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.

Increasing levels of air pollution are prompting researchers to develop more reliable air pollution modeling approaches in order to protect the public and the environment from toxic contaminants and airborne pathogens. Although land use regression has long been used to assess exposure to air pollution, researchers are increasingly using machine learning algorithms to quantify the concentration of harmful pollutants—for this study black carbon (BC) and particle number (PN). Additionally, researchers are moving away from using fixed-site data in favor of using mobile monitoring data in a variety of locations to develop hourly empirical models of particulate air pollution. This study uses secondary data describing BC and PN pollutant levels, which are obtained from roads that bikers share in the more rural location of Blacksburg (VA). Machine learning (ML) algorithms are then built to develop accurate and reliable short-term empirical prediction models. Different pre-processing methods for the mobile monitoring data and various input variables are tested to assess how ML can be used effectively in this process. Three types of time-average models are developed (daytime, hourly average, and one second models). Various combinations of spatial and temporal input variables are used in the short-term models. The impact of adding more spatiotemporal variables (e.g., emissions) to machine learning models to improve model performance is assessed in the short-term models. Incorporating spatial and temporal autocorrelation is intended to develop more sophisticated validation approaches for identifying ML performance patterns—the goal of which is to predict concentration levels more accurately in comparison to using raw data without data reprocessing. The results show that the model developed using refined disaggregated data is able to detect the spatial distribution of the pollutant concentration at equivalent levels as the smoothed data models, although the latter display fewer errors. The performance of the short-term model including all variables is equivalent to the model omitting emissions. The ML results are compared to earlier stepwise regression model results, suggesting that ML has the ability to improve both long-term and short-term model accuracy. Our findings indicate that ML demonstrates higher predictive capacity in comparison to stepwise regression. The results from this study may be useful in enhancing the performance of ML through the incorporation of different data preprocessing tasks, as well as showing how different input variables contribute to the ML modeling process. The findings from this study could be used toward the development of environmental/eco-friendly routes that would decrease the risk for exposure to harmful vehicle-related emissions. / Doctor of Philosophy / Air pollution is a major environmental threat to human health, claiming the lives of millions of people each year, primarily as a result of fine particulate matter entering the respiratory system. As such, it is important to develop reliable and accurate air pollution modeling approaches in order to protect the public and the environment from toxic contaminants and pathogens in the air. Although an approach known as land use regression has long been used to assess exposure to air pollution, researchers are increasingly using machine learning (ML) algorithms to quantify the concentration of harmful pollutants—for this study black carbon and particle number, which is a generic assessment that captures a number of known airborne hazards. Additionally, researchers are moving away from using fixed-site data in favor of using mobile monitoring data in a variety of locations to develop hourly empirical models of particulate air pollution. In this study, machine learning algorithms are developed using secondary data collected from roads that bikers share, which are representative of pollution levels of particle number and black carbon in the more rural location of Blacksburg (VA), in order to develop accurate and reliable short-term empirical prediction models. Different pre-processing methods of the mobile monitoring data and various input variables are tested to assess how machine learning can be efficiently used in this process. Our findings indicate that machine learning demonstrates higher predictive capacity in comparison to stepwise regression. The results from this study are expected to be useful in enhancing the performance of machine learning through the incorporation of different data preprocessing tasks, as well as how different input variables contribute to the machine learning modeling process. The findings from this study could assist transportation planners and other stakeholders better assess pollution risks for bike riders and pedestrians. As such, this study's findings could be used toward the development of environmental/eco-friendly routes that would decrease the risk for exposure to harmful vehicle-related emissions.

Biomass burning started to attract attention since the last decade because of its impacts on the atmosphere and the environmental air quality, as well as significant potential effects on human health and global climate change. Knowledge of particle emission characteristics from biomass burning is crucially important for the quantitative assessment of the potential impacts. This thesis presents the results of study aimed towards comprehensive characterization of particle emissions from biomass burning. The study was conducted both under controlled laboratory conditions, to quantify the particle size distribution and emission factors by taking into account various factors which may affect the particle characteristics, and in the field, to investigate biomass burning processes in the real life situations and to examine vertical profile of particles in the atmosphere. To simulate different environmental conditions, a new technique has been developed for investigating particle emissions from biomass burning in the laboratory. As biomass burning may occur in a field at various wind speeds and burning rates, the technique was designed to allow adjustment of the flow rates of the air introduced into the chamber, in order to control burning under different conditions. In addition, the technique design has enabled alteration of the high particle concentrations, allowing conducting measurements with the instrumentations that had the upper concentration limits exciding the concentrations characteristic to the biomass burning. The technique was applied to characterize particle emissions from burning of several tree species common to Australian forests. The aerosol particles were characterized in terms of size distribution and emission factors, such as PM2.5 particle mass emission factor and particle number emission factor, under various burning conditions. The characteristics of particles over a range of burning phases (e.g., ignition, flaming, and smoldering) were also investigated. The results showed that particle characteristics depend on the type of tree, part of tree, and the burning rate. In particular, fast burning of the wood samples produced particles with the CMD of 60 nm during the ignition phase and 30 nm for the rest of the burning process. Slow burning of the wood samples produced large particles with the CMD of 120 nm, 60 nm and 40 nm for the ignition, flaming and smoldering phases, respectively. The CMD of particles emitted by burning the leaves and branches was found to be 50 nm for the flaming phase and 30 nm for the smoldering phase, under fast burning conditions. Under slow burning conditions, the CMD of particles was found to be between 100 to 200 nm for the ignition and flaming phase, and 50 nm for the smoldering phase. For fast burning, the average particle number emission factors were between 3.3 to 5.7 x 1015 particles/kg for wood and 0.5 to 6.9 x 1015 particles/kg for leaves and branches. The PM2.5 emission factors were between 140 to 210 mg/kg for wood and 450 to 4700 mg/kg for leaves and branches. For slow burning conditions, the average particle number emission factors were between 2.8 to 44.8 x 1013 particles/kg for wood and 0.5 to 9.3 x 1013 particles/kg for leaves and branches, and the PM2.5 emissions factors were between 120 to 480 mg/kg for wood and 3300 to 4900 mg/kg for leaves and branches. The field measurements were conducted to investigate particle emissions from biomass burning in the Northern Territory of Australia over dry seasons. The results of field studies revealed that diameters of particles in ambient air emissions were within the size range observed during laboratory investigations. The laboratory measurements found that the particles released during the controlled burning were of a diameter between 30 and 210 nm, depending on the burning conditions. Under fast burning conditions, smaller particles were produced with a diameter in the range of 30 to 60 nm, whilst larger particles, with a diameter between 60 nm and 210 nm, were produced during slow burning. The airborne field measurements of biomass particles found that most of the particles measured under the boundary layer had a CMD of (83 ± 13) nm during the early dry season (EDS), and (127 ± 6) nm during the late dry season (LDS). The characteristics of ambient particles were found to be significantly different at the EDS and the LDS due to several factors including moisture content of vegetation, location of fires related to the flight paths, intensity of fires, and burned areas. Specifically, the investigations of the vertical profiles of particles in the atmosphere have revealed significant differences in the particle properties during early dry season and late dry season. The characteristics of particle size distribution played a significant role in these differences.

Many recent studies have highlighted the substantial health-related impacts of particle number (PMno) rather than particle mass. The aim of this study is to determine the correlation of trace gases with PMno, to identify the chemical composition of particle different sizes and to predict the NOx and PMno over Yanbu Industrial City (YIC). Trace gases (NOx, SO2, H2S, O3, CO), PMno with diameter (7nm-10μm), traffic and meteorological parameters were measured at three sampling sites in YIC. The maximum PMno (333,971 cm-3) at downwind site#1 was about 2.5 times higher than that (123,842 cm-3) at upwind site#2 and about 1.2 times higher than that (263,572 cm-3) at downwind site#3. The average PMno distribution at downwind sites consisted of one distinguishable mode (nucleation mode<20nm) whereas the upwind site had two modes (the nucleation and the accumulation modes). The correlation of PMno with NO/NOx (r>0.7) are generally stronger than with NO2 at sites#1 and 2, whereas for site #3 the correlation between PMno with NO2/NOx are better than with NO. PMno has generally either weak or poor correlation with SO2 and CO, respectively. Particle samples of different sizes (7nm-10?m) were chemically analysed using an ion chromatograph (IC) for inorganic ions and inductively coupled plasma mass spectrometry (ICP-MS) for trace metals at site#3. The ionic analysis revealed that sulfate and ammonium was mainly present in particle of size < 0.38μm while nitrate and chloride was mainly present in particles of size > 0.38μm. Non-sea salt sulfate was dominant in all particle sizes compared to the marine sulfate which is minor. The total sulfate and nitrate contributed 50.3% and 24.4% of the total ionic mass respectively followed by chloride (13.3%) and ammonium (10.6%). The trace-metals analysis results indicated that Na represented more than 94% of the total mass and the contributions of the remaining metals (Al, Sr, Zn, V, Cr, Fe, etc) were about 6%. A further part of this study consisted of the coupling of the WRF/CALMET system with the CALPUFF model, which was applied to predict NOx and PMno concentrations. The WRF model was employed to generate the meteorological input data for CALMET. WRF predictions were evaluated with surface data and upper air profiles using RASS/SODAR and radiosondes. WRF tends to underestimate the surface temperature on average with biases of up to -3.4°C and also underestimates temperature profiles with average biases ranging between -2.7 and -5.2oC when compared to the RASS profiler, but with a lower bias (< -2.4°C) when compared to radiosonde profiles. The mean wind speed bias for the majority of the cases was close to the benchmark of ±0.5m/s, but the mean wind direction bias for half of the cases exceeded the benchmark of 10o. It was concluded that WRF predictions can be used for air dispersion modeling to produce reasonable outputs. NOx predictions by CALPUFF showed that the contribution of the traffic to the highest concentrations during the nighttime was up to 80%, but after sunrise the contribution from industries became higher (up to 70%). The highest predicted NOx concentration (~313μg/m3) was much lower than the national ambient standard (660μg/m3) and the community area is affected much by industries during mid-morning hours when the wind shifting from land breeze to sea breeze. The fractional bias (FB) ranged between -0.1 and 1.06 indicating that the model tends to under-predict the NOx observations. PMno predictions of two sizes (7-40nm and 7nm-10μm) were derived based on the NOx predictions. All FB values were ranged between -0.1 and 0.5. It was concluded that PMno predictions were generally better than those of the NOx due mainly to adding the background term (intercept) for the PMno predictions.

This work focuses on the research and comparison of several types of air purifiers. It clarifies the principles of filtration and describes the basic types of air purifiers. Part of this work is designed methodology of measurement for comparison of filtration efficiency and filtration rate. The experimental part of this work contains the measurement and comparison made for two types of air purifiers. Selected purifiers were De’Longhi AC230 with mechanical filters and ionic air purifier Ionic-CARE Triton X6. Within the framework of this work an experimental set-up was constructed in the home environment for the simulation of real conditions for the function of the air purifiers. The measurement results provide information about aerosol number concentration process during the measurements and evaluation of filtration efficiency of air purifiers.

The understanding of human exposure to indoor particles of all sizes is important to enable exposure control and reduction, but especially for smaller particles since the smaller particles have a higher probability of penetration into the deeper parts of the respiratory tract and also contain higher levels of trace elements and toxins. Due to the limited understanding of the relationship between particle size and the health effects they cause, as well as instrument limitations, the available information on submicrometer (d < 1.0 µm) particles indoors, both in terms of mass and number concentrations, is still relatively limited. This PhD project was conducted as part of the South-East Queensland Air Quality program and Queensland Housing Study aimed at providing a better understanding of ambient particle concentrations within the indoor environment with a focus on exposure assessment and control. This PhD project was designed to investigate comprehensively the sources and sinks of indoor aerosol particles and the relationship between indoor and outdoor aerosol particles, particle and gaseous pollutant, as well as the association between indoor air pollutants and house characteristics by using, analysing and interpreting existing experimental data which were collected before this project commenced, as well as data from additional experiments which were designed and conducted for the purpose of this project. The focus of this research was on submicrometer particles with a diameter between 0.007 - 0.808 µm. The main outcome of this project may be summarised as following: * A comprehensive review of particle concentration levels and size distributions characteristics in the residential and non-industrial workplace environments was conducted. This review included only those studies in which more general trends were investigated, or could be concluded based on information provided in the papers. This review included four parts: 1) outdoor particles and their effect on indoor environments; 2) the relationship between indoor and outdoor concentration levels in the absence of indoor sources for naturally ventilated buildings; 3) indoor sources of particles: contribution to indoor concentration levels and the effect on I/O ratios for naturally ventilated buildings; and 4) indoor/outdoor relationship in mechanically ventilated buildings. * The relationship between indoor and outdoor airborne particles was investigated for sixteen residential houses in Brisbane, Australia, in the absence of operating indoor sources. Comparison of the ratios of indoor to outdoor particle concentrations revealed that while temporary values of the ratio vary in a broad range from 0.2 to 2.5 for both lower and higher ventilation conditions, average values of the ratios were very close to one regardless of ventilation conditions and of particle size range. The ratios were in the range from 0.78 to 1.07 for submicrometer particles, from 0.95 to 1.0 for supermicrometer particles and from 1.01 to 1.08 for PM2.5 fraction. Comparison of the time series of indoor to outdoor particle concentrations showed a clear positive relationship existing for many houses under normal ventilation conditions (estimated to be about and above 2 h-1), but not under minimum ventilation conditions (estimated to be about and below 1 h-1). These results suggest that for normal ventilation conditions and in the absence of operating indoor sources, outdoor particle concentrations could be used to predict instantaneous indoor particle concentrations but not for minium ventilation, unless air exchange rate is known, thus allowing for estimation of the "delay constant". * Diurnal variation of indoor submicrometer particle number and particle mass (approximation of PM2.5) concentrations was investigated in fifteen of the houses. The results show that there were clear diurnal variations in both particle number and approximation of PM2.5 concentrations, for all the investigated houses. The pattern of diurnal variations varied from house to house, however, there was always a close relationship between the concentration and human indoor activities. The average number and mass concentrations during indoor activities were (18.2±3.9)×10³ particles cm-³ and (15.5±7.9) µg m-³ respectively, and under non-activity conditions, (12.4±2.7)x10³ particles cm-³ (11.1±2.6) µg m-³, respectively. In general, there was a poor correlation between mass and number concentrations and the correlation coefficients were highly variable from day to day and from house to house. This implies that conclusions cannot be drawn about either one of the number or mass concentration characteristics of indoor particles, based on measurement of the other. The study also showed that it is unlikely that particle concentrations indoors could be represented by measurements conducted at a fixed monitoring station due to the large impact of indoor and local sources. * Emission characteristics of indoor particle sources in fourteen residential houses were quantified. In addition, characterizations of particles resulting from cooking conducted in an identical way in all the houses were measured. All the events of elevated particle concentrations were linked to indoor activities using house occupants diary entries, and catalogued into 21 different types of indoor activities. This enabled quantification of the effect of indoor sources on indoor particle concentrations as well as quantification of emission rates from the sources. For example, the study found that frying, grilling, stove use, toasting, cooking pizza, smoking, candle vaporizing eucalyptus oil and fan heater use, could elevate the indoor submicrometer particle number concentration levels by more than 5 times, while PM2.5 concentrations could be up to 3, 30 and 90 times higher than the background levels during smoking, frying and grilling, respectively. * Indoor particle deposition rates of size classified particles in the size range from 0.015 to 6 µm were quantified. Particle size distribution resulting from cooking, repeated under two different ventilation conditions in 14 houses, as well as changes to particle size distribution as a function of time, were measured using a scanning mobility particle sizer (SMPS), an aerodynamic particle sizer (APS), and a DustTrak. Deposition rates were determined by regression fitting of the measured size-resolved particle number and PM2.5 concentration decay curves, and accounting for air exchange rate. The measured deposition rates were shown to be particle size dependent and they varied from house to house. The lowest deposition rates were found for particles in the size range from 0.2 to 0.3 µm for both minimum (air exchange rate: 0.61±0.45 h-1) and normal (air exchange rate: 3.00±1.23 h-1) ventilation conditions. The results of statistical analysis indicated that ventilation condition (measured in terms of air exchange rate) was an important factor affecting deposition rates for particles in the size range from 0.08 to 1.0 µm, but not for particles smaller than 0.08 µm or larger than 1.0 µm. Particle coagulation was assessed to be negligible compared to the two other processes of removal: ventilation and deposition. This study of particle deposition rates, the largest conducted so far in terms of the number of residential houses investigated, demonstrated trends in deposition rates comparable with studies previously reported, usually for significantly smaller samples of houses (often only one). However, the results compare better with studies which, similarly to this study, investigated cooking as a source of particles (particle sources investigated in other studies included general activity, cleaning, artificial particles, etc). * Residential indoor and outdoor 48 h average levels of nitrogen dioxide (NO2), 48h indoor submicrometer particle number concentration and the approximation of PM2.5 concentrations were measured simultaneously for fourteen houses. Statistical analyses of the correlation between indoor and outdoor pollutants (NO2 and particles) and the association between house characteristics and indoor pollutants were conducted. The average indoor and outdoor NO2 levels were 13.8 ± 6.3 ppb and 16.7 ± 4.2 ppb, respectively. The indoor/outdoor NO2 concentration ratio ranged from 0.4 to 2.3, with a median value of 0.82. Despite statistically significant correlations between outdoor and fixed site NO2 monitoring station concentrations (p = 0.014, p = 0.008), there was no significant correlation between either indoor and outdoor NO2 concentrations (p = 0.428), or between indoor and fixed site NO2 monitoring station concentrations (p = 0.252, p = 0.465,). However, there was a significant correlation between indoor NO2 concentration and indoor submicrometer aerosol particle number concentrations (p = 0.001), as well as between indoor PM2.5 and outdoor NO2 (p = 0.004). These results imply that the outdoor or fixed site monitoring concentration alone is a poor predictor of indoor NO2 concentration. * Analysis of variance indicated that there was no significant association between indoor PM2.5 and any of the house characteristics investigated (p > 0.05). However, associations between indoor submicrometer particle number concentration and some house characteristics (stove type, water heater type, number of cars and condition of paintwork) were significant at the 5% level. Associations between indoor NO2 and some house characteristics (house age, stove type, heating system, water heater type and floor type) were also significant (p < 0.05). The results of these analyses thus strongly suggest that the gas stove, gas heating system and gas water heater system are main indoor sources of indoor submicrometer particle and NO2 concentrations in the studied residential houses. The significant contributions of this PhD project to the knowledge of indoor particle included: 1) improving an understanding of indoor particles behaviour in residential houses, especially for submicrometer particle; 2) improving an understanding of indoor particle source and indoor particle sink characteristics, as well as their effects on indoor particle concentration levels in residential houses; 3) improving an understanding of the relationship between indoor and outdoor particles, the relationship between particle mass and particle number, correlation between indoor NO2 and indoor particles, as well as association between indoor particle, NO2 and house characteristics.

Powerlines are important in the process of electricity transmission and distribution (T & D) and their essential role in transmitting electricity from the large generating stations to the final consumers cannot be over emphasized. Over the years, an increase in the demand for electrical energy (electricity) has led to the construction and inevitable use of high transmission voltage, sub-transmission voltage and distribution voltage power conducting lines, for the electricity T & D process. Along with this essential role, electricity conductors can also give rise to some electrically related effects such as interference with telecommunication circuits, electric shocks, electromagnetic fields, audible noise, corona ion discharges, etc. The presence of powerline generated corona ions in any ambient air environment can be associated with the local modification of the earth’s natural dc electric field (e-field), while the interactions between these ions and other airborne aerosol particles can be associated with the presence of charged aerosol particles in the environment of the corona ion emitting lines. When considering all the studies conducted to date on the possible direct and indirect effects of high voltage powerlines (HVPLs), of significant interest are those suggesting links between powerlines and some adverse human health effects – with such health effects alleged to be strongest amongst populations directly exposed to HVPLs. However, despite the numerous studies conducted on HVPLs, to date a lack of proper scientific understanding still exist in terms of the physical characterization of the electrical environment surrounding real-world HVPLs - mostly in terms of the entire dynamics of ions and charged particles, as well as the possible links/associations between the different parameters that characterize these electrical environments. Yet, gaining a sound understanding about the electrical environment surrounding energized real-world HVPLs is imperative for the accurate assessment of any possible human exposure or health effects that may be associated with powerlines. The research work presented in this thesis was motivated by the existing gaps in scientific understanding of the possible association between corona ions generated by real-world HVPLs and the production of ambient charged aerosol particles. The aim of this study was to supply some much needed scientific knowledge about the characteristics of the electrical environment surrounding real-world energized HVPLs. This was achieved by investigating the possible effects of corona ions generated by real-world overhead HVPLs on ambient aerosol particle number concentration level, ambient aerosol particle charge concentration level, ambient ion concentration level and the magnitude of the local vertical dc e-field; while also taking into consideration the possible effect of complex meteorological factors (such as temperature, pressure, wind speed wind direction, solar radiation and humidity) on the instantaneous value of these measured parameters, at different powerline sites. The existence of possible associations or links between these various parameters measured in the proximity of the powerlines was statistically investigated using simple linear regression, correlation and multivariate (principal component, factor, classification and regression tree-CART) analysis. The strength of the regression was tested with coefficient of determinations R2, while statistical significance was asserted at the 95 % confidence level. For the powerline sites investigated in this study, both positive and negative polarities of ions were found to be present in the ambient air environment. The presence of these ions was associated with perturbations in the local vertical dc e-field, increased net ambient ion concentrations and net particle charge concentration levels. The mean net ion concentration levels (with a range of 4922 ions cm-3 to -300 ions cm-3) in the ambient environment of these powerlines, were in excess of what was measured in a typical outdoor air (i.e -400 ions cm-3). The mean net particle charge concentration levels (1469 ions cm-3 to -1100 ions cm-3) near the powerlines were also found to be statistically significantly higher than what was obtained for a mechanically ventilated indoor room (-84 ± 49 ions cm-3) and a typical urban outdoor air (-486 ± 34 ions cm-3). In spite of all these measured differences however, the study also indicated that ambient ion concentration as well as its associated effects on ambient particle charge concentration and e-field perturbations gradually decreased with increase in distance from the powerlines. This observed trend provided the physical evidence of the localized effect of real-world HVPL generated corona ions. Particle number concentration levels remained constant (in the order of 103 particles cm-3) irrespective of the powerline site or the sampling distance from the lines. A close observation of the output signals of the sampling instruments used in this study consistently revealed large fluctuations in the instantaneous value of all the measured electrical parameters (i.e. non-periodic extremely high and low negative and positive polarities of ions/charged particles and e-field perturbations was recorded). Although the reason for these observed fluctuations is not particularly known at this stage, and hence in need of further investigations, it is however being hypothesized that, since these fluctuations appear to be characteristic of the highly charged environment surrounding corona ion emitting electrical infrastructures, they may be suggestive of the possibility that the release of corona ions by ac lines are not necessarily in the form of a continuous flow of ions. The results also showed that statistically significant correlations (R2 = 74 %, P < 0.05) exists between the instantaneous values of the ground-level ambient ion and the ground-level ambient particle charge concentration. This correlation is an indication of the strong relationship/association that exists between these two parameters. Lower correlations (R2 = 3.4 % to 9 %, P < 0.05) were however found to exist between the instantaneous values of the vertical dc e-field and the ground-level ambient particle charge concentration. These suggest that e-field measurements alone may not necessarily be a true indication of the ground-level ambient ion and particle charge concentration levels. Similarly, low statistical correlations (R2 = 0.2 % to 1.0 %, P < 0.05) were also found to exist between the instantaneous values of ambient aerosol particle charge concentration and ambient ultrafine (0.02 to 1 μm sized) aerosol particle number concentration. This low level of correlations suggests that the source contribution of aerosol particle charge and aerosol particle number concentration into the ambient air environment of the HVPLs were different. In terms of the implication of human exposure to charged aerosol particles, the results obtained from this study suggests that amongst other factors, exposure to the dynamic mixture of ions and charged particles is a function of : (a) distance from the powerlines; (b) concentration of ions generated by the powerlines; and (c) meteorology - wind turbulence and dispersal rate. In addition to all its significant findings, during this research, a novel measurement approach that can be used in future studies for the simultaneous monitoring of the various parameters characterizing the physical environment of different ion/charged particle emission sources (such as high voltage powerlines, electricity substations, industrial chimney stack, motor vehicle exhaust, etc.) was developed and validated. However, in spite of these significant findings, there is still a need for other future and more comprehensive studies to be carried out on this topic in order to extend the scientific contributions of in this research work.

Phenomenon of industrial grounds placed near residential areas can be frequently detected in European cities, which may cause decrease of air quality in these areas. The aim of this diploma thesis is to determine level of concentration and size distribution of aerosol in the planetary boundary layer above the residential area and industrial complex of Škoda auto a.s. in Mladá Boleslav city by using remotely controlled airship. Thereby, the thesis extends terrestrial experiment realized in February and March 2013 which revealed no significant impact of industry and traffic on air quality. Size distribution and concentration of aerosol particles in range from 11.5nm to 10µm with integration time one second or one minute (depending on measure mode - SINGLE or SCAN) was measured by two aerosol spectrometers placed in dirigible gondola during 13 flights on February 11, 2015. SINGLE mode lead the airship in one stable flight level during one flight above residential area and industrial complex of Škoda auto a.s. Whereas SCAN mode changed flight level every two minutes during the flight of airship above sports fields in residential zone only. Exhausts of car painting halls and place of automobile loading were identified as the sources of nanoparticles, PM1 a PM2.5 and coarse aerosol in the industrial area...

The German Ultrafine Aerosol Network (GUAN) has been continuously measuring the particle number size distribution (PNSD) and equivalent black carbon (eBC) mass concentration since 2009 at 17 atmospheric observatories in Germany, covering all environments from roadside to high-Alpine environments. GUAN provides us an opportunity to reduce the knowledge gaps about the spatio-temporal variation of sub-micrometer particles in different size ranges and eBC mass. These data are not only highly valuable for air pollution and health studies but also can help to reduce the uncertainties in the climate model predictions. With these long-term multi-site-category measurements, it was investigated for the first time how pollutant parameters interfere with spatial characteristics and site categories. Based on this first investigation, the long-term changes in size-resolved particle number concentrations (PNC) and eBC mass concentration were investigate to evaluate the effectiveness of the emission mitigation policies in Germany. The emission and pollutants near ground can be frequently transported to the free troposphere (FT) in the mountain areas. To identify if the decreased emissions at lower-altitudes have affected the aerosol loading in the aged, well-mixed FT air over Central Europe, the long-term trends in PNC and eBC mass concentration were analyzed for the FT and planetary boundary layer (PBL) conditions separately, at two high-Alpine observation sites. In summary, this dissertation aims to answer the following related scientific questions: Q1: How do the sub-micrometer PNSD, PNC, and eBC mass concentration interfere with spatial characteristics and site categories? (First publication) In the first publication (Sun et al., 2019), the spatio-temporal variability of aerosol parameters including PNSD, PNCs, and eBC mass concentration from the GUAN network were investigated for the period 2009−2014. Significant differences in the pollutant concentration were observed among various site categories. The six-year median value of sub-micrometer PNC (diameter range 20–800 nm) varies between 900 and 9000 cm−3, while median eBC mass concentration varies between 0.1 and 2.3 μg m-3 in 17 observation sites. PNCs in different size ranges were found in different spatial variabilities. A cross-correlation between PNSD and eBC mass concentration was analyzed to detect the influence of anthropogenic sources for different site categories. The size-dependent spatial variability analysis of PNCs extracted three size intervals: a higher spatial variability size range 10–30 nm, a transition size range 30–100 nm and a lower spatial variability size range 100–800 nm. Based on the evaluated spatial variability, the measured parameters at various sites were clustered by a hierarchical clustering approach, which revealed different spatial clusters for “source-driven” and “long-range transport” parameters. This result suggests that the traditional “site category” (i.e. urban, and regional background, etc.) concerning mainly the influence of local sources cannot always catch the variation of aerosol particle mass or number concentrations. The dominant factors for various parameter are different, leading to different variability and spatial distribution. The result of spatial clustering offers a sound scientific base to compare pollutant parameters measured in different locations and environments. By assessing the relationship between the measured parameters and geographical distance between different sites, the spatial variability of the aerosol parameters follows the “First Law of Geography” that everything is related to everything else, but near things are more related than distant things (Tobler, 1970). However, different parameters show different sensitivities on geographical distance. The analysis provides an important reference for setting up an observation network with a specific research purpose and is also useful for the regional scale dispersion models or land-use regression models. Q2: How do the sub-micrometer PNSD, PNC, and eBC mass concentration change at a decadal scale? Have the implementations of emission mitigation policies affected the observed decadal trend? (Second publication) In the second publication (Sun et al., 2020), long-term trends in atmospheric PNCs and eBC mass concentration for a 10 years period (2009–2018) were determined for 16 sites of the GUAN, ranging from roadside to high-Alpine. To ensure the data consistency for the trend detection, a thorough and detailed data quality check and data cleaning for the large GUAN dataset was performed. Statistically significant decreasing trends were found for 85% of the parameters and observation sites indicating an overall decreasing trend in sub-micrometer PNC (except N[10−30]) and eBC mass concentration all over Germany. Comparing the trends of measured parameters with the long-term change in total emission, we proofed that the observed trends of PNCs and eBC mass concentrations were mainly due to the emission reduction. The detailed diurnal and seasonal trends in eBC mass concentration and PNCs further confirmed that the observed decreasing trends were largely owing to the reduced emissions such as traffic emission, residential emission, and industry emission, etc. Moreover, the inter-annual changes of meteorological conditions and long-range transport pattern were found not to be the main reason for the decreases in pollutant parameters. This study suggests that a combination of emission mitigation policies can effectively improve the air quality over large spatial scales such as Germany. Given the relative novelty of the long-term measurements (PNSD, eBC mass concentration) in a network such as GUAN, the results proved to be quite robust and comprehensive. Q3: Have the decreased PNC and eBC mass concentration due to emission mitigation policies at the lower-altitudes affected the background air in lower FT over Central Europe? (Third publication) In the third publication (Sun et al., 2021), the long-term change of the eBC mass concentration and size-resolved PNCs were determined and analyzed at two high Alpine stations for the period 2009-2018: Schneefernerhaus at mountain Zugspitze in Germany (ZSF, 2671 m a.s.l.) and Jungfraujoch in Switzerland (JFJ, 3580 m a.s.l.). The trend analysis was performed for the FT and PBL-influenced conditions separately, aiming to assess whether the reduced emissions at lower-altitudes over Central Europe can affect the background air in the lower FT on a large spatial scale. The FT and PBL conditions at the two stations were segregated using the adaptive diurnal minimum variation selection (ADVS) method. The result showed that the FT condition in cold months is more prevalent than in warm months. Overall, the FT conditions frequency was ~25% and 6% in the cold and warm seasons at ZSF, respectively. At JFJ, the frequency of FT was ~45% and 10% in these two seasons, respectively. The PNC and eBC mass concentration showed a statistically significant decrease during PBL time. The observed decreasing trends in eBC mass concentration in the PBL-influenced condition are well consistent with the reported trends in total BC emission in Germany and Switzerland. For the FT conditions, decreases in PNC and eBC mass concentration over the years was detected at both sites, suggesting the background PNC and eBC mass in the lower FT over Central Europe has decreased as well. The implementation of emission mitigation policies is the most decisive factor but the weather pattern change over Central Europe also has contributed to the decreasing trends in FT condition.:List of Figures ……………………………………………………………………………………………..I List of Tables ..……………………………………………………………………………………………..I Abbreviations .……………………………………………………………………………………………II 1. Introduction …………………………………………………………………………………………….1 1.1 Role of atmospheric sub-micrometer aerosol particles…...………………………………………...1 1.2 Measurement of sub-micrometer particle number size distribution, particle number concentration, and eBC mass concentration…..……………………………………………….………………………….2 1.3 Previous long-term observations of PNSD, PNC, and eBC mass concentration…………………...4 1.4 Objectives...………………………………………………………………………………………….6 2. Data and Method…..……………………………………………………………………………………9 2.1 The German Ultrafine Aerosol Network (GUAN) …………………………………………………9 2.1.1 Measurement sites in GUAN…………………………………………………………………..10 2.1.2 Instrumental set-up.……….………………………………………………………….…………14 2.1.3 Quality assurance.………………………………………………………………………….……16 2.1.4 Data coverage…..………………………………………………………………………………..17 2.2. High-Alpine observatory Jungfraujoch (JFJ)……………………………………………………..18 2.2.1 Measurement site……….……………………………………………………………………….18 2.2.2 Instrumentation ..………………………………………………………………………………..19 2.3 Data analysis methods……………………………………………………………………………….19 2.3.1 Agglomerative hierarchical clustering….……………………………………………………...19 2.3.2 Customized Sen’s slope estimator…………………..…………………………………………...21 2.3.3 Generalized least-square regression and autoregressive bootstrap confidence intervals (GLS- ARB)…………………………………………………………………………………………………21 2.3.4 Seasonal Mann-Kendal test…..………………….………………………………………………22 2.3.5 Back-trajectory classification method….……………………………………………………...24 3. Results and Discussion…..………………………………………………………………………….27 3.1 First publication….…………………………………………………………………………………..27 3.1.1 Variability of black carbon mass concentrations, sub-micrometer particle number concentrations and size distributions: results of the German Ultrafine Aerosol Network ranging from city street to High Alpine locations……………………………………...………………………………………...27 3.1.2 Supporting information..……………………………………………………………………….41 3.2 Second publication…………………………………………………………………………………..45 3.2.1 Decreasing trends of particle number and black carbon mass concentrations at 16 observational sites in Germany from 2009 to 2018…..…………………………………………………………..45 3.2.2 Supporting information...……………………………………………………………………….66 3.3 Third publication……………………………...……………………………………………………..75 3.3.1 Long-term trends of black carbon and particle number concentration in the lower free troposphere in Central Europe…………………………………………………………………………75 3.3.2 Supporting information..…….……………………………………………………………….92 4. Summary and Conclusions..………………………………………………………………………… 95 5. Outlook….…………………………………………………………………………………………...99 Appendix A….………………………………………………………………………………………...100 Bibliography…………………………………………………………………………………………...101 Acknowledgements….…………………………………………………………………………………115

Les nanoparticules (NP) figurent aux premiers rangs des contaminants émergents prioritaires dans le champ de surveillance des grands organismes de santé et sécurité du travail. Parmi les NP les plus utilisées, on peut citer les NP d’argent (Ag). L’exposition humaine aux NP d’Ag augmente alors inévitablement avec l’accroissement de leur production et leur utilisation généralisée ce qui suscite des préoccupations sur les risques à la santé. L'objectif du projet est de mieux documenter le devenir des NP d’Ag dans l’organisme, à partir d’études expérimentales chez l’animal exposé sous différentes conditions par inhalation, la principale voie d’exposition des travailleurs. Ces informations sont nécessaires pour le développement sécuritaire de ces nouvelles technologies. Dans un premier temps, le profil toxicocinétique des NP d’Ag inhalées a été documenté. Les rats ont été exposés « nez seulement » à des NP de 20 nm pendant 6 h à une concentration cible de 15 mg/m3. L'évolution temporelle de l'élément Ag dans les poumons, le sang, les tissus et les excrétas a été déterminée pendant 14 jours après le début de l'inhalation. La cinétique des NP d’Ag inhalées a été ensuite comparée avec la cinétique d’une forme soluble de l’élément Ag suite à l’exposition au nitrate d’argent (AgNO3) dans de mêmes conditions expérimentales pour mieux comprendre leur comportement, principalement, en raison de leur dissolution et leur capacité à libérer progressivement des ions Ag+ en milieu biologique. Ainsi, dans un dernier temps, dans le but de déterminer la meilleure métrique à utiliser pour mieux évaluer les risques associés à ces NP d’Ag, nous avons étudié l’impact de la cinétique entre un nombre plus faible et un nombre plus élevé de particules. Les profils cinétiques des NP d’Ag inhalées ont montré que la fraction de la dose inhalée qui a atteint les poumons est rapidement éliminée au cours des 72 premières heures suivant l'inhalation, puis la fraction restante de la dose est lentement éliminée par la suite. La dose inhalée éliminée des poumons semble être transférée dans la circulation systémique et atteint un maximum entre 48 et 72 h après l'inhalation. Cependant, les niveaux d'Ag dans le sang étaient faibles, ce qui suggère une biodistribution rapide dans les tissus tels que le foie, l’organe cible des NP d’Ag chez le rat après inhalation. Une translocation vers le bulbe olfactif et les ganglions lymphatiques était évidente durant l'exposition par inhalation de 6 h jusqu'à 6 h après la fin de l'exposition, démontrant l’occurrence d’un transport direct des NP d’Ag via le nerf nasal par le transport axonal et via la circulation lymphatique après la clairance pulmonaire, respectivement. Les profils d'excrétion ont également révélé que l'excrétion fécale est la voie d'excrétion dominante pour les NP d’Ag. Les résultats obtenus après l'inhalation d'AgNO3 ont montré des différences dans la cinétique de l’Ag sous la forme soluble par rapport à la forme insoluble (nanoparticulaire) avec des niveaux plus élevés dans le sang, le tractus GI et les tissus extrapulmonaires, mais des niveaux plus faibles dans les poumons. En plus de ces observations, l'évolution temporelle de l’Ag dans le tube digestif et les fèces après l'exposition à la forme soluble était associée à une réabsorption intestinale de l'Ag. Une fraction plus élevée de la dose a été également récupérée dans les reins et l'urine pour les formes solubles d’Ag; en effet, la filtration glomérulaire des agrégats de NP d’Ag peut être limitée alors que le cation monovalent dissous peut plus facilement passer dans le filtrat du sang. Notre étude a également révélé des différences significatives dans les profils temporels de l'Ag dans les poumons, le sang, les ganglions lymphatiques et le tractus gastro-intestinal entre les rats exposés à des aérosols de NP d'Ag avec un nombre faible et un nombre élevé de particules, mais dont la concentration massique est identique. Certaines similitudes entre les deux conditions ont également été notées, telles que la distribution tissulaire relative, le temps jusqu'aux niveaux de pointe (Tmax) et les profils d'excrétion. Cependant, pour confirmer si le modèle de biodistribution des NPs d'Ag est conditionné par le nombre de particules, des investigations supplémentaires sont nécessaires. / Nanoparticles (NPs) are among the top priority emerging contaminants in the monitoring field of the major occupational health and safety organizations. Among the most widely used nanoparticles, we can cite silver nanoparticles (Ag). Human exposure to Ag NPs inevitably increases with the increase in their production and their widespread use which raises concerns about the health risks. The objective of the project is to better document the fate of Ag nanoparticles in the body, based on experimental studies in animals exposed under different conditions by inhalation, the main route of exposure for workers. This information is necessary for the safe development of these new technologies. First, the toxicokinetic profile of inhaled Ag NPs was documented. Rats were exposed "nose only" to 20 nm NPs for 6 h at a target concentration of 15 mg/m3. The temporal evolution of the Ag element in the lungs, blood, tissues and excreta was determined for 14 days after the start of inhalation. Thus, to better understand their behavior, mainly because of their dissolution and their capacity to progressively release Ag+ ions in the biological medium, the kinetics of inhaled Ag NPs were compared with the kinetics of a soluble form of the element Ag following exposure to silver nitrate (AgNO3) under the same experimental conditions. Thus, as a last step, in order to determine the best metric to use to better assess the risks associated with these Ag NPs, we studied their kinetic from inhalation studies by comparing the effect of a lower -number with a higher- number of particles. The kinetic profiles of inhaled Ag nanoparticles showed that the fraction of the inhaled dose that reached the lungs is rapidly eliminated during the first 72 hours after inhalation, and the remaining fraction of the dose is slowly eliminated thereafter. The inhaled dose cleared from the lungs appears to be transferred to the systemic circulation and reaches a maximum between 48 and 72 hours after inhalation. However, Ag levels in the blood were low, suggesting rapid biodistribution to tissues such as the liver, the target organ of Ag nanoparticles in rats after inhalation. A translocation of Ag NPs in olfactory bulbs and lymph nodes was apparent, demonstrating the occurrence of direct transport of Ag NPs through nasal nerve by axonal transport and via lymphatic circulation after lung clearance, respectively. The excretion profiles also revealed that fecal excretion is the dominant excretion route for Ag nanoparticles. The results obtained after inhalation of AgNO3 showed differences in the kinetics of soluble AgNO3 compared to insoluble Ag NPs, with higher levels in blood, GI tract and extrapulmonary tissues, but lower levels in lungs. In addition to these observations, the time courses of Ag elements in the GI tract and feces following ionic form exposure were compatible with an intestinal reabsorption of Ag. A higher fraction of the dose was further recovered in kidneys and urine after AgNO3 inhalation compared to Ag NP inhalation. Indeed, filtration of Ag NP aggregates may be restricted while the dissolved Ag+ monovalent ion can more easily pass into the filtrate from blood. Our study also revealed significant differences in the time profiles of Ag element in lungs, blood, lymphatic nodes and GI tract between rats exposed to Ag NPs aerosols of lower- and higher-total particle number counts, but with the same mass concentration. Some similarities between the two conditions were also noted, such as the relative tissue distribution, time-to-peak levels (Tmax) and excretion profiles. However, to confirm if the biodistribution pattern of Ag NPs is conditioned by the particle number, further investigations are needed.