Air quality management strategies in the US are developed largely from estimates of emissions, some highly uncertain, rather than actual measurements. Improved knowledge based on measurements of real-world emissions is needed to increase the effectiveness of these strategies. Consequently, the objectives of this research were to (1) quantify relationships among urban emissions sources, land use, and demographics, (2) determine the spatial and temporal variability of emissions, and (3) evaluate the accuracy of official emissions estimates. These objectives guided three field campaigns that employed a unique mobile laboratory equipped to measure pollutant fluxes by eddy covariance. The first campaign, conducted in Norfolk, Virginia, represented the first time fluxes of nitrogen oxides (NO_x) were measured by eddy covariance in an urban environment. Fluxes agreed to within 10% of estimates in the National Emissions Inventory (NEI), but were three times higher than those of an inventory used for air quality modeling and planning. Additionally, measured fluxes were correlated with road density and increased development. The second campaign took place in the Tijuana-San Diego border region. Distinct spatial differences in fluxes of carbon dioxide (CO₂), NO_x, and particles were revealed across four sampling locations with the lowest fluxes occurring in a residential neighborhood and the highest ones at a port of entry characterized by heavy motor vehicle traffic. Additionally, observed emissions of NO_x and carbon monoxide were significantly higher than those in emissions inventories, suggesting the need for further refinement of the inventories. The third campaign focused on emissions at a regional airport in Roanoke, Virginia. NOx and particle number emissions indices (EIs) were calculated for aircraft, in terms of grams of pollutant emitted per kilogram of fuel burned. Observed NO_x EIs were ~20% lower than those in an international databank. NO_x EIs from takeoffs were significantly higher than those from taxiing, but relative differences for particle EIs were mixed. Observed NO_x fluxes at the airport agreed to within 25% of estimates derived from the NEI. The results of this research will provide greater knowledge of urban impacts to air quality and will improve associated management strategies through increased accuracy of official emissions estimates. / Ph. D.

Master of Science

A "leveling off" trend in NOx emissions with high amounts of steam addition has been observed in industrial gas turbine diffusion flame combustors. Experiments were performed to try to reproduce this trend in a laminar, opposed flow diffusion flame burner. Experiments were performed with Cli4, C2H4, CO, COIH2 (1:1), and COIH2 (1:2) as fuels. Both hydrocarbon fuels and non-hydrocarbon fuels were tested to study the contribution of the Fenimore mechanism to the "leveling off" trend. Probe sampling with chemiluminescent analysis was used to fmd NOx concentrations; Pt/PtRh thermocouples corrected for radiation losses were used to measure flame temperatures. The experiments reproduced the "leveling off" of NOx emissions, but a "leveling off" of temperatures also occurred. There were no significant differences in the results from the hydrocarbon and non-hydrocarbon fuels. The "leveling off" of NOx emissions is attributed to the "leveling off" of temperatures in the burner. It is not necessary to invoke the Fenimore mechanism to explain this trend. At least 55% of the NOx was eliminated from the flames using steam injection, which implies that at least 55% of the NOx was formed by the Zeldovich mechanism Evidence of Fenimore NO was provided by the fact that the existence of hydrocarbon coking on the fuel nozzle encouraged NOx production in all flames. / Master of Science

The effect of temporal variations in equivalence ratio on the NO_x emissions of a premixed methane-air flame was measured in a burner. The NO_x emissions are compared among steady flames with spatially uniform equivalence ratio distributions, steady flames with spatially nonuniform equivalence ratio distributions, and unsteady flames with temporal equivalence ratio fluctuations. Time-varying equivalence ratio was measured optically, time-varying temperatures were measured with thermocouples, and mean NO_x emissions were measured by probe sampling and a chemiluminescent analyzer. These measurements quantify the effect of temporal unsteadiness and spatial nonuniformity of equivalence ratio on NO_x emissions. For lean flames, both spatial nonuniformities and temporal fluctuations in equivalence ratio contribute to an increase in NO_x emissions with respect to steady uniform flames at the same mean flame temperatures. For lean flames, higher amplitude temperature fluctuations result in larger increases in NO_x with respect to steady flames. The dissertation also describes the optical technique for nonintrusive temporal measurements of equivalence ratio fluctuations and techniques for thermocouple compensation at frequencies up to 10 Hz. / Ph. D.

This investigation examines the effects of load, speed, exhaust gas recirculation (EGR) level and hydrogen addition level on the exhaust gas emissions, particulate matter size distribution and chemical composition. The experiments were performed on a 2.0 litre, 4 cylinder, direct injection engine. EGR levels were then varied from 0% to 40%. Hydrogen induction was varied between 0 and 10% vol. of the inlet charge. In the case of using hydrogen and EGR, the hydrogen replaced air. The load was varied from 0 to 5.4 bar BMEP at two engine speeds, 1500 rpm and 2500 rpm. For this investigation the carbon monoxide (CO), total unburnt hydrocarbons (THC), nitrogen oxides (NOX) and the filter smoke number (FSN) were all measured. The in-cylinder pressure was also captured to allow the heat release rate to be calculated and, therefore, the combustion to be analysed. A gravimetric analysis of the particulate matter size distribution was conducted using a nano-MOUDI. Finally, a GC-MS was used to determine the chemical composition of the THC emissions. The experimental data showed that although CO, FSN and THC increase with EGR, NOX emissions decrease. Inversely, CO, FSN and THC emissions decrease with hydrogen, but NOX increases. When hydrogen was introduced the peak cylinder pressure was increased, as was the maximum rate of in-cylinder pressure rise. The position of the peak cylinder pressure was delayed as hydrogen addition increased. This together with the obtained heat release patterns shows an increase in ignition delay, and a higher proportion of premixed combustion. The experimental work showed that the particulate matter size distribution was not dramatically altered by the addition of EGR, but the main peak was slightly shifted towards the nucleation mode with the addition of hydrogen. Hydrogen addition does not appear to have a large effect on the chemical composition of the THC, but does dramatically decrease the emissions.

Os ânions inorgânicos nitrato (NO3-) e nitrito (NO2-) por muito tempo foram considerados produtos finais inertes do metabolismo do óxido nítrico (NO) e constituintes indesejáveis da dieta. Entretanto, é crescente o interesse das potenciais reações que podem se processar em meio fisiológico e, que envolvem especialmente o íon nitrito mediadas por complexos de metais de transição. Ferro-heme presente em proteínas como a mioglobina podem formar complexos porfirínicos com NO, gerando espécies que podem atuar principalmente como catalisadores em diversas vias biológicos importantes. Complexos com NOx coordenado a ferro-heme estão envolvidos tanto no processo da cura da carne (pigmentação da carne), como em processos redox, nos quais são capazes de oxidar substratos indiretamente pela produção de espécies reativas ou diretamente por reações de transferência de átomo de oxigênio (TAO). Os lipídeos, constituintes celulares fundamentais na composição de membranas e lipoproteínas, podem servir como substratos para essas reações e, sua oxidação pode ocasionar danos ao organismo. Tióis, importantes antioxidantes e constituintes de proteínas, também podem participar desse tipo de reações e, conseqüentemente gerar danos ao organismo. Considerando que o mecanismo e os parâmetros cinéticos e termodinâmicos destas reações ainda não foram completamente estabelecidos para explicar a vasta funcionalidade destes complexos, o presente projeto de pesquisa visa proporcionar um melhor conhecimento das reações redox envolvendo NOx e mediadas por porfirinas de ferro em alimentos e sistemas biológicos. / For long time, the anions nitrate (NO3-) and nitrite (NO2-) were considered inert end products of nitric oxide (NO) metabolism and undesirable constituents of the diet. Currently, there is an increasing interest for potential reactions which may occur in physiological conditions involving specially the nitrite ion and mediated by transition metal complexes. Heme NOx iron complexes are involved in meat curing process (meat pigmentation) and are able to oxidize substrates indirectly generating reactive species or directly by oxygen atom transfer reactions (OAT). Lipids, fundamental cellular constituents of membranes and lipoproteins, and thiols, important antioxidants and protein constituents, may serve as substrates to OAT and their oxidation may promote damage to the organism Considering that the mechanism and kinetic and thermodinamic parameters of these reaction have not yet been fully elucidated to explain the varied functionality of these complexes, the present research project aim to bring a better understanding of redox reactions involving NOx mediated by iron porphyrins in foods and biological systems. Thiols, important antioxidants and protein constituents, may serve as substrates to OAT and their oxidation may promote damage to the organism. The present work aims to bring a better understanding of the mechanism, kinetic and thermodynamic parameters of the reaction involving nitrite mediated by iron-porphyrins in food and biological systems.

Esta Tesis Doctoral evalúa la norma UNE EN 14211:2006 -Método normalizado de medida de la concentración de dióxido de nitrógeno y monóxido de nitrógeno por quimiluminiscencia-, citada como referencia técnica en la Directiva 2008/50/CE sobre calidad del aire y una atmósfera más limpia en Europa.La citada norma establece ensayos y criterios que deben superar los analizadores de los contaminantes citados antes de su comercialización en la Unión Europea, lo que se conoce como ensayo de aprobación de tipo. La Tesis Doctoral elaborada estudia en profundidad esta nueva norma, llevando a cabo un estudio crítico que analiza los aspectos operativos y los criterios exigidos. En algunos casos se proponen modificaciones que pueden ayudar a mejorarla. Así mismo se sugiere aplicar procedimientos correctivos de los datos obtenidos en campo, que resultan afectados por determinados parámetros físicos (presión, temperatura y humedad), modelizables mediante el empleo de leyes físicas o ajustes empíricos. / This Doctoral Thesis aims at evaluating the norm EN 14211: Standard method for the measurement of the concentration of nitrogen dioxide and nitrogen monoxide by chemiluminescence, mentioned in the Directive 2008/50/EC as technical reference document.The above standard specifies performance parameters that the analyzers must comply with prior to being sold, what is known as "Type Approval Test", and field calibration and verification guidelines, neither of which was considered in the previous standards.The study of the new Standard has revealed that some points could be improved in order to achieve a higher degree of accuracy and precision in the concentration data of nitrogen oxides. The improvement proposals cover certain aspects of the tests related to the Type Approval Test and data corrective procedures empirically obtained or by means of physical laws which are affected by physical parameters such as pressure, temperature or humidity.

In order to meet the US EPA's National Ambient Air Quality Standards as set under the provisions of the Clean Air Act, states and regions throughout the United States are designing cap and trade programs aimed at reducing the emissions of the two dominant precursors for ozone, nitrogen oxides (NOx) and Volatile Organic Compounds (VOCs). While emission cap and trade programs are becoming more common, relatively few analyses have examined the air quality implications of moving emissions from one location to another (due to trading of emissions between facilities), from one sector to another (due to the use of technologies such as Plug-in Electric Hybrid Vehicles - PHEVs), and changing the temporal distribution of emissions (through emissions trading among facilities with different temporal profiles). This thesis will examine, in detail, the air quality implications of two emission cap and trade programs. The first program is a NOx trading program that covers Electricity Generating Units (EGUs) in the Northeastern United States. Results show that refining the temporal limits on this cap and trade program, by charging facilities more to emit NOx on days when ozone is most likely to form, has the potential to significantly reduce NOx emissions and ozone concentrations. Additionally, this research also shows that, for this region, the spatial redistribution of NOx emissions due to trading leads to greater ozone reductions than similar amounts of NOx emission reductions applied evenly across all facilities. Analyses also indicate that displacing emissions from the on-road mobile sector (vehicles) to the EGU sector through the use of PHEVs decreases ozone in most areas, but some highly localized areas show increases in ozone concentration. The second trading program examined in this thesis is limited to Houston, Texas, where a VOC trading program is focused on a sub-set of four Highly Reactive Volatile Organic Compounds (HRVOCs), which have been identified as having substantial ozone formation potential. Work presented in this thesis examined whether this trading program, in its current form or in an expanded form, could lead to air pollution hot spots, due to spatial reallocation of emissions. Results show that the program as currently designed is unlikely to lead to ozone hot spots, so no further spatial limitations are required for this program. Expanding the trading to include Other VOCs, fugitive emissions and chlorine emissions, based on reactivity weighted trading, is also unlikely to lead to the formation of ozone hot spots, and could create more flexibility in a trading market that is currently not very active. Based on these air quality modeling results, policy suggestions are provided that may increase participation in the trading market. These case studies demonstrate that use of detailed air analyses can provide improved designs for increasingly popular emission cap and trade programs, with improved understanding of the impacts of modifying spatial and temporal distributions of emissions. / text

It is the need of the hour to reduce the pollutants which poison our atmosphere and harm our health. The diesel engines are the most efficient IC engines in the world today, but paradoxically, they are also the engines which create the largest amounts of NOx, the pollutant that is most difficult to control with the existing technologies. In fact, the existing technologies are unable to meet the increasingly stringent standards for NOx. Even in bio-diesels, which in the future may be adopted as an important alternative fuel, NOx is the major pollutant. Thus not having a safe and stable method for NOx removal from the diesel exhaust stream is a cause for concern. In this thesis, there has been an attempt to address this issue by means of non-thermal plasma and catalysts. In this thesis, first the performance of the three sources was evaluated individually, along with two different HV electrodes, a helical wire and a straight wire. Secondly, the efficiencies of these three different types of sources were compared. Thirdly, a catalyst (Red Mud) and an adsorbent (NaZSM5) were cascaded with the plasma reactor to enhance the performance of the NOx removal process with the AC source as it gave the best results. All the experiments were performed with real diesel engine exhaust. The conclusions drawn from the experiments are as follows: The helical electrode consumes much lower power than the straight electrode. Therefore it is energy efficient. It also causes corona inception at lower voltages due to the strong non-uniformity of its electric field. The drawbacks of the helical electrode are an excess production of NO2 .it also does not work with the HFAC source, because at high frequency, the voltage doesn’t build up owing to the presence of only a dielectric medium of 2 mm thickness between the two electrodes. The performances of the 3 sources were compared. The HVAC unit gave the best NOx removal, followed by the MPC and finally, the HFAC source. The differences in efficiencies were related to both the magnitude of the peak voltage achieved by each device and the time period. It was also seen that when the voltage was high, a better efficiency can be achieved with lower power consumption. The comparison of the sources leads us to conclude that the high voltage AC source can be used as an economic alternative for NOx control. This is because a standard AC unit is easily available at higher voltages, and contains less electrical or mechanical complexity, whereas a pulsed source is comparatively expensive and complex. The NaZSM5 zeolite showed excellent removal at room temperature as an adsorbent when cascaded after the AC source, by reducing the NO2 levels consistently. The Red Mud showed reasonable catalytic activity at 400 C with the AC source. It was also efficient in compensating for the increase in the NO2 and CO concentration in the plasma atmosphere. Hence, both Red Mud and ZSM 5 are good candidates for a hybrid plasma-adsorbent or plasma-catalyst system. The combination better NOx/CO removal is the AC energization coupled with spiral electrode with either ZSM-5 or red mud. Scaling up the plasma/ plasma- catalyst system for handling higher flow rates will be the main task next. A method to optimize the source and load matching for better power transfer to the plasma reactor from the different sources also need to be developed. The design of the compact high frequency AC source must be upgraded for higher powers.

Darbe tirta tiekiamo oro temperatūros, deginių recirkuliacijos ir degalų savybių įtaka suslėgimu uždegamo homogeninio oro – bioetanolio mišinio degimo procesui, variklio darbo ir deginių emisijos rodikliams. Nustatytos variklio darbo homogeniniu oro – bioetanolio mišiniu maksimalios apkrovos zona, kurią riboja slėgio didėjimo greitis ir susidarantis detonacinis degimas. Gautieji rezultatai varikliui veikiant bioetanoliu, lyginti su rezultatais gautais varikliui veikiant baziniais degalais – benzinu. Dyzeliniam varikliui dirbant homogeniniu oro ir bioetanolio mišiniu, keičiant tiekiamo oro temperatūrą, naudojant deginių recirkuliaciją ir įmaišant 20 % reaktyvinių degalų, azoto oksidų emisijos lieka dešimtis kartų mažesnės negu tradicinio dyzelinio variklio. Slegiamo homogeninio oro – bioetanolio mišinio užsiliepsnojimui valdyti pirmą kartą panaudoti reaktyviniai degalai. / It was found that the intake air temperature, exhaust gas recirculation and fuel properties have the influence on the combustion characteristics of homogeneous air – bioethanol mixture, engine performance and emissions. The operating region was found at which critical rate of pressure rise was unacceptably high and engine worked at “knocking” combustion. In order to assess the combustion process in homogeneous charged compression ignition (HCCI) mode fuelled with the air – bioethanol mixture, it was compared whit the combustion process in HCCI mode fuelled with the air – gasoline mixture. When the diesel engine works in HCCI mode fuelled with air – bioethanol mixture, the nitrogen oxides can be reduced more than 10 times compared with normal diesel operation. For the first time, to control the autoignition of compressed homogeneous air and bioethanol mixture, the JET A1 fuel was simultaneously added in to combustible mixture in this study.