Primär emittierte marine Aerosolpartikel haben einen wichtigen Einfluss auf den Strahlungshaushalt der Erde, indem sie unter anderem als Kondensations (CCN)- oder Eiskeime (INP) für die Bildung von Wolken wirken. In den ozeanisch geprägten Polarregionen dominieren diese marinen Aerosolpartikel in der Luft und können dort eine bedeutende bzw. sich noch verändernde Rolle im Rahmen des Klimawandels einnehmen. Sie entspringen vordergründig aus dem ozeanische Oberflächenwasser und dem hauchdünnen Oberflächenfilm, dem sogenannte sea surface microlayer (SML), und werden durch das Platzen von durch Wind eingetragene Luftblasen freigesetzt. Primär emittierte marine Aerosolpartikel bestehen aus anorganischem Meersalz und organischen Kohlenstoffverbindungen, deren relative Anteile sich stark in Abhängigkeit vom Aerosoldurchmessers unterscheiden. In diesem Zusammenhang stellen die marinen Kohlenhydrate eine wichtige organische Stoffgruppe dar, deren ozeanische Quellen, Übergang vom Ozean in die Atmosphäre, Veränderungen in der Atmosphäre als auch deren Beitrag bei der Kondensation und Eiskeimbildung noch nicht ausreichend verstanden sind. Dieser begrenzte Kenntnisstand ist unter anderem auf das mangelnde Vorhandensein analytischer Methoden zurückzuführen, die eine zuverlässige Bestimmung von Kohlenhydraten in den stark salzhaltigen Matrices bei sehr niedrigen Massekonzentrationen mit hohen Wiederfindungsraten gewährleisten. Im Rahmen dieser Doktorarbeit wurde durch Kombination der Hochleistungs-Anionenaustauschchromatographie mit gepulster amperometrischer Detektion (HPAEC-PAD) und einer Entsalzung durch Elektrodialyse eine analytische Methode entwickelt, welche die Bestimmung eines breiten Spektrums an gelösten Kohlenhydraten in freier (als Monosaccharide) und gebundener (als Oligo- oder Polysaccharide) Form in Meerwasser und anderen salzhaltigen Matrices ermöglicht. Mithilfe dieser neuen Methode wurde ein biogeochemischer Zusammenhang zwischen dem Vorkommen von freier Glucose und der eiskeimbildenden Aktivität im arktischen SML beobachtet. Außerdem wurde im meereisfreien Teil des Südlichen Ozeans der primäre Transfer von Kohlenhydraten vom Ozean über den SML in die Atmosphäre und deren sekundäre atmosphärische Veränderungen erforscht. Die umfangreichen Untersuchungen mariner Kohlenhydrate in polarem Meerwasser und Aerosolpartikeln zeigen Indizien einer bisher noch unterschätzten atmosphärischen Bedeutung mikrobiologischer Prozesse auf.:1. Introduction ............................................................................................................................................... 1 1.1 The Polar Oceans ................................................................................................................................. 3 1.1.1 Geographical Definitions and Characteristics.......................................................................... 3 1.1.2 Role in Earth’s Climate System ................................................................................................ 5 1.1.3 Changing Climate and Consequences ...................................................................................... 6 1.2 Sea Spray Aerosol over the Polar Oceans ........................................................................................... 9 1.2.1 Production Mechanisms of Sea Spray Aerosol ........................................................................ 9 1.2.2 Chemo-Selective Sea-Air Transfer and Atmospheric Aging ................................................... 10 1.2.3 Impact on Earth’s Radiation Budget ...................................................................................... 12 1.3 The Surface of the Polar Oceans ....................................................................................................... 15 1.3.1 The Sea Surface Microlayer ................................................................................................... 15 1.3.2 Selective Enrichment of Chemical Compounds ..................................................................... 15 1.3.3 Atmospheric Relevance for Atmospheric Chemistry and Cloud Microphysics ..................... 24 1.4 Marine Carbohydrates....................................................................................................................... 26 1.4.1 Chemical Structures ............................................................................................................... 26 1.4.2 Microbial Role ........................................................................................................................ 28 1.4.3 Marine Carbohydrates in the Atmosphere ............................................................................ 30 1.4.4 Chemical Analysis and Sea Salt Interference ......................................................................... 31 2. Results and Discussions ........................................................................................................................... 35 2.1 First Publication ................................................................................................................................. 35 2.1.1 Glucose as a Potential Chemical Marker for Ice Nucleating Activity in Arctic Seawater and Melt Pond Samples ......................................................................................................................... 35 2.1.2 Supporting Information ......................................................................................................... 47 2.2 Second Publication ............................................................................................................................ 55 A protocol for quantifying mono-and polysaccharides in seawater and related saline matrices by electro-dialysis (ED) – combined with HPAEC-PAD ........................................................................ 55 2.3 Third Publication ............................................................................................................................... 70 2.3.1 Aerosol Marine Primary Carbohydrates and Atmospheric Transformation in the Western Antarctic Peninsula ......................................................................................................................... 70 2.3.2 Supporting Information ......................................................................................................... 88 3. Atmospheric Implications ........................................................................................................................ 95 4. Summary ................................................................................................................................................ 98 5. References ............................................................................................................................................. 101 List of Abbreviations .................................................................................................................................. 121 List of Figures ............................................................................................................................................. 123 List of Tables .............................................................................................................................................. 124 Curriculum Vitae ........................................................................................................................................ 125 / Primary marine aerosol particles impact Earth’s radiation budget by acting, among other things, as cloud condensation nuclei (CCN) or ice nucleating particles (INP) for the formation of clouds. Over the polar oceans, primary marine aerosol emissions dominate the atmospheric particles and can play a significant and changing role there in the context of climate change. These particles are primarily emitted from the oceanic surface water and a thin surface film, the so-called sea surface microlayer (SML), by the bursting of air bubbles entrained by the wind. They consist of inorganic sea salt and organic matter (OM), whose relative proportions differ greatly depending on the aerosol diameter. In this context, the marine carbohydrates represent an important group of OM, whose oceanic sources, their transition from the sea to the atmosphere, atmospheric aging and contribution to the condensation of water droplets and ice nucleation are not well understood. This limited level of knowledge is due, among other things, to the lack of analytical methods that enable a reliable determination of carbohydrates at very low mass concentrations with high recovery rates in the salty matrices. Within the framework of this PhD thesis, an analytical method was developed by combining high-performance anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD) and a prior desalination by electro-dialysis (ED), which enables the determination of a wide range of dissolved carbohydrates in their free (as monosaccharides) and combined (as oligo- or polysaccharides) forms in seawater and other saline matrices. With this new method, a biogeochemical connection between the presence of free glucose and the ice nucleating activity in the Arctic SML could be observed. In addition, the primary transfer of carbohydrates from the ocean via the SML into the atmosphere and subsequent secondary atmospheric transformations were investigated in the sea ice-free part of the Southern Ocean. Consequently, the extensive investigations of marine carbohydrates in seawater and aerosol particles indicate an atmospheric importance of microbiological processes that has been underestimated until now.:1. Introduction ............................................................................................................................................... 1 1.1 The Polar Oceans ................................................................................................................................. 3 1.1.1 Geographical Definitions and Characteristics.......................................................................... 3 1.1.2 Role in Earth’s Climate System ................................................................................................ 5 1.1.3 Changing Climate and Consequences ...................................................................................... 6 1.2 Sea Spray Aerosol over the Polar Oceans ........................................................................................... 9 1.2.1 Production Mechanisms of Sea Spray Aerosol ........................................................................ 9 1.2.2 Chemo-Selective Sea-Air Transfer and Atmospheric Aging ................................................... 10 1.2.3 Impact on Earth’s Radiation Budget ...................................................................................... 12 1.3 The Surface of the Polar Oceans ....................................................................................................... 15 1.3.1 The Sea Surface Microlayer ................................................................................................... 15 1.3.2 Selective Enrichment of Chemical Compounds ..................................................................... 15 1.3.3 Atmospheric Relevance for Atmospheric Chemistry and Cloud Microphysics ..................... 24 1.4 Marine Carbohydrates....................................................................................................................... 26 1.4.1 Chemical Structures ............................................................................................................... 26 1.4.2 Microbial Role ........................................................................................................................ 28 1.4.3 Marine Carbohydrates in the Atmosphere ............................................................................ 30 1.4.4 Chemical Analysis and Sea Salt Interference ......................................................................... 31 2. Results and Discussions ........................................................................................................................... 35 2.1 First Publication ................................................................................................................................. 35 2.1.1 Glucose as a Potential Chemical Marker for Ice Nucleating Activity in Arctic Seawater and Melt Pond Samples ......................................................................................................................... 35 2.1.2 Supporting Information ......................................................................................................... 47 2.2 Second Publication ............................................................................................................................ 55 A protocol for quantifying mono-and polysaccharides in seawater and related saline matrices by electro-dialysis (ED) – combined with HPAEC-PAD ........................................................................ 55 2.3 Third Publication ............................................................................................................................... 70 2.3.1 Aerosol Marine Primary Carbohydrates and Atmospheric Transformation in the Western Antarctic Peninsula ......................................................................................................................... 70 2.3.2 Supporting Information ......................................................................................................... 88 3. Atmospheric Implications ........................................................................................................................ 95 4. Summary ................................................................................................................................................ 98 5. References ............................................................................................................................................. 101 List of Abbreviations .................................................................................................................................. 121 List of Figures ............................................................................................................................................. 123 List of Tables .............................................................................................................................................. 124 Curriculum Vitae ........................................................................................................................................ 125

No description available.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

Species must interact with air—aqueous interfaces in order to transport between either phase, however organic coated water surfaces are ubiquitous in the environment, and the physical and chemical processes that occur at organic coated aqueous surfaces are often different than those at pure air—water interfaces. Three studies were performed investigating the transport of species across air—aqueous interfaces with organic coatings in an effort to gain further insight into these processes. Gas and solution phase absorption spectroscopy were used to study the effect of octanol coatings on the formation of molecular iodine (I2) by the heterogeneous ozonation of iodide and its partitioning between phases. Compared to uncoated solutions, the presence of octanol monolayers had a minor effect on the total amount of I2 produced, however, it did significantly enhance the gas to solution partitioning of I2. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBC-EAS) was used to measure the gas-phase nitrogen dioxide (NO2) evolved via photolysis of aqueous nitrate solutions either uncoated or containing octanol, octanoic acid and stearic acid monolayers. Both octanol and stearic acid reduced the rate of gaseous NO2 evolution, and octanol also decreased the steady-state amount of gaseous NO2. Alternatively, octanoic acid enhanced the rate of gaseous NO2 evolution. Finally, the loss of aqueous carbon dioxide (CO2) from aqueous solutions saturated with CO2 was measured using a CO2 electrode in the absence and presence of stearic acid monolayers and octanol coatings, and a greenhouse gas analyzer was used to measure the evolution of gaseous CO2 from solutios with octanol monolayers. Enhanced losses of aqueous and evolved gaseous CO2 were observed with organic coated solutions compared to those uncoated. The results of these studies suggest that organic coatings influence the transport of I2, NO2 and CO2 via one, or a combination of: barrier effects, surface tension effects, chemistry effects and aqueous – surface – gas partitioning effects. These results, particularly the enhanced partitioning of these species to octanol coated aqueous surfaces, have important implications for species transport at air—aqueous interfaces, and may provide useful insight for future studies and parameters for atmospheric models of these species.

No description available.