Atmospheric deposition of organic contaminants
into the North Sea and the western Baltic Sea
Ph. D. Thesis
for the achievement of an academic degree as Dr. rer. nat.
at the Department of Chemistry of the University of Hamburg
Presented by
Carolin Mai born in Kirn
This thesis was written between 03.12.2008 and 31.05.2012 at the Federal Maritime and Hydrographic Agency of Germany (BSH) in Hamburg under support and supervision of Dr. N. Theobald, Prof. Dr. H. Hühnerfuss and Prof. Dr. G. Lammel.
1st Consultant: Prof. Dr. H. Hühnerfuss 2nd Consultant: Dr. M. Steiger
Acknowledgement
First, I would like to thank my Ph.D supervisor Prof. Dr. Hühnerfuss for the honour to be one of the last Ph. D. students in his well established and successful working group. Additionally, I thank Prof. Dr. Lammel for the scholarship at the International Max Planck Research School for Maritime Affairs (IMPRS) making this Ph. D. thesis possible, for his advice and support throughout my studies. In this sense, I also thank the directorate of the IMPRS for the permission of financial support throughout my Ph. D study.
Special thanks go to Dr. Theobald for the allocation of a very interesting Ph. D. topic, for the freedom of making it my own and for welcoming me into his working group. Furthermore, I would like to express my gratitude to the members of the division marine chemistry (M3) at the Federal Maritime and Hydrographic Agency (BSH) for their support, advice and appreciation throughout my time there. Especially Udo Ziebarth and Wolfgang Gerwinski are thanked for their support. My office mate Uta Kraus is thanked for making good times better and bad times less hard. The members of the mechanic workshop (M24) and the division of the marine monitoring network (M23) are thanked for providing their knowledge and support, which contributed to the success of the air sampling campaigns.
I deeply acknowledge Uwe Wiegand and Dr. Jan Rueß for their teamwork in data acquisition at Sylt and the Baltic Sea. Moreover, I would like to thank Dr. Annekatrin Dreyer and Dr. Christian Temme for showing me the right direction at the early beginning of my project. Further thanks go to the Research Centre for Toxic Compounds in the Environment (RECETOX) at the Masaryk University in Brno (Czech Republic) for the supply of the passive air sampling equipment and to the department of environmental chemistry of the Helmholtz-Zentrum Geesthacht (HZG) borrowing me the equipment for my first sampling campaign at sea. In addition, I thank the members of the Federal Environmental Agency (UBA), the Federal Maritime and Hydrographic Agency (BSH) and the Institute for Baltic Sea research (IOW) for the complementing data to my investigations.
Finally, I would like to show my gratitude to Prof. Dr. Knepper, the supervisor of my diploma thesis, for his advice and support helping me to start this Ph.D. project.
Last but certainly not least, I thank my family for their faith and never-ending support encouraging me to finish this work.
Table of contents
1. Introduction ……….. 1
1.1 Context ……….1
1.2 State of the art ………2
1.3 Objectives ………... 7
2. Theory ………. 9
2.1 Occurrence and fate of organic pollutants in the atmosphere ……….. 9
2.2 Atmospheric transport of organic pollutants ……..……….11
2.2.1 The role of aerosol particles in atmospheric transport and deposition………... 13
2.2.2 The role of clouds in atmospheric transport, deposition and transformation processes…. 16 2.3 Air-sea and sea-air exchange mechanisms of organic pollutants ……….16
2.3.1 Influence of biogeochemical processes in the water column ……… 17
2.3.2 Influence of bubbling processes in surface waters ………. 18
2.4 Atmospheric Deposition ……….. 20
2.4.1 Direction of the net flux of diffusive gas exchange ……… 20
2.4.2 Quantification of the dry gaseous deposition ……… 21
2.4.3 Quantification of the dry particulate deposition ……… 22
2.4.4 Quantification of the wet deposition ………... 24
3. Methodology ……….. 25
3.1 Air-sampling methods ………. 25
3.1.1 High-volume active air samplers ……… 25
3.1.2 PUF disk passive air samplers ……… 30
3.2 Air sampling campaigns ……….. 33
3.2.1 Active air sampling campaigns ……….. 33
3.2.2 Passive air sampling campaigns ………. 38
3.3 Target compounds ……….. .42
3.4 Analysis - Extraction, Evaporation, Clean-up and Quantification ……….. 53
3.5 Air mass backward trajectories ……….. .56
3.6 Surface Water Samples ……… 58
4. Method Validation ………. 59
4.1 Validation of air sampling ………... 59
4.1.1 Side-by-side air sampling experiments ……….……… 59
4.1.2 Desorption experiments ……… 60
4.2 Validation of air sample preparation methods ……… 68
4.2.1 Blanks ………... 69
4.2.2 Spike controls ………... 74
4.2.3 Reproducibility of air sample preparation ……… 78
4.2.4 Extraction efficiency ……… 80
4.3 Validation of Quantification ……….. 80
4.3.1 Limits of quantification ……… 80
4.3.2 Limits of detection ……… 82
5. Results and Discussion ………. 85
5.1 Assessment of the current status of the cycling processes of organic contaminants between the marine atmosphere and the sea surface water of the German EEZ, the North Sea and the Baltic Sea ……… 86
5.1.1 Polycyclic Aromatic Hydrocarbons ………. 86
5.1.2 Chlorinated Benzenes ……….. 102
5.1.3 Hexachlorocyclohexanes ……….. 111
5.1.4 Cyclodiene pesticides ……….. 120
5.1.5 DDT isomers and metabolites ……….. 126
5.1.6 Polychlorinated Biphenyls ……….. 136
5.1.7 Triazine Herbicides ………. 146
5.1.8 Organophosphate Insecticides ………. 159
5.1.9 Phenylurea Herbicides ………. 164
5.1.10 Phenoxyalkanoic acid and Thiadiazine Herbicides ……… 179
5.1.11 Dinitroaniline, Chloroacetanilide and Carbamate Pesticides ………. 189
5.1.12 Perfluorinated compounds ………. 207
5.1.13 Organophosphorus and Brominated Flame Retardants ………. 217
5.1.14 Pharmaceuticals ……… 220
5.2 Vertical distributions of organic contaminants in the North Sea atmosphere ………. 227
5.2.1 Influence of the vertical wind velocity profile on the sampling rates ……… 228
5.2.2 Vertical profiles of PAH abundances in the marine atmosphere ………. 230
5.2.3 Vertical profiles of organochlorine pesticides and PCBs in the marine atmosphere ….. 231
5.2.4 Vertical profiles of polar pesticides in the marine atmosphere ……… 232
5.2.5 Vertical profiles of perfluorinated compounds in the marine atmosphere ………... 234
5.3 Estimations of the dry particle and wet deposition fluxes to the surface seawaters ……….. 235
5.3.1 Wet deposition ……… 236
6. Summary ………... 241 7. Zusammenfassung ……… 244 8. Perspectives ……….. 247 9. Experimental ………. 248 9.1 List of materials ……… 248 9.2 List of instruments ……… 254 9.3 Standard Solutions ……… 255
9.3.1 Performance reference compound (PRC) standard solutions ………. 255
9.3.2 Internal standard (IS) solutions ……….. 255
9.3.3 Spike standard solutions of target compounds ……… 256
9.4 Processing methods ………... 257
9.4.1 Pre-cleaning of sampling material ……… 257
9.4.2 Sample collection ……….. 257
9.4.3 Sample preparation ………. 258
9.4.4 Quality control samples ……… 262
9.5 Mass spectrometry - Acquisition methods ……… 264
9.5.1 GC-MS ……… 264
9.5.2 GC-MS/MS ……….. 265
9.5.3 HPLC-MS/MS ………... 266
9.6 Mass spectrometry - Quantification methods ………... 267
9.6.1 GC-MS ………. 267
9.6.2 GC-MS/MS ……….. 268
9.6.3 HPLC-MS/MS ………. 268
9.7 Calculation of atmospheric concentrations ………... 269
10. References ………... 270
11. Annexes ………... 283
Annex 1 (A1): Atmospheric concentrations of target analytes ……….. 283
Annex 2 (A2): Field blanks and control samples ……….. 304
Annex 3 (A3): Recoveries of performance reference compounds (PRCs) ………... 339
Annex 4 (A4): Air mass backward trajectories – Original Hysplit 4.9 plottings ………... 344
Annex 5 (A5): Surface water concentrations of target analytes ……….383
Annex 6 (A6): Concentrations of target analytes in suspended particulate matter ……… 409
Annex 7 (A7): Henry´s law constants of target analytes ……… 410
List of figures
Figure 2.1: Schematic illustration of environmental mechanisms affecting the occurrence and fate of organic pollutants in the atmosphere ... 10 Figure 2.2: Illustration of thermodynamically expected atmospheric transport processes referring to
the global fractionation hypothesis and grasshopper-effect ... 11 Figure 2.3: Distribution characteristics of organic pollutants defined by the partition coefficients
(A); Transport behaviour categorization of several organic pollutants (B) ... 13 Figure 2.4: Overview of the mass size distribution, atmospheric lifetimes, sources and sinks of
aerosol particles ... 14 Figure 2.5: Schematic presentation of the air-water-phytoplankton coupling model ... 17 Figure 2.6: (A) Schematic presentation of sea-air-interactions via bubble bursting, (B) White
capping and sea spray ... 19 Figure 2.7: Surface size distribution of various aerosol types ………..23 Figure 3.1: Schematic diagrams of high-volume active air samplers including a photography of the
inlet, respectively; (A) AAS of the HZG; (B) AAS of the University of Hamburg ... 26 Figure 3.2: Schematic diagram of the Digitel DHM-60 high-volume active air sampler and a photography from the top deck of the research ship Pelagia ………. 27 Figure 3.3: (A) Gauze-insertions; (B) The fine-meshed gauze prevent the loss of XAD-2 from the adsorber cartridge (PUF/XAD-2/PUF sandwich) ……….. 27 Figure 3.4: Size segregation characteristic of the single-stage impactor in the Digitel DHM-60 high-volume active air sampler at 15°C ambient temperature, 1013 mbar air pressure and 50% relative humidity ………... 28 Figure 3.5: Housings of the adsorber cartridge of the Digitel DHM-60 systems; (A) Housing with a screw cap; (B) Housing with a hinged lid; (C) Adsorber cartridge fitting for insertion in the housings ………. 29 Figure 3.6: Schematic diagram of a conventional PUF disk passive air sampler and a photography illustrating the installation at the top deck of the research vessels ………. 30 Figure 3.7: Modified PUF disk passive air sampler ………. 32 Figure 3.8: Ship positions corresponding to air samples collected during the Baltic Sea research cruise in April 2009 ……… 34 Figure 3.9: Ship positions corresponding to air samples collected during the research cruise in the German EEZ in May/June 2009... 35 Figure 3.10: GFF contaminated by ship fumes (A); GFF air sample without ship fumes (B) ……. 36 Figure 3.11: Ship positions corresponding to air samples collected during the research cruise in the North Sea in August/September 2009………. 36 Figure 3.12: Ship positions corresponding to air samples collected during the research cruise in the German EEZ in May 2010 ………. 37 Figure 3.13: Geographical positions of the sampling sites in Sülldorf/Hamburg, Tinnum/Sylt and the FINO stations in the German EEZ ………... 39 Figure 3.14: PAS deployment at FINO 1 in the German EEZ ……… .41 Figure 3.15: Illustration of the parallel-evaporator with regard to adjustable parameters including the temperature profile established at a heating plate temperature of 50°C and at a water recirculation cooler temperature of 30°C ………... 53
Figure 3.16: Optimization of parallel-evaporation parameters; The quantification is standardized to the internal standard PCB 185, which resists evaporation; Target compounds are sorted by increasing retention time ……… 54 Figure 3.17: Schematic illustration of extraction, evaporation and clean-up of air samples ……… 55 Figure 3.18: Air mass backward trajectories (black arrows) of the air samples (red and green lines) collected over the German EEZ in May/June 2009 (A) and in May 2010 (B), respectively ……... 56 Figure 3.19: Air mass backward trajectories (black arrows) of the air samples (red lines) collected over the North Sea in August/September 2009 ……….. 57 Figure 3.20: Air mass backward trajectories (black arrows) of the air samples collected during the Baltic Sea research cruise in April 2009………... 57 Figure 3.21: Sea currents of the North Sea (A) and the Baltic Sea (B)………. 58 Figure 4.1: Desorption test for prometryn-D6; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ………... 61 Figure 4.2: Desorption test for simazine-D10; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ……….. 61 Figure 4.3: Desorption test for γ-HCH-13C6D6; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ………... 62 Figure 4.4: Desorption test for polychlorinated biphenyl 30; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ………... 62 Figure 4.5: Desorption test for polychlorinated biphenyl 104; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ……….. 62 Figure 4.6: Desorption test for polychlorinated biphenyl 145; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ……….. 63 Figure 4.7: Desorption test for polychlorinated biphenyl 204; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ……….. 63 Figure 4.8: Desorption test for phenanthrene-D10; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ……….. 63 Figure 4.9: Desorption test for fluoranthene-D10; (A) PUF plug adsorber cartridge;
(B) PUF/XAD-2/PUF adsorber cartridge ……….. 64 Figure 4.10: Desorption test for benzo[a]anthracene-D12; (A) PUF plug adsorber cartridge; (B) PUF/XAD-2/PUF adsorber cartridge ……….. 64 Figure 4.11: Stability test of prometryn-D6; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ……….. 65 Figure 4.12: Stability test of simazine-D10; (A) PUF/XAD-2/PUF adsorber cartridge,
(B) PUF disk ……….. 65 Figure 4.13: Stability test of γ-HCH-13C6D6; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ……….. 66 Figure 4.14: Stability test of polychlorinated biphenyl 30; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ……….. ………….66 Figure 4.15: Stability test of polychlorinated biphenyl 104; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ………... 66 Figure 4.16: Stability test of polychlorinated biphenyl 145; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ………... 67
Figure 4.17: Stability test of polychlorinated biphenyl 204; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ………... 67 Figure 4.18: Stability test of phenanthrene-D10; (A) PUF/XAD-2/PUF adsorber cartridge,
(B) PUF disk ………...67 Figure 4.19: Stability test of fluoranthene-D10; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ……….. 68 Figure 4.20: Stability test of benzo[a]anthracene-D12; (A) PUF/XAD-2/PUF adsorber cartridge, (B) PUF disk ………...68 Figure 4.21: Glass jars of the parallel-evaporator system glazed with tenacious PUF residues
………. 74 Figure 4.22: White and aged polyurethane foam (A) with respective methanol extracts (B) …… 79 Figure 4.23: PRC recovery results of (A) 20 GFF air samples and (B) of 12 PUF disk air samples ………... 79 Figure 4.24: PRC recovery results of (A) 10 PUF plug adsorber cartridge air samples and (B) 9 PUF/XAD-2/PUF adsorber cartridge air samples ………. 80 Figure 5.1: Atmospheric concentrations of organic pollutants in the atmosphere of the North Sea (plot of active air sampling data of the research cruises in the German EEZ 2009/2010 and the wider North Sea 2009) ………. 85 Figure 5.2: (A) Atmospheric bulk concentrations of PAHs above the German EEZ in May/Jun. 2009; (B) Interpretation by location and sources (backward trajectories) ………. 88 Figure 5.3: Atmospheric bulk concentrations of PAHs above the German EEZ in May 2010 …… 89 Figure 5.4: Atmospheric bulk concentrations of PAHs above the North Sea in Aug./Sep. 2009 … 90 Figure 5.5: Concentrations of PAHs in the gaseous mass fraction of the atmosphere above the Baltic Sea in Apr. 2009 ……….. 90 Figure 5.6: Seasonal variation of atmospheric PAH levels plotted in correlation with the ambient temperature for the PUF disk passive air sampler sampling sites Sülldorf/Hamburg (A) and Tinnum/Sylt (B) ………. 91 Figure 5.7: Comparison of atmospheric bulk concentrations of PAHs determined by active air sampling campaigns in winter (arithmetic mean of 20 air samples) and spring/summer (arithmetic mean of two air samples) ………. 92 Figure 5.8: Gas-particle partitioning of PAHs in correlation with ambient air temperatures 93 Figure 5.9: Gas-particle partitioning of individual PAH components sorted by their vapour
pressures [69], at different ambient air temperatures ………. 94
Figure 5.10: Occurrence and distribution of PAHs (aqueous and particulate phase) in the surface water (5m) of the German EEZ in May/Jun. 2009; (A) Spatial distribution; (B) PAH abundances in relation to suspended particulate matter (SPM) concentration and salinity for each water sampling site ……… 95 Figure 5.11: Occurrence and distribution of PAHs (aqueous and particulate phase) in the surface water (5m) of the German EEZ in May 2010; (A) Spatial distribution; (B) PAH abundances in relation to suspended particulate matter (SPM) concentration and salinity for each water sampling site ………... 96 Figure 5.12: Occurrence and distribution of PAHs (aqueous and particulate phase) in the surface water (5m) of the North Sea in Aug./Sep. 2009; (A) Spatial distribution; (B) PAH abundances in relation to suspended particulate matter (SPM) concentration and salinity for each water sampling site ……… 97
Figure 5.13: Spatial distribution of PAHs (aqueous and particulate phase) in the surface water (6m) of the Baltic Sea in Feb. 2005 ……… 98 Figure 5.14: PAH abundances of suspended particulate matter (SPM) collected in the estuary of the river Elbe (Apr./Jun. 2009) in relation to logKOW (obtained from [64]) ……… 99 Figure 5.15: Net flux of diffusive gas exchange of fluorene and phenanthrene; Fugacity ratio < 0.5: Atmosphere --> Sea; Fugacity ratio > 2; Sea --> Atmosphere; (A) German EEZ May/Jun. 2009; (B) German EEZ May 2010; (C) North Sea Aug./Sep. 2009; (D) Baltic Sea Apr. 2009 ………... 101 Figure 5.16: Gas phase concentrations of chlorinated benzenes in the atmosphere above the German EEZ in May/Jun. 2009 ……… 104 Figure 5.17: Gas phase concentrations of chlorinated benzenes in the atmosphere above the German EEZ in May 2010 ………104 Figure 5.18: Gas phase concentrations of chlorinated benzenes in the atmosphere above the North Sea in Aug./Sep. 2009 ……….. 105 Figure 5.19: Gas phase concentrations of chlorinated benzenes in the atmosphere above the Baltic Sea in Apr. 2009 ………... 105 Figure 5.20: Occurrence and spatial distribution of chlorinated benzenes in the surface water (5m) of the German EEZ in May/Jun. 2009 ………. 107 Figure 5.21: Occurrence and spatial distribution of chlorinated benzenes in the surface water (5m) of the German EEZ in May 2010 ………. 107 Figure 5.22: Occurrence and distribution of chlorinated benzenes in the surface water (5m) of the North Sea in Aug./Sep. 2009 ……… 108 Figure 5.23: Spatial distribution of hexachlorobenzene (HCB) in the surface water (6m) of the Baltic Sea in Feb. 2005 ……… 108 Figure 5.24: Net flux of diffusive gas exchange of chlorinated benzenes; Fugacity ratio < 0.5: Atmosphere --> Sea; Fugacity ratio > 2: Sea --> Atmosphere; (A) German EEZ May/Jun. 2009; (B) German EEZ May 2010; (C) North Sea Aug./Sep. 2009; (D) Baltic Sea Apr. 2009 ………... 109 Figure 5.25: (A) Gas phase concentrations of hexachlorocyclohexanes in the atmosphere above the German EEZ in May/Jun. 2009; (B) Air mass history (24 h backward trajectories) ……... 112 Figure 5.26: (A) Gas phase concentrations of hexachlorocyclohexanes in the atmosphere above the German EEZ in May 2010; (B) Air mass history (24 h backward trajectories) …………...112 Figure 5.27: (A) Gas phase concentrations of hexachlorocyclohexanes in the atmosphere above the North Sea in Aug./Sep. 2009; (B) Air mass history (24 h backward trajectories) ………... 113 Figure 5.28: (A) Gas phase concentrations of hexachlorocyclohexanes in the atmosphere above the Baltic Sea in Apr. 2009; (B) Air mass history (24 h backward trajectories) ………113 Figure 5.29: Seasonal variations in atmospheric hexachlorocyclohexane levels plotted in correlation with the ambient temperature for the PUF disk passive air sampler sampling sites Sülldorf/Hamburg (A) and Tinnum/Sylt (B) ……… 114 Figure 5.30: Occurrence and distribution of hexachlorocyclohexanes in the surface water (5m) of the German EEZ in Apr./May 2009 ………. 115 Figure 5.31: Occurrence and distribution of hexachlorocyclohexanes in the surface water (5m) of the German EEZ in May 2010 ………..116 Figure 5.32: Occurrence and distribution of hexachlorocyclohexanes in the surface water (5m) of the North Sea in Aug./Sep. 2009 ……….. 117
Figure 5.33: Occurrence and distribution of hexachlorocyclohexanes in the surface water (5m) of the German EEZ in the Baltic Sea in July 2009 ……….. 118 Figure 5.34: Net flux of diffusive gas exchange of α-HCH and γ-HCH; Fugacity ratio < 0.5: Atmosphere --> Sea; Fugacity ratio > 2: Sea --> Atmosphere; (A) German EEZ May/Jun. 2009; (B) German EEZ May 2010; (C) North Sea Aug./Sep. 2009; (D) Baltic Sea Apr. 2009 ………... 119 Figure 5.35: Atmospheric concentrations (gaseous phase) of dieldrin above the German EEZ in May/Jun. 2009 ……….. 121 Figure 5.36: Atmospheric concentrations (gaseous phase) of dieldrin above the German EEZ in May 2010 ……….. 122 Figure 5.37: Atmospheric concentrations (gaseous phase) of dieldrin above the North Sea in Aug./Sep. 2009 ………. 122 Figure 5.38: Occurrence and distribution of cyclodiene pesticides in the surface water (5 m) of the German EEZ in May/Jun. 2009 ……… 124 Figure 5.39: Occurrence and distribution of cyclodiene pesticides in the surface water (5 m) of the German EEZ in May 2010 ………124 Figure 5.40: Occurrence and distribution of cyclodiene pesticides in the surface water (5 m) of the North Sea in Aug./Sep. 2009 ……… 125 Figure 5.41: Net flux of diffusive gas exchange of dieldrin; Fugacity ratio < 0.5: Atmosphere --> Sea; Fugacity ratio > 2: Sea --> Atmosphere; (A) German EEZ May/Jun. 2009; (B) German EEZ May 2010; (C) North Sea Aug./Sep. 2009 ………... 125 Figure 5.42: Atmospheric bulk concentrations of DDT isomers and metabolites above the German EEZ in May/Jun. 2009 ………..127 Figure 5.43: Atmospheric bulk concentrations of DDT isomers and metabolites above the German EEZ in May 2010 ………..128 Figure 5.44: Atmospheric bulk concentrations of DDT isomers and metabolites above the North Sea in Aug./Sep. 2009 ……….. 129 Figure 5.45: Concentrations of DDT isomers and metabolites in the gaseous mass fraction of the atmosphere above the Baltic Sea in Apr. 2009 ……….130 Figure 5.46: Seasonal variability in atmospheric levels of the DDT isomers and metabolites of the PUF disk passive air sampler sampling sites in Sülldorf/Hamburg (A) and Tinnum/Sylt (B) ……….. 131 Figure 5.47: Occurrence and spatial distribution of DDTPP and metabolites in the surface water
(5m) of the German EEZ in May/Jun. 2009 ………. 133 Figure 5.48: Occurrence and spatial distribution of the DDTPP and metabolites in the surface water (5m) of the German EEZ in May 2010 ………134 Figure 5.49: Occurrence and distribution of DDTPP and metabolites in the surface water (5m) of the North Sea in Aug./Sep. 2009 ……….. 134 Figure 5.50: Occurrence and spatial distribution of DDTPP and metabolites in the surface water (6m) of the Baltic Sea in Feb. 2005 ………..135 Figure 5.51: Atmospheric bulk concentrations of PCBs above the German EEZ in May/Jun. 2009 ………... 137 Figure 5.52: Atmospheric bulk concentrations of PCBs above the German EEZ in May 2010 … 138
Figure 5.53: Atmospheric bulk concentrations of PCBs above the North Sea in Aug./Sep. 2009 ………... 138 Figure 5.54: Concentrations of PCBs in the gaseous mass fraction of the atmosphere above the Baltic Sea in Apr. 2009 ……….139 Figure 5.55: Seasonal variation in atmospheric abundances of PCBs at the PUF disk passive air sampler sampling sites Sülldorf/Hamburg (A) and Tinnum/Sylt (B) ……….. 140 Figure 5.56: Occurrence and distribution of PCBs in the surface water (5m) of the German EEZ in May/Jun. 2009 ……….. 143 Figure 5.57: Occurrence and distribution of PCBs in the surface water (5m) of the German EEZ in May 2010 ………. 143 Figure 5.58: Occurrence and distribution of PCBs in the surface water (5m) of the North Sea in Aug./Sep. 2009 ………. 144 Figure 5.59: Occurrence and distribution of PCBs in the surface water (6 m) of the Baltic Sea in Feb. 2005 ……….. 145 Figure 5.60: Atmospheric bulk concentrations of triazine herbicides above the German EEZ in May/Jun. 2009 ……….. 148 Figure 5.61: Concentrations of triazine herbicides in the gaseous mass fraction of the atmosphere above the Baltic Sea in Apr. 2009 ……… 148 Figure 5.62: Seasonal variations in atmospheric levels of the triazine herbicides terbuthylazine and terbutryn observed at the sampling sites Sülldorf/Hamburg and Tinnum/Sylt ……… 150 Figure 5.63: Occurrence and distribution of triazine herbicides in the aqueous phase of the surface water (5m) of the German EEZ in May/Jun. 2009 ………... 153 Figure 5.64: Occurrence and distribution of triazine herbicides in the aqueous phase of the surface water (5m) of the German EEZ in May 2010 ………...154 Figure 5.65: Occurrence and distribution of triazine herbicides in the aqueous phase of the surface water (5m) of the North Sea in Aug./Sep. 2009 ……….. 155 Figure 5.66: Seasonal variations in the surface water concentrations (5 m) of the triazine herbicides in the estuary of the river Elbe (A) and of terbuthylazine at selected sampling sites throughout the German EEZ (B) ……….. 156 Figure 5.67: Occurrence and distribution of triazine herbicides in the aqueous phase of the surface water (6m) of the Baltic Sea in Jun./Jul. 2008 ………. 157 Figure 5.68: Net flux of diffusive gas exchange of terbuthylazine and atrazine; Fugacity ratio < 0.5: Atmosphere --> Sea; Fugacity ratio > 2: Sea --> Atmosphere; (A) German EEZ May/Jun. 2009; (B) Baltic Sea Apr. 2009 ……… 158 Figure 5.69: Seasonal variations in the atmospheric abundances of the organophospate insecticides observed at the sampling sites Sülldorf/Hamburg and Tinnum/Sylt ……… 161 Figure 5.70: Occurrence and distribution of organophosphate insecticides in the aqueous phase of the surface water (5m) of the German EEZ in May/Jun. 2009 ……….162 Figure 5.71: Occurrence and distribution of organophosphate insecticides in the aqueous phase of the surface water (5m) of the German EEZ in May 2010 ……… 163 Figure 5.72: Occurrence and distribution of organophosphate insecticides in the aqueous phase of the surface water (5m) of the North Sea in Aug./Sep. 2009 ……….163
Figure 5.73: Net flux of diffusive gas exchange of diazinone between the surface water and the atmosphere of the North Sea in Aug./Sep. 2009; Fugacity ratio < 0.5: Atmosphere --> Sea; Fugacity ratio > 2: Sea --> Atmosphere ………... 164 Figure 5.74: Atmospheric bulk concentrations of phenylurea herbicides above the German EEZ in May/Jun. 2009 ……….. 166 Figure 5.75: Atmospheric bulk concentrations of phenylurea herbicides above the German EEZ in May 2010 ……….. 167 Figure 5.76: Atmospheric bulk concentrations of phenylurea herbicides above the North Sea in Aug./Sep. 2009 ………. 167 Figure 5.77: Concentrations of phenylurea herbicides in the gaseous mass fraction of the atmosphere above the Baltic Sea in Apr. 2009 ……….168 Figure 5.78: Seasonal variations in the atmospheric abundances of phenylurea herbicides observed at the sampling sites Sülldorf/Hamburg (A) and Tinnum/Sylt (B) ……….. 170 Figure 5.79: Occurrence and distribution of phenylurea herbicides in the aqueous phase of the surface water (5 m) of the German EEZ in May/Jun. 2009 ………. 173 Figure 5.80: Occurrence and distribution of phenylurea herbicides in the aqueous phase of the surface water (5 m) of the German EEZ in May 2010 ………. 174 Figure 5.81: Occurrence and distribution of phenylurea herbicides in the aqueous phase of the surface water (5 m) of the North Sea in Aug./Sep. 2009 ………. 175 Figure 5.82: Occurrence and distribution of phenylurea herbicides in the aqueous phase of the surface water (6 m) of the Baltic Sea in Jun./Jul. 2008 ……… 176 Figure 5.83: Seasonal variations in the surface water concentrations (5 m) of the phenylurea herbicides displayed for selected sampling sites in the German EEZ in 2009 ……….177 Figure 5.84: Atmospheric concentrations of phenoxyalkanoic acids (gaseous mass fraction) and bentazone (bulk concentrations) above the German EEZ in May/Jun. 2009 ……….. 180 Figure 5.85: Atmospheric concentrations of phenoxyalkanoic acids (gaseous mass fraction) and bentazone (bulk concentrations) above the German EEZ in May 2010 ………...181 Figure 5.86: Atmospheric concentrations of phenoxyalkanoic acids (gaseous mass fraction) and bentazone (bulk concentrations) above the North Sea in Aug./Sep. 2009 ………... 181 Figure 5.87: Seasonal variations in the atmospheric abundances of bentazone observed at the sampling sites Sülldorf/Hamburg (A) and Tinnum/Sylt (B) ……… 182 Figure 5.88: Occurrence and spatial distribution of phenoxyalkanoic acids and bentazone in the aqueous phase of the surface water (5 m) of the German EEZ in May/Jun. 2009 ………... 184 Figure 5.89: Occurrence and spatial distribution of phenoxyalkanoic acids and bentazone in the aqueous phase of the surface water (5 m) of the German EEZ in May 2010 ………...185 Figure 5.90: Occurrence and spatial distribution of phenoxyalkanoic acids and bentazone in the aqueous phase of the surface water (5 m) of the North Sea in Aug./Sep. 2009 …………... 185 Figure 5.91: Occurrence and spatial distribution of phenoxyalkanoic acids and bentazone in the aqueous phase of the surface water (6 m) of the Baltic Sea in Jun./Jul. 2008 ………. 186 Figure 5.92: Seasonal variations in the surface water concentrations (5 m) of the phenoxyalkanoic acids and bentazone displayed for selected sampling sites in the German EEZ in 2009 …. 187 Figure 5.93: Atmospheric bulk concentrations of dinitroaniline, chloroacetanilide and carbamate pesticides above the German EEZ in May/Jun. 2009 ………...190
Figure 5.94: Atmospheric bulk concentrations of dinitroaniline, chloroacetanilide and carbamate pesticides above the German EEZ in May 2010 ……….. 190 Figure 5.95: Atmospheric bulk concentrations of dinitroaniline, chloroacetanilide and carbamate pesticides above the North Sea in Aug./Sep. 2009 ………...191 Figure 5.96: Concentrations of dinitroaniline, chloroacetanilide and carbamate pesticides in the gaseous mass fraction of the atmosphere above the Baltic Sea in Apr. 2009 ……….. 191 Figure 5.97: Seasonal variations in the atmospheric abundances of dinitroaniline, chloroacetanilide and carbamate pesticides at the sampling sites Sülldorf/Hamburg and Tinnum/Sylt …….. 194 Figure 5.98: Gas-particle partitioning of pendimethalin in correlation with the ambient air temperatures ………. 195 Figure 5.99: Occurrence and distribution of dinitroaniline, chloroacetanilide and carbamate pesticides in the aqueous phase of the surface water (5 m) of the German EEZ in May/Jun. 2009 ……….. 197 Figure 5.100: Occurrence and distribution of dinitroaniline, chloroacetanilide and carbamate pesticides in the aqueous phase of the surface water (5 m) of the German EEZ in May 2010 ………... 198 Figure 5.101: Occurrence and distribution of dinitroaniline, chloroacetanilide and carbamate pesticides in the aqueous phase of the surface water (5 m) of the North Sea in Aug./Sep. 2009 ……….. 201 Figure 5.102: Occurrence and distribution of dinitroaniline, chloroacetanilide and carbamate pesticides in the aqueous phase of the surface water (6 m) of the Baltic Sea in Jun./Jul. 2008 ………... 202 Figure 5.103: Seasonal variations in the surface water concentrations (5 m) of the dinitroaniline, chloroacetanilide and carbamate pesticides displayed for selected sampling sites in the German EEZ in 2009 ……… 203 Figure 5.104: Net flux of diffusive gas exchange of the dinitroaniline and chloroacetanilide herbicides; Fugacity ratio < 0.5: Atmosphere --> Sea; Fugacity ratio > 2: Sea --> Atmosphere; (A) German EEZ May/Jun. 2009; (B) German EEZ May 2010; (C) North Sea
Aug./Sep. 2009; (D) Baltic Sea Apr. 2009 ……… 205
Figure 5.105: Atmospheric bulk concentrations of the PFCs above the German EEZ in May/Jun. 2009 ……….. 208 Figure 5.106: Atmospheric bulk concentrations of the PFCs above the German EEZ in May 2010 …... .209 Figure 5.107: Atmospheric bulk concentrations of PFCs above the North Sea in Aug./Sep. 2009
………... 210 Figure 5.108: Arithmetic mean bulk concentrations of PFOS and PFOA in pg/m³ at sea and land based sampling sites ………. 210 Figure 5.109: Occurrence and distribution of PFCs in the aqueous phase of the surface water (5 m) of the German EEZ in May/Jun. 2009 ………. 212 Figure 5.110: Occurrence and distribution of PFCs in the aqueous phase of the surface water (5 m) of the German EEZ in May 2010 ………. 213 Figure 5.111: Occurrence and distribution of PFCs in the aqueous phase of the surface water (5 m) of the North Sea in Aug./Sep. 2009 ………. 214 Figure 5.112: Occurrence and distribution of PFCs in the aqueous phase of the surface water (6 m) of the Baltic Sea in Jun./Jul. 2008 ……… 215
Figure 5.113: Composition of the targeted PFCs in the surface water (5-6 m) of the North Sea, the
German EEZ and the Baltic Sea ………... 216
Figure 5.114: Occurrence and spatial distribution of pharmaceuticals in the aqueous phase of the surface water of the German EEZ in May/Jun. 2009 ……….. 223
Figure 5.115: Occurrence and spatial distribution of pharmaceuticals in the aqueous phase of the surface water of the German EEZ in May 2010 ………... 224
Figure 5.116: Occurrence and spatial distribution of pharmaceuticals in the aqueous phase of the surface water of the North Sea in Aug./Sep. 2009 ……….. 225
Figure 5.117: Occurrence and spatial distribution of pharmaceuticals in the aqueous phase of the surface water of the Baltic Sea in Jun./Jul. 2008 ………. 226
Figure 5.118: Vertical wind profile monitored at the FINO 3 platform in the period of the 10 August to the 1 September 2010 ………. 228
Figure 5.119: Vertical gradients of the atmospheric abundances of PAHs in the marine atmosphere of the German EEZ in the period of August to October 2010 ………. 230
Figure 5.120: Vertical gradients of the atmospheric abundances of organochlorine pesticides and PCBs in the marine atmosphere of the German EEZ in the period of August to October 2010 ………... 232
Figure 5.121: Vertical gradients of the atmospheric abundances of polar pesticides in the marine atmosphere of the German EEZ in the period of August to October 2010 ……….. 233
Figure 5.122: Vertical gradients of the atmospheric abundances of perfluorinated compounds in the marine atmosphere of the German EEZ in the period of August to October 2010 ……….. 234
Figure 9.1. Insertion of the sampling material in respective sampler holders; (A) Adsorber cartridge; (B) Glass fibre filter; (C) PUF disk with stainless steel ring ………... 258
A4 Figure 1: Air mass backward trajectories of the air sample AL 1 ……… 344
A4 Figure 2: Air mass backward trajectories of the air sample AL 2 ……… 345
A4 Figure 3: Air mass backward trajectories of the air sample AL 3 ……… 346
A4 Figure 4: Air mass backward trajectories of the air sample AL 4 ……… 347
A4 Figure 5: Air mass backward trajectories of the air sample AL 5 ……… 348
A4 Figure 6: Air mass backward trajectories of the air sample AL 6 ……… 349
A4 Figure 7: Air mass backward trajectories of the air sample AL 7 ……… 350
A4 Figure 8: Air mass backward trajectories of the air sample AL 8 ……… 351
A4 Figure 9: Air mass backward trajectories of the air sample AL 9 ……… 352
A4 Figure 10: Air mass backward trajectories of the air sample AL 10 ……… 353
A4 Figure 11: Air mass backward trajectories of the air sample 09AT 2 ……….. 354
A4 Figure 12: Air mass backward trajectories of the air sample 09AT 3 ……….. 355
A4 Figure 13: Air mass backward trajectories of the air sample 09AT 4 ……….. 356
A4 Figure 14: Air mass backward trajectories of the air sample 09AT 5 ……….. 357
A4 Figure 15: Air mass backward trajectories of the air sample 09AT 7 ……….. 358
A4 Figure 16: Air mass backward trajectories of the air sample 09AT 8 ……….. 359
A4 Figure 18: Air mass backward trajectories of the air sample 09AT 11 ……… 361
A4 Figure 19: Air mass backward trajectories of the air sample 09AT 12 ……… 362
A4 Figure 20: Air mass backward trajectories of the air sample PE 1 ……….. 363
A4 Figure 21: Air mass backward trajectories of the air sample PE 3 ……….. 364
A4 Figure 22: Air mass backward trajectories of the air sample PE 4 ………... 365
A4 Figure 23: Air mass backward trajectories of the air sample PE 6..………. 366
A4 Figure 24: Air mass backward trajectories of the air sample PE 7 ………... 367
A4 Figure 25: Air mass backward trajectories of the air sample PE 8 ………... 368
A4 Figure 26: Air mass backward trajectories of the air sample PE 9 ………...369
A4 Figure 27: Air mass backward trajectories of the air sample PE 10 ……… 370
A4 Figure 28: Air mass backward trajectories of the air sample PE 11 ………. 371
A4 Figure 29: Air mass backward trajectories of the air sample PE 15 ……….372
A4 Figure 30: Air mass backward trajectories of the air sample PE 16 ………. 373
A4 Figure 31: Air mass backward trajectories of the air sample PE 17 ………. 374
A4 Figure 32: Air mass backward trajectories of the air sample PE 18 ………. 375
A4 Figure 33: Air mass backward trajectories of the air sample 10AT 1 ……….. 376
A4 Figure 34: Air mass backward trajectories of the air sample 10AT 2 ……….. 377
A4 Figure 35: Air mass backward trajectories of the air sample 10AT 3 ……….. 378
A4 Figure 36: Air mass backward trajectories of the air sample 10AT 4 ……….. 379
A4 Figure 37: Air mass backward trajectories of the air sample 10AT 5 ……….. 380
A4 Figure 38: Air mass backward trajectories of the air sample 10AT 6 ……….. 381
A4 Figure 39: Air mass backward trajectories of the air sample 10AT 7 ……….. 382
A5 Figure 1: Observational network of BSH water sampling sites in the German EEZ ………... 383
A5 Figure 2: Observational network of BSH water sampling sites in the North Sea ……… 384
A5 Figure 3: Observational network of water sampling sites in the Baltic Sea for the research cruise in Feb. 2005 ………..384
A5 Figure 4: Observational network of water sampling sites in the Baltic Sea for the research cruise in Jun./Jul. 2008 ………385
A5 Figure 5: Observational network of water sampling sites in the Baltic Sea for the research cruise in Jul. 2009 ………... 385
List of tables
Table 2.1: Predicted deposition velocities (cm/s) of (NH4)2SO4 aerosol particles with a mass median diameter of 0.56 µm at different wind speeds vD (m/s) and relative humidity (r.h.)
above natural waters ………...23
Table 3.1: Active air samples collected during the research cruise in the Baltic Sea in April 2009 ………. 33
Table 3.2: Active air samples collected during the research cruise in the German EEZ in May/June 2009 ……… 35
Table 3.3: Active air samples collected during the research cruise in the North Sea in August/September 2009 ………. 36
Table 3.4: Active air samples collected during the research cruise in the German EEZ in May 2010; ………. 37
Table 3.5: Active air samples collected in Sülldorf/Hamburg in November/December 2010 ……… ……….. 38
Table 3.6: Passive air samples collected during sea cruises ………. 39
Table 3.7: Passive air samples collected in Sülldorf/Hamburg ……… 40
Table 3.8: Passive air samples collected in Tinnum/Sylt ………. 40
Table 3.9: Passive air samples collected at the FINO research stations ……… 41
Table 3.10: Target compounds ………. 42
Table 4.1: Reproducibility (precision) of air sampling data based on all analytes exceeding LOQ in all samples collected simultaneously……….. 60
Table 4.2: Air sample preparation sequences ……….. 68
Table 4.3: Field blanks ………. 70
Table 4.4: Laboratory blanks ………... 73
Table 4.5: Recovery of target compounds in spike controls………. 75
Table 4.6: Limits of quantification in ng/mL extract applied to the air sample preparation sequences 1-5 ………... 81
Table 4.7: Limits of detection in ng/mL extract applied to the air sample preparation sequences 1-5 ………. 83
Table 5.1: Hexachlorobenzene (HCB) and pentachlorobenzene (QCB) concentrations in the marine atmosphere ………106
Table 5.2: Comparison of atmospheric concentrations of DDTPP and DDEPP determined at sea and land based sampling sites……….. 130
Table 5.3: Comparison of the atmospheric bulk concentrations of PCBs (in pg/m³) determined at sea and land based sampling sites………..………..………. 140
Table 5.4: Occurrence and concentrations (pg/m³) of triazine herbicides in the atmosphere above the German EEZ, the wider North Sea, the Baltic Sea and Sülldorf/Hamburg ………... 147
Table 5.5: Concentration ranges of the triazine herbicides in the surface water of the German EEZ, the wider North Sea and the Baltic Sea ……….. 152
Table 5.6: Occurrence and bulk concentrations (pg/m³) of organophosphate insecticides in the atmosphere above the German EEZ, North Sea, Baltic Sea and Sülldorf/Hamburg
………... 160
Table 5.7: Atmospheric concentrations of diuron and fenuron in Sülldorf/Hamburg in December 2010 determined during the side-by-side air sampling experiments ………. 169
Table 5.8: Occurrence and bulk concentrations (pg/m³) of organophosphorus and brominated flame retardants in the atmosphere above the German EEZ, the wider North Sea, the Baltic Sea and Sülldorf/Hamburg ………. 218
Table 5.9: Occurrence and bulk concentrations of carbamazepine, primidone and oxazepam and concentrations of clofibric acid, diclofenac and naproxen in the particle associated mass fraction of the atmosphere of the German EEZ, the wider North Sea, the Baltic Sea and of Sülldorf/Hamburg ………. 221
Table 5.10: Recovery (%) of PRCs in the PUF disk passive air samples exposed at the FINO research platforms ……… 229
Table 5.11: Scavenging ratios ……… 236
Table 5.12: Annual wet deposition fluxes of organic pollutants to the coastal sampling sites Tinnum and Zingst (calculated from the data of the UBA, annex 8) as well as estimated wet deposition fluxes to the surface seawater of the German EEZ, the wider North Sea and the Baltic Sea……….. 237
Table 5.13: Sea surface water concentrations calculated from the annual wet deposition fluxes and real water concentrations observed in 5-6 m of depth ………. 238
Table 5.14: Estimations of the dry particulate deposition fluxes to the sea surface water of the German EEZ and the North Sea ………... 239
Table 5.15: Estimations of the annual dry particle deposition fluxes of PFCs and organophosphorus flame retardants to the sea surface water of the German EEZ and the North Sea ………... 240
Table 5.16: Dry particulate deposition fluxes (FDD), deposition velocities (vD) and concentrations in the particulate mass fraction in the atmosphere (cp) reported in the literature ………. 240
Table 9.1: List of solvents ……….. 248
Table 9.2: List of chemicals ………248
Table 9.3: Further materials ……… 253
Table 9.4: PRC-LC (methanol solution) ……… 255
Table 9.5: PRC-GC (hexane solution) ……… 255
Table 9.6: IS-LC (methanol solution) ……… 255
Table 9.7: IS-GC (hexane solution) ……… 256
Table 9.8: Spike-LC (methanol solution) ………... 256
Table 9.9: Spike-GC (hexane solution) ……….. 256
Table 9.10: Büchi evaporation parameters and time-pressure gradient for the evaporation of 350 mL acetone/hexane/methanol (75/20/5, v/v/v) solvent mixture at rack 4 ………. 259
Table 9.11: Büchi evaporation parameters and time-pressure gradient for the evaporation of 100 mL acetone/hexane/methanol (75/20/5, v/v/v) solvent mixture at rack 12 …………... 260
Table 9.12: Büchi evaporation parameters and time-pressure gradient for the evaporation of 40 mL hexane at rack 4 ……… 260
Table 9.13: Büchi evaporation parameters and time-pressure gradient for the evaporation of 40 mL
methanol at rack 4 ……… 260
Table 9.14: Büchi evaporation parameters and time-pressure gradient for the evaporation of 40 mL hexane at rack 12 ……….. 260
Table 9.15: Büchi evaporation parameters and time-pressure gradient for the evaporation of 40 mL methanol at rack 12 ……….. 261
Table 9.16: Amounts of target analytes, performance reference compounds and internal standard added to laboratory blanks and spike control samples……… 262
Table 9.17: Composition of the single-point calibration standard LC-Cal (methanol solution) … 263 Table 9.18: Composition of the single-point calibration standard GC-Cal (hexane solution) …... 263
Table 9.19: GC gradient program (GC-MS method) ………. 264
Table 9.20: MS parameters (MS method type: segmented SIM) ………264
Table 9.21: GC gradient program (GC-MS/MS method) ………... 265
Table 9.22: MS parameters (MS method type: segmented MRM)………... 265
Table 9.23: HPLC gradient program ……….. 266
Table 9.24: Common scheduled MRM parameters in positive (p) and negative (n) ESI mode ….266 Table 9.25: Scheduled MRM mass transition parameters in positive (p) and negative (n) ESI mode ……….. 266
Table 9.26: GC-MS analytes and their corresponding internal standards ……….. 267
Table 9.27: GC-MS/MS analytes and their corresponding internal standards ………... 268
Table 9.28: HPLC-MS/MS analytes and their corresponding internal standards …..……… 268
A1 Table 1: Atmospheric concentrations of target compounds in pg/m³ determined by high-volume active air sampling……… 283
A1 Table 2: Atmospheric concentrations of target compounds in ng/PUF disk determined by passive air sampling………...297
A2 Table 1: Field blanks of Glass Fibre Filters (GFFs) ……… 304
A2 Table 2: Field blanks of PUF plug adsorber cartridges ………... 307
A2 Table 3: Field blanks of PUF/XAD-2/PUF adsorber cartridges ………... 308
A2 Table 4: Field blanks of PUF disk passive air samplers ………... 311
A2 Table 5: Laboratory blanks – Extraction blanks ……….. 318
A2 Table 6: Laboratory blanks – Bottle blanks ……….. 320
A2 Table 7: Laboratory blanks – Evaporation blanks ……… 321
A2 Table 8: Laboratory blanks – Clean-up blanks ……… 324
A2 Table 9: Recovery of target compounds in spike control samples ………326
A2 Table 10: Soxhlet extraction efficiency – Peak areas of labeled analytes (IS and PRCs) in the extract of the first sample prepation and in the extract of the second sample preparation .. 334
A2 Table 11: Efficiency of the GFF extraction – Peak areas of labeled analytes (IS and PRCs) in the extract of the first sample prepation and in the extract of the second sample preparation ………... 336
A3 Table 1: Reproducibility of the sample preparation for GFFs; Recoveries (%) of Performance Reference Compounds spiked prior extraction to the environmental samples ……… 339 A3 Table 2: Reproducibility of the sample preparation for PUF plug adsorber cartridges; Recoveries (%) of Performance Reference Compounds spiked prior extraction to the environmental samples ……….339 A3 Table 3: Reproducibility of the sample preparation for PUF/XAD-2/PUF adsorber cartridges; Recoveries (%) of Performance Reference Compounds spiked prior extraction to the environmental samples ………. 340 A3 Table 4: Reproducibility of the sample preparation for PUF disks; Recoveries (%) of Performance Reference Compounds spiked prior extraction to the environmental samples……… 340 A3 Table 5: Desorption from PUF plug adsorber cartridges; Recoveries (%) of Performance Reference Compounds spiked prior to air sampling………..340 A3 Table 6: Desorption from PUF/XAD-2/PUF adsorber cartridges; Recoveries (%) of Performance Reference Compounds spiked prior to air sampling ……… 341 A3 Table 7: Stability of frozen PUF/XAD-2/PUF adsorber cartridges; Recoveries (%) of Performance Reference Compounds in field blanks spiked prior to storage ………. 342 A3 Table 8: Stability of frozen PUF disks; Recoveries (%) of Performance Reference Compounds in field blanks spiked prior to storage ……….. 342 A3 Table 9: PRC recoveries (%) in the PUF disk passive air samples spiked prior to exposure at Tinnum/Sylt (28 days), Sülldorf/Hamburg (28 days) and at the FINO platforms ………... 343 A5 Table 1: Surface water concentrations (5 m, A5 figure 1) in ng/L determined during the research cruise in the German EEZ in May/Jun. 2009; with respective LOQs, PSU= Practical Salinity units; SPM = Suspended particulate matter in mg/L ……….. 386 A5 Table 2: Surface water concentrations (5 m, A5 figure 1) in ng/L determined during the research cruise in the German EEZ in May 2010; with respective LOQs, PSU = Practical Salinity units; SPM = Suspended particulate matter in mg/L ……….. 390 A5 Table 3: Surface water concentrations (5 m, A5 figure 2) in ng/L determined during the research cruise in the North Sea in Aug./Sep. 2009; with respective LOQs, PSU = Practical Salinity units; SPM = Suspended particulate matter in mg/L ……….. 394 A5 Table 4: Surface water concentrations (5 m, A5 figure 3) in ng/L of the Baltic Sea in Feb. 2005; data >LOQs, PSU = Practical Salinity units; SPM = Suspended particulate matter in mg/L ……….. 400 A5 Table 5: Surface water concentrations (6 m, A5 figure 4) in ng/L of the Baltic Sea in Jun./Jul. 2008; with respective LOQs, PSU = Practical Salinity units; SPM = Suspended particulate matter in mg/L ………. 400 A5 Table 6: Surface water concentrations (5 m, A5 figure 5) in ng/L of the Baltic Sea in Jul. 2009, data >LOQs, PSU = Practical Salinity units; SPM = Suspended particulate matter in mg/L ………... 403 A5 Table 7: Surface water concentrations (5 m, A5 figure 5) in ng/L of the German EEZ in September 2009; PSU = Practical Salinity units; SPM = Suspended particulate matter in mg/L ………. 403 A5 Table 8: Surface water concentrations (5 m, A5 figure 5) in ng/L of the German EEZ in November 2009; PSU = Practical Salinity units; SPM = Suspended particulate matter in mg/L ………. 406
A6 Table 1: Concentrations (ng/g) of target analytes in suspended particulate matter collected at four water sampling sites (refer to A4 figure 1) by centrifugation of surface water; TOC = Concentration (mg/g) of total organic carbon in the suspended particulate matter …….… 409 A7 Table 1: Henry´s law constants applied for the calculation of the net fluxof diffusive gas exchange of target analytes between the surface water and the atmosphere ………410 A8 Table 1: Concentrations (ng/L) of organic compounds in monthly rain water samples collected in Zingst in 2009 and 2010, respectively ………. 411 A8 Table 2: Concentrations (ng/L) of organic compounds in monthly rain water samples collected in Tinnum/Sylt in 2009 and 2010, respectively ………... 412
List of abbreviations
AAS Active air sampling
ABL Atmospheric boundary layer
ACE Acenaphthene
ACE-D10 Acenaphthene-D10
ACY Acenaphthylene
AL Research ship Alkor
ALD Aldrin
AMETRYN Ametryn
ANT Anthracene
ANT-D10 Anthracene-D10
ARGE-BLMP Arbeitsgemeinschaft Bund-Länder-Messprogramm
ARL Air resources laboratory
ASE Accelerated Soxhlet extraction
AT Research ship Atair
ATRAZ Atrazine ATRAZ-D5 Atrazine-D5 AZINPH-E Azinphos-ethyl AZINPH-M Azinphos-methyl AZINPH-M-D6 Azinphos-methyl-D6 B.S. Baltic Sea BAA Benzo[a]anthracene BAA-D12 Benzo[a]anthracene-D12 BAP Benzo[a]pyrene BBF Benzo[b]fluoranthene BENTAZ Bentazone BEP-D12 Benzo[e]pyrene-D12 BGHIP Benzo[g,h,i]perylene BGHIP-D12 Benzo[g,h,i]perylene-D12 BLMP Bund-Länder-Messprogramm
BSH Federal Maritime and Hydrographic Agency of Germany
C Cunningham slip correction factor
ca Concentration of a given compound in air (pg/m³)
CARBAMAZ Carbamazepine
CARBEND Carbendazim
CB145 Polychlorinated Biphenyl 145 CB204 Polychlorinated Biphenyl 204 CB30 Polychlorinated Biphenyl 30 CB138 Polychlorinated Biphenyl 138 CB153 Polychlorinated Biphenyl 153 CB153-13C12 Polychlorinated Biphenyl 153 – 13C12 CB185 Polychlorinated Biphenyl 185 CB28 Polychlorinated Biphenyl 28 CB52 Polychlorinated Biphenyl 52 CB52-13C12 Polychlorinated Biphenyl 52 – 13C12 CBzs Chlorinated benzenes
CCN Cloud condensation nuclei
CFC Chlorofluorocarbon
CHLORFENV Chlorfenvinphos
CHLORTUR Chlorotoluron
CHR Chrysene
CHRTR Sum parameter of chrysene and triphenylene
CLOFIBRS Clofibric acid
cPrec Concentration of an organic compound in precipitation (ng/L)
cr Concentration of a given compound in rain water (ng/L)
CUP Currently used pesticide
D Diffusion coefficient
d(ae)50 Aerodynamic diameter of particulate matter segregated with 50%
efficiency (µm) DBAHA Dibenzo[a,h]anthracene DDDPP p,p´-Dichlorodiphenyldichloroethane DDEPP p,p´-Dichlorodiphenyldichloroethylene DDT 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane DDTOP o,p´-Dichlorodiphenyltrichloroethane DDTPP p,p´-Dichlorodiphenyltrichloroethane DDTPP-D8 p,p´-Dichlorodiphenyltrichloroethane-D8 DEATRAZ Desethylatrazine DEATRAZ-D6 Desethylatrazine-D6
DHI German Hydrographic Institute
DIAZINON Diazinone
DICHLPR Dichlorprop
DIELD Dieldrin DIMETH Dimethoate DIURON Diuron DIURON-D6 Diuron-D6 dj Nozzle diameter (mm) DS Sampling duration (h) DWD Deutscher Wetterdienst
EEZ Exclusive economic zone
EMEP European Monitoring and Evaluation Programme
END Endrin
EVA Ethyl-vinyl-acetate
f Fugacity
fA Fugacity of a given compound in air
FAW Flux of diffusive air-water exchange (ng/(m² d)
FDD Flux of dry particulate deposition (ng/(m² d))
FENUR Fenuron
FL Fluorene
FLU Fluoranthene
FLU-D10 Fluoranthene-D10
FR Fugacity ratio
fW Fugacity of a given compound in water
FWet Flux of wet deposition (ng/(m² d))
G. EEZ German exclusive economic zone of the North Sea / German Bight
GAPS Global atmospheric passive sampling study
GC Gas chromatography
GDAS Global data assimilation system
GFF Glass fibre filter
QFF Quartz fibre filter
H Henry´s law constant (Pa m³ / mol)
H´ Dimensionless Henry´s law constant
HBCDA α-Hexabromocyclododecane
HBCDA-D18 α-Hexabromocyclododecane-D18
HBCDB β-Hexabromocyclododecane
HBCDG γ-Hexabromocyclododecane
HBCDBG Sum parameter of HBCDB and HBCDG
HCB Hexachlorobenzene
HCFC Hydrochlorofluorocarbon HCH Hexachlorocyclohexane HCHA α-Hexachlorocyclohexane HCHB β-Hexachlorocyclohexane HCHD δ-Hexachlorocyclohexane HCHE ε-Hexachlorocyclohexane HCHG γ-Hexachlorocyclohexane / Lindane HCHG-13C6D6 Lindane-13C6D6
HELCOM Baltic Marine Environment Protection Commission / Helsinki Commission
HEXAZIN Hexazinone
HVS High-volume sampler
HZG Helmholtz-Zentrum Geesthacht
I123P Indeno[1,2,3-cd]pyrene
IfM Institute of marine science
IOW Institute for Baltic Sea Research
IRGAROL Irgarol
ISOD Isodrin
ISOPRUR Isoproturon
kA Pollutant mass transfer rate in the air (m/d)
KA, H2O Mass transfer coefficient of H2O in the air
kAW Air-water mass transfer rate (m/d)
KAW Air-water partition coefficient
KOA Octanol-air partition coefficient
KOW Octanol-water partition coefficient
kW Pollutant mass transfer rate in the water (m/d)
KW,CO2 Mass transfer coefficient of CO2 in the water
LC Liquid chromatography
LDPE Low density polyethylene
LINUR Linuron
LLE Liquid-liquid-extraction
LOD Limit of detection
LOQBlank Limit of quantification calculated from field blanks
LOQS/N Limit of quantification calculated from the signal to noise ratio
LVS Low volume sampler
MAE Microwave assisted extraction
MALATH Malathion
MCPA (4-Chloro-2-methylphenoxy)ethanoic acid
MCPA-D3 (4-Chloro-2-methylphenoxy)ethanoic acid-D3
MECOPR Mecoprop
MECOPR-D3 Mecoprop-D3
METAZCHL Metazachlor
METHABZT Methabenzthiazuron
METOLA Metolachlor
MMD Mass median diameter
MS Mass spectrometry / Mass spectrometer
NAPROX Naproxen
NCEP National centers for environmental prediction
Ni Number of nozzles
NOAA National oceanic and atmospheric administration
Nt Total number of maritime aerosol particles
OC Organic carbon
OCP Organochlorine pesticide
OM Organic matter
OSPAR Convention for the protection of the marine environment of the North-East
Atlantic
OXAZEP Oxazepam
P di PUF disk
P pl PUF plug adsorber cartridge
p Air pressure (hPa)
P Total precipitation flux (L/(m² d))
PAH Polycyclic aromatic hydrocarbon
PAS Passive air sampler / Passive air sampling
PBDE Polybrominated diphenyl ethers
PBT Persistent bioaccumulative and toxic chemicals
PCB Polychlorinated biphenyl
PCDD Polychlorinated dibenzodioxin
PCDF Polychlorinated dibenzofuran
PE Research ship Pelagia
PENDIMETH Pendimethalin
PER-D12 Perylene-D12
PFBS Perfluorobutanesulfonic acid
PFC Perfluorinated compounds
PFDEA Perfluorodecanoic acid
PFHPA Perfluoroheptanoic acid
PFHXA Perfluorohexanoic acid
PFHXS Perfluorohexanesulfonic acid
PFHXS-18O2 Perfluorohexanesulfonic acid - 18O2
PFNOA Perfluorononanoic acid
PFOA Perfluorooctanoic acid
PFOA-13C2 Perfluorooctanoic acid - 13C2
PFOS Perfluorooctanesulfonic acid
PFOS-13C4 Perfluorooctanesulfonic acid – 13C4
PFOSA Perfluorooctanesulfonamide
PFSA Perfluoroalkyl sulfonate
PHEN Phenanthrene
PHEN-D10 Phenanthrene-D10
PIRIMIC Pirimicarb
PLE Automated pressurized liquid extraction
PM Particulate matter
POG Polymer coated glass
POP Persistent organic pollutant
PRC Performance reference compound
PRIMID Primidone
PROMETR Prometryn
PROMETR-D6 Prometryn-D6
PROPAZ Propazin
PSU Practical salinity units
PTFE Polytetrafluoroethylene
PTS Persistent toxic substances
PUF Polyurethane foam
PVDF Polyvinylidene fluoride
PXP PUF/XAD-2/PUF adsorber cartridge / sandwich cartridge
PYR Pyrene
QCB Pentachlorobenzene
R Ideal gas constant (8.314 Pa m³/(mol K))
r.h. Relative humidity (%)
Sc Schmidt number, dimensionless
SCCPs Short-chain chloroparaffins
SIMAZ-D10 Simazine-D10
SIP Sorbent-impregnated polyurethane foam
SPM Suspended particulate matter
SPMD Semi-permeable membrane device
Stk50 Dimensionless Stokes number
SVOC Semi-volatile organic compound
T Air temperature (°C)
t Precipitation sampling time (d)
TA Absolute air temperature (K)
TBEP Tris(2-butoxy-ethyl)phosphate TBP Tributyl phosphate TERBAZ Terbuthylazine TERBAZ-D5 Terbuthylazine-D5 TERBUTR Terbutryn TPP Triphenyl phosphate TR Triphenylene TRIFLU Trifluralin TRIFLU-D14 Trifluralin-D14
TWA Time-weighted averaged concentration
u wind velocity (m/s)
U10 Wind speed at 10 m height
UBA Federal Environmental Agency
UFP Ultrafine particles
UNEP United nations environment programme
V Volume collected by the wet deposition sampler (L)
VF Air volume flow (m³/s)
Vp Volume of a single maritime aerosol particle (m³)
Vt Total volume of maritime aerosol particles (m³)
Wt Total scavenging ratio
XAD-2 A hydrophobic cross-linked polystyrene copolymer resin
Z Fugacity capacity
ZA Fugacity capacity of air
ZW Fugacity capacity of water
a Sampling area of the wet deposition collector (m²)
η Dynamic viscosity (kg/(m s))
ρp Standard density of idealised spherical particles (kg/m³)
1. Introduction
1.1 Context
The monitoring and assessment of the environmental condition of the North Sea and the Baltic Sea was initiated in Germany in the 1970s. 1980 a common monitoring program, named “Bund-Länder-Messprogramm” (BLMP), for the North Sea was arranged between the German federation and the coastal federal states of Germany.
During the DDR era the Baltic Sea was monitored by the German Hydrographic Institute (DHI, Hamburg), by the institute of marine science at the University of Kiel, by the Leibniz Institute for Baltic Sea Research in Warnemünde (IfM) and by the “Wasserwirtschaftsdirektion Küste” in Stralsund. Since the German reunification in 1990 the monitoring of the Baltic Sea has been divided between the Federal Maritime and Hydrographic Agency of Germany (BSH) and the responsible agencies of the coastal federal states Mecklenburg-Vorpommern, Schleswig-Holstein and the Institute for Baltic Sea Research (IOW) in Warnemünde.
In April 1997 a consortium, named “Arbeitsgemeinschaft Bund-Länder-Messprogramm” (ARGE-BLMP), was founded including the responsible resorts of the German federation and the coastal federal states Hamburg, Mecklenburg-Vorpommern, Schleswig-Holstein and Lower Saxony for a joint monitoring of the North Sea and the Baltic Sea. The intention of this arrangement is to improve the coordination of several monitoring and assessment programmes. In addition, actual studies are accommodated to national and international agreements and regulations, like the international agreement for the protection of the marine environment of the Baltic Sea (HELCOM-Helsinki-Commission) and the North-East-Atlantic (OSPAR). [1-3]
Today several annual monitoring cruises in the North Sea and the Baltic Sea aim to investigate a variety of important physical, biological and chemical parameters, the occurrence and distribution of organic contaminants in sea surface water, among others. As a result of the extended observational network the riverine input of organic contaminants to the sea is well investigated. [1] By contrast, the atmospheric deposition, a further important and effective input pathway for several organic contaminants, is less examined so far. Organic compounds may undergo long-range transport in the atmosphere enabling the deposition from distant sources within and beyond Europe. For this reason knowledge about atmospheric concentrations and pathways of organic contaminants is essential for the establishment of effective national and international environmental regulations and politics. [4] Therefore, systematic field studies, investigating the atmospheric concentrations, spatial distribution and deposition of organic contaminants at sea are of great importance for the extension of the current state of knowledge and for the evaluation of model simulations. [5-8]
1.2 State of the art
In 1995 the Governing Council of the United Nations Environment Programme (UNEP) negotiated the Stockholm Convention in order to reduce the release of persistent organic pollutants (POPs) to the environment. POPs are hardly degradable in the environment and accumulate along the food chain causing possible health hazards to humans and wildlife. Today POPs are globally distributed. Enhanced concentrations have been detected even in remote regions like the Arctic, where they have never been used. [9] During the first period, twelve organic compounds (“dirty dozen”) have been subject to the convention, namely aldrin, chlordane, 1,1,1-trichloro-2,2-di(4-chlorophenyl)ethane (DDT), dieldrin, endrin, heptachlor, hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs). In May 2009 nine additional POPs were incorporated in the convention, i.e., α-hexachlorocyclohexane, β-hexachlorocyclohexane, lindane, chlordecone, hexabromo-biphenyl, hexabromodiphenyl ether and heptabromodiphenyl ether, pentachlorobenzene, perfluoroctane sulfonic acid and perfluorooctane sulfonyl fluoride, tetrabromodiphenyl ether and pentabromodiphenyl ether. Endosulfan was classified as 22nd POP in April 2011. Moreover, a further category named persistent bioaccumulative and toxic (PBT) chemicals is defined by UNEP, including the POPs as an integral part. The PBT group additionally contains among others trace metals and organo-metal compounds as well as further organic compounds, e.g., perfluorooctanoic acid and polycyclic musks, which may be prospective POP candidates. In order to verify the effectiveness of the Stockholm Convention, comprehensive monitoring data of all environmental compartments are required. Especially, the atmosphere is expected to be an efficient indicator of decreasing POP releases, because atmospheric concentrations change rapidly according to variations in primary sources. [10-13] Europe, USA, Canada and the Russian Federation additionally ratified the POP protocol of the Convention on Long-Range Transboundary Air Pollution originally negotiated in Geneva 1979. It was entered into force in 2003 and comprises a more extensive spectrum of organic compounds than the “dirty dozen” of the Stockholm convention, e.g., additionally including hexachlorocyclohexanes (HCHs) and polycyclic aromatic hydrocarbons (PAHs). In this context the European Monitoring and Evaluation Programme (EMEP) runs an air monitoring network throughout Europe. Currently the network encloses more than 100 sampling sites, whereof 20 sampling sites distributed in 14 countries are measuring POPs in the atmosphere. Sampling sites on sea are not established. [4, 6, 14]
A variety of air sampling methods has been developed for monitoring atmospheric concentrations of organic contaminants in ambient air. Principally they can be grouped in active air sampling (AAS) techniques and passive air sampling (PAS) techniques.
