Biomass energy is the oldest form of energy harnessed by humans. Currently, processed biofuels, which are derived from biomass, are being pursued as a possi- ble route to decarbonize the transport sector - a particularly difficult task for both technological and sociological reasons. In this thesis I explore the impacts that large scale biofuel use could have on atmospheric chemistry. I review the current state of biofuels politically and technologically, focusing on ethanol and biodiesel. I discuss the salient features of tropospheric chemistry and in particular the oxidation of isoprene, an important biogenic volatile organic compound. I examine the impact that including isoprene oxidation has in a new chemistry-climate computer model, UKCA; the response of ozone turns out to depend on local chemical conditions. To evaluate the global model, I use data from the OP3 field campaign in Malaysia and compare it with output from the model chemical mechanism. The mechanism is able to reproduce NOx and ozone measurements well, though is more sensitive to representations of physical rather than chemical processes. I also perform a simple sensitivity study which examines crop changes in the region of Southeast Asia. In the final two chapters, I turn to two distinct phases of the biofuel life cycle. I characterize a potential future atmosphere through an ozone attribution study, then examine the impact of future cropland expansion (phase I of a biofuel life cycle) on tropospheric chemistry. I find that land use change has a large impact on ozone, and that it is more acute than another perturbation (CO2 suppression) to isoprene emissions. I then move to phase III of the life cycle - combustion - and look at the sensitivity of the model chemistry to surface transport emissions from biofuels as a replacement for conventional fuels. I find that biodiesel reduces surface ozone, while ethanol increases it, and that the response has both a linear and nonlinear component.

Near the earth's surface, ozone is a highly toxic and reactive pollutant. In order to avoid potentially hazardous concentrations near densely populated areas, accurate forecasts of the temporal variability of ozone are necessary. Several statistical models which may be used to understand the temporal variability of ozone as well as to forecast short-term ozone fluctuations are developed. The models may be divided into two distinct categories: (1) those which forecast daily maximum one-hour average ozone concentrations and (2) those which forecast the diurnal behavior of one-hour average ozone concentrations. To assess the relative utility of each model, their forecast ability is evaluated by statistical comparison with data not used in model development. Most of the developed models appear to perform reasonably well; however, the utility of any forecast model is dependent upon the needs of the user. It is believed that the limits of the "pure time series" method (i.e., mathematical decomposition of time series into various elements) have been approached. Future investigations with these data should attempt to answer specific questions regarding the physical mechanisms governing ozone variability. / Arts, Faculty of / Geography, Department of / Graduate

Chemical processes and reactions are never perfect; there are always some problems in scope, scalability, applicability or safety. Sometimes, if these limitations pose a seemingly insurmountable barrier to the chemistry’s overall usefulness, decades can go by without a single new development even in fields that were initially very promising or popular in their infancy. By looking back on these forgotten topics through the lens of modern technology, new cutting-edge materials and methods can be applied to solve the problems that posed too great a challenge in previous decades. In this thesis, two such examples of reactions initially discovered and developed around the late 1960’s and remained largely untouched ever since will be explored. Chapter 1 will describe the use of ozone as an oxidant to transform amines into the corresponding alkyl nitro species. Ozone is a very powerful oxidant but tends to overreact with most organic substrates, which significantly reduces its potential as a commonplace synthetic tool. These limitations in applicability stem from an inherent lack of control over the reaction, which is the issue that we sought out to address. By applying modern principles of flow chemistry, the functional group tolerance of this oxidation reaction has been drastically increased from its initial state of simple small hydrocarbons. Chapter 2 will follow a similar narrative involving the use of ‘super-bases’ to activate benzylic C-H bonds and generate a variety of benzyllithium species. Organolithiums have also had historic issues with tolerance in transition metal-catalyzed cross coupling reactions. With a surge of new publications addressing this issue by using principles of flow chemistry, there remains a lack of easy methods to generate organolithium nucleophiles as coupling partners. Generation of benzyllithiums from toluene derivatives has historically been limited to require solvent quantities of substrate, along with unreasonably long reaction times at cryogenic temperatures. By utilizing modern tools and synthetic strategies, an easy and streamlined path from toluene derivatives to organolithiums for direct use in cross coupling has been developed.

A joint experimental and numerical project has been initiated at Virginia Tech to study the effect of ozone on diesel soot precursors. This thesis is the first stage of the numerical part of the project, and contains a study of the effect of the different ozone levels on diesel soot precursors. This numerical study is executed via the use of two computer programs, Senkin, and PSR. An idealistic model of the diesel engine was used in both analyses. The numerical studies were done at three different engine speeds, 1500, 2000, 2500 RPM and eight different levels of ozone. Studies were performed with ozone introduced with the intake air and with the fuel. Eleven product species, which include dominant soot precursors such as acetylene (C2H2) and the propargyl radical (C3H3), were examined and evaluated during this experiment. After analyzing both simulations, the PSR predictions were not useful since it omits the existence of temperature and species gradients. The PSR analysis was used as a preliminary model to get an overall idea of combustion pollutant formation and predicted the exit soot precursor concentrations were unaffected by any ozone addition. However, the Senkin analysis predicted the ozone injection did have the potential to reduce the formation of soot precursors. The Senkin analysis predicted more realistic results and therefore it is believed to yield the correct conclusion. However, it was suggested that an additional program, such as KIVA3, be utilized to predict a more practical view of the chemical kinetic behavior of ozone and its effect on the diesel engine. / Master of Science

The main objective was to develop a procedure based on differential optical absorption spectroscopy (DOAS) to measure atmospheric total column of ozone, using the automated instrument developed at the University of North Texas (UNT) by Nebgen in 2006. This project also explored the ability of this instrument to provide measurements of atmospheric total column nitrogen dioxide. The instrument is located on top of UNT’s Environmental Education, Science and Technology Building. It employs a low cost spectrometer coupled with fiber optics, which are aimed at the sun to collect solar radiation. Measurements taken throughout the day with this instrument exhibited a large variability. The DOAS procedure derives total column ozone from the analysis of daily DOAS Langley plots. This plot relates the measured differential column to the airmass factor. The use of such plots is conditioned by the time the concentration of ozone remains constant. Observations of ozone are typically conducted throughout the day. Observations of total column ozone were conducted for 5 months. Values were derived from both DOAS and Nebgen’s procedure and compared to satellite data. Although differences observed from both procedures to satellite data were similar, the variability found in measurements was reduced from 70 Dobson units, with Nebgen’s procedure, to 4 Dobson units, with the DOAS procedure.A methodology to measure atmospheric nitrogen dioxide using DOAS was also investigated. Although a similar approach to ozone measurements could be applied, it was found that such measurements were limited by the amount of solar radiation collected by the instrument. Observations of nitrogen dioxide are typically conducted near sunrise or sunset, when solar radiation experiences most of the atmospheric absorption.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Meteorology and Physical Oceanography, 1982. / Microfiche copy available in Archives and Science / Bibliography: leaves 40-41. / by Eduardo Pantig Olaguer. / M.S.

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