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Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

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La neige est un réacteur photochimique multiphasique complexe capable d'échanger de nombreuses espèces réactives avec l'atmosphère. Les émissions du manteau neigeux peuvent donc influencer de manière considérable la composition et la réactivité des atmosphères polaires. Parmi les composés réactifs ainsi échangés se trouvent de nombreux composés carbonylés dont les aldéhydes qui font l'objet de cette étude. La photolyse des aldéhydes est une source importante de radicaux HOx dans l'atmosphère arctique et l'étude des échanges de ces gaz est donc indispensable à la compréhension de la capacité oxydante de l'atmosphère des régions polaires. Le formaldéhyde (HCHO) est l'aldéhyde le plus abondant dans l'atmosphère et a fait l'objet d'une part importante de notre étude. Une étude expérimentale de la solubilité et de la diffusion de HCHO dans la glace nous a permis de confirmer que ce composé formait une solution solide dans la glace. Les résultats que nous avons obtenus, associés à une analyse critique des données bibliographiques sur la solubilité de HCHO en phase aqueuse, ont été utilisés pour construire le diagramme de phase pression partielle – température du système H2O-HCHO. Afin de comprendre les mécanismes mis en jeu dans les échanges d'aldéhydes entre la neige et le manteau neigeux, nous avons suivi les concentrations en aldéhydes dans le manteau neigeux à Barrow, un site côtier à l'extrême Nord de l'Alaska, lors de la campagne polaire OASIS 2009. Nos mesures ont été associées à celles de la microphysique de la neige et à la mesure en phase gazeuse du formaldéhyde. En développant un modèle numérique de diffusion de HCHO dans les cristaux de neige, nous avons montré que l'évolution des concentrations dans la neige pouvait être reproduite de manière quantitative par l'équilibre thermodynamique et la cinétique de diffusion du formaldéhyde dans la glace. Ce travail ne se limite pas à la seule étude de HCHO. D'autres aldéhydes présents dans l'atmosphère peuvent potentiellement jouer un rôle important dans la chimie atmosphérique. Nous avons donc réalisé des améliorations à notre méthode analytique afin de permettre la mesure non seulement du formaldéhyde et de l'acétaldéhyde, mais aussi du glyoxal, du méthylglyoxal et de l'hydroxyacétaldéhyde. Cette méthode analytique déployée pendant la campagne OASIS nous a ainsi permis de mesurer simultanément et pour la première fois, l'ensemble de ces aldéhydes dans la neige polaire. Ces mesures ont révélé des concentrations importantes de glyoxal et de méthylglyoxal dans la neige, ces composés étant probablement présents dans les aérosols organiques piégés par la neige. Le rôle de cette matière organique particulaire dans la chimie de la neige nous semble mériter de plus amples études, afin de mieux caractériser sa structure et sa réactivité. / Snow is a complex multiphase chemical reactor that exchanges many reactive species with the atmosphere. One consequence of such emissions is that snow dramatically impacts the composition and the reactivity of polar the atmosphere. Carbonyl compounds, including aldehydes, are some of theses noteworthy species emitted by the snowpack. Here, we focus on aldehydes whose photolysis can yield significant amounts of HOx radicals. The knowledge of processes involved in air-snow exchanges is therefore required to understand how snow impacts the oxidative capacity of polar atmospheres. A major part of our work is focused on formaldehyde (HCHO), the most abundant aldehyde in the atmosphere. We first performed an experimental study to measure both the solubility and the diffusivity of HCHO in ice. Our results confirm that the formation of a solid-solution is the process of incorporation of HCHO into snow. We also performed a reanalysis of existing data on the solubility of HCHO in liquid water solutions. Our work made it possible to construct the partial pressure – temperature phase diagram for the H2O-HCHO system. To investigate the processes involved in air-snow exchanges of aldehydes, we monitored their concentration in snow during the OASIS 2009 field campaign which took place at Barrow, Alaska. Our measures were complemented by the monitoring of the snow physical properties and by the measurement of formaldehyde concentration in the gas phase. We developed a numerical code to model HCHO diffusion in and out of ice crystals and showed that it was possible to quantitatively reproduce snow concentrations by considering the equilibration of the H2O-HCHO by solid solution in ice. Our work also focused on other aldehydes that can potentially impact the atmospheric oxidative capacity. Improvements to our analytical method made it possible to measure not only formaldehyde and acetaldehyde, but also glyoxal, methylglyoxal and hydroxyacetaldehyde. This method deployed during the OASIS campaign provided the first measurements of all these aldehydes in polar snow. We found significant amounts of glyoxal and methylglyoxal in snow and we hypothesize that such compounds are located in the particulate organic matter scavenged by snow. The reactivity and structural composition of this organic matter must be further investigated to understand quantitatively the exchanges of these other aldehydes between the snow and the atmosphere.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

In this research, used dimethyl ether as second fuel blended with diesel (mixed quantity with 10 L/min to 60 L/min, interval 10L/min), which test behavior of diesel engine and carbonyls emission investigated. The engine operated at steady-state condition of 1600 rpm, 145 Nm torque , eight kinds of carbonyls were sampling and analysis, and discuss the performance of the ozone formation potential (OFP). The results of regulated pollutant emissions, CO, THC and PM emission could increasing with the addition of DME, NOX emissions, along with the mixed rate of per minute from 10 L, 20 L, 30 L, 40 L, 50 L and 60 L of its reduction rate was 6.8%¡B8.3%¡B10.0%¡B10.6%¡B13.1% and 15.4%, shows that the DME can reduce NOX emissions. Add a various amount of dimethyl ether , which carbonyl compounds emission from the gas flow 0 L(with neat diesel), 10 L, 20 L, 30 L, 40 L, 50 L and 60 L concentrations were 2507.44 g/m3, 2665.27 g/m3, 2726.67 g/m3, 2958.07 g/m3, 4645.87 g/m3, 5470.20 g/m3 and 7279.91 g/m3; the emission factor of 143.58 mg/bhp-hr, 152.65 mg/bhp-hr, 156.62 mg/bhp-hr, 168.69 mg/bhp-hr, 266.22 mg/bhp-hr, 312.38 mg/bhp-hr and 416.36 mg/bhp-hr, shows the addition of DME will rising the carbonyl compound emissions of diesel engine. Gas of dimethyl ether (10,20,30,40,50 and 60 L/min) into the neat diesel fuel (0 L/min) as a mixture fuel additives, the effect of ozone formation potential as increase in the total ozone formation potential, 21945.93 g-O3/m3, 23698.40 g-O3/m3, 24427.46 g-O3/m3, 26672.98 g-O3/m3, 42683.69 g-O3/m3, 50519.26 g-O3/m3 and 67710.60 g-O3/m3 respectively, and ozone manufacturability will 0 L/min of 8.75 increased to 60 L/min of 9.30.

This research carries out all tests in diesel engine takes neat diesel and hydrogen+oxygen (H2/O2) which is used as an additive (H2/O2 mixture: 10 to 70 L/min, interval 10 L/min) in a stable state condition (engine was operated at one load steady-state condition of 1600 rpm with torque and power outputs of 145 Nm and 24.5 kW, respectively). Characteristics of carbonyls emissions from H2/O2 as an additive were investigated in a HDDE (heavy-duty diesel engine) and compared with those from neat diesel, contains the concentration, emission factor and elimination efficiency, whole of change tendency in order to help the understanding of diesel engine pollutant emissions, and appraises energy conservation of benefit which add to H2/O2. The regulated pollutants emission, using H2/O2 mixture (10 to 70 L/min), THC, CO, CO2 and PM emission all increased while H2/O2 showed signs of decrease; on the contrary, NOx emission increased while H2/O2 increased. Regarding Carbonyls emissions, the total carbonyls concentration of diesel engine take neat diesel was 3218.02 £gg/m3 and the emission factors for diesel engine take neat diesel were 180.882 mg/bhp-hr and 788.061 mg/L-fuel, respectively. When H2/O2 mixture was added, total carbonyls concentration of 3068.28, 3006.42, 2823.10, 2707.06, 2500.54, 2216.87 and 2178.27 mg/m3 were 10 L/min, 20 L/min, 30 L/min, 40 L/min, 50 L/min, 60 L/min and 70 L/min, respectively. The emission factor may be divided into mg/bhp-hr and mg/L-fuel; the emission factor of total carbonyls were 231.36¡B226.18¡B211.41¡B203.14¡B186.98¡B167.17 and 164.23 mg/bhp-hr, respectively; the emission factor of total carbonyls were 764.95¡B755.15¡B719.97¡B707.36¡B704.40¡B694.27 and 690.47 mg/L-fuel, respectively. Increases in H2/O2 can reduce total carbonyls emissions with an eliminating efficiency rate of 4.7, 6.6, 12.3, 15.9, 22.3, 31.1 and 32.3%, respectively. Energy conservation of appraisal increase H2/O2, diesel equivalent sun of fuel consumption of diesel engine and electricity consumption of H2/O2 generator, namely can distinguish that its energy consumption, whole consumes were 2.51, 2.58, 2.59, 2.57, 2.60, 2.43, 2.26 and 2.25, respectively. When compared with neat diesel, result showed in H2/O2 from 10 L/min to 40 L/min, diesel equivalent increased while H2/O2 showed increase; but in H2/O2 from 50 L/min to 70 L/min reflected in a gradual decrease in diesel equivalent, indicating that increases in H2/O2 can effectively achieve energy conservation. The result showed that energy conservation was 3.4%, 10.0% and 10.6% for 50 L/min, 60 L/min and 70 L/min, respectively. The result indicated H2/O2 was 60 L/min when energy conservation benefit was most remarkable, therefore this had the best energy conservation.

This research conducted exhaust tests in an HDDE (heavy-duty diesel engine) using pure diesel fuel mixed with 10 to 30% isobutanol under the condition of U.S. Transient Cycle. Characteristics of 18 carbonyls emissions were investigated and compared with those using pure diesel. Results showed that the brake power (BP) and brake thermal efficiency (BTE) were decreased with increasing isobutanol mixtures (10 to 30%). Brake specific fuel consumption (BSFC) was increased for isubutanol ¡Ø 10%, but was decreased for isubutanol above 10%. The regulated emissions of CO, PM and NOx were decreased, but CO2 and THC were increased, due to variations of cetane number and heating value. Total carbonyls emission concentrations with pure diesel fuel were 893.25 £gg/m3, with emission factors being 52.57 mg/bhp-hr or 218.44 mg/L-fuel. When 10 to 30% isobutanol mixture was added, total carbonyls concentrations ranged from 1108.21 to 2622.27 £gg/m3, with emission factors being 268.83 to 610.94 mg/L-fuel, or 68.93 to 175.25 mg/bhp-hr. The ozone formation potential of diesel engine with pure diesel fuel was 7132.72 g-O3/m3.When 10 to 30% isobutanol mixture was used, total ozone formation potential ranged from 8764.39 to 20168.73 g-O3/m3. Total carbonyls emissions were increased with increasing isobutanol contents. In summary, addition 10% isobutanol was an optimal blend, since both fuel saving and reductions of pollutant emissions can be achieved.