Šiuo metu vis gausėjantis transporto priemonių skaičius ir didėjantys išmetamų teršalų kiekiai atmosferoje, skatina vyriausybes griežtinti reikalavimus VDV deginių emisijai. Vieni iš kenksmingiausių elementų deginiuose yra azoto oksidai NOX, kurie sąveikaudami atmosferoje sudaro rūgštinius junginius. Vandens dalyvavimas degimo procese taip pat mažina šių teršalų koncentraciją deginiuose. VDV maitinant vandens ir degalų emulsijomis gaunama mažesnė NOX koncentraciją deginiuose, bet tai neigiamai veikia visą variklio maitinimo sistemą. Šiame tiriamajame darbe nagrinėjamas vandens poveikis dyzelinio VDV deginių emisijai. Siekiant išvengti galimo neigiamo poveikio variklio maitinimo sistemai bei dėl paprastesnio dozavimo, vanduo įvedamas į variklio įsiurbimo traktą garų pavidalu. Tyrimai atlikti varikliui dirbant be vandens garų bei įvedant vandens garus į variklio įsiurbimo traktą trimis skirtingomis koncentracijomis. Tyrimais nustatyta 12 % didesnės lyginamosios efektyviosios degalų sąnaudos vidutinių apkrovų zonoje bei 5 % mažesnės maksimalių apkrovų zonoje, iki 8 % didesnė CO koncentracija, taip pat nustatyta iki 26 % mažesnė bendra NOX koncentracija deginiuose įvedant maksimalų 13,0 g/min vandens garų kiekį VDV vidutinių apkrovų zonoje. / Recently growing number of vehicles increases the amount of emitted pollutants into the atmosphere. This fact rushes the governments to tighten requirements for the ICE exhaust emissions. Some of the most harmful elements in the exhaust gases are nitrogen oxides NOX, which interact in the atmosphere and compose acidic compounds. However, presence of water in the combustion process reduces the concentration of pollutants in the exhaust gases. ICE fueled by water and fuel emulsions produces less NOX in the exhaust gases, but it adversely affects the fuel supply system. This study examined the effect of water on ICE diesel exhaust emissions. In order to avoid possible negative effects on fuel supply system and to simplify dosing, water is infused into the engine inlet tract in the form of vapor. Investigations were carried the engine operating without water vapor and with the introduction of water vapor into the engine inlet tract in three different concentrations. The research revealed that basic fuel consumption was 12 % higher in the average load area and 5% lower at the maximum load area. CO concentration was found to be up to 8 % higher, moreover total concentration of NOX was revealed to be 26 % lower in the exhaust gases entering the maximum 13,0 g/min of water vapor in the average load area.

The object of this research program has been to provide a baseline for microwave remote sensing of ammonia and water vapor in the atmosphere of Jupiter through laboratory measurements of their microwave absorption properties. Jupiter is not only the largest planet in our solar system, but one of the most interesting and complex. Despite a handful of spacecraft missions and many astronomical measurements, much of Jupiter s atmospheric dynamics and composition remain a mystery. Although constraints have been formed on the amount of certain gases present, the global abundances and distributions of water vapor (H2O) and ammonia (NH3) are relatively unknown. Measurements of H2O and NH3 in the Jovian atmosphere to hundreds of bars of pressure are best accomplished via passive microwave emission measurements. For these measurements to be accurately interpreted, however, the hydrogen and helium pressure-broadened microwave opacities of H2O and NH3 must be well characterized, a task that is very difficult if based solely on theory and limited laboratory measurements. Therefore, accurate laboratory measurements have been taken under a broad range of conditions that mimic those of the Jovian atmosphere. These measurements, performed using a newly redesigned high-accuracy system, and the corresponding models of microwave opacity that have been developed from them comprise the majority of this work. The models allow more accurate retrievals of H2O and NH3 abundances from previous as well as future missions to Jupiter and the outer planets, such as the NASA New Frontiers class Juno mission scheduled for launch in 2011. This information will enable a greater understanding of the concentration and distribution of H2O and NH3 in the Jovian atmosphere, which will reveal much about how Jupiter and our solar system formed and how similar planets could form in other solar systems, even planets that may be hospitable to life.

Un spectromètre utilisant la technique CRDS a été développé entre 2.00 et 2.35 µm afin de réaliser la spectroscopie en absorption de molécules d’intérêt atmosphérique et planétologique avec une très grande sensibilité et à haute résolution spectrale. Cette région du spectre correspond à une fenêtre de transparence de la vapeur d’eau et du dioxyde de carbone. Ces fenêtres sont des zones de très faible absorption utilisées pour le sondage des atmosphères terrestre et vénusienne dans lesquelles la vapeur d’eau et le dioxyde de carbone représentent respectivement les absorbants gazeux principaux dans l’infrarouge.La technique CRDS consiste à injecter des photons dans une cavité optique de haute finesse et à mesurer la durée de vie des photons dans cette cavité. Celle-ci est mesurée en interrompant l’injection des photons dans la cavité optique lors du passage en résonance du laser avec l’un des modes longitudinaux. Cette durée de vie dépend de la réflectivité des miroirs et des pertes intra-cavité comme celles induites par un gaz qui absorbe. Mesurer ces pertes en fonction de la longueur d’onde permet d’obtenir le spectre d’absorption du gaz en question. L’extrême réflectivité des miroirs permet d’atteindre dans une cavité d’un peu plus d’1 m de longueur une sensibilité équivalente à celle qui serait obtenue classiquement avec une cellule d’absorption longue de plusieurs milliers de kilomètres.Trois diodes laser DFB émettant autour de 2.35, 2.26 et 2.21 µm ont été utilisées avec ce spectromètre. Grâce à une rétro-action optique provenant d’une cavité externe, certaines de ces diodes ont pu être affinées, ce qui a permis de mieux injecter la cavité haute finesse et ainsi de réduire le niveau de bruit du spectromètre. Parallèlement grâce à une collaboration avec l’Institut d’Electronique (IES, UMR 5214) à Montpellier et la société Innoptics nous avons pu tester le prototype d’un VECSEL (Vertical-External-Cavity Surface-Emitting-Laser). Ce laser a permis de couvrir une gamme spectrale de 80 cm-1, entre 4300 et 4380 cm-1, équivalente à quatre diodes laser DFB. La sensibilité obtenue en routine avec ce spectromètre, correspondant au coefficient minimum détectable, est typiquement de 1×10-10 cm-1. Le chapitre introductif (Chapitre 1) fait le point sur les différentes techniques permettant d’acquérir des spectres en absorption dans la gamme spectrale étudiée et sur les sensibilités atteintes. A notre connaissance l’instrument développé ici est le plus sensible dans cette région du spectre. Le fonctionnement de ce spectromètre CRDS est détaillé dans le chapitre 2.Pour démontrer les performances obtenues avec notre instrument celui-ci a été utilisé pour enregistrer des transitions quadrupolaires donc de très faible intensité. Ainsi la transition S(3) de la bande 1–0 de HD a été enregistrée pour la première fois et son intensité mesurée (S=2.5×10-27 cm/molecule). La sensibilité obtenue en routine a encore pu être améliorée en réalisant une moyenne d’une centaine de spectres sur une gamme spectrale réduite pour atteindre 1×10-11 cm-1. Grâce à cela nous avons pu mesurer la position et l’intensité de la raie quadrupolaire électrique O(14) de la bande 2–0 de N2 qui est très fortement interdite avec une intensité de 1.5×10-30 cm/molecule. Ces mesures font l’objet du chapitre 3 de cette thèse.Les deux derniers chapitres sont dédiés à la caractérisation de l’absorption du CO2, au centre de la fenêtre de transparence, et à celle de la vapeur d’eau. Dans les deux cas, les transitions permises du monomère et la contribution du continuum ont été étudiées. Ce dernier correspond à une absorption variant lentement avec la longueur d’onde. Les sections efficaces du « self-continuum » de la vapeur d’eau ont notamment été mesurées en plusieurs points de la fenêtre de transparence avec une incertitude beaucoup plus faible que les mesures existantes. Elles représentent un jeu de données décisif pour tester les modèles décrivant ce continuum. / A cavity ring down spectrometer has been developed in the 2.00-2.35 µm spectral range to achieve highly sensitive absorption spectroscopy of molecules of atmospheric and planetologic interest and at high spectral resolution. This spectral region corresponds to a transparency window for water vapor and carbon dioxide. Atmospheric windows, where absorption is weak, are used to sound the Earth’s and Venus’ atmospheres where water vapor and carbon dioxide represent the main gaseous absorbers in the infrared, respectively.The CRDS technique consists of injecting photons inside a high finesse optical cavity and measuring the photon’s life time of this cavity. This life-time depends on the mirror reflectivity and on the intra-cavity losses due to the absorbing gas in the cavity. Measuring these losses versus the wavelength allow obtaining the absorption spectrum of the gas. The extreme reflectivity of the mirrors allows reaching, for a 1-meter long cavity, a sensitivity equivalent to the one obtained classically with absorption cells of several thousands of kilometers.Three DFB laser diodes emitting around 2.35, 2.26, 2.21 µm were used with this spectrometer giving access to the 4249-4257, 4422-4442 and 4516-4534 cm-1 interval, respectively. Thanks to optical feedback from an external cavity, two of these diodes were spectrally narrowed leading to a better injection of the high finesse cavity thus reducing the noise level of the spectrometer. In parallel, we tested a VECSEL (Vertical-external-Cavity, Surface Emitting laser) through a collaboration with the Institu d’Electronique (IES, UMR 5214) in Montpellier and the Innoptics firm. This laser source is able to cover a 80 cm-1 spectral range centered at 4340 cm-1, equivalent to four DFB laser diodes. In routine the achieved sensitivity with this spectrometer, corresponding to the minimum detectable coefficient is typically of 1×10-10 cm-1. The introductive chapter (Chapter 1) makes the point on the different techniques allowing absorption spectra recordings in the studied spectral region and on their sensitivity. The experimental set-up, the characteristics and performances by the CRD spectrometer developed in this work are detailed in Chapter 2. To our knowledge this instrument is the most sensitive in the considered spectral region.In Chapter 3, detection of quadrupolar electric transitions of HD and N2 illustrate the level of sensitivity reached: (i) the S(3) transition in the 1-0 band of HD has been recorded for the first time and its intensity measured (S=2.5×10-27 cm/molecule), (ii) the position and intensity of the highly forbidden O(14) quadrupolar electric transition of the 2-0 band of N2 have also been newly determined.The two last chapters are devoted to the characterization of the CO2 absorption, in the centre of the transparency window, and of the water vapor absorption. In both cases, we not only studied the allowed transitions of the monomer, but also the continuum absorption. This latter correspond to a weak background absorption varying slowly with the wave length. The self-continuum cross-sections of the water vapor continuum were measured in many spectral points through the transparency window with a much better accuracy compared to existing measurements. These CRDS data constitute a valuable data set to validate the reference model (MT_CKD) for the continuum which is implemented in most of the atmospheric radiative transfer codes.

Submitted by Lucienne Costa (lucienneferreira@ufcg.edu.br) on 2018-08-27T15:03:16Z No. of bitstreams: 1 DANILO ERICKSEN COSTA CABRAL – DISSERTAÇÃO (PPGMET) 2018.pdf: 3103151 bytes, checksum: 21c39f5e775ca2cffae4904318258171 (MD5) / Made available in DSpace on 2018-08-27T15:03:16Z (GMT). No. of bitstreams: 1 DANILO ERICKSEN COSTA CABRAL – DISSERTAÇÃO (PPGMET) 2018.pdf: 3103151 bytes, checksum: 21c39f5e775ca2cffae4904318258171 (MD5) Previous issue date: 2017-12-22 / Analisou-se neste estudo a tendência anual e a média global da Água Precipitável (AP) no período de 1986 a 2016. Foram utilizados dados extraídos das reanálises do ERAInterim/ European Center for Medium-Range Weather Forecasts (ECMWF). A partir destes dados avaliou-se a distribuição espacial da tendência de Água Precipitável. Para a análise da tendência climática aplicou-se testes estatísticos de Mann-Kendall e t de Student observandose o comportamento das séries globais. Para a variável AP, foi encontrado o valor médio de 24,4mm para todo o período, correspondendo a um volume estimado para toda a atmosfera. Os resultados apontam tendências significativas de 0,0246; 0,0121 e 0,0203 mm/ano para o HN; HS e todo o Globo, respectivamente. Foi observada uma tendência positiva para algumas áreas do globo bem como outras negativas, resultando em uma distribuição não homogênea, denotando-se uma provável tendência de aumento do vapor d’água no globo. / In this study was analyzed the annual trend and the global mean of Precipitation Water (WP) from 1986 to 2016. Data extracted from the ERA-Interim / European Center for Medium-Range Weather Forecasts (ECMWF) reanalysis were used. From these data was evaluated the Precipitation Water tendency spatial distribution. For the analysis of the climatic trend, Mann-Kendall and t-Student statistical tests were applied, observing the behavior of the global series. For the WP variable was found the average value of 24.4 mm for the whole period, corresponding to estimated volume for the whole atmosphere. The results indicate significant trends of 0.0246, 0.0121 and 0.0203 mm /year for HN; HS and the whole Globe, respectively. A positive trend was observed for some areas of globe as well as negative values, resulting the not homogeneous distribution, denoting a probable tendency to increase water vapor in the globe.

Les décharges plasma dans la vapeur d’eau sont d’un grand intérêt pour de nombreuses applications potentielles, telles que le traitement biomédical, la production d’hydrogène ou la combustion assistée par plasma. Cette thèse propose une caractérisation expérimentale détaillée de l’effet thermique et chimique des décharges non-thermique nanosecondes répétitives pulsées (NRP) à la pression atmosphérique dans la vapeur d’eau pure. Un réacteur a été conçu pour fonctionner avec la vapeur d’eau préchauffée à 400-500 K. Les conditions opératoires retenues sont un débit de 300 g/h à 500 K et une décharge avec une énergie moyenne de 20 à 100 W, en régime Spark. Différents diagnostics ont été développés afin de déterminer les produits de cette décharge en termes d’espèces intermédiaires, de densité électronique et des produits stables. La concentration des produits de réaction stables (H2 et O2) et leurs débits respectifs ont été mesurés par chromatographie en phase gazeuse. Une valeur maximale de 0,85 g-H2/kWh a été obtenue. La densité électronique a été mesurée par spectroscopie d’émission optique (OES) résolue en temps grâce à l’élargissement par effet Stark des raies (H, H et O). La densité électronique maximale mesurée est 2X1018 cm-3 pendant l’impulsion. La température du gaz a été mesurée lors de la décharge de 20 ns par OES ainsi que entre deux décharges (100 us) par fluorescence induite par laser du radical OH (OH-PLIF) à deux couleurs. L’élévation maximale de la température est de 950 K après l’impulsion, et la température décroît ensuite de façon exponentielle avec un temps de décroissance caractéristique de 5 us. La densité relative du radical OH a été mesurée par OH-PLIF, révélant la durée de vie relativement longue de OH avec un temps de décroissance d’environ 50 us. En utilisant un modèle cinétique 0-D, la densité absolue OH à la fin de l’impulsion a été estimée à 400 plus ou moins 200 ppm. Les résultats obtenus ont permis d’éclairer les mécanismes sous-jacents à la génération de décharges NRP en régime Spark dans la vapeur d’eau pure à basse température. / Plasma discharges in water vapor are of great interest for a variety of potential applications, such as biomedical treatment, hydrogen production, or plasma assisted combustion. This thesis proposes a detailed experimental characterization of the thermal and chemical effects of non thermal discharge, particularly Nanosecond Repetitively Pulsed (NRP) discharges at atmospheric pressure in pure water vapor. A reactor has been designed to operate with water vapor preheated at 400-500 K. We investigated the various discharge regimes and the operating conditions for each regime. The selected operating conditions are a flow rate of 300 g/h at 500 K. The discharge has an average energy from 20 to 100 W in the spark regime. Various diagnostics have been developed in order to infer the products of this discharge in terms of intermediate species, electrons, and stable products. The concentration of the reaction products (H2 and O2) and their respective flow rates were measured using gas chromatography. A maximal value of 0.85 g- H2/kWh was obtained. The electron number density has been measured using time-resolved optical emission spectroscopy (OES) via Stark-broadened lines (H, H and O). The maximum measured electron density is 2X1018 cm-3 during the pulse, and a slow recombination process was observed. The gas temperature was measured during the 20-ns discharge by OES as well as between two discharges (100 us) by two-color OH-Planar Laser Induced Fluorescence (OH-PLIF). The maximum temperature elevation is 950 K after the pulse ; the temperature then decays exponentially with a characteristic time of 5 us. Between two successive discharges, the relative density of the OH radical was measured by OH-PLIF. An interesting result is the relatively long-lived nature of OH, with a 1/e decay time of about 50 us. Using a 0D-chemical kinetics model, the absolute OH density at the end of the pulse was estimated to 400 more or less 200 ppm. These results provide useful information to better understand the mechanisms underlying the generation of NRP spark discharges in low temperature pure water vapor.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / Embalagens biodegradÃveis sÃo coberturas utilizadas em alimentos na forma de filmes ou revestimentos, formadas por macromolÃculas tanto de origem vegetal como de origem animal, que garantem propriedades de barreira e podem servir como veÃculo para compostos antimicrobianos. Os polissacarÃdeos de reserva de parede celular, principalmente as hemiceluloses como as galactomananas, vÃm sendo extensamente usadas como matrizes polimÃricas de filmes biodegradÃveis. O objetivo deste trabalho foi avaliar a incorporaÃÃo de Ãleo essencial de manjericÃo (OEM) (Ocimum basilicum) em filmes biodegradÃveis à base de galactomanana endospÃrmica de sementes de flamboyant (Delonix regia) e Ãleo canola (OC) (Brassica napus L.). A Galactomanana (Gal) foi isolada por extraÃÃo aquosa, seguida por precipitaÃÃo em etanol. O rendimento determinado foi de 12,0%, com alto grau de pureza apresentado pelo baixo teor de nitrogÃnio expresso em proteÃna (0,67%). A Gal apresentou viscosidade intrÃnseca mÃdia de 3,79 dL/g e massa molar estimada de 1,04x106 g/mol. Os espectros de infravermelho por transformada de Fourier (FTIR) e ressonÃncia magnÃtica nuclear (RMN) de 1H e 13C foram similares aos encontrados na literatura para outras galactomananas. A composiÃÃo em Ãcidos graxos do OC por cromatografia a gÃs (GC-FID) apresentou teores de Ãcido oleico (62,07%), linoleico (18,91%) e heneicosanÃico (6,61%). Os componentes majoritÃrios do OEM determinados por cromatografia a gÃs acoplado à espectrometria de massas (GC-MS) foram cÃnfora (14,85%) e 1,8-cineol (3,48%). Os filmes foram formulados com Gal 1% (m/v), glicerol 0,5% (m/v) e OC em diferentes concentraÃÃes, 0,25, 0,5 e 0,75% (m/v). Os filmes foram obtidos pelo mÃtodo de evaporaÃÃo de solvente (casting) e caracterizados quanto ao teor de umidade, espessura, permeabilidade ao vapor de Ãgua (PVA), cor e opacidade. O OC promoveu aumento de PVA e diminuiÃÃo do teor de umidade quando comparado ao filme apenas de galactomanana, mas sem diferenÃa significativa entre as concentraÃÃes. O OEM foi testado frente Ãs cepas bacterianas de Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Salmonella choleraesuis, Staphylococcus aureus e levedura Candida albicans por microdiluiÃÃo em caldo e apresentou concentraÃÃo inibitÃria mÃnima (CIM) variando entre 2,5 e 5,0 mg/mL e concentraÃÃo bactericida mÃnima (CBM) entre 5,0 e 20,0 mg/mL. A partir do filme com formulaÃÃo de 0,5 % (m/v) de OC incorporou-se OEM em diferentes concentraÃÃes (2,5, 5,0 e 7,5 mg/mL). Os filmes antimicrobianos foram obtidos por casting e discos de 1 cm de diÃmetro foram excisados e testados por mÃtodo de difusÃo em Ãgar e a zona de contato e os halos de inibiÃÃo analisados. S. aureus, E. coli e P. aeruginosa foram sensÃveis ao filme contendo 5,0 mg/mL de OEM apresentando halos de 14, 15 e 16,3 mm, respectivamente. K. pneumoniae foi inibida apenas na zona de contato do filme, enquanto que S. choleraesuis e C. albicans foram resistentes à todas as formulaÃÃes. Contudo, O OC promoveu alteraÃÃes nas propriedades fÃsicas e de barreira dos filmes de galactomanana e OEM quando incorporado ao filme apresentou uma atividade antimicrobiana moderada para potencial aplicaÃÃo como embalagens bioativas. / Biodegradable Packaging are used in foods as films or coatings formed by plant macromolecules such as animal, ensuring barrier properties and can serve as a carrier for antimicrobial compounds. The cell wall polysaccharides reservation, especially hemicelluloses as galactomannans, have been used widely as biodegradable polymer matrices films. The objective of this study was to evaluate the Basil essential oil (BEO) (Ocimum basilicum) incorporation in biodegradable films based on endospermic galactomannan Delonix regia seeds and canola oil (CO) (Brassica napus L.). The galactomannan (Gal) was isolated by aqueous extraction, followed by ethanol precipitation. The yield was 12.0% with high purity presented by low nitrogen content expressed protein (0.67%). The Gal showed an average intrinsic viscosity of 3.79 dL/g and molecular weight estimated in 1,04x106 g/mol. Infrared spectra by Fourier transform (FTIR) and nuclear magnetic resonance (NMR) 1H and 13C were similar to those found in the literature for other galactomannans. The fatty acid composition of CO by gas chromatography (GC-FID) showed oleic acid (62.07%), linoleic (18.91%) and heneicosanÃico (6.61%) content. The major components of BEO determined by gas chromatography coupled to mass spectrometry (GC-MS) were camphor (14.85%) and 1.8-cineole (3.48%). The films were formulated with galactomannan 1% (w/v), glycerol 0.5% (w/v) and CO at different concentrations, 0.25, 0.5 and 0.75% (w/v). The films were obtained by the solvent evaporation method (casting) and characterized as the moisture content, thickness, water vapor permeability (WVP), color and opacity. The CO promoted increase of WPV and reduced moisture content when compared to the film based only in galactomannan but no significant difference between concentrations. BEO was tested against the bacterial strains of Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Salmonella choleraesuis, Staphylococcus aureus and Candida albicans yeast by broth microdilution and showed minimum inhibitory concentration (MIC) ranging between 2.5 and 5.0 mg/ml and minimum bactericidal concentration (MBC) between 5.0 and 20.0 mg/ml. BEO was incorporated into film formulation with CO 0.5% (w/v) in different concentrations (2.5, 5.0 and 7.5 mg/ml). The antimicrobial films were obtained by casting and disks of 1 cm in diameter were excised and tested by the agar diffusion method and a contact zone and inhibition halos analyzed. S. aureus, E. coli and P. aeruginosa were sensitive to film containing BEO 5.0 mg/ml showed halos of 14, 15 and 16.3 mm, respectively. K. pneumoniae was inhibited only in the contact zone of the film, while S. choleraesuis and C. albicans were resistant to all formulations. However, the OC promoted changes in physical and barrier properties of the films of with galactomannan. BEO when incorporated into the film showed a moderate antimicrobial activity for potential application as bioactive packaging.

Doctor of Philosophy / Department of Agronomy / Clenton E. Owensby / Most rangelands are harvested at some point during the year and removal of plant leaf area and biomass alters a host of ecosystem processes including gas exchange. An experiment was conducted in 2005 and 2006 to study the effects of clipping tallgrass prairie at different dates on water vapor and CO2 fluxes. A portable, non-steady-state chamber was designed to measure CO2 and water vapor fluxes from small plots in less than 40 s. A combination of sunlit and shaded readings allowed measurements of net carbon exchange (NCE) and ecosystem respiration (RE); by summing NCE and RE, gross canopy photosynthesis (GCP) was calculated. Throughout the two-year study, the chamber had a minimal effect on microclimate, i.e., average chamber temperature increased 2.9° C, while chamber pressure increased only 0.3 Pa during measurements, and photosynthetically active radiation attenuation was 10%. The immediate effect of all clipping treatments was a loss of leaf area that led to reductions in GCP, NCE, and RE and in most cases decreased water vapor flux. Further patterns of carbon flux were governed by the amount of water stress during canopy development, while water vapor flux rates varied with water availability. Canopies that developed during periods of low water stress quickly increased carbon flux rates following precipitation after a mid-season drought. However, flux rates of canopies, which developed during the mid-season drought, responded considerably slower to subsequent water availability. A separate experiment was conducted from June-October of 2006 to estimate GCP, leaf area index (LAI), and total aboveground biomass with a hyperspectral radiometer. Indices such as the Normalized Difference Vegetation Index and the Simple Ratio were used to estimate LAI and biomass had poor correlations with measured values. However, GCP was significantly correlated to all six indices derived in this study. While GCP measured from June-October was significantly correlated with all indices, removal of the senesced canopy scans recorded during October greatly increased the relationship.

Content: In order to solve the negative impact of coating on water vapor permeability of leather and overcome the poor water resistance of polyacrylate leather finishing agent, it was proposed that the mesoporous SiO2 spheres with hollow structure instead of traditional surfactant were introduced into polyacrylate by Pickering emulsion polymerization. It was expected to increase the water vapor permeability of polyacrylate film by increasing the path and shortening the route of water vapor molecules through the film, and improve the water resistance of film by avoiding the use of surfactant. Hence, stable Pickering emulsion stabilized by mesoporous hollow SiO2 spheres was prepared and its stability was investigated by Turbiscan Lab in this paper. Water vapor permeability, water uptake and mechanical property of polyacrylate film were also studied. Compared with emulsion stabilized by surfactant, Pickering emulsion indicated excellent stability with lower TSI value of 0.5. Contrasted with polyacrylate film with SDS, the introduction of mesoporous hollow SiO2 spheres can improve the water vapor permeability of polyacrylate film. Meanwhile, water absorption measurements showed that the water absorption ratio of the film with mesoporous hollow SiO2 spheres decreased from 112.34 to 40.84%, possessing the ideal ability to water resistance of polyacrylate film. Its film with mesoporous hollow SiO2 spheres also revealed increases of up to 188% in tensile strength and 41.15% in elongation at break. This study can provide a theoretical foundation for designing and synthesizing leather finishing agent with excellent stability, water vapor permeability and water resistance synchronously. Take-Away: 1. Mesoporous hollow SiO2 spheres stabilized Pickering emulsion exhibits outstanding stability. 2. The introduction of mesoporous hollow SiO2 spheres can improve the water vapor permeability of polyacrylate membrane. 3. Polyacrylate membrane shows excellent water resistance.

Der Wasserdampfgehalt der Atmosphäre gehört zu den Hauptkontrolleuren des Treibhauseffektes und spielt eine Schlüsselrolle im globalen Energiekreislauf, wobei den Polargebieten als globale Wärmesenken eine besondere Bedeutung zukommt. Im Rahmen dieser Arbeit wurde aus Messungen des Global Positioning System (GPS) der integrierte Wasserdampfgehalt innerhalb der letzten Dekade bestimmt und analysiert. Die Untersuchungen stützen sich auf die Reprozessierung eines aus 195 Stationen bestehenden globalen GPS-Netzes. Die aus den geschätzten GPS-Troposphärenparameter bestimmten Wasserdampf- zeitreihen wurden hinsichtlich Genauigkeit und Homogenität untersucht. Nach Korrektion der Inhomogenit äten ist es möglich, mit GPS mehrjährige Schwankungen im potenziellen Niederschlagswasser mit einer Genauigkeit besser als 0,3 mm Höhe der Wassersäule zu erfassen. Als Ergebnis der Untersuchungen zeigen sich in Europa und großen Teilen Nordamerikas Anomalien des Wasserdampfgehaltes im Bereich eines Millimeters, welche sich vor allem auf thermodynamische Effekte zurückführen lassen. In den Tropen und im Südosten der USA können die Wasserdampfanomalien 3 bis 5 mm betragen. Sie sind durch dynamische Prozesse bedingt, die mit der Südlichen Oszillation im Zusammenhang stehen. Eine Anwendung der aus GPS-Beobachtungen bestimmten Wasserdampfzeitreihen ist die Validierung des Wasserdampfes im globalen Wettervorhersagemodell des National Center for Environmental Predicton (NCEP). Über Europa und großen Teilen Nordamerikas reproduziert NCEP die Schwankungen des Wasserdampfgehaltes sehr gut und stellt damit eine gute Datengrundlage für ?ächendeckende Untersuchungen langfristiger Veränderungen im Wasserdampfgehalt dar. In der Antarktis und den Tropen wird jedoch das saisonale und mehrjährige Signal des Wasserdampfes von NCEP um 25% bis 40% unterschätzt. Als zweite Anwendung der GPS-Wasserdampfzeitreihen erfolgt die Validierung satellitenbasierter Radiometermessungen über der Antarktis. Sie zeigt eine gute Übereinstimmung der Wasserdampfwerte aus GPSund Radiometermessungen. Die im Rahmen dieser Arbeit aus GPS-Beobachtungen bestimmten Wasserdampfzeitreihen bilden eine sehr gute Datengrundlage für weitergehende Untersuchungen der Wetter- und Klimaforschung. / The atmospheric water vapour is one of the main variables controlling the greenhouse effect and it plays a crucial role in the global energy cycle. In this context the polar regions which act as global heat sinks are especially important. This study uses observations from the Global Positioning System (GPS) to investigate changes of the integrated atmospheric water vapour. It is based on a reprocessing of a global GPS network consisting of 195 stations. A strong emphasis was placed on the investigation of the accuracy and the homogeneity of the GPS derived water vapour time series. After correcting the inhomogeneities interannual ?uctuations in the precipitable water can be determined from GPS data with an accuracy of 0.3 mm in water column height. As a result, the interannual variations in the water vapour content are in the order of one millimetre over Europe and over large areas of North America. They are mainly related to thermodynamic effects. In the tropics and in the south east of the USA water vapour anomalies can reach 3 to 5 mm caused by dynamic processes connected to the Southern Oscillation. As one application of the estimated GPS water vapour time series a validation of water vapour from the global numerical weather prediction model of the National Center for Environmental Prediction (NCEP) was carried out. Over Europe and large parts of North America the seasonal signal and the interannual variations of the water vapour are very well reproduced by NCEP. Hence, in these regions NCEP presents a good database for area-wide investigations of long-term changes in the water vapour content. However, in Antarctica and in the Tropics the seasonal and also the interannual signals of the NCEP water vapour are strongly underestimated by 25% to 40%. A second application of the estimated GPS water vapour time series is the validation of satellite-based radiometer measurements over Antarctica. A good agreement was found between the water vapour derived from GPS and radiometer data. The water vapour time series estimated in this study provide a good basis for further weather and climate related investigations.

Biogenic volatile organic compounds (VOCs) react with Cl and OH radicals and the resulting radicals combine with oxygen to form peroxy radicals RO2. Organic peroxy radicals can then react with NO to form NO2, a precursor of tropospheric ozone. The work presented here explored the initial reaction between Cl and thujone, a VOC emitted by Great Basin sagebrush. The rate constant for the reaction of thujone + Cl at 296 K was measured with the method of relative rates with FTIR for detection of reactants. LEDs were used to photolyze Cl2 to generate Cl in the reaction cell. Thujone was also photolyzed by the LEDs and therefore the relative rates model was revised to account for this photolysis. With toluene as the reference compound, the rate constant for thujone + Cl at 296 K is 2.62 ± 1.90 × 10-12 molecules-1 s-1, giving an atmospheric lifetime of 0.5--2.6 minutes for thujone. Cline et al. showed that the rate of the self-reaction of HO2CH2CH2O2 (β-HEP) increases in the presence of water vapor. This enhancement has a strong temperature dependence with a greater enhancement observed at colder temperatures. The observed rate enhancement has been attributed to the formation of a β-HEP--H2O complex. In this work, the equilibrium constant for the formation of the β-HEP--H2O complex was calculated by ab initio calculations. Given the energy available at room temperature, the complex will populate three local minimum geometries and β-HEP will populate two local minimum geometries. The partition function for each of these geometries was calculated and used to calculate the equilibrium constant for complex formation as a function of temperature. Based on these computational results, the observed temperature dependence for the rate enhancement can be attributed to the strong temperature dependence for the rate constant of the reaction of β-HEP--H2O + β-HEP rather than the temperature dependence of complex formation.