Dynamics of the cold surface layer of polythermal Storglaciären, Sweden

Polythermal glaciers, i.e. glaciers with a combination of ice at and below the freezing point, are widespread in arctic and subarctic environments. The polythermal structure has major implications for glacier hydrology, ice flow and glacial erosion. However, the interplay of factors governing its spatial and temporal variations such as net mass balance, ice advection and water content in the ice is poorly investigated and as yet not fully understood. This study deals with a thorough investigation of the polythermal regime on Storglaciären, northern Sweden, a small valley glacier with a cold surface layer in the ablation area. Extensive field work was performed including mapping of the cold surface layer using ground-penetrating radar, ice temperature measurements, mass balance and ice velocity measurements. Analyses of these data combined with numerical modelling were used specifically to investigate the spatial and temporal variability of the cold surface layer, the spatial distribution of the water content just below the cold surface layer transition, the effect of radar frequency on the detection of the surface layer, and the sensitivity of the cold surface layer to changes in forcing. A comparison between direct temperature measurements in boreholes and ground-penetrating surveys shows that the radar-inferred cold-temperate transition depth is within ±1 m from the melting point of ice at frequencies above ~300 MHz. At frequencies below ~155 MHz, the accuracy degrades because of reduced scattering efficiency that occurs when the scatterers become much smaller compared to the wavelength. The mapped spatial pattern of the englacial cold-temperate transition boundary is complex. This pattern reflects the observed spatial variation in net loss of ice at the surface by ablation and vertical advection of ice, which is suggested to provide the predominant forcing of the cold surface layer thickness pattern. This is further supported by thermomechanical modeling of the cold surface layer, which indicates high sensitivity of the cold surface layer thickness to changes in vertical advection rates. The water content is the least investigated quantity that is relevant for the thermal regime of glaciers, but also the most difficult to assess. Spatial variability of absolute water content in the temperate ice immediately below the cold surface layer on Storglaciären was determined by combining relative estimates of water content from ground-penetrating radar data with absolute determination from temperature measurements and the thermal boundary condition at the freezing front. These measurements indicate large-scale spatial variability in the water content, which seems to arise from variations in entrapment of water at the firn-ice transition. However, this variability cannot alone explain the spatial pattern in the thermal regime on Storglaciären. Repeated surveys of the cold surface layer show a 22% average thinning of the cold surface layer on Storglaciären between 1989 and 2001. Transient thermomechanical modeling results suggest that the cold surface layer adapts to new equilibrium conditions in only a few decades after a perturbation in the forcing is introduced. An increased winter air temperature since mid-1980s seems to be the cause of the observed thinning of the cold surface layer. Over the last decades, mass balance measurements indicate that the glacier has been close to a steady state. The quasi-steady state situation is also reflected in the vertical advection, which shows no significant changes during the last decades. Increased winter temperatures at the ice surface would result in a slow-down of the formation of cold ice at the base of the cold surface layer and lead to a larger imbalance between net loss of ice at the surface and freezing of temperate ice at the cold-temperate transition.

Structural investigation of Nb-based layer sulfides

In this work we have investigated the intercalation of electron-donors between NbS2 slabs in Nb-based layer sulfides. Two series of Sr substituted Nb-based misfit sulfides belonging to the 1.5Q/1H and 1Q/1H series of misfit layer compounds have been synthesised. For large lanthanides (Ln=La, Ce), only the 1Q/1H compounds formed whereas for smaller lanthanides and yttrium, both types of phases can be obtained. The crystal structure of misfit sulfide (Pr0.55Sr0.45S)1.15NbS2 has been refined using the composite approach. In the Q-slab, Pr-atoms are partly replaced by Sr with a random distribution over one cation position. The crystal structure of misfit sulfide [(Sm1/3Sr2/3S)1.5]1.15NbS2 belonging to the 1.5Q/1H series have also been determined. The obtained results suggest a preferred occupancy of the cation positions in the slab where Sr atoms mainly occupy positions on the exterior of the slab while Sm atoms are in the center of the slab. The (La1-xSrxS)1.15NbS2 solid solution (0.1<x<0.9) has also been studied. It was found that the maximum value of Sr substitution is 40-50% and therefore, the minimal value of charge transfer to stabilize this structure type is about 0.6ē per Nb atom. An attempt to synthesize SrxNbS2 (0.1≤x≤0.5) intercalates was made but single phases were not obtained and increasing the temperature from 1000оС to 1100оС leads to the decomposition of these intercalates. Single crystals of Sr0.22Nb1.05S2 and Sr0.23NbS2 were found and their structures were determined. The structures belong to two different types of packings with statistical distribution of Sr between layers. A new superconducting sulfide, "EuNb2S5", was investigated by ED and HREM and its structure model consisting of Nb7S14 and (Eu3S4)2 slabs alternating along the c-axis is suggested. An attempt to suggest a model for the structure of "SrNb2S5" by means of X-ray single crystal diffraction was made. The proposed structure consists of two types of slabs: a Nb7S14 and a [Sr6(NbS4)2S] slab with niobium in tetrahedral coordination. It is shown that "SrNb2S5" and "EuNb2S5" are have similar structures. For the first time, single crystals of the complex sulfide BaNb0.9S3 have also been studied by means of X-ray single crystal diffraction. The single crystal refinement and EDX analysis showed the existence of cation vacancies at the niobium position. BaNb0.9S3 has also been studied by ED and no superstructure was found which implies that and the vacancies are statistically distributed. No improvement of the magnetic properties of the studied compounds was observed in comparison to NbS2.

Coupling between upper ocean layer variability and size-fractionated phytoplankton in a non-nutrient-limited environment

[EN] We describe the coupling between upper ocean layer variability and size-fractionated phytoplankton distribution in the non-nutrient-limited Bransfield Strait region (BS) of Antarctica. For this purpose we use hydrographic and size-fractionated chlorophyll a data from a transect that crossed 2 fronts and an eddy, together with data from 3 stations located in a deeply mixed region, the Antarctic Sound (AS). In the BS transect, small phytoplankton (<20 μm equivalent spherical diameter [ESD]) accounted for 80% of total chl a and their distribution appeared to be linked to cross-frontal variability. On the deepening upper mixed layer (UML) sides of both fronts we observed a deep subducting column-like structure of small phytoplankton biomass. On the shoaling UML sides of both fronts, where there were signs of restratification, we observed a local shallow maximum of small phytoplankton biomass. We propose that this observed phytoplankton distribution may be a response to the development of frontal vertical circulation cells. In the deep, turbulent environment of the AS, larger phytoplankton (>20 μm ESD) accounted for 80% of total chl a. The proportion of large phytoplankton increases as the depth of the upper mixed layer (ZUML), and the corresponding rate of vertical mixing, increases. We hypothesize that this change in phytoplankton composition with varying ZUML is related to the competition for light, and results from modification of the light regime caused by vertical mixing.

Cross-layer optimizations in multi-hop ad hoc networks

Unlike traditional wireless networks, characterized by the presence of last-mile, static and reliable infrastructures, Mobile ad Hoc Networks (MANETs) are dynamically formed by collections of mobile and static terminals that exchange data by enabling each other's communication. Supporting multi-hop communication in a MANET is a challenging research area because it requires cooperation between different protocol layers (MAC, routing, transport). In particular, MAC and routing protocols could be considered mutually cooperative protocol layers. When a route is established, the exposed and hidden terminal problems at MAC layer may decrease the end-to-end performance proportionally with the length of each route. Conversely, the contention at MAC layer may cause a routing protocol to respond by initiating new routes queries and routing table updates. Multi-hop communication may also benefit the presence of pseudo-centralized virtual infrastructures obtained by grouping nodes into clusters. Clustering structures may facilitate the spatial reuse of resources by increasing the system capacity: at the same time, the clustering hierarchy may be used to coordinate transmissions events inside the network and to support intra-cluster routing schemes. Again, MAC and clustering protocols could be considered mutually cooperative protocol layers: the clustering scheme could support MAC layer coordination among nodes, by shifting the distributed MAC paradigm towards a pseudo-centralized MAC paradigm. On the other hand, the system benefits of the clustering scheme could be emphasized by the pseudo-centralized MAC layer with the support for differentiated access priorities and controlled contention. In this thesis, we propose cross-layer solutions involving joint design of MAC, clustering and routing protocols in MANETs. As main contribution, we study and analyze the integration of MAC and clustering schemes to support multi-hop communication in large-scale ad hoc networks. A novel clustering protocol, named Availability Clustering (AC), is defined under general nodes' heterogeneity assumptions in terms of connectivity, available energy and relative mobility. On this basis, we design and analyze a distributed and adaptive MAC protocol, named Differentiated Distributed Coordination Function (DDCF), whose focus is to implement adaptive access differentiation based on the node roles, which have been assigned by the upper-layer's clustering scheme. We extensively simulate the proposed clustering scheme by showing its effectiveness in dominating the network dynamics, under some stressing mobility models and different mobility rates. Based on these results, we propose a possible application of the cross-layer MAC+Clustering scheme to support the fast propagation of alert messages in a vehicular environment. At the same time, we investigate the integration of MAC and routing protocols in large scale multi-hop ad-hoc networks. A novel multipath routing scheme is proposed, by extending the AOMDV protocol with a novel load-balancing approach to concurrently distribute the traffic among the multiple paths. We also study the composition effect of a IEEE 802.11-based enhanced MAC forwarding mechanism called Fast Forward (FF), used to reduce the effects of self-contention among frames at the MAC layer. The protocol framework is modelled and extensively simulated for a large set of metrics and scenarios. For both the schemes, the simulation results reveal the benefits of the cross-layer MAC+routing and MAC+clustering approaches over single-layer solutions.

Modeling the gas and aqueous phase chemistry of the marine boundary layer

Ein eindimensionales numerisches Modell der maritimenGrenzschicht (MBL) wurde erweitert, um chemische Reaktionenin der Gasphase, von Aerosolpartikeln und Wolkentropfen zu beschreiben. Ein Schwerpunkt war dabei die Betrachtung derReaktionszyklen von Halogenen. Soweit Ergebnisse vonMesskampagnen zur Verfuegung standen, wurden diese zurValidierung des Modells benutzt. Die Ergebnisse von frueheren Boxmodellstudien konntenbestaetigt werden. Diese zeigten die saeurekatalysierteAktivierung von Brom aus Seesalzaerosolen, die Bedeutung vonHalogenradikalen fuer die Zerstoerung von O3, diepotentielle Rolle von BrO bei der Oxidation von DMS und dievon HOBr und HOCl in der Oxidation von S(IV). Es wurde gezeigt, dass die Beruecksichtigung derVertikalprofile von meteorologischen und chemischen Groessenvon grosser Bedeutung ist. Dies spiegelt sich darin wider,dass Maxima des Saeuregehaltes von Seesalzaerosolen und vonreaktiven Halogenen am Oberrand der MBL gefunden wurden.Darueber hinaus wurde die Bedeutung von Sulfataerosolen beidem aktiven Recyceln von weniger aktiven zu photolysierbarenBromspezies gezeigt. Wolken haben grosse Auswirkungen auf die Evolution und denTagesgang der Halogene. Dies ist nicht auf Wolkenschichtenbeschraenkt. Der Tagesgang der meisten Halogene ist aufgrundeiner erhoehten Aufnahme der chemischen Substanzen in die Fluessigphase veraendert. Diese Ergebnisse betonen dieWichtigkeit der genauen Dokumentation der meteorologischenBedingungen bei Messkampagnen (besonders Wolkenbedeckungsgrad und Fluessigwassergehalt), um dieErgebnisse richtig interpretieren und mit Modellresultatenvergleichen zu koennen. Dieses eindimensionale Modell wurde zusammen mit einemBoxmodell der MBL verwendet, um die Auswirkungen vonSchiffemissionen auf die MBL abzuschaetzen, wobei dieVerduennung der Abgasfahne parameterisiert wurde. DieAuswirkungen der Emissionen sind am staerksten, wenn sie insauberen Gebieten stattfinden, die Hoehe der MBL gering istund das Einmischen von Hintergrundluft schwach ist.Chemische Reaktionen auf Hintergrundaerosolen spielen nureine geringe Rolle. In Ozeangebieten mit schwachemSchiffsverkehr sind die Auswirkungen auf die Chemie der MBL beschraenkt. In staerker befahrenen Gebieten ueberlappensich die Abgasfahnen mehrerer Schiffe und sorgen fuerdeutliche Auswirkungen. Diese Abschaetzung wurde mitSimulationen verglichen, bei denen die Emissionen alskontinuierliche Quellen behandelt wurden, wie das inglobalen Chemiemodellen der Fall ist. Wenn die Entwicklungder Abgasfahne beruecksichtigt wird, sind die Auswirkungendeutlich geringer da die Lebenszeit der Abgase in der erstenPhase nach Emission deutlich reduziert ist.

Charakterisierung von S-Layer-Proteinen bei Prokaryoten

S-Layer sind kristalline Proteinschichten, die als Komponenten von Zellwänden in allen Zweigen der Bakterien und Archaebakterien vorkommen. Aus der Domäne der Archaea wurden die S-Layer-Proteine mesophiler, thermophiler und hyperthermophiler Methanococcales verglichen. Die Zellwand dieser Organismen besteht nur aus einer S-Layerschicht, die die Zellen vor äußeren Einflüssen schützt. Analog zu den Methanococcales wurden S-Layer-Proteine mesophiler und thermophiler Vertreter aus der Familie der Bacillaceae verglichen.Ziel dieser Arbeit war es, die S-Layer-Gensequenzen von Methanotorris igneus, Methanothermococcus thermolithotrophicus, Methanococcus vannielii, Geobacillus stearothermophilus, Bacillus sphaericus und Bacillus fusiformis zu ermitteln. Durch Vergleiche der Primärsequenzen mesophiler und (hyper)thermophiler S-Layer-Proteine sollten Hinweise auf thermostabilisierende Faktoren abgeleitet werden. Durch Verwendung geeigneter bio-chemischer und gentechnischer Arbeitsmethoden wurden die Gen- und Proteinsequenzen der S-Layer-Proteine ermittelt. Die unbekannten Genbereiche wurden durch die Entwicklung einer modifizierten Zwei- und Drei-Schritt-PCR ermittelt.Die Sequenzanalyse der archaebakteriellen und bakteriellen S-Layer-Proteine erbrachte nur für erstere Hinweise auf thermostabilisierende Faktoren. Die (hyper)thermophilen S-Layer-Hüllproteine aus der Ordnung Methanococcales zeigten gegenüber den mesophilen folgende Unterschiede:1. Zunahme von geladenen Resten;2. Abnahme von Alanin und unpolaren Resten3. Vorhandensein von Cystein4. Erhöhte Anzahl an N-glykosidischen BindungsstellenDas hyperthermophile S-Layer-Protein von Mcc. jannaschii wurde in Escherichia coli erfolgreich expremiert. Für das native Hüllprotein wurde, als ein möglicherweise weiterer thermostabilisierender Faktor eine Glykosilierung detektiert. Zudem wies das native S-Layer-Protein eine Konformationsänderung im Verlauf einer Temperaturerhöhung, bei verschiedenen pH-Werten und in Anwesenheit zweiwertigen Mangans auf. Auch das Expressionsprotein zeigte im Verlauf der Temperaturerhöhung und bei verschiedenen pH-Werten eine Konformationsänderung. Mn2+ hatte dagegen keinen Effekt und eine Glykosi-lierung war nicht nachweisbar.Die transkriptionellen und translationellen Erkennungsregionen der S-Layer-Gene aus der Ordnung Methanococcales wurden bestimmt. Basierend auf Sequenzähnlichkeiten und Gemeinsamkeiten der archaebakteriellen S-Layer-Proteine wurden diese in vier Gruppen eingeteilt.Aus dem bakteriellen Zweig wurde die Gen- und Primärsequenzen der S-Layer-Proteine von Gb. stearothermophilus DSM 2358, B. sphaericus DSM 396, B. fusiformis B3 und DSM 2898T ermittelt. Die Proteine wiesen z. T. eine geringere molekulare Masse auf als die be-kannten S-Layer-Hüllproteine aus der Familie der Bacillaceae. Das Protein von B. sphaericus DSM 396 zeigte eine Diskrepanz zwischen der theoretischen (85 kDA) und experimentell (120 kDa) ermittelten Molmasse. Erstmals wurde für die S-Layer-Proteine von B. fusiformis B3 und DSM 2898T eine vermutliche Dimerbildung festgestellt. Basierend auf den N-terminalen Sequenzähnlichkeiten wurden die S-Layer-Proteine aus der Familie der Bacillaceae in vier Gruppen eingeteilt.

Multilayer thin films by layer-by-layer (LBL) assembly of functional polyelectrolytes

Nanoscience aims at manipulating atoms, molecules and nano-size particles in a precise and controlled manner. Nano-scale control of the thin film structures of organic/polymeric materials is a prerequisite to the fabrication of sophisticated functional devices. The work presented in this thesis is a compilation of various polymer thin films with newly synthesized functional polymers. Cationic and anionic LC amphotropic polymers, p-type and n-type semiconducting polymers with triarylamine, oxadiazole, thiadiazole and triazine moieties are suitable materials to fabricate multilayers by layer-by-layer (LBL) self-assembly with a well defined internal structure. The LBL assembly is the ideal processing technique to prepare thin polymer film composites with fine control over morphology and composition at nano-scale thickness, which may have applications in photo-detectors, light-emitting diodes (LEDs), displays and sensors, as well as in solar cells. The multilayer build-up was investigated with amphotropic LC polymers individually by solution-dipping and spin-coating methods; they showed different internal orders with respect to layering and orientation of the mesogens, as a result of the liquid crystalline phase. The synthesized p-type and n-type semiconducting polymers were examined optically and electrochemically, suggesting that they are favorably promising as hole-(p-type) or electron-(n-type) transport materials in electronic and optoelectronic devices. In addition, we report a successful film deposition of polymers by the vacuum deposition method. The vapor deposition method provides a clean environment; it is solvent free and well suited to sequential depositions in hetero-structured multilayer system. As the potential applications, the fabricated polymer thin films were used as simple electrochromic films and also used as hole transporting layers in LEDs. Electrochemical and electrochromic characterizations of assembled films reveal that the newly synthesized polymers give rise to high contrast ratio and fast switching electrochromic films. The LEDs with vacuum deposited films show dramatic improvements in device characteristics, indicating that the films are promising as hole transporting layers. These are the result of not only the thin nano-scale film structures but also the combination with the high charge carrier mobility of synthesized semiconducting polymers.

Detection and Modeling of Boundary Layer Height

This thesis tackles the problem of the automated detection of the atmospheric boundary layer (BL) height, h, from aerosol lidar/ceilometer observations. A new method, the Bayesian Selective Method (BSM), is presented. It implements a Bayesian statistical inference procedure which combines in an statistically optimal way different sources of information. Firstly atmospheric stratification boundaries are located from discontinuities in the ceilometer back-scattered signal. The BSM then identifies the discontinuity edge that has the highest probability to effectively mark the BL height. Information from the contemporaneus physical boundary layer model simulations and a climatological dataset of BL height evolution are combined in the assimilation framework to assist this choice. The BSM algorithm has been tested for four months of continuous ceilometer measurements collected during the BASE:ALFA project and is shown to realistically diagnose the BL depth evolution in many different weather conditions. Then the BASE:ALFA dataset is used to investigate the boundary layer structure in stable conditions. Functions from the Obukhov similarity theory are used as regression curves to fit observed velocity and temperature profiles in the lower half of the stable boundary layer. Surface fluxes of heat and momentum are best-fitting parameters in this exercise and are compared with what measured by a sonic anemometer. The comparison shows remarkable discrepancies, more evident in cases for which the bulk Richardson number turns out to be quite large. This analysis supports earlier results, that surface turbulent fluxes are not the appropriate scaling parameters for profiles of mean quantities in very stable conditions. One of the practical consequences is that boundary layer height diagnostic formulations which mainly rely on surface fluxes are in disagreement to what obtained by inspecting co-located radiosounding profiles.

Surface layer formation in polymer melts and in solutions

In this work the surface layer formation in polymer melts and in polymer solutions have been investigated with the atomic force microscope (AFM). In polymer melts, the formation of an immobile surface layer results in a steric repulsion, which can be measured by the AFM. From former work it is know, that polydimethyl siloxane (PDMS) forms a stable surface layer for molecular weights above 12 kDa. In the present thesis, polyisoprene (PI) was investigated apart from PDMS, by a)measuring the steric surface interactions and b)measuring the surface slip in hydrodynamic experiments. If a polymer flows over a surface, the flow velocity at the surface is larger then zero. If case of a surface layer formation the flow plane changes to the top of the adsorbed layer and the surface slip is reduced to zero. By measuring the surface slip in hydrodynamic experiments, it is therefore possible to determine the presence of a stable surface layer. The results show no stable repulsion for PI and only a small decrease of the surface slip. This indicates that PI does not form a stable surface layer, but is only adsorbed weakly to the surface. Furthermore for 8 kDa PDMS the timescale of the formation of a surface layer was investigated by changing themaximal force the tip applied to the surface. With a repulsive force present, applying a higher force than 15 nN resulted in a destruction of the surface layer, indicated by attractive forces. Reducing the applied force below 15 nN then resulted in an increase of the repulsion to the former state during one minute, thus indicating that a surface layer can be formed within one minute even under the influence of continuous measurements. As a next step, mixtures of two PDMS homopolymers with different chain lengths have been investigated. The aim was to verify theoretical predictions that shorter chains should predominate at the surface due to their smaller loss in conformational entropy. The measurements where done in dependence of the volume fractions of short and long chain PMDS. The results confirmed the short chain dominance for all mixtures with less then 90 vol.% long chain PDMS. Surface layer formation in solution was investigated for superplasticizers which are industrially used as an additive to cement. They change the surface interaction between the cement grains from attractive to repulsive and the freshlymixed cement paste therefore becomes liquid. The aimin this part of the thesis was, to investigate cement particle interactions in a close to real environment. Therefore calcium silicate hydrate phases have been precipitated onto an AFM tip and onto a calcite crystal and the interaction between these surfaces have beenmeasured with and without addition of superplasticizers. The measurements confirmed the change from attraction to repulsion upon addition of superplasticizers. The repulsive steric interaction increased with the length of the sidechain of the superplasticizer, and the dependence of the range of the steric interactions on the sidechain length indicated that the sidechains are in a coiled conformation.

Modelling the stable, nocturnal boundary layer: different approaches to turbulence closure problem

Il lavoro è dedicato all'analisi fisica e alla modellizzazione dello strato limite atmosferico in condizioni stabili. L'obiettivo principale è quello di migliorare i modelli di parametrizzazione della turbulenza attualmente utilizzati dai modelli meteorologici a grande scala. Questi modelli di parametrizzazione della turbolenza consistono nell' esprimere gli stress di Reynolds come funzioni dei campi medi (componenti orizzontali della velocità e temperatura potenziale) usando delle chiusure. La maggior parte delle chiusure sono state sviluppate per i casi quasi-neutrali, e la difficoltà è trattare l'effetto della stabilità in modo rigoroso. Studieremo in dettaglio due differenti modelli di chiusura della turbolenza per lo strato limite stabile basati su assunzioni diverse: uno schema TKE-l (Mellor-Yamada,1982), che è usato nel modello di previsione BOLAM (Bologna Limited Area Model), e uno schema sviluppato recentemente da Mauritsen et al. (2007). Le assunzioni delle chiusure dei due schemi sono analizzate con dati sperimentali provenienti dalla torre di Cabauw in Olanda e dal sito CIBA in Spagna. Questi schemi di parametrizzazione della turbolenza sono quindi inseriti all'interno di un modello colonnare dello strato limite atmosferico, per testare le loro predizioni senza influenze esterne. Il confronto tra i differenti schemi è effettuato su un caso ben documentato in letteratura, il "GABLS1". Per confermare la validità delle predizioni, un dataset tridimensionale è creato simulando lo stesso caso GABLS1 con una Large Eddy Simulation. ARPS (Advanced Regional Prediction System) è stato usato per questo scopo. La stratificazione stabile vincola il passo di griglia, poichè la LES deve essere ad una risoluzione abbastanza elevata affinchè le tipiche scale verticali di moto siano correttamente risolte. Il confronto di questo dataset tridimensionale con le predizioni degli schemi turbolenti permettono di proporre un insieme di nuove chiusure atte a migliorare il modello di turbolenza di BOLAM. Il lavoro è stato compiuto all' ISAC-CNR di Bologna e al LEGI di Grenoble.

Iodine speciation in atmospheric aerosols in the marine boundary layer

Iodine chemistry plays an important role in the tropospheric ozone depletion and the new particle formation in the Marine Boundary Layer (MBL). The sources, reaction pathways, and the sinks of iodine are investigated using lab experiments and field observations. The aims of this work are, firstly, to develop analytical methods for iodine measurements of marine aerosol samples especially for iodine speciation in the soluble iodine; secondly, to apply the analytical methods in field collected aerosol samples, and to estimate the characteristics of aerosol iodine in the MBL. Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) was the technique used for iodine measurements. Offline methods using water extraction and Tetra-methyl-ammonium-hydroxide (TMAH) extraction were applied to measure total soluble iodine (TSI) and total insoluble iodine (TII) in the marine aerosol samples. External standard calibration and isotope dilution analysis (IDA) were both conducted for iodine quantification and the limits of detection (LODs) were both 0.1 μg L-1 for TSI and TII measurements. Online couplings of Ion Chromatography (IC)-ICP-MS and Gel electrophoresis (GE)-ICP-MS were both developed for soluble iodine speciation. Anion exchange columns were adopted for IC-ICP-MS systems. Iodide, iodate, and unknown signal(s) were observed in these methods. Iodide and iodate were separated successfully and the LODs were 0.1 and 0.5 μg L-1, respectively. Unknown signals were soluble organic iodine species (SOI) and quantified by the calibration curve of iodide, but not clearly identified and quantified yet. These analytical methods were all applied to the iodine measurements of marine aerosol samples from the worldwide filed campaigns. The TSI and TII concentrations (medians) in PM2.5 were found to be 240.87 pmol m-3 and 105.37 pmol m-3 at Mace Head, west coast of Ireland, as well as 119.10 pmol m-3 and 97.88 pmol m-3 in the cruise campaign over the North Atlantic Ocean, during June – July 2006. Inorganic iodine, namely iodide and iodate, was the minor iodine fraction in both campaigns, accounting for 7.3% (median) and 5.8% (median) in PM2.5 iodine at Mace Head and over the North Atlantic Ocean, respectively. Iodide concentrations were higher than iodate in most of the samples. In the contrast, more than 90% of TSI was SOI and the SOI concentration was correlated significantly with the iodide concentration. The correlation coefficients (R2) were both higher than 0.5 at Mace Head and in the first leg of the cruise. Size fractionated aerosol samples collected by 5 stage Berner impactor cascade sampler showed similar proportions of inorganic and organic iodine. Significant correlations were obtained in the particle size ranges of 0.25 – 0.71 μm and 0.71 – 2.0 μm between SOI and iodide, and better correlations were found in sunny days. TSI and iodide existed mainly in fine particle size range (< 2.0 μm) and iodate resided in coarse range (2.0 – 10 μm). Aerosol iodine was suggested to be related to the primary iodine release in the tidal zone. Natural meteorological conditions such as solar radiation, raining etc were observed to have influence on the aerosol iodine. During the ship campaign over the North Atlantic Ocean (January – February 2007), the TSI concentrations (medians) ranged 35.14 – 60.63 pmol m-3 among the 5 stages. Likewise, SOI was found to be the most abundant iodine fraction in TSI with a median of 98.6%. Significant correlation also presented between SOI and iodide in the size range of 2.0 – 5.9 μm. Higher iodate concentration was again found in the higher particle size range, similar to that at Mace Head. Airmass transport from the biogenic bloom region and the Antarctic ice front sector was observed to play an important role in aerosol iodine enhancement. The TSI concentrations observed along the 30,000 km long cruise round trip from East Asia to Antarctica during November 2005 – March 2006 were much lower than in the other campaigns, with a median of 6.51 pmol m-3. Approximately 70% of the TSI was SOI on average. The abundances of inorganic iodine including iodine and iodide were less than 30% of TSI. The median value of iodide was 1.49 pmol m-3, which was more than four fold higher than that of iodate (median, 0.28 pmol m-3). Spatial variation indicated highest aerosol iodine appearing in the tropical area. Iodine level was considerably lower in coastal Antarctica with the TSI median of 3.22 pmol m-3. However, airmass transport from the ice front sector was correlated with the enhance TSI level, suggesting the unrevealed source of iodine in the polar region. In addition, significant correlation between SOI and iodide was also shown in this campaign. A global distribution in aerosol was shown in the field campaigns in this work. SOI was verified globally ubiquitous due to the presence in the different sampling locations and its high proportion in TSI in the marine aerosols. The correlations between SOI and iodide were obtained not only in different locations but also in different seasons, implying the possible mechanism of iodide production through SOI decomposition. Nevertheless, future studies are needed for improving the current understanding of iodine chemistry in the MBL (e.g. SOI identification and quantification as well as the update modeling involving organic matters).

An alternative blocking layer for titanium dioxide (TiO 2) solar cell applications

In hybrid organic solar cells a blocking layer between transparent electrode and nanocrystalline titania particles is essential to prevent short-circuiting and current loss through recombination at the electrode interface. Here the preparation of a uniform hybrid blocking layer which is composed of conducting titania nanoparticles embedded in an insulating polymer derived ceramic is presented. This blocking layer is prepared by sol-gel chemistry where an amphiphilic block copolymer is used as a templating agent. A novel poly(dimethylsiloxane) containing amphiphilic block copolymer poly(ethyleneglycol)methylethermethacrylate-block-poly(dimethylsiloxane)-block-poly(ethyleneglycol)methylethermethacrylate has been synthesized to act as the templating agent. Plasma treatment uncovered titania surface from any polymer. Annealing at 450°C under nitrogen resulted in anatase titania with polymer derived silicon oxycarbide ceramic. Electrical characterization by conductive scanning probe microscopy experiments revealed a percolating titania network separated by an insulating ceramic matrix. Scanning Kelvin probe force microscopy showed predominant presence of titania particles on the surface creating a large surface area for dye absorption. The uniformity of the percolating structures was proven by microbeam grazing incidence small angle x-ray scattering. First applications in hybrid organic solar cells in comparison with conventional titanium dioxide blocking layer containing devices revealed 15 fold increases in corresponding efficiencies. Poly(dimethylsiloxane)-block-poly(ethyleneglycol)methylethermethacrylate and poly(ethyleneoxide)-poly(dimethylsiloxane)methylmethacrylate diblock copolymers were also synthesized. Their titania nanocomposite films were compared with the integrated blocking layer. Liner poly(ethyleneoxide) containing diblock copolymer resulted in highly ordered foam like structures. The effect of heating temperature rise to 600°C and 1000°C on titania morphology was investigated by scanning electron and force microscopy and x-ray scattering. Sol-gel contents, hydrochloric acid, titania precursor and amphiphilic triblock copolymer were altered to see their effect on titania morphology. Increase in block copolymer content resulted in titania particles of diameter 15-20 nm.

The impact of ice crystals on radiative forcing and remote sensing of arctic boundary-layer mixed-phase clouds

This PhD thesis is embedded into the Arctic Study of Tropospheric Aerosol, Clouds and Radiation (ASTAR) and investigates the radiative transfer through Arctic boundary-layer mixed-phase (ABM) clouds. For this purpose airborne spectral solar radiation measurements and simulations of the solar and thermal infrared radiative transfer have been performed. This work reports on measurements with the Spectral Modular Airborne Radiation measurement sysTem (SMART-Albedometer) conducted in the framework of ASTAR in April 2007 close to Svalbard. For ASTAR the SMART-Albedometer was extended to measure spectral radiance. The development and calibration of the radiance measurements are described in this work. In combination with in situ measurements of cloud particle properties provided by the Laboratoire de M¶et¶eorologie Physique (LaMP) and simultaneous airborne lidar measurements by the Alfred Wegener Institute for Polar and Marine Research (AWI) ABM clouds were sampled. The SMART-Albedometer measurements were used to retrieve the cloud thermodynamic phase by three different approaches. A comparison of these results with the in situ and lidar measurements is presented in two case studies. Beside the dominating mixed-phase clouds pure ice clouds were found in cloud gaps and at the edge of a large cloud field. Furthermore the vertical distribution of ice crystals within ABM clouds was investigated. It was found that ice crystals at cloud top are necessary to describe the observed SMART-Albedometer measurements. The impact of ice crystals on the radiative forcing of ABM clouds is in vestigated by extensive radiative transfer simulations. The solar and net radiative forcing was found to depend on the ice crystal size, shape and the mixing ratio of ice crystals and liquid water droplets.