The aim of this thesis is to give suggestions on what measures to take to improve the VOC emission situation in refineries in Tianjin, China, through existing technologies in refineries in Sweden. This has been done by identifying the main places of leakage in oil refineries in Sweden, identifying what VOC compounds are emitted from the plants and the amounts emitted, mapping out different measures taken by oil refineries in Sweden to minimize VOC emissions, evaluating the different measures and suggesting how to move forward with VOC control in Tianjin. Six case studies have been done in Sweden; at Preemraff Lysekil, Shell refinery in Gothenburg, Berg depot Statoil Sweden situated in Nacka, Nynas refinery situated in Nynäshamn, Scandinavian Tank Storage situated in Torshamnen and Oxelösund harbor. Two case studies at Chinese refineries were made, PetroChina Dagang Petrohemical Company and China Petroleum and Chemical Corporation, Sinopec, Tianjin Branch, both situated in Tianjin Binhai New Area. Since the data retrieved from the Chinese refineries is insufficient to make a qualitative evaluation of the state of their VOC treatment it is not possible to propose measures for these two refineries. Instead this evaluation is focused on general problems and solutions at refineries and gives an idea of what can be done to improve the VOC emission situation at refineries. The report contains an evaluation of internal measures and technical solutions at Swedish refineries and other petrochemical companies. The evaluation is focused as much as possible on the Chinese situation. The technologies have been evaluated from an environmental, technical and economical point of view. This has resulted in recommendations for refineries that wish to enhance their VOC control. / Detta examensarbete har gjorts som en avslutande del i utbildningen Civilingenjör i Kemiteknik vid Kungliga Tekniska högskolan, Stockholm. Idén för arbetet introducerades av Östen Ekengren, IVL Svenska Miljöinstitutet, och har utförts vid IVL:s kontor i Stockholm. Den har handletts från Institutionen för Industriell Ekologi, KTH. Oljeraffinaderier släpper ut stora mängder VOC. På grund av den stora produktionsskalan och fabriksområdets omfattning är det svårt att veta hur mycket och vad som släpps ut. Lättflyktiga organiska ämnen (Volatile organic compounds, VOC) är organiska föreningar som har ett tillräckligt högt ångtrycker för att förångas under normala förhållanden. Stora mängder VOC läcker från oljeraffinaderier varje år. Tianjin är en industristad med stora investeringar. På grund av den stora industriella aktiviteten i området är VOC-problemen stora. En av de stora utsläppsbovarna är den petrokemiska industrin. Tianjin Academy of Environmental Science (TAES) har frågat efter Svensk teknik att minimera VOC-utsläpp från petrokemisk industri. Målet med detta examensarbete är att ge förslag på vilka åtgärder som kan tas för att förbättra VOC-utsläppssituationen i raffinaderier i Kina genom befintlig teknik på Svenska raffinaderier. Detta har gjorts genom följande steg: Identifiera de största utsläppsområdena på oljeraffinaderier i Sverige Identifiera vilka VOC-föreningar som emitteras från raffinaderierna samt i vilken mängd. Kartlägga olika åtgärder vid oljeraffinaderier i Sverige och i Tianjin, Kina för VOC-utsläpp. Utvärdera de olika åtgärderna och föreslå hur man kan gå vidare med VOC-kontroll i Kina. Sex fallstudier har genomförts i Sverige; Preemraff Lysekil, Shell raffinaderi i Göteborg, Bergs depot Statoil Sweden i Nacka, Nynas refinery i Nynäshamn, Scandinavian Tank Storage i Torshmnen och Oxelösunds hamn, Oxelösund. Två fallstudier har genomförts vid Kinesiska raffinaderier; PetroChina Dagang Petrochemical Comapany och China Petroleum and Chemical Corporation, Sinopec, Tianjin Branch, båda placerade i Tianjin Binhai New Area. Eftersom otillräcklig data från de Kinesiska raffinaderierna har gjort det svårt att göra en kvalitativ utvärdering av hur långt de kommit i VOC-arbetet har det inte varit möjligt att föreslå åtgärder för dessa två raffinaderier specifikt. Istället har utvärderingen fokuserats på generella problem och lösningar vid raffinaderier och att ge en ide om vad som kan göras för att förbättra VOC-utsläppssituationen vid raffinaderier. VOC från oljeraffinaderier med traditionell aktivitet består i huvudsak av alkaner, alkener och aromater där alkaner utgör den största delen. Alla dessa tre grupper förekommer naturligt i råolja. Vilka föreningar som förekommer i VOC-plymen från en fabriksanläggning beror på vilken råolja som används, hur processen ser ut och vilka produkter som produceras. Sammansättningen av VOC-plymen varierar därför från raffinaderi till raffinaderi. De största emissionskällorna vid raffinaderier som producerar i första hand bensin och diesel är tankparkerna, speciellt under fyllning. Tankparker som innehåller råolja utgör den största emissionspunkten vid dessa raffinaderier. Den näst största källan är processområdet. Detta medför att tankparker och processområde är de områden där störst fokus på minimering skall ligga för raffinaderier med samma typ av verksamhet. Produktionen vid Nynas Refinery kräver en annan råolja Här är det processen som utgör den största utsläppskällan tillsammans med vattenrening. Uppvärmda bitumencisterner utan rening utgör också en stor utsläppspunkt. Eftersom processområdet och tankparkerna har många potentiella läckpunkter är det primära sättet att minimera VOC-utsläpp tätning och underhåll på hela fabriksområdet. Införandet av rutiner för detta har visat sig mycket effektivt speciellt vid Shell raffinaderi. En annan idé skulle kunna vara att inkludera VOC-utsläppsmätning i on-line system för produktkvalitet. Detta skulle medföra ett inbyggt VOC-kontrollsysem. Detta har inte gjorts än men det kan vara värt att ta en närmare titt på. Kina har stort fokus på luktkontroll. Detta är bara en liten del av VOC-problemet. Metan utgör en stor del av utsläppen från råoljecisterner, vilka är vanliga luktbovar. För att eliminera lukt är adsorbtion med aktivt kol effektivt. Filtret fångar däremot inte kortare kolkedjor som metan och etan. För att eliminera dessa är förbränning den enda lösningen. Ingen luktsanerningsmetod som presenteras i denna rapport genererar någon vinst för företagen. Gasåterföringsanläggningar (VRU) har visats vara en gynnsam metod för att behandla emissioner vid tankning. En snabb överslagsräkning baserat på den återförda mängden bensin och diesel vid Preemraff Lysekil 2008 ger en vinst på 0,9 – 1,3 miljoner Euro/år. En stor andel VOC förbränns i fackla på raffinaderier. Denna gas skulle kunna användas som bränngas eller för energiåtervinning. Penningvärdet på energin i gasen som facklas är stor. Genom att installera en kompressor kan gas som skulle facklas användas som bränngas i raffinaderierna istället. Båda de studerade raffinaderierna i Kina angav fackling som den primära VOC-åtgärden. Man kan därmed anta att stora mängder gas facklas där. Detta visar att det finns mycket att tjäna på att hitta alternativa sätt att använda gasen. Flyktiga utsläpp är en stor del av VOC-källorna vid oljeraffinaderier. Utsläppunkterna beror på typ av råolja, process och produkter. Varje raffinaderi ar unikt och måste därför mäta sin a utsläpp. Vid mätning av ett helt fabriksområde med Solar Occulation Flux-metoden, som är en on-lineteknik som mäter VOC-utsläpp i from av alkaner, fås en bild av totala utsläppen från hela fabriken. Detta är till stor hjälp vid identifiering av problemområden och behandling av dessa. När VOC-behandling skall påbörjas vid ett raffinaderi rekommenderas följande: Mätning av VOC över hela raffinaderiområdetAnvända on-lineteknik, så som SOF Identifiera sammansättning av plymen genom kanisterprov etc. Läcksökning / Underhåll Om följande tekniska lösningar går att applicera vid raffinaderiet föreslås det att de prioriteras. Införa VRU-anläggning Energiåtervinning (minimerad fackling) Införa kommunicerande kärl För fortsatt arbete rekommenderas följande. Undersöka om det finns intresse och möjlighet att införa on-line VOC-konrollsystem eller on-line konstrollsystem för produktkvalitet. Är det tekniskt möjligt och ekonomiskt hållbart? För att kunna utvärdera miljöpåverkan av NMVOC från oljeraffinaderier har en studie av effekterna från emissionerna från Preemraff Lysekil och Shell Göteborg gjorts genom att använda karakteriseringsdata från databaserna CLM2001 och EDIP97. Detta resulterade i ett värde som ger hur många gånger fler de två raffinaderierna per ton satsad råolja bidrar till ozonformationspotentialen och globala uppvärmningspotentialen i förhållande till årspersonsekvivalenten (vad en normalperson bidrar med per år). Det visade sig att de bidrar med mycket mindre än årspersonsekvialenten per ton råolja, 0,03 gåner för Preemraff och 0,02 gånger för Shell. Men med antalet ton råolja som processas per år i åtanke så blir oljeraffinaderierna en stor källa till miljöpåverkan. Toxicitetsvärdena visade att Shell hade mycket större andel toxiska utsläpp än Preemraff. I förbränning, som fackling, så förbränns VOC till CO2. Detta medför att VOC har en sekundär GWP. Om hänsyn tas till detta kan man se att den totala GWP av VOC främst utgörs av den sekundära effekten genom fackling. Denna utvärdering visar att miljöpåverkan är olika för olika raffinaderier, även de med samma typ av verksamhet.

This diploma thesis deals with analysis of horizontal governance structures in the model of VOC wines in the Czech Republic. Theoretical part deals with characteristics of hybrid forms of integration, cluster and their use in viticulture. Subsequently, development of viticulture in the Czech Republic is analysed as well as its impact on the alternative food networks. Further the thesis presents appellation system abroad and in the Czech Republic. All of the VOC networks are described and one of them is characterized and analysed in detail. According to this analysis the current status of this certification model.

The ultimate goal of this research is to provide a low cost, efficient, reproducible, quantitative, non-invasive screening method to diagnose diseases at an early stage through identification of volatile biomarkers of disease. Progress has been made in the areas towards development of an analytical system that can provide a rapid and specific assay for above mentioned Volatile Organic Compounds (VOCs). (i) Methods have been designed for the collection, concentration, identification and quantification of volatile biomarkers. (ii) Advanced signal processing evaluation of data has tentatively identified key VOCs patterns with breath and body odor. (iii) Novel absorbent coatings have been studied for use with miniature chemical sensors that one day may be part of a portable analytical system. Both breath and body odor contain a complex mixture of chemicals, which are influenced by many internal and external factors. Breath and skin odor samples were collected with minimum external contaminations using traditional SPME and active SPME GCMS techniques. Body odor from 65 human subjects was tested with and without selected scent removal products. Breath samples were collected from 21 canine subjects. The VOCs profiles of these samples were determined and then statistically treated with principal component analysis, discriminant analysis, and tree regression techniques to simplify and interpret the complex mixtures. While much of our work has utilized large bench-top equipment, our over-arching goal is to provide a portable device that can diagnose diseases at an early stage. Concurrent work was done to enhance the performance of a miniaturized detector for the detection of potential biomarkers. Two organic polymers mixed with conductive carbon nanoparticles were deposited between the microcapacitor plates of microsensors using ink-jet technology. Microsensors were also fabricated using conducting ionic liquids. The performances of the individual chemicapacitive sensors were characterized through exposure to different concentrations of varied volatile organic compounds with different functional groups in a climate-controlled vapor delivery system.

The objective of this study was to determine if the method of incorporation of a silicate layered nanoclay into a polymer matrix can affect the barrier properties of the pristine polymer in order to decrease the transport of volatile organic compounds (VOC) in indoor air. Building materials are a primary source for VOCs. These emissions are a probable cause of acute health effects and discomfort among occupants and are known to diminish productivity. The predicted concentrations of several of the VOCs emitted by structural insulated panels (SIP) are of concern with respect to health and comfort of occupants. The main issue related to the barrier membranes is the dispersion properties of the nanoclays in the polymer matrix, and the generation of a tortuous pathway that will decrease gas permeation. The tortuous pathway is created by a nanoclay filler, whose ideal exfoliated structure has high surface area, and high aspect ratio. By choosing the appropriate surfactants, the nanoclays can be modified to allow improved molecular interactions between the nanoclay and the polymer matrix. Several studies were performed in order to evaluate the dispersion properties of the nanoclay in the polymer matrix. Polymer/clay nanocomposites barrier membranes were generated via different synthesis methods. In the first study, barrier membranes were composed of a polyurethane, Estane ® 58315, and different nanoclays, Cloisite ® 10A, Cloisite ® 20A, Cloisite ® 30B. The interaction of the polyurethane and the different surfactants used to organically modify the nanoclay was evaluated. The dispersion of the clay platelets was analyzed by varying the pre-processing method; sonication vs stirring. The decrease in gas permeability results was enhanced by the effect of pre-processing via sonciation in comparison to plain stirring. These results also suggest that nanoclay platelets modified with alkylammonium groups with one tallow tail Cloisite ® 10A and Cloisite ® 30B, allow better dispersion and penetration of the polymer within the basal spacing of the nanoclays. Once the decrease in gas permeability was confirmed, the next challenge was to study and evaluate the performance of the polyurethane/clay nanocomposites barrier membranes in the determination of diffusivity coefficients for volatile organic compounds (VOCs). This was achieved via gravimetric sorption characterization. This method allowed for characterization of the sorption and desorption phenomena of VOC in barrier membranes. Barrier membranes pretreated with sonication demonstrated lower diffusivity coefficients than those only treated with stirring. At high clay loadings, 50 wt% of nanoclay in the polymer, the decrease in diffusivity coefficients for VOCs such as butanol and toluene, was found to be one order of magnitude. Other VOCs such as decane and tetradecane also showed a significant decrease in diffusivity coefficient. The results for VOC sorption studies suggest that there is some variability. In order to enhance the exfoliation of the clay, we decided to examine in situ polymerization of poly (n-butyl methacrylate) in the presence of nanoclay. In this study the clay wt% was kept at a low concentration of 1-5 wt%. The surface modification of natural montmorillonite, Cloisite ® Na+, was achieved via ion exchange, and the effect of pre-processing was also explored. The modification rendered a tethered group on the surface of the clay that was able to react with the monomer/oligomer chains and thus expand and exfoliate the clay platelets. Gas permeation data suggest that sonication also produced better barrier properties than its counterpart stirring. XRD diffractograms also confirmed exfoliation of the clay platelets in the poly (n-butyl methacrylate) polymer matrix. Thermogravimetric analysis (TGA) suggested that exfoliation of the clay platelets led to improved thermal stability by increasing the decomposition temperature of the membranes. A small increase in Tg also suggested restricted segmental chain motion within the clay platelets. Overall gas permeation decreased even at low clay content. Phenomenological models such as those of Cussler and Nielsen were used to model the experimental permeation results. These models suggest that although the aspect ratio of the clay platelets is within the specifications provided by the manufacturer, it does not reflect the ideal behavior of the models. The last step of this work was to achieve exfoliation of the modified nanoclay platelets via emulsion polymerization of poly (n-butyl methacrylate). The clay concentration in the emulsion was kept the same as in the in situ polymerization. DLS results suggest a uniform distribution of the polymer/clay nanocomposites particles in the emulsion. Permeation data indicated higher permeation values than the in situ method of synthesis of the nanocomposite membranes. This led us to explore the use of glassy co-polymer of poly(n-butyl methacrylate)-poly(methyl methacrylate) as the matrix. The addition of a more glassy component in the polymer matrix led to improved barrier properties of the nanocomposite membranes. As expected, the copolymer had a higher Tg than the PMMA polymer. Analysis via phenomenological models, also suggested that the chemistry of the co-polymer played an important role in decreasing gas permeability within the polymer/clay nanocomposite membranes, although the effect of the glassy component in the matrix was not quantified by the phenomenological models. / Ph. D.

Building materials are a major source of indoor air contaminants. Volatile organic compounds (VOCs) are an important class of contaminants prevalent in indoor air. Attempts have been made to model the emission of VOCs from building materials. Diffusion has been shown to control the rate of mass transfer within certain types of building materials. The primary objective of this research is to develop a fundamental diffusion-based model for single and double layer building materials. The single-layer model considers a slab of material located on the floor of a chamber or room with the material acting either as a source or a sink for VOCs. The behavior of the model is governed by the material phase diffusion coefficient (D), the material/air partition coefficient (K), the concentration of VOC in the influent air stream, and the initial concentration within the material phase. The single-layer model extends a previously developed version, incorporating the non-uniform initial concentration inside the building material and a transient influent concentration. Experimental work is performed to check the validity of the model. A steel chamber housing a piece of vinyl flooring is used to simulate building material within a room. D and K values for two representative VOCs, n-dodecane and phenol, are available from earlier experiments. These parameters are used in the model to predict the VOC concentration inside the chamber. The predicted values compare very well to the observed experimental data. A double layer version of the model is developed and studied from a theoretical perspective. The model also permits a time dependent influent concentration and a non-uniform initial concentration profile within each of the two layers. A parametric analysis is performed varying the ratio of the diffusion coefficients, the partition coefficients and the thickness of the two layers. Three cases of practical interest are studied using the double-layer model. The use of a thin low-permeability barrier layer placed on top of a building material is shown to hold considerable promise for reducing the emission rate of VOCs into indoor air. / Master of Science

Benzene, toluene, ethylbenzene, and xylenes (BTEX) are hazardous air pollutants commonly found in outdoor air. Several studies have explored the potential of vegetation to mitigate BTEX in outdoor air, but they are limited to a northern temperate climate and present conflicting results. To investigate this issue in a subtropical climate, we deployed passive air samplers for two weeks in parks and nearby residences at four locations: three in an urban area and one in a rural area in Alabama, USA. All BTEX concentrations were below health-based guidelines and were comparable to those found in several other studies in populated settings. Concentrations of TEX, but not benzene, were 3-39% lower in parks than at nearby residences, and the differences were significant. In and around two of the parks, toluene:benzene ratios fell outside the range expected for vehicular emissions (p<0.01), suggesting that there are additional, industrial sources of benzene near these two locations. The ratio of m-,p-xylene:ethylbenzene was high at all locations except one residential area, indicating that BTEX were freshly emitted. Concentrations of individual BTEX compounds were highly correlated with each other in most cases, except for locations that may be impacted by nearby industrial sources of benzene. Results of this study suggest that parks can help reduce BTEX exposure by a modest amount, but future research is needed to ascertain this potential through more measurements at higher spatial and temporal resolution and analysis of vegetation for evidence of uptake of BTEX. / Master of Science

Many models for predicting volatile organic compounds (VOC) emissions from latex paints have been developed. Earlier models were developed for solvent-borne paints, particularly since these paints evaporate rapidly and can be modeled with simple decay models. However, paint has changed in the past fifty years, and a transition has been made towards water-borne paints. These paints were introduced for indoor applications because they lacked the health hazards and odors of their solvent-borne counterparts. These paints also have organic modifiers, therefore it is very important to predict how these modifiers evaporate from the coated material. New mechanistic models that can predict slow emitting VOCs over long periods of time are not available. An improved ability to predict VOC emissions from latex paints could lead to improved understanding, better policy-making and promotion of environmental regulations that benefit both the consumer and producers of architectural coatings. This research improves on existing models used to estimate VOC emissions off-gassed from latex paints. The developed two layer model (2LM) has a layer for paint and substrate material, and accounts for mass transfer at the paint layer, and diffusion transport between paint and material layers. The model provides a semi-mechanistic way to predict paint drying and VOC emissions from coatings on a variety of substrates. The model only requires the estimation of one parameter (the paint layer diffusion coefficient), unlike other models available that require multiple parameter estimations. This model is robust in the sense that it could be used to predict VOC emissions from paint, as well as predicting the variation of the internal VOC distribution on both paint and material layers with time. The model was tested and validated with empirical data collected from previous controlled chamber experiments, and also with data collected from short evaporation experiments. Critical paint components like polymer and pigment composition and its relation to VOC fate and transport after paint application, both initially and over long periods of time, were explored. Modeling results indicated that the diffusion coefficient of 2,2,4-trimethyl-1,3-pentadediol monoisobutyrate (TMPD-MIB) in the paint layer does not depend on the thickness of the wet paint film, but it depends on the pigment volume concentration (PVC) of the paint. Additionally, a constant diffusion coefficient used in the 2LM was successful for modeling emissions of TMPD-MIB from low pigment volume concentration (LPVC) paints, but it failed to capture the physical mechanisms of the drying film for high pigment volume concentration (HPVC) paints. A major finding from this research was that a detailed gas phase analysis of mass transport for TMPD-MIB would have negligible effects on the predicted overall evaporation rate. Therefore, the entire wet and dry emissions processes are likely dominated by diffusion processes. / text

The widespread usage of products containing volatile organic compounds (VOC) has lead to a general human exposure to these chemicals in work places or homes being suspected to contribute to the growing incidence of environmental diseases. Since the causal molecular mechanisms for the development of these disorders are not completely understood, the overall objective of this thesis was to investigate VOC-mediated molecular effects on human lung cells in vitro at VOC concentrations comparable to exposure scenarios below current occupational limits. Although differential expression of single proteins in response to VOCs has been reported, effects on complex protein networks (proteome) have not been investigated. However, this information is indispensable when trying to ascertain a mechanism for VOC action on the cellular level and establishing preventive strategies. For this study, the alveolar epithelial cell line A549 has been used. This cell line, cultured in a two-phase (air/liquid) model allows the most direct exposure and had been successfully applied for the analysis of inflammatory effects in response to VOCs. Mass spectrometric identification of 266 protein spots provided the first proteomic map of A549 cell line to this extent that may foster future work with this frequently used cellular model. The distribution of three typical air contaminants, monochlorobenzene (CB), styrene and 1,2 dichlorobenzene (1,2-DCB), between gas and liquid phase of the exposure model has been analyzed by gas chromatography. The obtained VOC partitioning was in agreement with available literature data. Subsequently the adapted in vitro system has been successfully employed to characterize the effects of the aromatic compound styrene on the proteome of A549 cells (Chapter 4). Initially, the cell toxicity has been assessed in order to ensure that most of the concentrations used in the following proteomic approach were not cytotoxic. Significant changes in abundance and phosphorylation in the total soluble protein fraction of A549 cells have been detected following styrene exposure. All proteins have been identified using mass spectrometry and the main cellular functions have been assigned. Validation experiments on protein and transcript level confirmed the results of the 2-DE experiments. From the results, two main cellular pathways have been identified that were induced by styrene: the cellular oxidative stress response combined with moderate pro-apoptotic signaling. Measurement of cellular reactive oxygen species (ROS) as well as the styrene-mediated induction of oxidative stress marker proteins confirmed the hypothesis of oxidative stress as the main molecular response mechanism. Finally, adducts of cellular proteins with the reactive styrene metabolite styrene 7,8 oxide (SO) have been identified. Especially the SO-adducts observed at both the reactive centers of thioredoxin reductase 1, which is a key element in the control of the cellular redox state, may be involved in styrene-induced ROS formation and apoptosis. A similar proteomic approach has been carried out with the halobenzenes CB and 1,2-DCB (Chapter 5). In accordance with previous findings, cell toxicity assessment showed enhanced toxicity compared to the one caused by styrene. Significant changes in abundance and phosphorylation of total soluble proteins of A549 cells have been detected following exposure to subtoxic concentrations of CB and 1,2-DCB. All proteins have been identified using mass spectrometry and the main cellular functions have been assigned. As for the styrene experiment, the results indicated two main pathways to be affected in the presence of chlorinated benzenes, cell death signaling and oxidative stress response. The strong induction of pro-apoptotic signaling has been confirmed for both treatments by detection of the cleavage of caspase 3. Likewise, the induction of redox-sensitive protein species could be correlated to an increased cellular level of ROS observed following CB treatment. Finally, common mechanisms in the cellular response to aromatic VOCs have been investigated (Chapter 6). A similar number (4.6-6.9%) of all quantified protein spots showed differential expression (p<0.05) following cell exposure to styrene, CB or 1,2-DCB. However, not more than three protein spots showed significant regulation in the same direction for all three volatile compounds: voltage-dependent anion-selective channel protein 2, peroxiredoxin 1 and elongation factor 2. However, all of these proteins are important molecular targets in stress- and cell death-related signaling pathways. / Die vermehrte Verwendung von Produkten, welche flüchtige organische Substanzen (VOC - volatile organic compound) enthalten, hat eine generelle Exposition der Bevölkerung mit diesen Substanzen an Arbeitsplätzen aber auch in Wohnräumen bedingt. VOCs stehen im Verdacht, zur zunehmenden Inzidenz umweltbedingter Erkrankungen beizutragen. Da die molekularen Ursachen dieser Erkrankungen bisher noch unverstanden sind, war es ein übergeordnetes Ziel dieser Arbeit, VOC-vermittelte molekulare Effekte in menschlichen Lungenepithelzellen anhand eines in vitro Modells zu untersuchen. Dabei sollten vor allem Konzentrationen unterhalb der gültigen Arbeitsplatzgrenzwerte untersucht werden. Obwohl Effekte auf einzelne Proteine bekannt sind, wurden bisher keine Effekte der VOC-Exposition auf das komplexe Netzwerk der zellulären Proteine (Proteom) untersucht. Dieses Wissen ist essentiell, um induzierte zelluläre Mechanismen zu verstehen und Strategien zu deren Vermeidung zu entwickeln. Für die hier durchgeführten Untersuchungen wurde die Lungenepithelzelllinie A549 in einem Zweiphasenexpositionsmodell eingesetzt. Dieses ermöglichte eine möglichst direkte zelluläre Exposition und wurde bereits erfolgreich verwendet, um durch VOC hervorgerufene Entzündungseffekte zu identifizieren. Die massen-spektrometrische Identifikation von 266 Proteinflecken lieferte die erste umfassende Proteomkarte der A549 Zelllinie, welche nachfolgende Untersuchungen mit diesem häufig verwendeten Zelltyp erleichtern wird. Zusätzlich wurde die Verteilung der drei gängigen Luftkontaminanten Chlorbenzol (CB), Styrol and 1,2-Dichlorobenzol (1,2-DCB) zwischen den beiden Phasen (gas/flüssig) des Expositionsmodells gaschromatographisch bestimmt. Die Verteilung entsprach den verfügbaren Literaturdaten. Anschließend wurde das modifizierte Expositionsmodell erfolgreich eingesetzt, um styrol-vermittelte Effekte auf das Proteom der A549 Zellen zu charakterisieren (Kapitel 4). Zu Beginn erfolgte die Erfassung der Zelltoxizität der Substanz, um sicher zu stellen, daß der überwiegende Teil der späteren Expositionsexperimente mit subtoxischen Konzentrationen durchgeführt wird. Es konnte eine signifikant veränderte Expression und Phosphorylierung der löslichen Proteinfraktion der A549 Zellen als Reaktion auf die Styrolexposition festgestellt werden. Die regulierten Proteine wurden massenspektrometrisch identifiziert und ihre wichtigsten Funktionen wurden zugewiesen. Validierungsexperimente auf Protein- und auf Transkriptebene bestätigten die 2-DE Ergebnisse. Insgesamt konnte die zelluläre Reaktion durch die styrol-vermittelte Induktion zweier zentraler Mechanismen erklärt werden: oxidativer zellulärer Stress und beginnende Apoptose. Folgeexperimente wie die Messung der Menge der zellulären reaktiven Sauerstoffspezies (ROS) und die Induktion von redox-sensitiven Markerproteinen konnte die Hypothese eines styrol-induzierten oxidativen Milieus bestätigen. Schließlich wurden Proteinaddukte des reaktiven Styrolmetaboliten Styrol 7,8 epoxide (SO) identifiziert. Besonders die SO-Addukte, welche and den beiden aktiven Zentren der Thioredoxin Reduktase 1 gefunden wurden könnten eine wichtige Rolle bei der styrol-induzierten ROS-Bildung sowie der beginnenden Apoptose spielen. In Analogie zum Styrolexperiment wurden die Effekte der halogenierten Benzole CB und 1,2-DCB untersucht (Kapitel 5). Es konnten ebenfalls sämtliche Proteine identifiziert und die wichtigsten zellulären Funktionen zugewiesen werden. Diese Substanzen modulierten ebenfalls apoptotische Signalwege und die zelluläre Antwort auf oxidativen Streß. Der beobachtete starke pro-apoptotische Effekt konnte für beide Substanzen mit der Spaltung der Caspase 3 nachgewiesen werden. Weiterhin konnte für CB die Induktion redox-sensitiver Proteinspezies mit einem beobachteten höherem Gehalt an ROS erklärt werden. Schließlich wurden ähnliche Mechanismen der zellulären Antwort auf die Exposition mit den drei untersuchten aromatischen VOCs diskutiert (Kapitel 6). Alle getesteten VOCs verursachten eine vergleichbare differentielle Expression (p<0,05) von 4,6-6,9% aller quantifizierten Proteinspezies. Nur drei Proteinspots wurden dabei gemeinsam für alle VOCs reguliert: voltage-dependent anion-selective channel protein 2, peroxiredoxin 1 and elongation factor 2. Allerdings gehören diese drei Proteine zu wichtigen zellulären Zielstrukturen der Signalwege für Stressantwort und Zelltod.

L’histoire de l’expansion de la consommation du vin à travers le monde à partir de conquêtes européennes quifirent suite aux Grandes découvertes, reste largement à découvrir et donc à écrire. C’est ce vide que veutcombler la présente étude en examinant les diverses modalités d’utilisation des vins européens par laCompagnie hollandaise des Indes orientales, plus connue sous le nom de VOC, aux XVIIème et XVIIIèmesiècles ; elle a pour objectif de mettre en évidence l’importante circulation internationale et l’expansionorientale de cette boisson typique de la civilisation occidentale. Nos analyses s’appuient majoritairement sur lesabondantes archives laissées par cette grosse entreprise commerciale des Pays-Bas à propos de ses activitésdans les mers asiatiques, mais aussi sur les récits de voyageurs contemporains écrits en diverses langueseuropéennes, ainsi que sur des documents locaux, notamment japonais. En se déplaçant successivementd’Amsterdam à Batavia, pour enfin arriver au Japon, notre thèse souligne la forte consommation de vin à bord,mais aussi à terre par les Européens expatriés dans les Indes orientales ; on y découvre aussi l’apparition etl’évolution d’un marché local du vin dans les sociétés asiatiques, avant tout le Japon. Notre recherche élargitdonc le cadre quasi strictement continental jusqu’ici de l’histoire du vin européen aux Temps modernes. Le vinest un produit qui nous permet de lier, d’une manière horizontale, différentes cultures et sociétés existant à lamême époque sur notre planète. C’est l’histoire d’un monde de plus en plus globalisant. / The history of growth of wine consumption throughout the world, following European expansion dating back tothe Age of Discovery, remains largely to be discovered and written about. By examining the practical details ofvarious usages of European wines, by the Dutch East India Company’s commercial enterprise in Asia, betterknown as the VOC, during the Seventeenth and the Eighteenth centuries, this study aims to partly fill thepresent gap in our understanding of the history of European wines. The main objective is to highlight theimportant international circulation and expansion of this typically western beverage into the easternhemisphere. This analysis is based mainly on the rarely used archives of the VOC and several contemporarytravel accounts written in various European languages, like Dutch, English and French. Local documents suchas Japanese records have also been brought into usage. Moving successively from Amsterdam to Batavia, totheir final destination of Japan, this thesis emphasizes the mass consumption of wine on board the ships as wellas on land by European expatriates in the East Indies. We also discover the appearance and development of alocal market for wine in Asian societies, primarily in Japan. This research therefore enlarges the rathercontinental framework of the history of European wine during the Early Modern period, by discovering theconsumption and trade of European wine in Asia. Wine is a product that allows us to horizontally link differentcultures and societies that existed in early modern times. In world history, this study brings forth trends ofincreasing globalization.

In USA, the Municipal Solid Waste (MSW) landfills accumulate about 130 million tons of solid waste every year. A significant amount of biodegradable solid waste is converted to landfill gas due to anaerobic stabilization by bacteria. These biochemical reactions produce volatile organic compounds (VOCs) like methane and others. Due to heterogeneity in refuse composition, unpredictable distribution of favorable environmental conditions for bacterial actions and highly uncertain pathway of gases, estimation of landfill gas emission for a particular landfill is complex. However, it is important to quantify landfill gases for health risk assessment and energy recovery purposes. This research is based on the monitoring and modeling methodology proposed by researchers at University of Central Florida is reported in this thesis. River Birch Sub-title D landfill, Westwego, LA was selected as the study area. The total emission calculated using the mathematical model ran on MATLAB is comparable with the result obtained from EPA LandGEM model, using historical waste deposition records