Abstract: Although CO2 conversion by plasma technology is gaining increasing interest, the
underlying mechanisms for an energy-efficient process are still far from understood. In this work, a reduced non-equilibrium CO2 plasma chemistry set, based on level lumping of the vibrational levels, is proposed and the reliability of this level-lumping method is tested by a self-consistent zero-dimensional code. A severe reduction of the number of equations to be solved is achieved, which is crucial to be able to model non-equilibrium CO2 plasmas by 2-dimensional models. Typical conditions of pressure and power used in a microwave plasma for CO2 conversion are investigated. Several different sets, using different numbers of lumped groups, are considered. The lumped models with 1, 2 or 3 groups are able to reproduce the gas temperature, electron density and electron temperature profiles, as calculated by the full model treating all individual excited levels, in the entire pressure range investigated. Furthermore, a 3-groups model is also able to reproduce the shape of the vibrational distribution function (VDF) and gives the most reliable prediction of the CO2 conversion. A strong influence of the vibrational excitation on the plasma characteristics is observed. Finally, the limitations of the lumped-levels method are discussed.

Abstract: Although adult and embryonic stem cell-based therapy for central nervous system (CNS) injury is being developed worldwide, less attention is given to the immunological aspects of allogeneic cell implantation in the CNS. The latter is of major importance because, from a practical point of view, future stem cell-based therapy for CNS injury will likely be performed using well-characterised allogeneic stem cell populations. In this study, we aimed to further describe the immunological mechanism leading to rejection of allogeneic bone marrow-derived stromal cells (BM-SC) after implantation in murine CNS. For this, we first investigated the impact of autologous and allogeneic BM-SC on microglia activation in vitro. Although the results indicate that both autologous and allogeneic BM-SC do not activate microglia themselves in vitro, they also do not inhibit activation of microglia after exogenous stimuli in vitro. Next, we investigated the impact of allogeneic BM-SC on microglia activation in vivo. In contrast to the in vitro observations, microglia become highly activated in vivo after implantation of allogeneic BM-SC in the CNS of immune-competent mice. Moreover, our results suggest that microglia, rather than T-cells, are the major contributors to allograft rejection in the CNS.

Abstract: Almost seventy years after artists such as Frank Stella (1936), Andy Warhol (1928-1987), James Rosenquist (1933-2017), Herb Aach (1923-1985) and Richard Bowman (1918-2001) started to incorporate Daylight Fluorescent Pigments (DFPs) in their artworks, the extent of the conservation problems that are associated with these pigments has increased progressively. Since their first appearance on the market, their composition has constantly been improved in terms of permanency. However, conservation practices on the artworks that are used in, are complicated by the fact that the composition of DFPs is proprietary and the information provided by the manufactures is limited. To be able to propose adequate conservation strategies for artworks containing DFPs, a thorough understanding of the DFPs composition must be acquired. In contrast with previous research that concentrated on identification of the coloring dye, this paper focuses on the characterization of the resin, used as the carrier for the dye. The proposed approach, involving ATR-FTIR, SPME-GC-MS and XRF analysis, provided additional insights on the organic and inorganic components of the resin. Using this approach, we investigated historical DFPs and new formulations, as well as different series from the main manufacturing companies (DayGlo, Swada, Radiant Color and Kremer) in order to obtain a full characterization of DFPs used by the artists along the years. First, the initial PCA-assisted ATR-FTIR spectroscopy allowed for an efficient classification of the main monomers in the resin polymer. Next, a further distinction was made by mass spectrometry and XRF which were optimized to allow a more specific classification of the resin and for detection of additives. In this paper we show the potential of SPME-GC-MS, never applied for the characterization of artistic materials, at present undervalued for heritage science purposes. We anticipate that this information will be highly relevant in the future stability studies and for defining (preventive) conservation strategies of fluorescent artworks.

Abstract: Alloyed metal nanocatalysts are of environmental and economic importance in a plethora of chemical technologies. During the catalyst lifetime, supported alloy nanoparticles undergo dynamic changes which are well-recognized but still poorly understood. High-temperature O-2-H-2 redox cycling was applied to mimic the lifetime changes in model Pt13In9 nanocatalysts, while monitoring the induced changes by insitu quick X-ray absorption spectroscopy with one-second resolution. The different reaction steps involved in repeated Pt13In9 segregation-alloying are identified and kinetically characterized at the single-cycle level. Over longer time scales, sintering phenomena are substantiated and the intraparticle structure is revealed throughout the catalyst lifetime. The insitu time-resolved observation of the dynamic habits of alloyed nanoparticles and their kinetic description can impact catalysis and other fields involving (bi)metallic nanoalloys.

Abstract: All-inorganic lead-free halide double perovskites offer a promising avenue toward non-toxic, stable optoelec-tronic materials, properties that are missing in their prominent lead-containing counterparts. Their large ther-mopowers and high carrier mobilities also make them promising for thermoelectric applications. Here, we present a first-principles study of the lattice vibrations and thermal transport behaviors of Cs2SnI6 and gamma-CsSnI3, two prototypical compounds in this materials class. We show that conventional static zero temperature density functional theory (DFT) calculations severely underestimate the lattice thermal conductivities (kappa l) of these compounds, indicating the importance of dynamical effects. By calculating anharmonic renormalized phonon dispersions, we show that some optic phonons significantly harden with increasing temperature (T), which reduces the scattering of heat carrying phonons and enhances calculated kappa l values when compared with standard zero temperature DFT. Furthermore, we demonstrate that coherence contributions to kappa l, arising from wave like phonon tunneling, are important in both compounds. Overall, calculated kappa l with temperature-dependent inter-atomic force constants, built from particle and coherence contributions, are in good agreement with available measured data, for both magnitude and temperature dependence. Large anharmonicity combined with low phonon group velocities yield ultralow kappa l values, with room temperature values of 0.26 W/m-K and 0.72 W/m-K predicted for Cs2SnI6 and gamma-CsSnI3, respectively. We further show that the lattice dynamics of these compounds are highly anharmonic, largely mediated by rotation of the SnI6 octahedra and localized modes originating from Cs rattling motion. These thermal characteristics combined with their previously computed excellent electronic properties make these perovskites promising candidates for optoelectronic and room temperature thermoelectric applications.

Abstract: AlGaN/GaN heterostructures were grown on “on-axis” and 2° off (0001) 4H-SiC substrates by metalorganic vapor phase epitaxy (MOVPE). Structural characterization was performed by transmission electron microscopy. The dislocation density, being greater in the on-axis case, is gradually reduced in the GaN layer and is forming
dislocation loops in the lower region. Steps aligned along [11̅00] in the off-axis case give rise to simultaneous defect formation. In the on-axis case, an almost zero density of steps is observed, with the main origin of defects probably being the orientation mismatch at the grain boundaries between the small not fully coalesced AlN grains. V-shaped formations are observed in the AlN nucleation layer, but are more frequent in the off-axis case, probably enhanced by the presence of steps. These V-shaped formations are completely overgrown by the GaN layer, during the subsequent deposition, presenting AlGaN areas in the walls of the defect, indicating an interdiffusion between the layers. Finally, at the AlGaN/GaN heterostructure surface in the on-axis case, V-shapes are observed, with the AlN spacer and AlGaN (21% Al) thickness on relaxed GaN exceeding the critical thickness for relaxation. On the other hand, no relaxation in the form of V-shape creation is observed in the off-axis case, probably due to the smaller AlGaN thickness (less than 21% Al). The AlN spacer layer, grown in between the heterostructure, presents a uniform thickness and clear interfaces.

Abstract: Al-Zn-Mg-based high strength alloys are widely used in aerospace applications due to their low density and excellent mechanical properties. A systematic study of the structural evolution of the nano-precipitation phase and its growth mechanism is an important guide for the design of new high-strength alloys. In this work, the Laves structure precipitates in Al-Zn-Mg(-Cu/Y) alloy was systematically characterized. Based on the structure evolution, the structure of submicron Laves particles and quasicrystalline particles in the alloy at microscale, as well as the regulation of the precipitation behavior after adding Y at nanoscale were further investigated. The main innovative results are summarized as follows: (1) Investigation on coexistence of defect structures in Laves structural nanoprecipitates. Three types of Laves structures can coexist within the η-MgZn2 precipitates: C14, C15 and C36, and the Laves structure transition sequence of C14→C36→C15 in this system was determined. Meanwhile, it was found that there are diverse defect structures in the MgZn2 phase, including stacking faults, planar defects and five-fold domain structures, which have significant effects on relieving the internal stress/strain of the precipitates. (2) Investigation on multiple phase transition of Laves structural nanoprecipitates from C14 to C36 and from C14 to quasicrystal clusters. It is found that C14 precipitates can be completely transformed into the C36 precipitates. And it is also found that the C14 Laves phase structure can also transform into quasicrystalline clusters. These investigations on various phase transition mechanisms among Laves phases provide theoretical support for the microstructural characterization of materials containing multi-scale Laves phases. (3) Characterization of Laves and quasicrystal structural particles in submicron scale. Submicron-scale quasicrystal particles were obtained in conventional casting Al-Zn-Mg-Cu alloys for the first time. Industrial impurity elements Fe and Ni can induce the formation of quasicrystalline particles. When there is no Fe/Ni enriched in particles, the structure is characterized as C15-Laves phase. When Fe/Ni is as quasicrystalline core, a stable core-shell quasicrystalline structure with Al-Fe-Ni nucleus and Mg-Cu-Zn shell can be formed. (4) Investigation on the regulation of nanoscale Laves precipitates’ growth. To regulate the defect structure of the precipitates, rare earth element Y was added in Al-Zn-Mg alloys and its influence on the precipitation behavior was investigated. The addition of Y element can dynamically combine with different alloying elements during aging process, which can refine the size of precipitate and further improve the nucleation rate and precipitation rate of the precipitates.

Abstract: Airborne particulate matter (PM) includes semi-volatile organic compounds (SVOCs), which can be deposited on vegetation matrices such as plant leaves. In alternative to air-point measurements or artificial passive substrates, leaf monitoring offers a cost-effective, time-integrating means of assessing local air quality. In this study, leaf washing solutions from ivy (Hedera hibernica) leaves exposed during one-month at different land use classes were explored via comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GCxGC-TOFMS). The composition of leaf-deposited SVOCs, corrected for those of unexposed leaves, was compared against routinely monitored pollutants concentrations (PM10, PM2.5, O3, NO2, SO2) measured at co-located air monitoring stations. The first study on leaf-deposited SVOCs retrieved from washing solutions, herein reported, delivered a total of 911 detected compounds. While no significant land use (rural, urban, industrial, traffic, mixed) effects were observed, increasing exposure time (from one to 28 days) resulted in a higher number and diversity of SVOCs, suggesting cumulative time-integration to be more relevant than local source variations between sites. After one day, leaf-deposited SVOCs were mainly due to alcohols, N-containing compounds, carboxylic acids, esters and lactones, while ketones, diketones and hydrocarbons compounds gained relevance after one week, and phenol compounds after one month. As leaf-deposited SVOCs became overall more oxidized throughout exposure time, SVOCs transformation or degradation at the leaf surface is suggested to be an important phenomenon. This study confirmed the applicability of GCxGC-TOFMS to analyze SVOCs from leaf washing solutions, further research should include validation of the methodology and comparison with atmospheric organic pollutants.

Abstract: Air quality currently poses a major risk to human health worldwide. Transportation is one of the principal contributors to air pollution due to the quality of exhaust gases. For example, the widely used diesel fuel is a significant source of nitrogen oxides (NOx) and particulate matter (PM). To reduce the content NOx and PM, different oxygenated compounds were mixed into a mineral diesel available at the pump, and their effect on the composition of exhaust gas emissions was measured using a one-cylinder diesel generator. In this setup, adding methanol gave the best relative results. The addition of 2000 ppm of methanol decreased the content of NO by 56%, 2000 ppm of isopropanol decreased NO2 by 50%, and 2000 ppm ethanol decreased PM by 63%. An interesting question is whether it is possible to reduce the impact of hazardous components in the exhaust gas even more by adding oxygenates to biodiesels. In this article, alcohol is added to biodiesel in order to establish the impact on PM and NOx concentrations in the exhaust gases. Adding methanol, ethanol, and isopropanol at concentrations of 2000 ppm and 4000 ppm did not improve NOx emissions. The best results were using pure RME for a low NO content, pure diesel for a low NO2 content, and for PM there were no statistically significant differences.

Abstract: Air pollution, especially particulate matter (PM), is an increasingly urgent problem in urban environments, causing both short and long-term health problems, climate interference and aesthetical problems due to building fouling. Photocatalysis has been shown to be a possible solution to that end. In this work two complementary detection methods for photocatalytic soot oxidation are studied and their advantages and disadvantages are discussed. First, a colour-based digital image analysis method is drastically improved towards an accurate, detailed and straightforward detection tool, that enables simultaneous measurement of the degradation of different grades of soot fouling (for instance a shallow soot haze versus condensed soot deposits). In the next part, a second soot oxidation detection method is presented based on in situ FTIR spectroscopy. This method has the additional advantage of providing more insight into the photocatalytic soot degradation process by monitoring both gaseous and adsorbed intermediates as well as reaction products while the reactions are ongoing. As an illustration, the proposed detection strategies were applied on four different commercially available and synthesized photocatalytic materials. The digital image analysis showed that P25 (Evonik) is the fastest photocatalytic soot degrader of all studied materials for both a uniform soot haze as well as concentrated soot spots. Application of the in situ method showed that for all studied materials adsorbed formate-related surface species were formed and that commercially available ZnO nanopowder has the highest specificity towards complete mineralization into CO2. With this we aim to provide a set of complementary experimental tools for the convenient, reliable, realistic and standardised detection of photocatalytic soot degradation.

Abstract: Air pollution is proclaimed by the World Health Organiaation (WHO) as the biggest environmental threat to human health. Street canyons, or urban roads flanked by a continuous row of high buildings on both sides, are perceived as typical bottleneck areas for air quality due to their lack of natural ventilation. This doctoral thesis aims to integrate expert knowledge on in-canyon flow fields and pollution dispersion in street canyons from the specialized field of (bio)engineering into the field of urban planning and vice versa. In Chapter 1, a Geospatial Information System (GIS) method was developed to detect exposure zones and hotspot street canyons. A critical combination between aspect ratio (AR > 0.65) and traffic volume (TVmax > 300) was detected and subsequently used to detect hotspot street canyons in three major European cities (Antwerp, London and Paris). Chapter 2 focusses on acquiring in-depth knowledge on flow and concentration fields in street canyons by conducting an extensive literature review on over 200 studies and translates this knowledge into nineteen guidelines and eleven spatial tools, comprised in a toolbox for urban planning. Subsequently, computational fluid dynamics (CFD) was used into a research trough design process (Chapter 4) to illustrate how the design tools can be applied to a specific case study (Belgiëlei, Antwerp). Alternations to traffic lanes (traffic lane reduction and lateral displacement) combined with low boundary walls (LBWs), were found to reduce NO2 levels in the entire pedestrian area up to – 3.6 % and peak pollutions were reduced by -8 %. A maximum NO2 reduction was reached by combining a traffic lane displacement with hedges, adjustments to the tree planting pattern and an increased ground-level permeability, leading to reductions up to – 4.5 % in the pedestrian areas. In conclusion, urban design was found to be a valuable tool to enhance the effect of emission reduction strategies and draw in-canyon concentrations closer to the value of the background concentration. However, the background concentration seemed to dominate the efficiency of the urban design interventions and therefore, additional measures should be taken to reduce background pollution levels. This dissertation aims to contribute to the awareness of air pollution in street canyons, as well as support local governments in taking action by delivering spatial tools and guidelines applicable for urban planning and represents a framework for the dissemination of expert information on air quality in street canyons to the field of urban planning.

Abstract: Air pollution caused by the lime production industry has become a serious problem with potential effects to human health, especially in developing countries. Colombo is a city included in the Metropolitan Region of Curitiba (capital of Parana State) in South Brazil. In Colombo city, a correlation has been shown between the lime production and the number of persons who need respiratory treatment in a local hospital, indicating that the lime industry can cause deleterious health effects in the exposed workers and population. This research was conducted to deal firstly with the characterization of the size distribution and chemical compositions of particles emitted from lime manufacturing and subsequently to assess the deposition rate of inhaled dolomitic lime aerosol particles in the human respiratory tract. The elemental chemical composition and particle size of individual atmospheric particles was quantitatively elucidated, including low-Z components like C, N and 0, as well as higher-Z elements, using automated electron probe microanalysis. Information concerning the bulk composition is provided by energy-dispersive X-ray detection. The majority of the respirable particulate matter identified was composed of aluminosilicates, Ca-Mg oxides, carbon-rich particles, mixtures of organic particles and Ca-Mg carbonates, soot and biogenic particles. In view of the chemical composition and size distribution of the aerosol particles, local deposition efficiencies in the human respiratory system were calculated, revealing the deposition of CaO center dot MgO at extrathoracic, tracheobronchial and pulmonary levels. The results of this study offer evidence to the threat of the fine and coarse particles emitted from dolomite lime manufacturing, allowing policy-makers to better focus their mitigation strategies in an effective way, as well as to the dolomite producers for the purpose of designing and/or implementing improved emission controls.

Abstract: Air pollutants from fossil fuel fired power plants harm the environment and human health. More than 91% of Irans electricity production is from thermal power plants that use natural gas, diesel, and fuel oil. We apply the impact pathway approach to estimate the health impacts arising from Iranian fossil-based electricity generation emission, and in a next step, we calculate monetary costs of the estimated damages, for a one-year period starting from 20 March 2016 through 2017. We use the new version of SIMPACTS (International Atomic Energy Agency, Vienna, Austria) to investigate the health effects from 61 major Iran fossil-based power plants separately. The selected plants represent 95.6% of total Iran fossil-based power generation. Using the individual and different power plant estimates, we avoid extrapolation and our results can be considered more reliable, taking into account spatial differences. The total damage cost is 723.42 million USD (2000). The damage cost per generated electricity varies from 0.06 to 22.41 USD/MWh and average plant damage cost is 2.85 USD/MWh. Accounting for these external costs indicates the actual costs of fossil energy. The results are useful for policy makers to compare the health costs from these plants and to decide on cleaner energy sources and to take measures to increase benefits for society.

Abstract: Aim: We aimed to assess the impact of road disturbances on the dominant mycorrhizal types in ecosystems at the global level and how this mechanism can potentially lead to lasting plant community changes. Location: Globally distributed mountain regions Time Period: 2007-2018 Taxa studied: Plants (linked to their associated mycorrhizal fungi) Methods: We used a database of coordinated plant community surveys following mountain roads from 894 plots in 11 mountain regions across the globe in combination with an existing database of mycorrhizal-plant associations in order to approximate the relative abundance of mycorrhizal types in natural and disturbed environments. Results: Our findings show that roadside disturbance promotes the cover of plants associated with arbuscular mycorrhizal (AM) fungi. This effect is especially strong in colder mountain environments and in mountain regions where plant communities are dominated by ectomycorrhizal (EcM) or ericoid-mycorrhizal (ErM) associations. Furthermore, non-native plant species, which we confirmed to be mostly AM plants, are more successful in environments dominated by AM associations. Main Conclusions: These biogeographical patterns suggest that changes in mycorrhizal types could be a crucial factor in the worldwide impact of anthropogenic disturbances on mountain ecosystems. Indeed, roadsides foster AM-dominated systems, where AM-fungi might aid AM-associated plant species while potentially reducing the biotic resistance against invasive non-native species, often also associated with AM networks. Restoration efforts in mountain ecosystems will have to contend with changes in the fundamental make-up of EcM- and ErM plant communities induced by roadside disturbance.

Abstract: Agricultural practices enhancing soil organic carbon (SOC) show potential to buffer negative effects of climate change on forage grass performance. We tested this by subjecting five forage grass varieties differing in fodder quality and drought/flooding resistance to increased persistence in summer precipitation regimes (PR) across sandy and sandy-loam soils from either permanent (high SOC) or temporary grasslands (low SOC) in adjacent parcels. Over the course of two consecutive summers, monoculture mesocosms were subjected to rainy/dry weather alternation either every 3 days or every 30 days, whilst keeping total precipitation equal. Increased PR persistence induced species-specific drought damage and productivity declines. Soils from permanent grasslands with elevated SOC buffered plant quality, but buffering effects of SOC on drought damage, nutrient availability and yield differed between texture classes. In the more persistent PR, Festuca arundinacea FERMINA was the most productive species but had the lowest quality under both ample water supply and mild soil drought, whilst under the most intense soil droughts, Festulolium FESTILO maintained the highest yields. The hybrid Lolium × boucheanum kunth MELCOMBI had intermediate productivity and both Lolium perenne varieties showed the lowest yields under soil drought, but the highest forage quality (especially the tetraploid variety MELFORCE). Performance varied with plant maturity stage and across seasons/years and was driven by altered water and nutrient availability and related nitrogen nutrition among species during drought and upon rewetting. Moreover, whilst permanent grassland soils showed the most consistent positive effects on plant performance, their available water capacity also declined under increased PR persistence. We conclude that permanent grassland soils with historically elevated SOC likely buffer negative effects of increasing summer weather persistence on forage grass performance, but may also be more sensitive to degradation under climate change.