Le méthane a la deuxième plus grande contribution à au forçage radiatif global des gaz à effet de serre anthropiques. Après une période de stabilité, son taux de croissance atmosphérique a augmenté rapidement depuis 2007. Les émissions anthropiques de méthane ont un potentiel important d'atténuation ce qui encourage les efforts visant à réduire ses émissions conformément à l'accord de Paris. Toutefois, beaucoup d’incertitudes demeurent concernant la contribution de différentes sources de méthane, les processus et les estimations des émissions, même à une échelle locale ; ce qui entrave la mise en œuvre efficace des stratégies d'atténuation du méthane. Jusqu’à maintenant, de nombreuses études ont été réalisées pour mesurer les flux globaux de méthane, la répartition et la caractérisation des sources de méthane par région mais les processus doivent encore être mieux déterminés.Cette thèse présente et applique des méthodes pour caractériser les différentes sources de CH4 présentes dans les mesures de l'air ambiant des sites industriels et développe des outils ciblés pour répondre à cette question. Le premier chapitre traite des améliorations apportées à un instrument CRDS fréquemment déployé pour les mesures de CH4 et de δ13CH4. Nous proposons un schéma d'étalonnage pour corriger les interférences C2H6 sur δ13CH4 et permettre des mesures fiables de C2H6. Les résultats de ces travaux sont ensuite utilisés pour explorer la valeur ajoutée sur les données de la mise en œuvre de cette méthode sur une station de compresseur de gaz naturel, où une forte corrélation de C2H6 et de CH4 est normalement attendue. Le deuxième chapitre poursuit la caractérisation des sources de CH4 sur le même site mais porte plus sur l'application et la comparaison des différentes méthodes de répartition des sources. Les contributions des sources de CH4 et composés organiques volatils (COV) sont explorées selon la méthode de l'analyse isotopique, de l'analyse des séries temporelles multi-espèces à l’aide de modèles source-récepteur (PCA et PMF), des données météorologiques et des échantillons directs de gaz naturel. Le troisième chapitre présente une utilisation des méthodes de répartition des sources de CH4 sur les mesures ambiantes des sources de CH4 biogénique dans la région Ile de France et aide ainsi à compléter l'étude des sources anthropiques de CH4 les plus pertinentes.Cette thèse identifie et documente les signatures en δ13CH4 de différentes sources de CH4 sur des environnements contrastés à proximité de fermes d’élevage intensif, de stations d’épuration des eaux usées, de décharges d’enfouissement des déchets ou encore de sites de compression du gaz naturel, et étudie leur variabilité spatiale et temporelle pour faciliter la contrainte des émissions. Les résultats obtenus suggèrent que l’identification de différentes sources biogéniques et thermogéniques avec le δ13CH4 est robuste et adaptable à une grande diversité d’environnements. L'utilisation d'une combinaison d'outils est idéale pour étudier la variabilité à court terme et long terme. Cette thèse présente différentes utilisations de ces nouveaux outils pour diriger les investigations des émissions anthropiques de méthane et sont la base pour de futurs travaux dans ce domaine. / Methane has the second largest contribution to global radiative forcing impact of anthropogenic greenhouse gasses. Since 2007 its atmospheric growth rate, after a period of stability, has again been rising rapidly. Anthropogenic methane emissions hold a large mitigation potential, promoting efforts to curb emissions in accordance with the Paris Agreement. However, the considerable uncertainties regarding methane contributors, drivers and emission estimates even at local scales, hinder the effective implementation of methane mitigation strategies. While many approaches have been established to measure total methane fluxes, the partitioning and characterisation of methane sources by region and processes still need to be better constrained.This thesis presents practical methods for characterising different CH4 sources in ambient air measurements at industrial sites, as well as developing more targeted tools. The first chapter focuses on improvements to a CRDS instrument that is commonly deployed for CH4 and δ13CH4 field measurements. We propose a calibration scheme to correct for C2H6 interference on δ13CH4, and enable robust C2H6 measurements. The results of this work are then used to explore the added value gained when implemented on data from a natural gas compressor station, a site where high correlation of C2H6 and CH4 is expected. The second chapter continues the investigation of CH4 sources at the same site; with focus shifted towards the application and comparison of different source apportionment methods from time series analysis based on measurements of multiple species, some co-emitted with CH4. Here the CH4 and Volatile Organic Compounds (VOC) source contributions are explored through the use of isotopic analysis, receptor model analysis (PCA and PMF), metrological data and direct samples of natural gas. The third chapter applies a selection of the developed CH4 source apportionment methods to ambient measurements at biogenic CH4 sites in the Ile de France region and helps complete the survey of the most relevant anthropogenic CH4 sources.This thesis identifies and reports local δ13CH4 source signatures for livestock, wastewater, landfill and natural gas and studies their spatial and temporal variability to aid the constraint of emission inventories. Our findings suggest that source apportionment from δ13CH4 is robust, and adaptable to the majority of sites. Using a combination of tools is ideal for more specific source determination and for an understanding of long and short term variability. The work presented in this thesis offers example applications of these new tools to directed investigations of anthropogenic methane emissions and lays the foundation for future work in this field.

Environmental contamination has become a significant threat to the health and well-being of mankind as well as to the environment, prompting the establishment and implementation of stringent environmental regulations. The ability to accurately detect and quantify contaminants, such as mercury (Hg), uranium (U), and volatile organic compounds (VOCs), in real-time, in situ is of significant importance to monitoring and remediation efforts. In an effort to develop a real-time, fast-response detector that is portable, highly sensitive, and cost efficient, this research explored the feasibility of utilizing cavity ringdown spectroscopy (CRDS) in conjunction with various plasma sources and vacuum cavities to accurately detect trace quantities of contaminants. The feasibility of detecting Hg with a low power, low temperature candle-shaped microwave-induced plasma (MIP) and a copper surfatron microwave cavity with various plasma discharge tube configurations in conjunction with cavity ringdown spectroscopy (MIP-CRDS) is discussed. Detection limits were on the order of 221 ppt Hg in the vapor phase for the candle-shaped MIP and improved by a factor of 10 with the tube-shaped plasma. The ability to detect elemental Hg naturally-evaporating from contaminated soils and solutions was evaluated, and 10’s of ppt were consistently obtained. Additionally, the fine structure of the Hg 253.65 nm transition was observed with each iteration of this approach. The potential of effectively generating uranium atoms and ions with a low-power, lowlow rate microwave-induced plasma was evaluated. Uranium emission spectra covering 320 – 430 nm were obtained, labeled, and compared to the available literature values. Calibration curves were generated, and the detection limits were determined to be ~0.4 ppm. The feasibility of measuring U incorporating diode laser-plasma-CRDS was explored. The preliminary studies clearly show the ability to detect U vapor with this technique and sub-ppm detection limits were obtained. A continuous wave cavity ringdown spectroscopy system (CW-CRDS) incorporating commercially available telecommunications diode lasers was constructed, and the overall sensitivity of this system was evaluated by utilizing the absorption of the asymmetric C-H stretch overtones of several VOCs, including benzene, chlorobenzene, 1,2-dichlorobenzene, toluene, and acetone. Detection limits are determined to be in the ppb’s for each of the organics examined.

Tidigare studier har visat att äggläggande malariavektorer attraheras till vissa flyktiga organiska ämnen (VOC) som finns i olika gräsarter. Syftet med den här studien var att verifiera att flyktiga organiska ämnen finns i fyra olika gräsarter från Kenya; Panicum repens,Cynodon dactylon och Cyperus papyrus med Pennisetum setaceum rubrum som kontroll förde andra gräsarterna. För att analysera de flyktiga organiska ämnena extraherades gräset medhjälp av ultraljudsextraktion (UAE) och fastfasextraktion (SPE). De flyktiga organiska ämnena analyserades med gaskromatografi- masspektrometri (GC-MS). På grund av utbrottet av COVID-19 så analyserades istället resultat från en tidigare studie som använde samma metod. Det visades att Cyperus rotundus innehöll flera olika terpener och det antogs att Cyperus papyrus också innehåller några av dess föreningar. Det drogs också slutsatsen attbåde UAE och SPE ska användas för att ge bästa resultat med avseende på mängden analytersom extraherats. Fortsättningsvis så drogs slutsatsen att då UAE ska användas så är acetonitril att föredra över metanol som lösningsmedel. Den här studien är en översikt av den tidigare nämnda metodiken.

The analysis of real-world data and the development of mathematical models played a fundamental role in understanding the epidemiology of COVID-19 and informing public policies throughout the recent pandemic. This thesis presents a collection of modeling approaches and results addressing key questions that arose during the COVID-19 crisis, with a specific focus on the emergence and epidemiological features of SARS-CoV-2 variants of concern (VOC) in Italy and related public health implications. In the first chapter, conducted analyses suggest that the Alpha variant was approximately 50% more transmissible than historical lineages of SARS-CoV-2, and that this transmissibility advantage was enough to outcompete a variant associated with immune escape phenomena and circulating in central Italy in February 2021 (i.e., the Gamma variant). In the second chapter, by investigating the potential impact of new hypothetical VOCs in Italy in late 2021, modeling results highlighted that the emergence of variants associated with significant immune escape (i.e., with a rate at which vaccinated or recovered individuals from infection with pre-circulating lineages become infected being at least one-fifth that of unvaccinated individuals who never experienced SARS-CoV-2 infection) would have been able to replace pre-circulating lineages in a couple of weeks. Strict restrictions would have been required to prevent a new large epidemic wave. In the third chapter, the analysis of genomic and epidemiological data associated with the expansion of the Omicron variant over the Italian territory revealed that this variant was able to become dominant at the national level in less than a month, increasing the net reproduction number from 1.15 to 1.83. Despite the marked growth advantage of Omicron compared to the previously circulating Delta variant, a moderate impact on the number of severe cases was observed, likely due to the high proportion of vaccinated individuals in the country by the end of 2021. In the fourth chapter, the estimation of the intrinsic generation time of the Omicron variant (mean: 6.84 days) was found to be similar to that of previous lineages. Such estimates have been key to define adequate isolation, quarantine, surveillance, and contact tracing protocols in 2022. The prevention of SARS-CoV-2 transmission in educational settings represented a key challenge during the pandemic, due to the large proportion of asymptomatic carriers in young individuals. The last chapter presented in this thesis shows that, when the Alpha variant was circulating in Italy, almost half of positive students and school personnel ascertained during in-person education were likely infected by school contacts. The mean number of secondary cases caused at schools was found to be 0.33, with high heterogeneity in the chance of onward transmission. Provided estimates suggest that the timely identification of cases combined with reactive quarantine policies had the potential of reducing SARS-CoV-2 transmission in schools by at least 30%.

Indoor air quality is recognized as one of the most important environmental concerns, since people spend almost 90% of their lifetime indoors. Indoor sources of volatile organic compounds (VOCs) are a determinant of air quality in houses. Many materials used to construct and finish the interiors of new houses emit VOCs. These emissions are a probable cause of acute health effects and discomfort among occupants. Ventilation is another determinant of indoor air quality in houses, because it serves as the primary mechanism for removal of gaseous contaminants generated indoors. Thus, higher contaminant concentrations are expected at lower ventilation rates given constant emission rates. The trend in new construction is to make house envelopes tighter for higher energy efficiency. The use of Structural Insulated Panels (SIPs) in new construction and major renovation to create very tight building envelopes is one popular approach to realizing this goal. The basic SIPs configuration uses oriented strand board (OSB) and polystyrene foam (PSF) in a multi-layered sandwich-like structure. Specific benefits of SIPs include lower energy consumption, stronger more durable structures and better resource efficiency. These advantages make panelized systems very attractive from both environmental impact and energy use perspectives. However, there is a potential for houses constructed with SIPs to have degraded air quality relative to conventionally constructed houses that utilize fewer engineered wood products. OSB emits pentanal and hexanal, two odorous aldehydes. These contaminants originate in the wood drying process through the breakdown of wood tissue and are, thus, inherent to most engineered wood products. The PSF in SIPs is a major source of styrene. The large surface area of installed SIPs systems (typically the entire exterior shell), combined with the resulting decrease in ventilation rate due to very low infiltration, exacerbates the indoor air problem. Thus, the potential release of volatile contaminants must be taken into careful consideration when designing homes constructed with SIPs. The ability to predict and ultimately minimize the negative impact of panel systems on indoor concentrations of contaminants of concern would be extremely useful for advancing housing technologies. No prior investigations of VOC emissions from SIPs have been reported in the literature. Two main methods are used to characterize emissions from building materials: chamber studies and mathematical modeling. While chamber studies are costly and time-consuming, mathematical modeling is becoming an economical and effective alternative. Physically-based models are especially useful because they provide insight into the governing mechanisms and the factors that control the emissions process. Although emissions from building materials have traditionally been empirically characterized in chambers, we have recently validated a mechanistic model that predicts VOC emissions from vinyl flooring. The approach involved independently measuring C0 (the initial material-phase concentration), D (the material-phase diffusion coefficient), K (the material/air partition coefficient) and then predicting the emission rate a priori using a fundamental mass-transfer model We now wish to generalize this approach and use it to predict emissions from multi-layered SIPs. To begin with, we will apply a single-layer model to predict emissions from each of the two SIP components: OSB and PSF. Once this has been accomplished, it should be possible to develop a multi-layer model to predict emissions from the composite SIPs. Our first research objective was to characterize transport of volatile organic compounds (VOCs) in polystyrene foam (PSF), a diffusion-controlled building material. The sorption/desorption behavior of the polystyrene foam was investigated using a single-component system. A microbalance was used to measure the sorption/desorption kinetics and to obtain equilibrium relationships. Hexanal and styrene were selected as the target compounds. While styrene transport in PSF can be described by Fickian diffusion with a symmetrical and reversible sorption/desorption process, the hexanal transport process exhibited significant hysteresis, with desorption being much slower than sorption. To address this hysteresis, a porous media diffusion model that assumes local equilibrium governed by a non-linear Freundlich isotherm was developed. The model was found to conform closely to the experimental kinetic data for both sorption and desorption. By incorporating the Freundlich sorption mechanism into the traditional Fickian diffusion model, the hysteresis in the hexanal transport process in PSF was explained. Contaminant emissions from building materials may tail extensively and require longer times to desorb than absorb. This slow desorption or hysteresis problem has been an obstacle to understanding VOC emissions from building materials. The overall goal of our second research objective was to (i) develop a predictive nonlinear emission model by incorporating a local Freundlich sorption equilibrium to account for the slow desorption; (ii) validate the new nonlinear emission model using independent chamber data; and (iii) compare the new nonlinear emission model with a previously published linear emission model. Styrene in polystyrene foam (PSF) and hexanal in oriented strand board (OSB) were selected as the target compounds and materials, respectively. Sorption/desorption kinetic experimental data show that while styrene sorption/desorption in PSF is symmetrical, hexanal sorption/desorption in OSB is not symmetrical. For hexanal in OSB, slower desorption was observed. Model validation results show that while the simple linear emission model can predict styrene emissions from PSF, it underestimates hexanal emissions from OSB. With the new nonlinear emission model developed in this research, hexanal emission from OSB can be predicted. These results suggest that local sorption equilibrium needs to be considered when predicting the emission rate of polar compounds from building materials. The final objective was to develop a new multi-layer model for a layered SIP system. Composite layered building materials are widely used in indoor environments due to their environmental and energy advantages. However, the tight structure may result in degraded indoor air quality and the potential release of volatile organic compounds (VOCs) from these layered materials must be considered. A theoretical physically-based diffusion model for predicting VOCs emissions from such multi-layer materials is described in this research. It is assumed that the individual layers are flat homogeneous slabs, that internal mass transfer is governed by diffusion, and that the indoor air is well mixed. For each layer, the material-phase diffusion coefficient (D), the material-phase partition coefficient (K), and the initial material-phase concentration (C0) are the key model parameters. In this model, fugacity is used to numerically solve the model because this eliminates the discontinuities in concentration at the interface between layers. This overcomes an insurmountable obstacle associated with numerically simulating mass transfer in composite layers. The fugacity-based numerical model is checked by comparing predicted concentrations to those obtained with a previously published analytical model for double-layered materials. In addition, transport of hexanal and styrene within, and emissions of hexanal and styrene from, multi-layer Structural Insulated Panels (SIPs) are simulated to demonstrate the usefulness of the model. These preliminary results establish the viability of the fugacity approach. Finally, the multi-layer layer model is used to demonstrate the impact that barrier materials can have. Results show that contaminant gas phase concentration can be reduced greatly with a barrier layer on the surface. This deomonstrates the potential of thin barrier layers to minimize the environmental impact of panelized systems. Future work will focus on a more complete experimental validation of the multi-layer model. / Ph. D.

The adverse effects of contaminated outdoor air have been recognized and subject to control for many years. More recently environmental engineers and health professionals have become cognizant of the hazards associated with contaminated indoor air. It is now understood that contaminated indoor air negatively impacts human health, worker productivity, and physical property. Volatile organic compounds (VOCs) are a common class of indoor air pollutants. Building materials such as treated wood, pressed-wood products, wallboard, sealants, adhesives, floor coverings, and paints can be sources of VOC emissions. The knowledge-base necessary to develop effective solutions to indoor air quality problems requires an understanding of the emissions behavior of indoor materials. Environmental chambers are often utilized to characterize indoor material as sources of VOC emissions to indoor air. Chamber studies, although expensive and time consuming, can be utilized to provide estimates of the rates at which a particular material emits VOCs under a specific set of environmental conditions. By fitting curves to emissions data obtained through chamber studies, VOC emissions models have been constructed. These models are frequently empirical and as a consequence, 1) apply only to the specific material and environmental conditions investigated, 2) provide little understanding of the source/sink characteristics of the material, and 3) provide little knowledge of the mass transfer processes governing emissions behavior. As a result, our understanding of the mechanisms that control VOC emissions from indoor materials remains rudimentary. Physically-based models that describe the emissions characteristics of building materials would greatly facilitate the process of improving indoor air quality. Evidence exists suggesting well-established fundamental mass transfer mechanisms govern emissions from indoor materials. Of the various mechanisms governing emissions behaviors, diffusion appears to be one of the most significant. The primary objective of this research was to demonstrate that the VOC emissions source behavior of a diffusion-controlled homogenous building material could be predicted using a mechanistic mathematical model. A commercial grade sheet vinyl flooring (VF) was selected for study because VF is present in many residential and commercial buildings, is relatively homogenous, and has been shown to emit hazardous organic chemicals. If successful, this research would demonstrate that the proposed strategy could be generalized to other VOC sources using appropriately constructed mathematical models. Satisfying the research objective required development of a physically-based model to predict gas-phase VOC concentrations resulting from exposure to a diffusion-controlled material. Key parameters for this model are the solid-phase diffusion coefficient, D; the solid/air partition coefficient, K; and the initial solid-phase VOC concentration, C0. D and K have been previously quantified for only a few indoor materials and methods for determining C0 are rudimentary. Therefore, this research project required development and execution of methods for quantifying D, K, and C0. D and K were quantified using a recording microbalance. C0 was evaluated using a new technique of cryogenic milling followed by fluidized bed desorption. The model was validated by exposing a VF sample in an environmental chamber and directly measuring gas-phase VOC concentrations resulting from mass transfer from the solid material. Further model validation was achieved by directly measuring the VOC concentration profiles after exposure in environmental chambers. Because the key model parameters were quantified independently of chamber studies, the model validation process provided a rigorous test of the validity of the mass transfer model in particular and of the source characterization strategy in general. The results of this research contribute to our understanding of the fundamental mechanisms that govern emissions of VOCs from vinyl flooring and provide a sound theoretical foundation for characterization of a wide range of other sources of indoor VOCs. This understanding could facilitate product reformulation strategies aimed at preventing or reducing indoor air contamination. Mass transfer models could also be utilized to develop standards for the environmental performance of indoor materials. The proposed approach will prove useful in conjunction with broader studies on sick building syndrome to identify sources that may have a critical impact on the health and comfort of building occupants. / Ph. D.

A queima de biomassa é uma atividade amplamente difundida em muitos países tropicais em desenvolvimento. Esta atividade tem implicações em escala regional e global devido à emissão de quantidades significativas de gases traço para a atmosfera, tais como: CO, hidrocarbonetos não metanicos (HCNM) e material particulado (MP). Os resíduos da cana-de-açúcar representam 11% da produção mundial de resíduos agrícolas, cuja queima libera quantidades expressivas de gases e partículas que influenciam a química da atmosfera. No Brasil, nos últimos anos houve um aumento do uso de etanol como combustível e um aumento nas plantações de cana-de-açúcar no Estado de São Paulo. Apesar da proibição das queimadas, episódios de queima são ainda muito freqüentes, uma vez que 50 % dos canaviais paulistas são queimados na etapa de pré-colheita. O presente estudo teve como objetivo avaliar as emissões de VOCs provenientes da queima da palha de cana-de-açúcar. Para estimar o impacto ambiental causado por esse processo de combustão em regiões urbanas próximas as queimadas foram feitos estudos em laboratório e campo. A contribuição biogênica dos compostos carbonílicos na região do canavial foi avaliada e os resultados mostraram que as folhas de cana-de-açucar, na maioria dos experimentos, não atuaram como fonte de emissão. Os experimentos de laboratório permitiram determinar os produtos de combustão incompleta na pluma. Medidas de emissão de CO, CO2, e VOC foram caracterizadas pela razão de emissão (ER) e fator de emissão (EF). Razões de mistura, em ppbv, de formaldeído (175 - 309), acetaldeído (2 - 71), acetona (1 - 36), acroleína (0,3 - 3), propionaldeído (0,2 - 10), crotonaldeído (3 -10), butiraldeído (1 - 3), benzaldeído (0,5 - 6), valeraldeído - total (2 - 60) e hexaldeído (4 - 136) foram identificados e quantificados; e outros VOCs, tais como, aromáticos, haletos de alquila, compostos contendo nitrogênio, furanos foram apenas identificados. No laboratório também foi avaliado a eficiência da combustão da palha de cana-deaçúcar (ΔCO/CO2 = 4,0±0,4%) e foi observado que a fase flaming foi predominante neste processo. A contribuição dos compostos carbonílicos na atmosfera de regiões urbanas próximas às queimadas foi avaliada através da comparação entre as medidas feitas antes e durante a queima. Os resultados estatísticos mostraram que as medidas nos dois períodos são diferentes sugerindo que a origem dos compostos é diferente. Fontes de emissão direta e principalmente reações fotoquímicas foram responsáveis pela presença de formaldeído e acetaldeído nas amostras coletadas antes da queima (medidas diurnas), enquanto que apenas fontes de emissão direta foram responsáveis pela presença desses compostos nas amostras coletadas durante a queima (medidas noturnas). Trajetórias de massas de ar que chegaram à área urbana e os focos de queima registrados nos dias de coleta mostraram que a região urbana estudada foi afetada pelas queimadas. / Biomass burning is an activity widely practiced in many tropical developing countries. This activity has implications at regional and global scales due to the emissions of significant quantities of trace gases to the atmosphere such as CO, non-methane hydrocarbons (NMHC) and particulate matter (PM). The sugar cane residues represent 11% of worldwide production of agricultural residues whose burning releases significant amounts of gases and particles that influence the atmospheric chemistry. In the last years, in Brazil, there has been an increase of the use of the ethanol as fuel and an increase of the sugar cane plantations in the State of São Paulo. Although the sugar cane burning prohibition, burning episodes are still very frequent, as 50% of the sugar cane plantations of São Paulo are burned in the the pre-harvest stage. The aim of this study was to evaluate VOC emissions of sugar cane burning. In order to estimate the environmental impact caused by the combustion process in urban regions near fires laboratory and field studies were conducted. The contribution of biogenic carbonyl compounds in the area of sugar cane was evaluated and results showed that the cane sugar leaves, in the most of the experiments, do not act as emission source. Laboratory experiments were carried out to determine incomplete combustion products in plume. Measurements of CO, CO2, and VOC were characterized by the emission ratio (ER) and emission factor (EF). Mixture ratio, in ppbv, of formaldehyde (175 - 309), acetaldehyde (2 - 71), acetone (1 - 36), acrolein (0,3 - 3), propionaldehyde (0,2 - 10), crotonaldehyde (3 -10), butyraldehyde (1 - 3), benzaldehyde (0,5 - 6), valeraldehyde-total (2 - 60) and hexaldehyde (4 - 136) were identified and quantified; and other VOCs, such as aromatic hydrocarbons, alkyl halides, nitrogen containing compounds and furans were only identified. The efficiency of the sugar cane combustion was evaluated (ΔCO/CO2 = 4.0±0.4%) in the laboratory and the predominant burning phase was the flaming phase. By comparing statistically filed measurements done before and during fire in the atmosphere of urban areas near fires, it was possible to distinguish two different groups of the measurements suggesting that the origin of the compounds is different. Direct emission sources and mainly photochemical reactions were responsible by the presence of formaldehyde and acetaldehyde in samples collected before fire (daytime measurements), whereas only direct emission sources were responsible by the presence of these compounds in samples collected during the fire (night measurements). Trajectories of air masses that reached the urban area and spots of burning recorded in the sampling days showed that the region studied was affected by fires.

In nature, organic matter is degraded by microorganisms. During the degradation gases formedincludes methane, carbon dioxide, hydrogen sulfide, and small amounts of other gases such asVOCs. This has been utilized with help of anaerobic digesters, where environments have beencreated, in which these organisms thrive. In these chambers the gases are collected together intosomething called biogas.Biogas is a renewable energy source where the methane gas natural affinity for combustion inoxygen-containing environments is being used. By separating the methane from the other gases, theenergy value becomes closer to that of natural gas. The upgraded biogas can thus act as a substitutefor natural gas and be used as a fuel for vehicles, a need that has increased during the last years.This is preferred since natural gas is a fossil fuel.A technique used for upgrading biogas is water scrubbers. By using the gases different tendency todissolve into the water, carbon dioxide and hydrogen sulfide can be removed. During this process asmall amount methane and VOC becomes absorbed as well. The upgraded biogas obtains a methanecontent of approximately 98 % and can then be used as a fuel for vehicles. The removed gases are atthe same time released from the water to the effluent air leaving the upgrading plant. This has beendeemed inappropriate since the hydrogen sulfide is a corrosive and highly toxic gas. The methaneand VOCs that leaves with the effluent air provides negative effects to the greenhouse effect andglobal environment.This study has examined the issue of how to treat the gases that are emitted by the effluent air.Using measurements to find the percentage amounts of the different gases in the effluent air and inthe raw biogas, annual quantities of emissions could be calculated. From these, various treatmentmethods have been analyzed where the author finally concluded that a reduction of hydrogensulfide should be achieved with help of iron in a filter. Methane has instead been proposed to betreated with a compost filter. / I naturen bryts organiska ämnen ned med hjälp av mikroorganismer. Under nedbrytningen bildasbland annat metan, koldioxid, svavelväte samt flera andra gaser så som VOC. Detta har utnyttjats dåman med hjälp av anaeroba rötkammare skapat miljöer där dessa mikroorganismer trivs. I dessakammare samlas gaserna ihop till någonting som kallas för biogas.Biogas är en förnyelsebar energikälla där man utnyttjar metangasens naturliga förutsättningar till attförbrännas i syrehaltiga miljöer. Genom att separera metangasen från de övriga gaserna, kanenergivärden nära naturgas fås. Den uppgraderade gasen kan på så vis agera som ett substitut tillnaturgas och därmed användas som drivmedel till fordon, ett behov som ökat under de senaste åren.Detta är att föredra då naturgas är ett fossilt bränsle.En teknik som används för separeringen av gaserna är vattenskrubbrar. Genom att utnyttja gasernasolika benägenhet att lösa sig i vatten så kan koldioxiden och svavelvätet tas bort. Under dennaprocess absorberas även mindre mängder metan och VOC. Den uppgraderade biogasen får genomprocessen cirka 98 % metanhalt och kan därefter användas för att driva fordon. De borttagnagaserna frigörs samtidigt från vattnet och släpps istället ut från uppgraderingsanläggningen medhjälp av en luftström. Detta har bedömts vara olämpligt då svavelvätet är korrosivt och en mycketgiftig gas. Metanen och VOCn som följer med den utgående luften har negativa egenskaper förväxthuseffekten och den globala miljön.Denna studie har undersökt hur de gaser som normalt släpps ut med det utgående luftflödet skallbehandla. Med hjälp av mätningar av de procentuella gasmängderna i den utgående luften samt iden råa biogasen har kvantiteter på årliga emissionerna kunnat uppskattas. Utifrån dessa har olikareningsmetoder analyserats där slutsatsen är att reducera svavelvätet med hjälp av Järn i ett filter.Metangasen har istället föreslagits bli renad i ett kompost filter.

Flüchtige organische Verbindungen (Volatile organic compounds (VOC)) sind ubiquitär vorkommende kohlenstoffhaltige Substanzen. Untersuchungen haben relevante VOC-Konzentrationen im Inneren von Gebäuden nachgewiesen. Da der Innenraum zum typischen Aufenthaltsort des modernen Menschen geworden ist, sind diese Schadstoffe in das Interesse der Forschung gerückt. Kinder reagieren unter Schadstoffexposition besonders sensibel, denn viele wichtige Organsysteme befinden sich noch in ihrer Entwicklung. In der vorliegenden Arbeit wurden Leipziger Daten der LISA-Studie („Einfluss von Lebensbedingungen und Verhaltensweisen auf die Entwicklung von Immunsystem und Allergien im Ost-West-Vergleich“) hinsichtlich möglicher Effekte einer VOC-Exposition auf Erkrankungen der Kinder im 4. Lebensjahr analysiert. Bei der LISA-Studie handelt es sich um eine multizentrische prospektive Geburts-Kohortenstudie, in die von November 1997 bis Januar 1999 insgesamt 3097 gesunde und reife Neugeborene deutscher Herkunft mit einem Geburtsgewicht > 2500 g rekrutiert wurden. Die Berechnungen der vorliegenden Arbeit erfolgten mit VOC-Messwerten um den 3. Geburtstag der Kinder. Die jeweiligen logistischen Regressionsmodelle wurden auf das Geschlecht, die atopische Familienanamnese, eine passive Tabakrauchexposition, das Aufstellen neuer Möbel im Kinderzimmer, Renovierungen und die Erneuerung des Fußbodenbelags in der Wohnung adjustiert. Es ließen sich VOC bestimmen, die bei Konzentrationserhöhungen eine erhöhte Chance für eine akute Bronchitis zur Folge hatten. Als Risikofaktor einer akuten Bronchitis ließ sich außerdem die Erneuerung des Fußbodenbelags in der Wohnung ermitteln. Während sich für eine akute Bronchitis in Abhängigkeit der VOC-Konzentration erstmals eine Dosis-Wirkungs-Kurve ableiten ließ, war dies für allergische Erkrankungen nicht möglich. Weitere Untersuchungen sind notwendig um Pathomechanismen der VOC-Einwirkungen auf den kindlichen Organismus aufzuklären.

A queima de biomassa é uma atividade amplamente difundida em muitos países tropicais em desenvolvimento. Esta atividade tem implicações em escala regional e global devido à emissão de quantidades significativas de gases traço para a atmosfera, tais como: CO, hidrocarbonetos não metanicos (HCNM) e material particulado (MP). Os resíduos da cana-de-açúcar representam 11% da produção mundial de resíduos agrícolas, cuja queima libera quantidades expressivas de gases e partículas que influenciam a química da atmosfera. No Brasil, nos últimos anos houve um aumento do uso de etanol como combustível e um aumento nas plantações de cana-de-açúcar no Estado de São Paulo. Apesar da proibição das queimadas, episódios de queima são ainda muito freqüentes, uma vez que 50 % dos canaviais paulistas são queimados na etapa de pré-colheita. O presente estudo teve como objetivo avaliar as emissões de VOCs provenientes da queima da palha de cana-de-açúcar. Para estimar o impacto ambiental causado por esse processo de combustão em regiões urbanas próximas as queimadas foram feitos estudos em laboratório e campo. A contribuição biogênica dos compostos carbonílicos na região do canavial foi avaliada e os resultados mostraram que as folhas de cana-de-açucar, na maioria dos experimentos, não atuaram como fonte de emissão. Os experimentos de laboratório permitiram determinar os produtos de combustão incompleta na pluma. Medidas de emissão de CO, CO2, e VOC foram caracterizadas pela razão de emissão (ER) e fator de emissão (EF). Razões de mistura, em ppbv, de formaldeído (175 - 309), acetaldeído (2 - 71), acetona (1 - 36), acroleína (0,3 - 3), propionaldeído (0,2 - 10), crotonaldeído (3 -10), butiraldeído (1 - 3), benzaldeído (0,5 - 6), valeraldeído - total (2 - 60) e hexaldeído (4 - 136) foram identificados e quantificados; e outros VOCs, tais como, aromáticos, haletos de alquila, compostos contendo nitrogênio, furanos foram apenas identificados. No laboratório também foi avaliado a eficiência da combustão da palha de cana-deaçúcar (ΔCO/CO2 = 4,0±0,4%) e foi observado que a fase flaming foi predominante neste processo. A contribuição dos compostos carbonílicos na atmosfera de regiões urbanas próximas às queimadas foi avaliada através da comparação entre as medidas feitas antes e durante a queima. Os resultados estatísticos mostraram que as medidas nos dois períodos são diferentes sugerindo que a origem dos compostos é diferente. Fontes de emissão direta e principalmente reações fotoquímicas foram responsáveis pela presença de formaldeído e acetaldeído nas amostras coletadas antes da queima (medidas diurnas), enquanto que apenas fontes de emissão direta foram responsáveis pela presença desses compostos nas amostras coletadas durante a queima (medidas noturnas). Trajetórias de massas de ar que chegaram à área urbana e os focos de queima registrados nos dias de coleta mostraram que a região urbana estudada foi afetada pelas queimadas. / Biomass burning is an activity widely practiced in many tropical developing countries. This activity has implications at regional and global scales due to the emissions of significant quantities of trace gases to the atmosphere such as CO, non-methane hydrocarbons (NMHC) and particulate matter (PM). The sugar cane residues represent 11% of worldwide production of agricultural residues whose burning releases significant amounts of gases and particles that influence the atmospheric chemistry. In the last years, in Brazil, there has been an increase of the use of the ethanol as fuel and an increase of the sugar cane plantations in the State of São Paulo. Although the sugar cane burning prohibition, burning episodes are still very frequent, as 50% of the sugar cane plantations of São Paulo are burned in the the pre-harvest stage. The aim of this study was to evaluate VOC emissions of sugar cane burning. In order to estimate the environmental impact caused by the combustion process in urban regions near fires laboratory and field studies were conducted. The contribution of biogenic carbonyl compounds in the area of sugar cane was evaluated and results showed that the cane sugar leaves, in the most of the experiments, do not act as emission source. Laboratory experiments were carried out to determine incomplete combustion products in plume. Measurements of CO, CO2, and VOC were characterized by the emission ratio (ER) and emission factor (EF). Mixture ratio, in ppbv, of formaldehyde (175 - 309), acetaldehyde (2 - 71), acetone (1 - 36), acrolein (0,3 - 3), propionaldehyde (0,2 - 10), crotonaldehyde (3 -10), butyraldehyde (1 - 3), benzaldehyde (0,5 - 6), valeraldehyde-total (2 - 60) and hexaldehyde (4 - 136) were identified and quantified; and other VOCs, such as aromatic hydrocarbons, alkyl halides, nitrogen containing compounds and furans were only identified. The efficiency of the sugar cane combustion was evaluated (ΔCO/CO2 = 4.0±0.4%) in the laboratory and the predominant burning phase was the flaming phase. By comparing statistically filed measurements done before and during fire in the atmosphere of urban areas near fires, it was possible to distinguish two different groups of the measurements suggesting that the origin of the compounds is different. Direct emission sources and mainly photochemical reactions were responsible by the presence of formaldehyde and acetaldehyde in samples collected before fire (daytime measurements), whereas only direct emission sources were responsible by the presence of these compounds in samples collected during the fire (night measurements). Trajectories of air masses that reached the urban area and spots of burning recorded in the sampling days showed that the region studied was affected by fires.