Aerosols and clouds provide the largest uncertainty in the atmospheric radiation budget. The main focus of this thesis was to investigate the ability of organic compounds in aerosol particles to form clouds, and more specifically those emitted by living organisms. The cloud forming properties of the highly water-soluble methyltetrols and polyols, which are compounds produced by plants and fungi that are common in aerosol, were studied. All compounds and their salt mixtures have a moderate potential to serve as cloud condensation nuclei (CCN). They are thus not likely to have a significant global impact on cloudiness. The potential presence of surfactants released by microorganisms was investigated for aerosols sampled at different locations. Very low surface tension values were measured for these aerosol extracts (30 mN/m), which implies that these aerosols have good CCN properties and indicate the presence of biosurfactants. Their occurrence in aerosols still needs to be confirmed directly by chemical identification. Reactions of organic compounds in sulfate salt solutions exposed to UV-light were studied and found to produce surface active compounds. Thus, mixed sulfate/organic aerosol could have more favourable CCN properties after exposure to light than when kept in the dark. The surface active compounds were proposed to be long-chained organosulfates with hydrophilic and hydrophobic parts, similar to other amphiphilic surfactants. Mixtures of salt and strong surfactants formed by bacteria were studied using two different techniques for determining their CCN properties. There were inconsistencies between the two methods which could be accounted for by surface partitioning. The studied mixtures were determined to be good potential CCN material in both techniques. All these aspects require further investigation, but if the impact of strong biogenic surfactants on cloud formation is confirmed, a new link between living organisms and climate would be identified. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript.

This thesis project describes how the retrieval of aerosol extinction and backscatter coefficients is computed from data obtained with a Raman lidar at FOI, Swedish Defense Research Agency. The theory is described, the implementation is done and problems discovered along the way are discussed. The lidar use the wavelength 355 nm and the Raman shift in nitrogen at 387 nm. The retrieved algorithm gives extinction coefficient between 1 500 and 10 000 meters while the backscatter coefficient covers the span 800 to 15 000 meters. However there is skewness in the backscatter coefficient that needs to be further investigated. Tests indicate that the skewness comes from the way the measurements are done at FOI.

Atmospheric aerosols may be emitted directly as particles (primary) or formed from gaseous precursors (secondary) from different natural and anthropogenic sources. The highly populated South and East Asia regions are currently in a phase of rapid economic growth to which high emissions of carbonaceous aerosols are coupled. This leads to generally poor air quality and a substantial impact of anthropogenic aerosols on the regional climate. However, the emissions of different carbon aerosol components are still poorly constrained. Water-soluble organic carbon (WSOC) is a large (20-80%) component of carbonaceous aerosols that can absorb solar light and enhance cloud formation, influencing both the direct and indirect climate effects of the aerosols. A novel method for carbon isotope-based studies, including source apportionment, of the WSOC component of ambient aerosols was developed and tested for recovery efficiency and the risk of contamination using both synthetic test substances and ambient aerosols (paper I). The application of this method for the source apportionment of aerosols in South and East Asia shows that fossil fuel input to WSOC is significant in both South Asia (about 17-23%) highly impacted by biomass combustion practices and in East Asia (up to 50%) dominated by fossil energy sources (papers II, III, IV). Fossil fraction in WSOC in the outflow from northern China is considerably larger than what has been measured in South Asia, Europe and USA (paper IV). A trend of enrichment in heavy stable carbon isotopes in WSOC with distance the particles have been transported from the source is observed in the South Asian region (papers II, III). Dual-isotope (Δ14C and δ13C) analysis demonstrates that WSOC is highly influenced by atmospheric aging processes. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Submitted.</p>

Secondary organic aerosol (SOA) generated through the partitioning of gas phase volatile organic carbon compounds (VOCs) into the condensed phase has both epidemiological and climatic impacts through the growth of particulate matter into relevant sizes for respiratory interactions and cloud condensation nuclei activity. Considering the complex chemistry involved with VOC oxidation and subsequent formation of SOA, bulk properties like oxidation state, often represented by O:C ratio, and volatility are used to simplify the representation of SOA in chemical transport models (CTMs) and the like [e.g. Tsimpidi et al. 2010]. This preference for bulk properties is supported by the availability of ambient measurement techniques to constrain model parameters and scenarios. The volatility of SOA is often described by treating it as a mixture of components with differing partitioning coefficients through the volatility basis set (VBS) approach rather than explicitly resolving the complex chemistry [Donahue et al., 2006]. This study presents a method of determining the volatility of an aerosol sample through the use of an optimizing thermodenuder (TD) instrument model that is used to fit laboratory data. Data collected using a volatility tandem differential mobility analyzer (VTDMA) setup consist of inlet and outlet particle size and number concentrations for select dicarboxylic acids - compounds known to contribute to atmospheric SOA. These are interpreted by the model through an iterative optimization routine to obtain estimates of volatility parameters (e.g. saturation concentrations) which are compared to available literature data. The instrument model is currently divided into two decoupled modules. The first resolves the flow field characteristics, obtaining the temperature profile, pressure variations, and radial velocity distribution of the TD, and the second resolves the gas to particle partitioning of aerosol with a given condensed-phase volatility distribution in the TD using the VBS approach as described in the literature. Solving the full hydrodynamic equations for the flow characteristics provides a better numeric representation of entry length and radial velocity variations and is an improvement over similar TD modeling studies in the literature. However, results indicate that coupling the two modules is necessary to more accurately resolve the suppression of evaporation due to buildup of organic vapors in the TD, even at the low mass concentrations involved with the presented experiments.

Atmospheric aerosols are known to exert a significant influence on the Earth's climate system; however, the magnitude of this influence is highly uncertain because of the complex interaction between aerosols and water vapor to form clouds. Toward reducing this uncertainty, this dissertation outlines a series of laboratory and in-situ field measurements, instrument technique development, and model simulations designed to characterize the ability of aerosols to act as cloud condensation nuclei (CCN) and form cloud droplets. Specifically, we empirically quantify the mixing state and thermodynamic properties of organic aerosols (e.g., hygroscopicity and droplet condensational uptake coefficient) measured in polluted and non-polluted environments including Alaska, California, and Georgia. It is shown that organic aerosols comprise a substantial portion of the aerosol mass and are often water soluble. CCN measurements are compared to predictions from theory in order to determine the error associated with simplified composition and mixing state assumptions employed by current large-scale models, and these errors are used to constrain the uncertainty of global and regional cloud droplet number and albedo using a recently-developed cloud droplet parameterization adjoint coupled with the GMI chemical transport model. These sensitivities are important because they describe the main determinants of climate forcing. We also present two novel techniques for fast measurements of CCN concentrations with high size, supersaturation, and temporal resolution that substantially improve the state of the art by several orders of magnitude. Ultimately, this work represents a step toward better understanding how atmospheric aerosols influence cloud properties and Earth's climate.

I händelse av ett radioaktivt utsläpp är det viktigt att ha bra beredskap med skyddsåtgärder som bidrarmed det bästa skyddet för den utsatta delen av befolkningen. Direkt efter ett utsläpp utgör exponering viainandning det största problemet eftersom partiklar och gaser ännu inte hunnit deponerats på mark, imoln och så vidare. Byggnader bidrar med ett skydd mot inhalation eftersom luften utanför och inutibostaden byts ut relativt långsamt. Hur stor del av föroreningen som tar sig in till inomhusluften och hurlång tid detta tar är viktig information för att avgöra om befolkningen är tillräckligt skyddade inutibyggnader eller om evakuering bör ske. I detta arbete har kunskap från befintlig litteratur samtmodellering använts för att beskriva generella förhållanden med vilka en förorening kan ta sig in i och utur en byggnad. Differentialekvationer med huvudprocesser och ingående parametrar har studerats för attge en uppfattning om vilket skydd en byggnad kan ge mot inhalation av partiklar och gaser i ettradioaktivt moln. Olika typer av ventilationssystem med eller utan tillhörande partikelfilter diskuteras ochinhalationsdos för olika åldersklasser och aktivitetsnivåer undersöks.Genom att jämföra mängd förorening i luften utanför mot inuti en byggnad talar man om byggnadensskyddskoefficient. De tre huvudprocesser som styr transporten är ventilation, penetration samtdeponering. Ventilationen uppkommer av luftutbytet mellan inomhus‐ och utomhusluften. Ventilationenstyrs antingen mekaniskt eller naturligt. Penetrationen beskriver hur stor andel av partiklarna ellergaserna som tar sig in över byggnadens fasad och deponeringen hur partiklar och gaser tenderar attfastna på de ytor de passerar under transporten. Deponeringen sker även på samtliga ytor inutibyggnaden. Efter att ämnen deponerats kan de resuspendera och åter komma upp till luften vilketmöjliggör för inandning innan de åter kan deponera på tillgängliga ytor. Deponeringen ses som en sänkamedan resuspensionen fungerar som en källa för inomhuskoncentrationen.En av de faktorer som påverkar skyddskoefficienten till störst del är partikeldiametern eftersomdeponerings‐ och penetrationsprocessen är starkt storleksberoende. Stora och små partiklar deponeraslättare och kvar finns den så kallade mellanfraktionen, 0,2‐1 μm i diameter, som håller sig i luften längsttid. Gaser rör sig lätt in och ut ur byggnaden och hindras inte av partikelfilter. Däremot finns särskildafilter att installera som hindrar gaser att ta sig in, exempelvis kolfilter. Sönderfallshastigheten hos de olikaradionukliderna påverkar även skyddsfaktorn. Då ämnena sönderfaller minskar koncentrationen i luften,sönderfallet är då en sänka för koncentrationen inomhus. Ventilationshastigheten har en viss påverkan påskyddskoefficienten. En ökad ventilationshastighet leder till att koncentrationen inomhus kommer att gåmot penetrationsfaktorn. Detta gäller om ventilationshastigheten kan antas vara mycket större ändepositionshastigheten. Ventilationssystem utrustade med partikelfilter kan hålla en stor del avföroreningen utanför byggnaden. Partikelfiltren har olika effektivitet och klassificeras som grov‐, mediumsamtfinfilter. En hög filtereffektivitet har stor påverkan på skyddskoefficienten. Ett filter skall däremotses som en färskvara. De kräver underhåll och bör bytas ut i tid för att kunna fungera som de ska.Inhalationsdosen beror av partikelstorlek eftersom deponeringen som sker i luftvägarna fungerar påliknande sätt som i transporten in och ut ur byggnaden. Mellanfraktionen har tendens att tränga djupt nedi lungorna efter inandning. Effekten från inhalation beror på en individs ålder, storlek och fysisk aktivitet. / In case of a radioactive release, it is important to have good preparedness with the right actions to contribute the best protection for the vulnerable section of the population. Immediately after a release theexposure through inhalation will be the biggest problem, since particles and gases have not beendeposited on land, clouds and so on. Buildings contribute to protection against inhalation. The reason forthis is that the air outside and inside the dwelling is changed relatively slowly. How much of the pollutionthat enter the indoor air and how long time it takes is important information to determine if thepopulation is sufficiently protected inside buildings or if evacuation is needed. In this work knowledgefrom existing literature and modelling has been used to describe general conditions with which apollutant moves in and out of a building. Differential equations with main processes and parameters havebeen studied to give a estimation as to the protection a building can provide against exposure throughinhalation of particles and gases in a radioactive cloud. Different types of ventilation systems, with orwithout associated particle filter are discussed and inhalation dose for different age groups and activitylevels are examined.A buildings protection coefficient is defined by comparing the amount of pollution in the air outside withthe air inside a building. The three main processes that control the transport of the pollution in and outfrom a building are ventilation, penetration and deposition. Ventilation arises of air exchange betweenindoor and outdoor air. Ventilation is controlled either mechanically or naturally. Penetration describesthe proportion of the particles or gases that enter trough the buildings shell. Deposition of particles andgases accurse due to the fact that they tend to stick to the surfaces they pass in transit. The deposition alsooccurs on all surfaces inside the building. After the particles and gases have become deposited, they mayre‐suspend and come back up into the air permitting inhalation before they once more deposit onavailable surfaces. The deposit is seen as a sink while re‐suspension acts as a source for indoor airconcentration.One of the factors that have a large impact of a buildings protection factor is the particle diameter, due tothe deposition and penetration process strongly dependent on particles size. Large and small particlesdeposited easier and the remaining fraction, the midfraction (0.2 to 1 micron in diameter), remains. Thisfraction will stay in the air longer since the deposition process does not affect it strongly. Gases moveeasily in and out of the building and are not prevented by the particle filter. However, there are specialfilters to install that prevent gases to penetrate, such as carbon filters. The rate of decay of the variousradionuclides also affects the protection factor. When nuclides decay the concentration in the airdecreases, the decay is then a sink of the concentration indoors. Ventilation rate has a certain influence onprotection coefficient. An increased ventilation rate leads to the concentration inside approaching thepenetration factor; this is applied if the ventilation rate can be assumed to be much higher than thedeposit rate. Ventilation system equipped with a particle filter can keep a large part of the pollutantoutside the building. Particle filters have different efficiency and are classified as coarse, medium and finefilter. High filter efficiency has a major impact on the protection coefficient. For a filter to functionproperly it demands maintenance and should be replaced in time.Inhalation dose depends on the particle size, since the deposition process affected in respiratory functionis similar to the transport in and out of a building. The midfraction tends to penetrate deep into the lungsafter inhalation. The effect of inhalation is due to an individual's age, size, and physical activity.

A concentric pneumatic nebulizer (CPN) and a custom designed flow focusing nebulizer (FFN) are characterized. As will be shown, the classical Nukiyama-Tanasawa and Rizk-Lefebvre models lead to erroneous size prediction for the concentric nebulizer under typical operating conditions due to its specific design, geometry, dimension and different flow regimes. The models are then modified to improve the agreement with the experimental results. The size prediction of the modified models together with the spray velocity characterization are used to determine the overall nebulizer efficiency and also employed as input to a new Maximum Entropy Principle (MEP) based model to predict joint size-velocity distribution analytically. The new MEP model is exploited to study the local variation of size-velocity distribution in contrast to the classical models where MEP is applied globally to the entire spray cross section. As will be demonstrated, the velocity distribution of the classical MEP models shows poor agreement with experiments for the cases under study. Modifications to the original MEP modeling are proposed to overcome this deficiency. In addition, the new joint size-velocity distribution agrees better with our general understanding of the drag law and yields realistic results.

A concentric pneumatic nebulizer (CPN) and a custom designed flow focusing nebulizer (FFN) are characterized. As will be shown, the classical Nukiyama-Tanasawa and Rizk-Lefebvre models lead to erroneous size prediction for the concentric nebulizer under typical operating conditions due to its specific design, geometry, dimension and different flow regimes. The models are then modified to improve the agreement with the experimental results. The size prediction of the modified models together with the spray velocity characterization are used to determine the overall nebulizer efficiency and also employed as input to a new Maximum Entropy Principle (MEP) based model to predict joint size-velocity distribution analytically. The new MEP model is exploited to study the local variation of size-velocity distribution in contrast to the classical models where MEP is applied globally to the entire spray cross section. As will be demonstrated, the velocity distribution of the classical MEP models shows poor agreement with experiments for the cases under study. Modifications to the original MEP modeling are proposed to overcome this deficiency. In addition, the new joint size-velocity distribution agrees better with our general understanding of the drag law and yields realistic results.

El impacto de la contaminación del aire es un tema crítico para el medioambiente y el clima. Una mala calidad del aire es un tema de importancia para la salud pública, especialmente en ambientes urbanos. El material particulado (PM), el ozono (O3) y el dióxido de nitrógeno (NO2) son los contaminantes más problemáticos en Europa y España. La Comisión Europea ha mostrado una gran preocupación por desarrollar técnicas que permitan incrementar el conocimiento sobre la dinámica de los contaminantes atmosféricos para asegurar el cumplimiento de la legislación y para informar a la población acerca de sus niveles. Además, la directiva europea 2008/50/CE establece la posibilidad de usar técnicas de modelización para informar sobre calidad del aire. Esta tesis doctoral está desarrollada en el marco de dos proyectos: El proyecto CALIOPE y el proyecto CICYT CGL2006-08903, ambos basados en la necesidad de desarrollar un sistema de calidad del aire que permita informar y entender los niveles de contaminación en Europa y España, con el objetivo de obtener un preciso pronóstico de la calidad del aire. Con ese propósito, el sistema de modelización CALIOPE se ha desarrollado con alta resolución espacial y temporal sobre Europa (12 km x 12 km y 15 capas, 1 hora), dominio madre, y España (4 km x 4 km y 15 capas, 1 hora), dominio anidado. CALIOPE consiste en un conjunto de modelos que tienen en cuenta la contaminación tanto antropogénica como natural. La disponibilidad del supercomputador MareNostrum, alojado en el Barcelona Supercomputer Center- Centro Nacional de Supercomputación, ha permitido trabajar a tan alta resolución. El objetivo principal de esta tesis es aumentar la confianza científica en el sistema CALIOPE, identificando sus puntos fuertes y débiles con un nivel de detalle que contribuya a establecer necesidades de mejora en el proceso de modelización. Por tanto, el presente trabajo ha evaluado espacial y temporalmente las simulaciones de calidad del aire sobre Europa y España en términos de O3, NO2, SO2, PM2.5 y PM10 en superficie sobre el año completo 2004. Para identificar el origen de las incertidumbres en la modelización del PM, su composición química ha sido también evaluada en ambos dominios. Las evaluaciones han sido realizadas sobre más de 150 estaciones de calidad del aire (más de 2 millones de datos experimentales). Además, esta tesis ha usado el sistema CALIOPE para analizar los patrones de calidad del aire sobre 2004, identificando claramente las áreas de contaminación. Las ideas más importantes que se desprenden de esta tesis son tres. Primero, las condiciones de contorno químicas basadas en un modelo global, como el LMDz-INCA2, son esenciales para modelizar el O3 troposférico sobre los dominios de estudio. Segundo, para simular la concentración de PM en el sur de Europa, tanto a escala rural como urbana, la contribución de polvo procedente del desierto del Sahara deber ser considerada debido a la proximidad al continente africano. La contribución del polvo del desierto a través del modelo BSC-DREAM8b ayuda satisfactoriamente a modelizar los picos de PM10 observados. Tercero, para ser capaz de modelizar la calidad del aire a escala urbana sobre España es esencial (1) una alta resolución espacial y temporal que permita describir fenómenos mesoescalares en áreas de topografía compleja , (2) un modelo de emisiones altamente desagregado como HERMES; (3) unos modelos que representen el estado actual del conocimiento en meteorología y química atmosférica / The impact of air pollution is a critical topic in environment and climate. Poor air quality is an important public health issue, especially in urban environments. Particulate matter (PM), tropospheric ozone (O3) and nitrogen dioxide (NO2) are the main problematic pollutants in Europe and Spain. The European Commission has shown a great concern for developing actions that allow increasing the knowledge on dynamics of atmospheric pollutants to assure the accomplishment of legislation and to inform the population about their levels. The European directive 2008/50/EC establishes the possibility of using modelling techniques to assess air quality. This Ph.D. thesis is developed in the framework of two projects: the CALIOPE project and the CGL2006-08903 CICYT project, both based on the necessity to develop an air quality modelling system that allows assessing and understanding the air pollution levels in Europe and Spain, with the aim of obtaining a precise air quality forecast. For that purpose, the CALIOPE air quality modelling system has been developed with high spatial and temporal resolution over Europe (12 km x 12 km, 1 h), as a mother domain; and Spain (4 km x 4 km, 1 h), as the nested domain. The CALIOPE system consists in a set of models that take into account both anthropogenic and natural pollution. The availability of the MareNostrum supercomputer, held in Barcelona Supercomputing Center- Centro Nacional de Supercomputación, has allowed such configuration of the CALIOPE system. The main objective of the present Ph.D. thesis is to increase the scientific confidence on the CALIOPE system, identifying skills and weakness with a degree of detail that contributes to establish necessities of improvements in the modelling process. Therefore, the present work has spatially and temporally evaluated CALIOPE air quality simulations over Europe and Spain in terms of O3, NO2, SO2, PM2.5, PM10 concentrations over the full year 2004. In order to identify the origin of uncertainties in PM modelling, PM chemical composition has been also evaluated in both target domains. Evaluations have been performed across more than 150 air quality-monitoring stations and over more than 2 million of experimental data. Furthermore, this Ph.D. thesis has used the CALIOPE system to assess air quality pattern over the year 2004, identifying clearly the areas of air pollution. There are three major thrusts of the present Ph.D. thesis. First, chemical boundary condition based on a global model, such as LMDz-INCA2, becomes essential to model O3 background concentrations in the target domains. Second, to simulate PM concentration in southern Europe, both regional and urban scales, the contribution of dust from the Saharan desert should be taken into account, since that region is frequently affected by dust outbreaks due to its proximity to the African continent. The contribution of desert dust through the BSC-DREAM8b helps to satisfactory model the observed episodic PM10 concentration peaks. Even more, the contribution of sea-salt aerosol is especially important over coastal areas. Third, to be able to model the air quality in urban scale over Spain it is essential (1) a high spatial (4 km x 4 km and 15 layers) and temporal (1h) resolution that allows describing mesoscale phenomena in very complex terrains; (2) a high disaggregated emission model to describe the sources, such as HERMES; and (3) an state-of-the-science meteorological and chemical models. This Ph.D. thesis has demonstrated that CALIOPE system applied over Europe and Spain is a useful tool which may contribute to (1) forecast air pollution in urban/suburban areas with a pervasive influence of anthropogenic emissions on a local scale and over very complex terrains and meteorology patterns; (2) assess about air pollution, discriminating between anthropogenic and natural episodes; and (3) manage air pollution, by means of modification of urban strategies or requirements of the legislation.

Introduction: The use of heat moisture exchangers (HMEs) is becoming more popular with many institutions delivering aerosolized medications between the HME and the endotracheal tube of patients being mechanically ventilated. When HMEs become saturated resistance can increase which can cause changes that can lead to patient-ventilator dysnchrony, development of intrinsic PEEP, and weaning difficulty. The purpose of this study was to determine the effects of aerosol drug delivery on resistance through heat-moisture exchangers. Method: An in-vitro model to simulate exhaled heat and humidity from a patient’s lungs was developed by connecting the test lung to a cascade humidifier that was placed between the endotracheal tube and the test lung. Temperature (37 ºC) and relative humidity (100%) were held constant through all test runs. Ventilator settings used for the study were as follows: Tidal volume 500 mL, frequency 15/min, PEF 60 L/min, PEEP 5 cmH2O, bias flow 2 L/min and I:E ratio 1:3.The pressurized metered-dose inhaler (pMDI; ProAir HFA) with a minispacer (Thayer Medical), hand-held nebulizer (HHN; Salter Labs) and placebo (No aerosol generator or medication) were compared. Albuterol sulfate (2.5 mg/3 ml) was administered through continuous HHN and six puffs of albuterol were given from a pMDI equaling one treatment. Neither medication nor aerosol device was used with the placebo group in order to determine the effect of HME on airway resistance during mechanical ventilation. Six aerosolized treatments were given to simulate a patient receiving albuterol every four hours over a twenty-four hour period. While five minutes was allowed between treatments, airway resistance was measured via the ventilator before and after the administration of the placebo, pMDI and HHN, which equaled five-minute intervals. Data Analysis: Descriptive statistics, dependent t-tests, one-way analysis of variance (ANOVA), repeated measures ANOVA and post-hoc multiple comparisons were utilized for the data analysis of this study, using SPSS version 16.0. A p-value<0.05 was considered significant. Results: There is a linear time effect with means of airway resistance increasing overtime not only with the placebo but also with the pMDI and nebulizer. At the end of all treatments, the means of resistance with the placebo, pMDI and nebulizer were 9.31 cmH2O/L/sec, 9.37 cmH2O/L/sec and 11.20 cmH2O/L/sec, respectively. While no significant difference was found between the placebo and the pMDI (p=0.452), the nebulizer significantly increased airway resistance when compared to placebo (p=0.004) and the pMDI (p=0.02). Conclusion: Airway resistance increases with use of the placebo, pMDI, and JN groups. Aerosol generators showed a greater increase in resistance when compared to placebo with the greater increase in resistance by HHN.