No description available.

The development of industry, transport, agriculture and power engineering inevitably create problems related to the impact of generated waste on the environment as well as other undesirable processes. The atmosphere is the main component of the Earth’s climate system because changes occurring due to the human economic activity result in serious environmental impacts in all components of the ecosystem as well as the Earth’s climate self-regulation system is disturbed. The objective of this work was to investigate the origin, sources and formation of organic compounds and black carbon in atmospheric aerosol particles and to develop new research methods. To attain this objective the following tasks have been formulated: Development of the identification method for the aerosol origin and source by investigating the carbon isotope mass ratios, illustration of possibilities of the carbon isotope ratio method by identifying the aerosol particle origin during the air mass long-range transport at the Preila Environmental pollution research station, investigation of variation of the black carbon amount in aerosol particles in the diesel engine exhaust depending on the engine working parameters and fuel composition, investigation of the carbon isotope ratio variation in natural aerosol depending on the aerosol particle size distribution, determination of the partial contribution of natural and anthropogenic particles in aerosol by investigation of stable carbon and radiocarbon isotope... [to full text] / Žemės atmosfera yra svarbiausia klimato sferos dalis ir jautriausias antropogeninei taršai aplinkos sandas. Atmosferoje vykstantys procesai pakeičia ekosistemose per šimtmečius nusistovėjusius procesus – stebime įvairias globalinės klimato kaitos sukeltas pasekmes. Mokslinė šio darbo idėja nukreipta į įvairiapusį atmosferos aerozolio dalelių savybių ir prigimties tyrimą bei tyrimo metodų plėtrą, pasiremiant naujausiomis aplinkotyros mokslo žiniomis, akcentuojant pastarojo dešimtmečio masių spektrometrijos pasiekimus. Šio darbo tikslas yra organinių medžiagų ir juodosios anglies atmosferos aerozolio dalelėse kilmės, aerozolio sudėties ir formavimosi tyrimai bei naujų tyrimo metodų plėtra. Darbe eksperimentiškai įrodyta, kad anglies izotopų santykis antropogeninės kilmės aerozolio dalelėse atitinka deginamo kuro izotopų santykį ir šis parametras tinka, identifikuojant aerozolio dalelių šaltinį. Šis izotopų santykis, kaip metodinė priemonė, buvo panaudotas tiriant įvairios prigimties aerozolio sudėtį, savybes ir kilmę. Tiriant aerozolio daleles tolimojoje oro pernašoje stebėjome elementinės anglies δ13C verčių kaitą akumuliacinėje modoje nuo -22,9 ‰ iki -26,3 ‰, organinės anglies δ13C = -28 ‰. Iš δ13C verčių nustatyta, jog elementinės anglies pirmtakai aerozolio dalelėse buvo degimo produktai, organinės anglies šaltinis – lakūs organiniai junginiai iš augalų. Vietinės kilmės dalelių, didesnių už 1 μm, stebėta karbonatinė komponentė. Apjungus masių ir izotopų santykių masių... [toliau žr. visą tekstą]

Žemės atmosfera yra svarbiausia klimato sferos dalis ir jautriausias antropogeninei taršai aplinkos sandas. Atmosferoje vykstantys procesai pakeičia ekosistemose per šimtmečius nusistovėjusius procesus – stebime įvairias globalinės klimato kaitos sukeltas pasekmes. Mokslinė šio darbo idėja nukreipta į įvairiapusį atmosferos aerozolio dalelių savybių ir prigimties tyrimą bei tyrimo metodų plėtrą, pasiremiant naujausiomis aplinkotyros mokslo žiniomis, akcentuojant pastarojo dešimtmečio masių spektrometrijos pasiekimus. Šio darbo tikslas yra organinių medžiagų ir juodosios anglies atmosferos aerozolio dalelėse kilmės, aerozolio sudėties ir formavimosi tyrimai bei naujų tyrimo metodų plėtra. Darbe eksperimentiškai įrodyta, kad anglies izotopų santykis antropogeninės kilmės aerozolio dalelėse atitinka deginamo kuro izotopų santykį ir šis parametras tinka, identifikuojant aerozolio dalelių šaltinį. Šis izotopų santykis, kaip metodinė priemonė, buvo panaudotas tiriant įvairios prigimties aerozolio sudėtį, savybes ir kilmę. Tiriant aerozolio daleles tolimojoje oro pernašoje stebėjome elementinės anglies δ13C verčių kaitą akumuliacinėje modoje nuo -22,9 ‰ iki -26,3 ‰, organinės anglies δ13C = -28 ‰. Iš δ13C verčių nustatyta, jog elementinės anglies pirmtakai aerozolio dalelėse buvo degimo produktai, organinės anglies šaltinis – lakūs organiniai junginiai iš augalų. Vietinės kilmės dalelių, didesnių už 1 μm, stebėta karbonatinė komponentė. Apjungus masių ir izotopų santykių masių... [toliau žr. visą tekstą] / The development of industry, transport, agriculture and power engineering inevitably create problems related to the impact of generated waste on the environment as well as other undesirable processes. The atmosphere is the main component of the Earth’s climate system because changes occurring due to the human economic activity result in serious environmental impacts in all components of the ecosystem as well as the Earth’s climate self-regulation system is disturbed. The objective of this work was to investigate the origin, sources and formation of organic compounds and black carbon in atmospheric aerosol particles and to develop new research methods. To attain this objective the following tasks have been formulated: Development of the identification method for the aerosol origin and source by investigating the carbon isotope mass ratios, illustration of possibilities of the carbon isotope ratio method by identifying the aerosol particle origin during the air mass long-range transport at the Preila Environmental pollution research station, investigation of variation of the black carbon amount in aerosol particles in the diesel engine exhaust depending on the engine working parameters and fuel composition, investigation of the carbon isotope ratio variation in natural aerosol depending on the aerosol particle size distribution, determination of the partial contribution of natural and anthropogenic particles in aerosol by investigation of stable carbon and radiocarbon isotope... [to full text]

Indiana University-Purdue University Indianapolis (IUPUI) / Ion Mobility Spectrometry (IMS) is an analytical technique for separation of charged particles in the gas phase. The history of IMS is not very old, and in this century, the IMS technique has grown rapidly in the advent of modern instruments. Among currently available ion mobility spectrometers, the DTIMS, FAIMS, TWIMS, DMA are notable. Though all the IMS systems have some uniqueness in case of particle separation and detection, however, all instruments have common shortcomings. They lack in resolution, which is independent of mobility of different charged particles and they are not able to separate bigger particles (20 120 nm) with good accuracy. The work presented here demonstrates a new concept of IMS technique at atmospheric pressure which has a resolution much higher than that of the currently available DTIMS (Drift Tube Ion Mobility Spectrometry) instruments. The unique feature of this instrument is the diffusion auto-correction. Being tunable, It can separate the wide range of particles of different diameters. The working principle of this new IMS technique is different from the typical DTIMS and to simply put, it can be considered as an inversion of commonly used technique, so termed as Inverted Drift Tube (IDT).The whole work performed here can be divided into three major phases. In the first phase, the analytical solution was derived for two new separation techniques: IPF (Intermittent push flow) and NSP (Nearly stopping potential) separations. In the next phase, simulations were done to show the accuracy of the analytical solution. An ion optics simulator software called SIMION 8.1 was used for conducting the simulation works. These simulations adopted the statistical diffusion (SDS) collision algorithm to emulate the real scenario in gas phase more precisely. In the last phase, a prototype of experimental setup was built. The experimental results were then validated by simulated results.

Die natürliche Umgebungsluft enthält Aerosolpartikel, deren Größe von wenigen Nanometern bis zu einigen Mikrometern reicht. Insbesondere anthropogenen ultrafeinen Partikeln, die kleiner als 100 nm sind, werden negative Wirkungen auf die menschliche Gesundheit zugeschrieben. Die gravimetrische Messung der Partikelmassekonzentration erfasst ultrafeine Partikel nur ungenügend, da die Masse dieser Partikel sehr gering ist. Deutlich empfindlicher gelingt die Quantifizierung ultrafeiner Partikel durch die Messung der Partikelanzahlkonzentration. Die Arbeit beschreibt ein Verfahren zur Messung der Anzahlkonzentration von Partikeln in Umweltaerosolen. Es verknüpft die elektrische Aufladung der Partikel mit deren Klassierung im elektrischen Feld und ihre Mengenbestimmung anhand der elektrischen Ladung. Mittels des entwickelten Sensormodells gelingt die Verbindung der gemessenen Rohdaten mit der Anzahlgrößenverteilung der Partikel durch eine Kernfunktion in einer Fredholmschen Integralgleichung erster Art. Zur Dateninversion wird diese Gleichung in diskreter Form als lineares Gleichungssystem genutzt. Dessen Koeffizienten bilden die Kernmatrix, welche mit einer neu entwickelten Methode experimentell bestimmt wird. Vergleichsmessungen zeigen eine gute Übereinstimmung des Verfahrens mit Referenzverfahren der Aerosolmesstechnik und unterstreichen die Eignung des Verfahrens zur Partikelquantifizierung in Umweltmessnetzen.

No description available.

Deactivation of catalysts were investigated focusing on three industrial processes: 1) Selective Catalytic Reduction (SCR) for abatement of NOx from biomass combustion using V2O5-WO3 /TiO2 catalysts; 2) Catalytic oxidation of volatile organic compounds (VOC) from printing industries using a Pt/γ-Al2O3 catalyst; and 3) Ni and Pt/Rh catalysts used in steam reforming reaction of bio-syngas obtained from biomass gasification. The aim has been to simulate industrial conditions in laboratory experiments in order to comprehend influence of compounds affecting catalysts performance. Typical catalyst lifetimes in industrial processes are several years, which are a challenge when accelerating deactivation in laboratory scale experiments where possible exposure times are few hours or days. Catalysts can be introduced to deactivating compounds through different routes. The first method examined was gaseous exposure, which was applied to deactivate VOC oxidation catalyst through exposure of gaseous hexamethyldisiloxane. The second method involved wet impregnation and was used for impregnation of SCR catalyst with salt solutions. The third method was based on exposure and deposition of size selected particles of deactivating substances on the catalyst. The latter device was developed during this work. It was applied to monolithic SCR catalysts as well as to pellet catalysts intended for steam reforming of biomass gasification syngas. Deactivated SCR catalyst samples by size selected exposure method were verified and compared with SCR catalysts used in a commercial biomass boiler for 6 500 h. Evaluations of fresh and deactivated samples were investigated using BET surface area; chemisorption and temperature programmed desorption (TPD); surface morphology using Scanning Electron Microscopy (SEM) and poison penetration profile through SEM with an Electron Micro Probe Analyser (EMPA) also equipped with a energy dispersive spectrometer (EDS); chemical analysis of accumulation of exposed compounds by Inductively Coupled Plasma - Atomic Emission Spectroscopy (ICP-AES); and influence on catalyst performance. The size selected generated particles of deactivating substances were characterized with respect to mean diameter and number size distribution through Scanning Mobility Particle Sizer (SMPS) and mass size distribution applying an Electric Low Pressure Impactor (ELPI). Results from catalyst characterization methods were useful tools in evaluation of catalyst deactivation routes. Understanding deactivation processes and impact on catalyst performance is vital for further optimization of catalysts with respect to performance and lifetime. Further research in this field can provide more resistant catalysts for application in industry leading to higher commercial benefits and further application of environmental catalysts in thermo-chemical conversion of biomass.

Thesis advisor: Paul Davidovits / Aerosol particles are an important component of the Earth-Atmosphere system because of their influence on the radiation budget both directly (through absorption and scattering) and indirectly (through cloud condensation nuclei (CCN) activity). The magnitude of the raditaive forcing attributed to the direct and indirect aerosol effects is highly uncertain, leading to large uncertainties in projections of global climate change. Real-time measurements of aerosol properties are a critical step toward constraining the uncertainties in current global climate modeling and understanding the influence that anthropogenic activities have on the climate. The objective of the work presented in this thesis is to gain a more complete understanding of the atmospheric transformations of aerosol particles and how such transformations influence the direct and indirect radiative effects of the particles. The work focuses on real-time measurements of aerosol particles made with the Aerodyne Aerosol Mass Spectrometer (AMS) developed in collaboration with the Boston College research group. A key feature of the work described is the development of a lightscattering module for the AMS. Here we present the first results obtained with the integrated light scattering – AMS system. The unique and powerful capabilities of this new instrument combination are demonstrated through laboratory experiments and field deployments. Results from two field studies are presented: (1) The Northeast Air Quality Study (NEAQS), in the summer of 2004, conducted at Chebogue Point, Nova Scotia and (2) The Megacity Initiative: Local and Global Research Observations (MILAGRO) field campaign conducted in and around Mexico City, Mexico in March of 2006. Both field studies were designed to study the transformations that occur within pollution plumes as they are transported throughout the atmosphere. During the NEAQS campaign, the pollution plume from the Northeastern United States was intercepted as it was transported towards Europe. In this study, particles were highly processed prior to sampling, with residence times of a few days in the atmosphere. The MILAGRO campaign focused on the evolution of the Mexico City plume as it was transported north. During this study, regional and locally emitted particles were measured with residence times varying from minutes to days in the atmosphere. In both studies, the light scattering – AMS system provided detailed information about the density and composition of single particles, leading to important insights into how atmospheric processing transforms the particle properties. In Mexico City, the light scattering-AMS system was used for the first time as a true single particle mass spectrometer and revealed specific details about the atmospheric processing of primary particles from combustion sources.To quantify the radiative effects of the particles on climate, the processing and ultimate fate of primary emissions (often containing black carbon or soot) must be understood. To provide a solid basis for the interpretation of the data obtained during the field studies, experiments were conducted with a well characterized soot generation-sampling system developed by the Boston College research group. The laboratory soot source was combined with the light scattering – AMS system and a Cloud Condensation Nuclei Counter (CCNC) to measure the change in cloud-forming activity of soot particles as they are processed in the atmosphere. Because of the importance of black carbon in the atmosphere, several instruments have been developed to measure black carbon. In July of 2008, an intercomparison study of 18 instruments was conducted in the Boston College laboratory, with soot particles produced and processed to mimic a wide range of atmospherically-relevant conditions. Transformations in the physical, chemical, and optical properties of soot particles were monitored with the combined suite of aerosol instrumentation. Results from the intercomparison study not only calibrated the different instruments used in the study, but also provided critical details about how atmospheric processing influences the radiative effects of primary combustion particles. / Thesis (PhD) — Boston College, 2008. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Soot particles are a major absorber of shortwave radiation in the atmosphere. They exert a rather uncertain direct and semi-direct radiative effect, which causes a heating or in some cases a cooling of the atmosphere. The mass absorption coefficient is an essential quantity to describe this light absorption process. This work presents new experimental data on the mass absorption coefficient of soot particles in the troposphere over Central Europe. Mass absorption coefficients were derived as the ratio between the light absorption coefficient determined by multi angle absorption photometry (MAAP), and the soot mass concentration determined by Raman spectroscopy. The Raman method is sensitive to graphitic structures present in the particle samples, and was calibrated in the laboratory using Printex90 model particles. The mass absorption coefficients were determined for a number of seven observation sites, ranging between 3.9 and 7.4 m²/g depending on measurement site and observational period. The highest values were found in an continentally aged air mass in winter, where we presumed soot particles to be present mainly in internal mixture. The regional model WRF-Chem was used in conjunction with a high resolution soot emission inventory to simulate soot mass concentrations and absorption coefficients for the Central European Troposphere. The model was validated using soot mass concentrations from Raman measurements and absorption coefficients. Simulated soot mass concentrations were found to be too low by around 50 %, which could be improved by scaling the emissions by a factor of two. In contrast, the absorption coefficient was positively biased by around 20%. Adjusting the modeled mass absorption coefficient to measurements, the simulation of soot light absorption was improved. Finally, the positive direct radiative forcing at top of the atmosphere was found to be lowered by up to 70% for the model run with adjusted soot absorption behaviour, , indicating a decreased heating effect on the atmosphere.

Im Rahmen dieser Dissertation werden eine Serie von Grundlagenexperimenten zur Ablagerung (Deposition) und Remobilisierung (Resuspension) von Aerosolpartikeln in turbulenten Strömungen beschrieben. Die Kernmotivation stellt die Quelltermanalyse von Druckentlastungsstörfällen von Hochtemperaturreaktoren (HTR) dar. Im Primärkreislauf früherer HTR-Forschungsanlagen wurden größere Mengen an radiologisch belastetem Graphitstaub gefunden. Dieser Staub scheint größtenteils durch Abrieb zwischen den graphitischen Kernstrukturen entstanden zu sein und verteilte sich während des fortlaufenden Reaktorbetriebs über sämtliche Oberflächen des Primärkreislaufs. Während eines Druckentlastungsstörfalls kann dieser Staub durch die Gasströmung remobilisiert und aus dem Primärkreislauf ausgetragen werden. Eine Quelltermanalyse solch eines Störfallszenarios erfordert die Kenntnis über die Menge und die räumliche Verteilung des Staubs, die radiologische Belastung sowie das Remobilisierungsverhalten in Bezug auf die zu erwartenden Strömungstransienten. Nach dem heutigen Stand von Wissenschaft und Technik kann die räumlich-zeitliche Verteilung des Staubs im Primärkreislauf für stationären Reaktorbetrieb unter Verwendung eindimensionaler Systemcodes abgeschätzt werden. Jedoch ist unbekannt, welcher Anteil des Staubinventars durch die Gasströmung remobilisiert und aus dem Primärkreislauf ausgetragen werden würde. Zur systematischen Untersuchung des Staubtransportverhaltens in turbulenten Strömungen wurden zwei kleinskalige Versuchsanlagen entwickelt und eine Serie von Depositions- und Resuspensionsexperimenten durchgeführt. Die partikelbeladene Strömung in der Heißgasumgebung des HTR-Primärkreislaufs wurde über die Verwendung von Ähnlichkeitskennzahlen auf eine Luftströmung bei Umgebungsbedingungen herunterskaliert. Die Strömung und die Partikel wurden mittels hochauflösender, bildgebender und nichtinvasiver Messverfahren räumlich und zeitlich vermessen, um eine umfangreiche Datenbasis für die Analyse der Partikeltransportprozesse zu erstellen. Inhaltlich lassen sich die durchgeführten Untersuchungen in drei Teile gliedern. Der erste Teil besteht aus zwei Studien über die Deposition und Resuspension monodisperser, sphärischer Einzelpartikel in einer ungestörten, horizontalen Kanalströmung. Die systematische Variation experimenteller Randbedingungen wie der Partikelgröße, der Oberflächenrauheit und der Strömungsgeschwindigkeit ermöglichte die Quantifizierung der einzelnen Einflussgrößen. Im zweiten und dritten Teil der Dissertation wurden die Deposition und Resuspension einer mehrschichtigen Ablagerung (Partikel-Multilayer) zwischen periodischen Stufen und in einer Kugelschüttung untersucht, um die komplexe Interaktion zwischen der turbulenten Strömung und der Multilayer-Ablagerung weiter zu erforschen. Die gewonnenen Erkenntnisse leisten einen Beitrag für die Quelltermanalyse des Staubtransports im HTR-Primärkreislauf und können für die Weiterentwicklung numerischer Strömungssimulationen des Partikeltransports in turbulenten Strömungen verwendet werden. / Aerosol particle deposition and resuspension experiments in turbulent flows were performed to investigate the complex particle transport phenomena and to provide a database for the development and validation of computational fluid dynamics (CFD) codes. The background motivation is related to the source term analysis of an accidental depressurization scenario of a High Temperature Reactor (HTR). During the operation of former HTR pilot plants, larger amounts of radio-contaminated graphite dust were found in the primary circuit. This dust most likely arose due to abrasion between the graphitic core components and was deposited on the inner wall surfaces of the primary circuit. In case of an accident scenario, such as a depressurization of the primary circuit, the dust may be remobilized and may escape the system boundaries. The estimation of the source term being discharged during such a scenario requires fundamental knowledge of the particle deposition, the amount of contaminants per unit mass as well as the resuspension phenomena. Nowadays, the graphite dust distribution in the primary circuit of an HTR can be calculated for stationary conditions using one-dimensional reactor system codes. However, it is rather unknown which fraction of the graphite dust inventory may be remobilized during a depressurization of the HTR primary circuit. Two small-scale experimental facilities were designed and a set of experiments was performed to investigate particle transport, deposition and resuspension in turbulent flows. The facility design concept is based on the fluid dynamic downscaling of the helium pressure boundary in the HTR primary circuit to an airflow at ambient conditions in the laboratory. The turbulent flow and the particles were recorded by high-resolution, non-invasive imaging techniques to provide a spatio-temporal insight into the particle transport processes. The different investigations of this thesis can be grouped into three categories. Firstly, the deposition and resuspension of monodisperse single particles in a horizontal turbulent channel flow was studied. The systematic variation of the experimental boundary conditions allows for the quantification of the influences of particle size, surface roughness, and fluid velocity. In the second and third part of this thesis, the deposition and resuspension of a particle multilayer between periodic steps and in a pebble bed was studied to explore the complex interaction between the turbulent flow and the particles, respectively. The findings of this thesis are a contribution to the source term analysis of HTR related accidental depressurizations. Furthermore, the database can be applied to CFD code developments for the numerical simulation of particle transport processes in turbulent flows.