Volatile Organic Compounds (VOCs) constitute an important class of indoor air contaminants and they may cause adverse health effects for occupants in buildings. Indoor generated contaminants may be transferred between the supply and exhaust air streams of the building’s Heating, Ventilation and Air-conditioning (HVAC) system when air-to-air energy recovery devices are used. The run-around membrane energy exchanger (RAMEE) is a novel exchanger, which uses aqueous magnesium chloride (MgCl2) salt solution (34-35 wt%) as a liquid desiccant to transfer heat and moisture between remote supply and exhaust air streams. In the RAMEE, a gas-phase porous membrane is placed between the air stream and the liquid desiccant stream in each exchanger and the membrane prevents the salt solution from entering the air stream but still allows the transfer of water vapor through the semi-permeable membrane. In the RAMEE, VOCs may transfer between the exhaust and supply air streams due to (i) air leakage or (ii) due to dissolution of VOCs into the liquid desiccant in the exhaust exchanger and their subsequent evaporation into the air stream of the supply exchanger. These two transfer mechanisms were tested in the laboratory using two counter-cross-flow RAMEE prototypes (Prototype #4 and Prototype #6). Tests were conducted at different air and desiccant flow rates at AHRI standard summer and winter operating conditions. Sulfur hexafluoride (SF6) was used as a tracer gas to test air leakage and toluene (C7H8) and formaldehyde (HCHO) were used to test VOC dissolution and transfer. From an external source, a known concentration of VOC was injected into the exhaust air inlet stream and the transfer fraction of VOC to the supply air stream was calculated. This transfer fraction or Exhaust Air Transfer Ratio (EATR) defined by ANSI/ASHRAE Standard 84 (2012) at steady state conditions was used to quantify and compare the transfer fraction of contaminants in both prototypes. The uncertainty in the transfer fraction was calculated and all the uncertainty bounds were calculated for 95% confidence interval. The transfer fraction of sulfur hexafluoride was 0.02 +/- 3.6% for both prototypes tested, which means that the air leakage between the air streams is negligible. The transfer of toluene, which has a low solubility in water, was less than the uncertainty in the measurement. EATR* values for toluene were 2.3-3.4% and the uncertainties were 3.4-3.6%. The transfer of formaldehyde between the exhaust and the supply air streams was the highest and the EATR* values just exceeded the uncertainties in the EATR* measurement. The highest EATR* values for the transfer of formaldehyde in Prototype #4 and Prototype #6 were 6.4 +/- 3.6% and 5.3 +/- 3.6%, respectively. At steady state, the measured EATR* values for both prototypes were insensitive to changes in the air flow rate, the liquid desiccant flow rate, the latent effectiveness and the environmental conditions but time delays to reach steady state were significant. These results imply that there is a negligible transfer of contaminants due to air leakage between the air streams, a negligible transfer of low water soluble VOCs (such as toluene), but possibly a small detectable transfer of very water soluble VOCs (such as formaldehyde) between the exhaust and supply air streams of the RAMEE.

Chalcogenide phase change (PC) materials can be reversibly transformed between the high resistivity (~ 1 Ω∙m) amorphous state (OFF-state) and low resistivity (~ 10-6 Ω∙m) crystalline state (ON-state) thermally, both are stable at the room temperature. This makes them well suited as reconfigurable RF switches and non-volatile memories. This work will present the understandings of two key characteristics of PC materials, the crystallization dynamics and the threshold voltage (Vth), as they determine performance limitations in these applications. Crystallization dynamics describe the correlations of the states, temperature and time; the Vth is the trigger of the threshold switching which leads to the “break down” of PC materials from OFF-state to ON-state. The four-terminal indirectly-heated RF switches with high cut-off frequency (> 5 THz) has advantages over other technologies but its programming power (~ 1.5 W) is yet to be reduced. Measuring the maximum allowed RESET quench time in the crystallization dynamics is critical for designing low power switches. As a major contribution, this work provides a universal methodology for accurate heater thermometry and in-situ crystallization measurements for this study. On the other hand, understanding the Vth is essential for high power handling applications as it determines the maximum power that an OFF-state switch can withstand without being spontaneously turned on. This work will discuss new observations and learnings from Vth measurements including the geometry dependent Vth variations which provide insights into the threshold switching mechanism. Unlike RF switches, faster crystallization is desired for memories to improve the write speed. The non-Arrhenius crystallization needs to be explored to achieve short crystallization time (< 10 ns) at high temperature (> 700 K). As another major contribution, this work will present a nano-scale (~ 100 nm) high-speed (thermal time constant < 5 ns) PC device for assessing the crystallization time in this regime, and provide a comprehensive learning for the crystallization dynamics from 300 K to 1000 K by developing a unified framework based on the fragility model and growth-dominated crystallization. This can be used to accurately simulate the crystallization process for any device geometry and estimate the RF switches power and Vth.

O principal polo produtor de banana no estado de São Paulo está na Divisão Regional e Agrícola de Registro, que se estende do Vale do Ribeira até o litoral sul do estado. Nesta região, a produção de banana é a principal atividade dos produtores rurais e é responsável pela principal demanda de insumos e serviços de comercialização. No entanto, o Vale do Ribeira se caracteriza por ser uma região com baixos níveis de tecnologia e mecanização e a qualidade de vida é bastante baixa, fatores que contribuem para a baixa produtividade da banana. Este trabalho teve como objetivo estabelecer os efeitos que a proximidade da biodiversidade nativa da Mata Atlântica promove nos atributos físico-químicos e bioquímicos do fruto da bananeira, em decorrência da proximidade da biodiversidade. Duas parcelas foram escolhidas para fornecer as amostras posteriormente analisadas quanto a parâmetros fisiológicos, químicos e bioquímicos: a parcela \"Controle\" plenamente inserida em um bananal convencional e a parcela \"Biodiversidade\" com 60% de seu perímetro rodeado pela biodiversidade da Mata Atlântica. Foram feitas as seguintes avaliações nos frutos colhidos destas parcelas: análise dos perfis de etileno e CO2 endógenos por cromatografia gasosa, quantificação de amido por método enzimático, e açúcares solúveis por CLAE-DAD, análise de textura (penetrômetro) e cor (colorímetro), determinação de compostos voláteis relacionados ao aroma por cromatografia gasosa e espectrometria de massas. Além de avaliações em campo de incidência e severidade de pragas e doenças, de luminosidade, radiação fotossinteticamente ativa, análise de solo e foliar, monitoramento da Umidade Relativa e temperatura. Os resultados mostraram que as plantas na parcela próxima à Mata Atlântica foram menos atacadas pela Sigatoka Negra (cerca de 15%) quando comparada à parcela Controle (cerca de 36%). Nos frutos colhidos, foram encontradas diferenças nos padrões de etileno, respiração, textura, cor, açúcares e perfil de compostos voláteis. Os resultados relativos ao perfil destes compostos mostraram alterações na rede de vias de biossíntese de compostos voláteis diferentes dos comumente detectados em bananas. Compostos típicos de frutos imaturos, conhecidos na literatura como Voláteis de Folhas Verdes (VFVs) foram detectados nos perfis de compostos voláteis de frutos maduros das amostras da parcela Biodiversidade, indicando o desencadeamento de vias metabólicas relacionadas à defesa de plantas, tais como a Via da enzima Lipoxigenase (LOX) e a Via de Biossíntese de Terpenos. Este fato provavelmente teve origem na maior quantidade de sistemas ecológicos originários do fragmento florestal próximo à parcela, que favoreceram uma rede mais rica de relações entre as bananeiras e outros organismos, bem como entre as bananeiras e outras plantas, em comparação às plantas da parcela Controle. Constatou-se que as condições de cultivo no campo têm influência direta sobre o produto final, refletindo no processo de amadurecimento dos frutos. / In São Paulo, the main banana producing region is the Divisão Regional e Agrícola de Registro, extending from the Vale do Ribeira to the southern coast of the state. In this region, the banana producing is the farmer\'s main activity and is responsible for the main demand of inputs and commercialization services. However, the Vale do Ribeira is characterized as a region with low levels of technology and mechanization and the quality of life is quite low, factors that contribute to low banana\'s productivity. This study aimed to stablish the effects that the proximity of native Atlantic Forest biodiversity promotes on the physical, chemical and biochemical of banana, due to the proximity of biodiversity attributes. Two plots were chosen to provide samples subsequently analysed for physiological, biochemical and chemical parameters: a control plot fully inserted into a conventional banana produce and another plot, called by Biodiversity Plot, with 60% of its perimeter surrounded by the Atlantic Forest biodiversity. The following evaluations were made in the fruits harvested from such plots: analyses of endogenous ethylene and CO2 profiles by gas chromatography, quantification of starch by enzymatic method, and soluble sugars by HPLC-DAD, texture analyses (penetrometer) and color (colorimeter), determination of volatile compounds related to flavor by gas chromatography and mass spectrometry. Apart from field evaluations of incidence and severity of pests and diseases, brightness photosynthetically active radiation, soil and leaf analyses, monitoring of relative humidity and temperature. The results showed that the plants in the plot next to the Atlantic Forest were less attacked by Black Sigatoka (about 15%) compared to the plants from the control plot (about 36%). In harvested fruits, differences were found in ethylene profiles, texture, color, sugars and volatile compound profile. The results for the profile of these compounds showed changes in the biosynthetic pathways of volatile compounds network, commonly found in bananas. Typical compounds immature fruit, known in the literature as Green Leaf Volatiles (GLVs) were detected in volatiles from samples of mature fruits portion Biodiversity profiles, indicating triggering of defense-related pathways in plants such as the Lipoxygenase Pathway and biosynthesis of terpenes pathway. This fact probably originated from the most amount of ecological systems originated near the plot forest fragment, wich favored a richer network of relations among the banana plants and other organisms as well as between the banana trees and other plants, compared to plants of the control plot. The growing conditions in the field have direct influence on the final product, reflecting on the fruit ripening process.

Thesis (MTech (Horticulture))--Cape Peninsula University of Technology, 2018. / Global demand for environmentally-friendly grapevine cultivation and pest control has necessitated an improved understanding of the relationship between soil properties and beneficial naturally occurring antagonists like entomopathogenic fungi (EPF). This group of fungi presents a viable alternative for the control of destructive pests such as the grapevine mealybug. Sixty-six soil samples were collected from 22 vineyards in the Western Cape, South Africa. The association between soil nutrient status and EPF prevalence was then examined. Fungi were isolated with methods of insect baiting and selective media. Fungal strains were identified and characterized using light microscopy and DNA analysis (ITS and BTub). In addition, fungal isolates were tested against a key grapevine pest, Planococcus ficus (Signoret) (Hemiptera: Pseudococcidae) using an immersion bioassay at a concentration of 1 x 108 conidia ml-1. Twenty-three fungal strains were isolated and correspondence analysis (CA) of data indicated a positive association between fungal occurrence and moderate to high levels of soil-based macronutrients. Binomial logistic regression analysis revealed that soil N, K, Ca, Mg and S concentrations and C/N ratio were correlated with at least one EPF species. This study showed that some soil nutrient properties correspond to greater occurrence of EPF in grapevine soils. Strains of Beauvaria bassiana (Hypocreales: Clavicipitaceae) caused the highest mortalities (82% to 87%). In chapter three, I examined the effect of B. bassiana inoculation of grape plants on the infestation level of P. ficus, and the growth and volatile constituents of potted grape plants. The grapevines were inoculated with 1 x 108 conidia ml-1 of B. bassiana by drenching before experimentally infesting them with thirty P. ficus adult females. At four weeks post treatments, the fungus was re-isolated from leaves of 50% of the fungus exposed plants. No significant difference (P > 0.05) was observed in all the plant growth parameters measured in the fungus treated and control plants. Plant tissue analysis revealed markedly higher contents of Ca and Mg in leaf tissue of plants exposed to the B. bassiana relative to the control. GC-MS analyses showed that a significantly (X2=5.1; P<0.02) higher number of known anti-insect volatile compounds (9) including napthtalene were present among fungus treated plants compared to the control plants (5). However, B. bassiana did not have any significant effect on total polyphenol, alkaloid and flavonoids. Overall, treatment with fungus did not offer any protection against infestation of P. ficus. In conclusion, this is the first study to report on the isolation of indigenous entomopathogenic fungal (EPF) strains within vineyards of the Western Cape. The study revealed that inoculating grapevine plants during cultivation had a net positive effect on the production of volatile compounds in grapevines. These findings shed light on the mechanisms involved in endophytic fungus-plant-insect interactions. This study contributes valuable information to future development of ecological approaches involving EPF for insect control in vineyards and in general, agricultural settings.

by Yuk-Lin Chan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves 78-83). / Abstracts in English and Chinese. / Abstract (English version) --- p.i / Abstract (Chinese version) --- p.ii / Acknowledgments --- p.iii / Table of Contents --- p.iv / List of Figures --- p.vi / List of Tables --- p.vii / Chapter 1. --- Introduction / Chapter 1.1 --- Indoor Air Pollution --- p.1 / Chapter 1.2 --- Typical Treatment of Air Pollutant --- p.6 / Chapter 1.3 --- Photocatalytic Degradation over Titanium Dioxide --- p.7 / Chapter 1.4 --- Advantages of Titanium Dioxide as a Photocatalyst --- p.12 / Chapter 1.5 --- Applications of Photocatalytic Degradation in Pollution Control --- p.14 / Chapter 1.5.1 --- Aqueous Phase Decontamination --- p.15 / Chapter 1.5.2 --- Gas Phase Decontamination --- p.15 / Chapter 1.6 --- Development of the Photocatalytic Degradation Technique --- p.16 / Chapter 1.6.1 --- Pure Ti02 --- p.17 / Chapter 1.6.2 --- Design of the Reactors --- p.18 / Chapter 1.6.3 --- Metal Ion Dopants --- p.21 / Chapter 1.6.4 --- Mixture with Supports --- p.21 / Chapter 1.7 --- Adsorbent-Supported Titanium Dioxide --- p.22 / Chapter 1.7.1 --- Use of Adsorbents other than Zeolites --- p.22 / Chapter 1.7.2 --- Use of Zeolites --- p.25 / Chapter 1.8 --- Molecular Sieves --- p.29 / Chapter 2. --- Experimental / Chapter 2.1 --- Block diagram of the Reaction Setup --- p.31 / Chapter 2.2 --- Fixed Volume Batch Reactor --- p.32 / Chapter 2.3 --- Reagents --- p.34 / Chapter 2.3.1 --- Degussa P25 Ti02 powder --- p.34 / Chapter 2.3.2 --- Aldrich Molecular Sieves (Organophilic) --- p.35 / Chapter 2.3.3 --- Other Adsorbents Used for Comparison --- p.35 / Chapter 2.4 --- Instrumental Analysis --- p.36 / Chapter 2.4.1 --- Photoacoustic Multi-gas Monitor --- p.36 / Chapter 2.4.2 --- X-Ray Diffraction Analysis --- p.42 / Chapter 2.4.3 --- Scanning Electron Microscopy --- p.42 / Chapter 2.4.4 --- UV-vis Diffuse Reflectance Spectroscopy --- p.42 / Chapter 2.4.5 --- Iso-electron Point Measurements --- p.43 / Chapter 2.5 --- Photocatalytic Degradation of Simple Alkanes by P25 Titanium Dioxide --- p.45 / Chapter 2.6 --- Photocatalytic Degradation of Gaseous Acetone over Organophilic Molecular Sieves-Supported Titanium Dioxide --- p.49 / Chapter 3. --- Results and Discussion / Chapter 3.1 --- Photocatalytic Degradation of Simple Alkanes by P25 Titanium Dioxide --- p.52 / Chapter 3.1.1 --- Rate of Photocatalytic Degradation of Simple Alkanes --- p.52 / Chapter 3.1.2 --- Summary of Rate of Photocatalytic Degradation of Simple Alkanes --- p.57 / Chapter 3.2 --- Photocatalytic Degradation of Gaseous Acetone over Organophilic Molecular Sieves-Supported Titanium Dioxide --- p.58 / Chapter 3.2.1 --- The Adsorption Ability of Various Adsorbents --- p.58 / Chapter 3.2.2 --- XRD Pattern Measurement --- p.60 / Chapter 3.2.3 --- Scanning Electron Microscopy --- p.64 / Chapter 3.2.4 --- UV-vis Diffuse Reflectance Spectroscopy --- p.65 / Chapter 3.2.5 --- Iso-electron Point Measurements --- p.67 / Chapter 3.2.6 --- Photocatalytic Activity of Various Catalysts --- p.69 / Chapter 4. --- Conclusion --- p.76 / Bibliography --- p.78 / Appendix / "A Demonstration of Photocatalytic Degradation by Gaseous Organic Pollutant, Dichloromethane " --- p.83

Resumo: Investigou-se a influência da utilização de inóculos sobre a digestão anaeróbia de resíduos de aves de postura, frangos de corte e suínos em biodigestores modelo batelada com volume útil de 60 L operados à temperatura ambiente, por meio da caracterização do potencial e distribuição da produção de biogás ao longo do tempo, o estudo da redução de sólidos, a análise das características dos efluentes quanto à concentração de ácidos graxos voláteis e por meio da determinação do número mais provável (NMP) de coliformes fecais e totais nos afluentes e efluentes. Avaliou-se também a atividade metanogênica nos biodigestores com 10 % de inóculo. Foram testadas três concentrações de inóculo: 0, 10 e 15 %. Os resultados mostraram que os resíduos de aves de postura, frangos de corte e suínos são bons substratos para o processo de digestão anaeróbia, apresentando potenciais médios que variaram de 0,3828 a 0,4403 m3, de 0,3495 a 0, 3915 m3, e de 0,1949 a 0,4466 m3 de biogás por kg de ST adicionados, respectivamente para resíduos de aves de postura, frangos de corte e suínos. Com base em todos os parâmetros estudados, as concentrações de inóculo que promoveram melhores resultados foram 10 % para resíduos de aves de postura e frangos de corte, e 15 % para resíduos de suínos. O tratamento anaeróbio revelou-se eficiente na remoção de coliformes totais e fecais independente da concentração de inóculo, alcançando porcentagens médias de redução de NMP que variaram de 99,71 % de 1,09 x 102 a 100 %. A atividade metanogênica específica foi mais elevada nas amostras provenientes dos biodigestores operados com resíduos de aves de postura (0,0340 mmol CH4 g-1 SV h-1), seguida pelos resíduos de frangos de corte (0,0188 mmol CH4 g-1 SV h-1) e suínos (0,0029 mmol CH4 g-1 SV h-1). Estes resultados parecem estar mais associados aos teores...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study was carried out in 60 L volume batch digesters at ambient temperature and investigated the inoculums concentration effects on anaerobic digestion of laying hens, poultry and piggery wastes through evaluation of potential and distribution of biogas production along the time, solids removal, analyze of volatile fatty acids efluent concentration and by monitoring the most probable number (MNP) of total and faecal coliforms in the inffluents and effluents. Specific methanogenic activity (SMA) into the 10 % inoculum digesters was also measured. Three inoculum concentrations (0, 10 and 15 %) were tested. Results showed that laying hens, poultry litter and piggery wastes are good substrats to anaerobic digestion. The potential biogas production varied from 0.03828 to 0.4403 m3, 0.3495 to 0.3915 m3 and 0.1949 to 0.4466 m3 of biogas kg-1 of total solids added, respectively for laying hens, poultry and piggery wastes. The best results for inoculum concentration were 10 % for laying hens and poultry wastes, and 15 % for piggery wastes. Anaerobic digestion was efficient for reduction of the most probable mean number of total and faecal coliforms. Reduction of MNP mean varied from 99.71 of 1,09 x 102 to 100 %. SMA test showed the best activity was from laying hens wastes (0,03400 mmol CH4 g-1 SV h-1), followed by poultry wastes (0,01877 mmol CH4 g-1 SV h- 1) and by piggery wastes (0,00293 mmol CH4 g-1 SV h-1). Results of SMA test appear to be most affected by volatile solids content of the samples than the best ability of the microrganisms to convert substrate. The best organic load rate for activity test were 0,25 g DQO g-1 SV. / Orientador: Jorge de Lucas Junior / Coorientador: Roberto Alves de Oliveira / Banca: Rosana Filomena Vazoller / Banca: Edson Aparecido Abdul Nour / Mestre

In the context of emerging non-volatile memory (NVM) where data structures can persist in-memory and are accessed through CPU loads and stores, we study how to efficiently manage data evolution. This is an extensively applied problem in both the scientific and business domains and is rapidly becoming an important component for a wider range of applications. We argue that the best way to achieve a smoother transition to the new programming model is to design a solution that is non-intrusive and generic i.e. not bound to a specific data model. We propose a novel library-level approach where the user can manage historical data directly from programming language code. This is achieved with a combination of two software layers: REWIND and VARIANT. At the bottom, lies REWIND (REcovery Write-Ahead System for In- Memory Non-Volatile Data Structures) which handles the low level specifics of NVM by dealing with write-ordering problems that arise in such context and allows recoverability of arbitrary data structures. Then, VARIANT (Versioning ARbItrary dAta structures in Non-volatile memory for Time-travel) focuses on versioning and time travel (moving between versions). We adopt a logging approach and we tightly integrate both systems for best performance by utilizing a common physical log of memory operations. With REWIND, we propose a novel recoverable log structure that permits atomic and durable appends and removals of log records. This is the keystone for building recoverable systems on top of NVM. Because latencies in recent NVM technologies such as Phase-change memory (PCM) are asymmetric, we propose novel techniques for reducing the write pressure of the recoverable log as well as mitigating the effect of synchronization control primitives such as memory fences (enhanced for NVM), i.e. barriers that enforce ordering and persistence to preceding instructions. We also propose different implementations for trading logging performance for rollback performance when this is appropriate. Finally, we revisit state-of-the-art recovery algorithms for the new context given the different latencies and synchronization control. Our results clearly indicate that current approaches for recoverability are ill-fitted for persisting data structures in the new context and it is possible to achieve low-overhead logging with customized mechanisms. Next, we focus on data evolution. We expose a simple API that allows versioning and time travel with minimal intrusiveness. We propose mechanisms for efficient and transparent cloning of Versionable data structures. This allows high concurrency since past images are returned as copies of the original data structure which remains intact. Then, we propose novel indexing techniques that significantly improve time travel performance as well as cloning with lazy schemes. We achieve a low overhead architecture by employing a mix of volatile and non-volatile data structures as well as hybrid structures that reside in both volatile and non-volatile memories. We perform an extensive evaluation of the proposed techniques and conclude that, in our context, by carefully mitigating the drawbacks of physical logging it is possible to create efficient systems for managing data evolution that are both data structure agnostic and non-intrusive.

Production of volatile sulfur compounds in cheese is associated with desirable flavors. The direct source of these compounds has been assumed to arise from the metabolism of methionine and cysteine. However, the methionine concentration in cheese rises above the amount found in casein during aging, suggesting that alternative sulfur sources are present in milk. This led us to hypothesize that lactococci may acquire sulfur from the inorganic sulfur pool of milk, in addition to methionine and cysteine, to generate volatile sulfur compounds during cheese ripening. A turbidimetric method to determine total sulfate content in milk samples was developed. The average sulfate content of milk was determined to be ~49 mg/L ± 2.0 mg/L. The limit of detection of the test was ~2.5 mg/L in Tris buffer and ~10 mg/L in milk. Skim milk samples had significantly higher total sulfate content as compared to whole milk samples. Transport of sulfate by three strains of Lactococcus sp. was studied after we determined that milk had small, but measurable amounts of inorganic sulfate. A decrease in the environmental pH increased sulfate transport. The maximum transport occurred during exponential cellular growth phase. All strains tested had the ability to transport much more sulfate than is native in milk. The last phase of study was to determine the metabolic fate of sulfate. Incorporation of radio-labeled sulfate into cellular protein was studied by two-dimensional gel-electrophoresis of crude cellular lysate followed by auto-radiography. Production of volatile sulfur compounds from inorganic sulfur was determined with analysis of the head space gas with gas chromatography and scintillation counting. The incorporation of radio-labeled sulfur from sulfate was not detected in proteins on two-dimensional gels. Detectable volatile sulfur compounds were found only in the case of gas chromatographic analysis of ML3 head space. However, radio-labeled volatile sulfur was detected in the head space of all the three strains with scintillation counting. This study defined that lactococci can fix inorganic sulfur into volatile sulfur compounds in small amounts.

Nowadays, there is an increasing awareness on the importance of biomass waste as a renewable source of energy, materials and chemicals. In this context, the European project MOBILE FLIP aims at developing and demonstrating mobile conversion processes suitable with variousunderexploited agro- and forest based biomass resources in order to produce energy carriers, materials and chemicals. One of these processes is torrefaction, which consists in a mild thermal treatment, occurring typically between 200 and 300°C during a few tens of minutes in a defaultoxygen atmosphere. The solid product obtained has thermal and processing properties closer to coal, and thus is suitable as fuel for combustion or gasification. During torrefaction, condensable coproducts are released, that may also be source of “green” chemicals. It is therefore crucial to characterize them to optimize the torrefaction process and design industrial units. Up to now, only few works have been focused on characterizing and modelling both solid and condensable species during torrefaction versus operating conditions and feedstock type. Furthermore, these studies typically include a reduced number of biomasses. Cellulose, hemicellulose and lignin,which constitute biomass macromolecular composition, are determining properties to predict biomass behaviour during torrefaction. However, torrefaction tests on these constituents are rare and always based on commercial compounds, which were proved as little representative of the native biomass. The objective of this study is to analyse the influence of biomass characteristics, mainly represented by the macromolecular composition in cellulose, hemicellulose and lignin, on the global behaviour of biomass in torrefaction, both in terms of solid mass loss and of productionprofiles of the volatile species released, in function of the operating conditions.14 biomasses from the main biomass families (deciduouswood, coniferous wood, agricultural byproductsand herbaceous crops) were selected for this study. An optimized extraction procedure was proposed to recover cellulose, hemicellulose and lignin fractions from 5 reference biomasses. Experiments were performed on a thermogravimetric analyzer coupled to a gas chromatography mass spectrometer device through a heated storage loop system (TGA-GC/MS). Solid degradation kinetics and volatile release profiles were followed during torrefaction experiments combining non-isothermal (200 to 300°C at 3°C/min) and isothermal (300°C, 30 min) conditions, ensuring the chemical regime thanks to the appropriate operating conditions. The results obtained with the raw materials demonstrated that biomass macromolecular composition is a main factor influencing biomass behavior in torrefaction. Consequently, the heterogeneity of the resource results in a diverse behavior in torrefaction, particularly in the case of agricultural biomasses. The results with the extracted components evidenced their very different behavior compared to thecommercial compounds, particularly in the case of cellulose. This suggests that a limitation could be induced by the common use in literature of commercial components for torrefaction modelling. The impact on the characterization of macromolecular components was also shown to be prevailing in their behavior in torrefaction, especially in the case of hemicellulose sugar composition and cellulose crystallinity. Furthermore, differences in release kinetics of volatile species during torrefaction were observed, even for volatiles belonging to the same chemical family (acids, furans, ketones). Derived from these results, a torrefaction model based on the additive contribution of extracted cellulose, hemicelluloses and lignin to the global behavior of biomass in torrefaction was proposed, and this for the 5 representative biomasses.

Atmospheric formaldehyde (H2CO) is an intermediate product common to the degradation of many volatile organic compounds and therefore it is a central component of the tropospheric chemistry. While the global formaldehyde background is due to methane oxidation, emissions of non-methane volatile organic compounds (NMVOCs) from biogenic, biomass burning and anthropogenic continental sources result in important and localised enhancements of the H2CO concentration. Recent spaceborne nadir sensors provide an opportunity to quantify the abundance of tropospheric formaldehyde at the global scale, and thereby to improve our knowledge of NMVOC emissions. This is essential for a better understanding of the processes that control the production and the evolution of tropospheric ozone, a key actor in air quality and climate change, but also of the hydroxyl radical OH, the main cleansing agent of our troposphere. For this reason, H2CO satellite observations are increasingly used in combination with tropospheric chemistry transport models to constrain NMVOC emission inventories in so-called top-down inversion approaches. Such inverse modelling applications require well characterised satellite data products consistently retrieved over long time periods. This work reports on global observations of formaldehyde columns retrieved from the successive solar backscatter nadir sensors GOME, SCIAMACHY and GOME-2, respectively launched in 1995, 2002 and 2006. The retrieval procedure is based on the differential optical absorption spectroscopy technique (DOAS). Formaldehyde concentrations integrated along the mean atmospheric optical path are derived from the recorded spectra in the UV region, and further converted to vertical columns by means of calculated air mass factors. These are obtained from radiative transfer simulations, accounting for cloud coverage, surface properties and best-guess H2CO profiles, the latter being derived from the IMAGES chemistry transport model. A key task of the thesis has consisted in the optimisation of the H2CO retrieval settings from multiple sensors, taking into account the instrumental specificities of each sounder. As a result of these efforts, a homogeneous dataset of formaldehyde columns covering the period from 1996 to 2010 has been created. This comes with a comprehensive error budget that treats errors related to the spectral fit of the columns as well as those associated to the air mass factor evaluation. The time series of the GOME, SCIAMACHY and GOME-2 H2CO observations is shown to be consistent and stable over time. In addition, GOME-2 brings a significant reduction of the noise on spatiotemporally averaged observations, leading to a better identification of the emission sources. Our dataset is used to study the regional formaldehyde distribution, as well as its seasonal and interannual variations, principally related to temperature changes and fire events, but also to anthropogenic activities. Moreover, building on the quality of our 15-year time series, we present the first analysis of long-term changes in the H2CO columns. Positive trends, in the range of 1.5 to 4% yr-1, are found in Asia, more particularly in Eastern China and India, and are related to the known increase of anthropogenic NMVOC emissions in these regions. Finally, our dataset has been extensively used in several studies, in particular by the BIRA-IASB modelling team to constrain NMVOC emission fluxes. The results demonstrate the high potential of satellite data as top-down constraint for biogenic and biomass burning NMVOC emission inventories, especially in Tropical ecosystems, in Southeastern Asia, and in Southeastern US. / Le formaldéhyde (H2CO) joue un rôle central dans la chimie de la troposphère en tant que produit intermédiaire commun à la dégradation chimique de la plupart des composés organiques volatils dans l’atmosphère. L’oxydation du méthane est responsable de plus de la moitié de la concentration moyenne globale du formaldéhyde. Sur les continents en revanche, les hydrocarbures non-méthaniques (NMVOCs) émis par la végétation, les feux de biomasse et les activités humaines, augmentent de façon significative et localisée la concentration de H2CO. Les récents senseurs satellitaires à visée nadir offrent la possibilité de quantifier à l’échelle globale l’abondance du formaldéhyde dans la troposphère et de ce fait, d’améliorer notre connaissance des émissions de NMVOCs. Ceci est essentiel à la compréhension des mécanismes contrôlant la production et l’évolution de l’ozone troposphérique, élément clé pour la qualité de l’air et les changements climatiques, mais aussi du composé hydroxyle OH, le principal agent nettoyant de notre troposphère. C’est pourquoi, une méthode de plus en plus répandue pour améliorer les inventaires d’émissions des NMVOCs consiste en l’utilisation d’observations satellitaires de H2CO en combinaison avec un modèle de chimie et de transport troposphérique, dans une approche appelée modélisation inverse. Ce genre d’application demande des produits satellitaires bien caractérisés et dérivés de façon cohérente sur de longues périodes de temps. Le travail présenté dans ce manuscrit porte sur l’inversion des colonnes de formaldéhyde à partir de spectres de la radiation solaire rétrodiffusée par l’atmosphère terrestre, mesurés par les senseurs GOME, SCIAMACHY et GOME-2, lancés successivement en 1995, 2002 et 2006. La méthode d’inversion est basée sur la spectroscopie d’absorption optique différentielle (DOAS). Les concentrations de formaldéhyde intégrées le long du chemin optique moyen dans l’atmosphère sont dérivées à partir des spectres mesurés, et ensuite transformées en colonnes verticales par le biais de facteurs de conversion appelés facteurs de masse d’air. Ces derniers sont calculés à l’aide d’un modèle de transfert radiatif, en tenant compte de la présence de nuages, des propriétés de la surface terrestre et la distribution verticale supposée du formaldéhyde, fournie par le modèle IMAGES. Un des objectifs principaux de la thèse a été d’optimiser les paramètres d’inversion pour H2CO, et ceci pour les trois senseurs, tout en tenant compte des spécificités de chaque instrument. Ces efforts ont conduit à la création d’un jeu de données homogène, couvrant la période de 1996 à 2010. Les colonnes sont fournies avec un bilan d’erreur complet, incluant les erreurs liées à l’inversion des concentrations dans les spectres, ainsi que celles provenant de l’évaluation des facteurs de masse d’air. La série temporelle des observations de GOME, SCIAMACHY et GOME-2 présente une bonne cohérence et stabilité sur toute la période. Nous montrons aussi que la meilleure couverture terrestre de GOME-2 entraîne une réduction significative du bruit sur les observations moyennées, permettant une meilleure identification des sources d’émission. Notre jeu de données est exploité pour étudier la distribution régionale du formaldéhyde, ainsi que ses variations saisonnières et interannuelles, principalement liées aux variations de température et aux feux de végétation, mais aussi aux activités anthropiques. De plus, en s’appuyant sur la qualité de la série temporelle de 15 ans, nous présentons la première analyse des variations à long terme des concentrations de H2CO. Des tendances positives, de l’ordre de 1.5 à 4% par an, sont observées en Asie, en particulier dans l’est de la Chine et en Inde, liées à l’augmentation des émissions anthropiques d’hydrocarbures dans ces régions. Finalement, nos données ont été largement exploitées par le groupe de modélisation de l’IASB pour faire des études de modélisation inverse des émissions de NMVOCs. Les résultats démontrent le haut potentiel des données satellitaires pour contraindre les inventaires d’émissions dues à la végétation et aux feux de biomasse, particulièrement dans les écosystèmes tropicaux, en Asie du sud-est, et dans le sud-est des Etats-Unis.