas-phase concentrations determined
during several cruises in the Baltic Sea, the Atlantic and Southern Ocean. ............................... 30
Figure VII: Concentrations of 8:2 fluorotelomer alcohol at Barsbüttel in dependence on main air mass
origins. ........................................................................................................................................ 32
Figure VIII: Total gas-phase concentrations of polyfluorinated compounds as a function of air mass
history................... 32
Figure 1-1: Average analyte recoveries of different solvents. ....................................................................... 65
Figure 1-2: SIM chromatogram of polyfluorinated compounds and acetic acid measured in
evaporated ethyl acetate SupraSolv. ............................................................................................ 67
Figure 1-3: SIM chromatograms of acetic acid in evaporated ethyl acetate SupraSolv, evaporated
ethyl acetate Picograde, ethyl acetate SupraSolv that did not undergo evaporation, and an
acetic acid standard solution. ...................................................................................................... 68
Figure 1-4: Recoveries of polyfluorinated compounds after the evaporation of ethyl acetate
SupraSolv using a 30 m and a 60 m Supelcowax10 capillary column. ....................................... 69
Figure 1-5: Average relative recoveries of volatile and semi-volatile polyfluorinated compounds
spiked to cartridges using ethyl acetate SupraSolv, acetone, methyl-tert-butyl ether, and
dichloromethane as extraction solvents. ...................................................................................... 70
Figure 1-6: Relative recovery rates of volatile fluorinated compounds using acetone: methyl-tert-
butyl ether 1:1 as extraction solvent. ........................................................................................... 70
Figure S1-1: Total ion chromatogram and scan of pure ethyl acetate SupraSolv. ........................................... 84
Figure S1-2: hromatogram and scan of evaporated ethyl acetate SupraSolv. ................................ 84
Figure S1-3: Total ion chromatogram and scan of acetic acid added to pure pure ethyl acetate. .................... 85
Figure S1-4: Recovery rates of certain polyfluorinated compounds in a standard solution based on
ethyl acetate fortified with acetic acid. ........................................................................................ 85
Figure S1-5: Break-through experiment of two parallel air samples. .............................................................. 86
Figure S1-6: Analyte Recoveries of five extraction steps. ............................................................................... 88
iv

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