Physical Sciences and Mathematics Commons^™

Ozone And Reactive Oxidized Nitrogen Chemistry In The Northeast U.S, Matthew Ninneman

Legacy Theses & Dissertations (2009 - 2024)

Ongoing reductions in oxides of nitrogen concentrations ([NOx] = nitric oxide ([NO]) + nitrogen dioxide ([NO2])) throughout the continental United States (U.S.) have important implications for tropospheric ozone (O3) and reactive oxidized nitrogen chemistry (NOy ≈ NOx + nitric acid (HNO3) + particle nitrate (pNO3) + peroxy nitrates (PNs) + alkyl nitrates (ANs)). Specifically, decreasing [NOx] concentrations have likely (1) increased the sensitivity of O3 to the [NOx] level, and (2) affected NOy speciation and partitioning. An understanding of the impacts of continued [NOx] reductions is needed to inform current and future air pollution control strategies, especially since the National …

Electrochemical Investigation Of The Kinetics Of Chloride Substitution Upon Reduction Of [Ru(Porphyrin)(No)Cl] Complexes In Thf., Jeremy R. Zink, E G. Abucayon, Anthony R. Ramuglia, Arghavan Fadamin, James E. Eilers, George B. Richter-Addo, Michael J. Shaw

SIUE Faculty Research, Scholarship, and Creative Activity

The electrochemistry of several ruthenium porphyrin nitrosyl chloride complexes [Ru(por)(NO)Cl] have been examined in tetrahydrofuran. The complexes undergo 1-electron irreversible reductions which result in the diffusion-limited substitutions of the chloride ligands for THF. This chloride metathesis is reversible in the presence of added NBu₄Cl, and equilibrium constants and rate constants for chloride loss have been estimated. These parameters correlate with the NO stretching frequencies of the parent complexes, with more electron-donating porphyrin ligands favouring chloride loss from the reduced complexes. The [Ru(por)(NO)(THF)] products of the reductions can be detected by IR, EPR and visible spectroscopies. These species undergo …

Investigation Of Ambient Reactive Nitrogen Emissions Sources And Deposition In The Columbia River Gorge National Scenic Area, Jacinda L. Mainord

Dissertations and Theses

Anthropogenic reactive nitrogen is emitted into the atmosphere from fossil fuel combustion (nitrogen oxides) and agricultural activities (nitrogen oxides and ammonia). Nitrogen oxide emissions have long been controlled for their role in ambient air pollution and human health effects. However, reactive nitrogen deposition is less understood even though it can play a significant role in altering biodiversity, impairing ecosystem and biogeochemical function and degrading cultural artifacts. Although nitrogen deposition is a natural part of biogeochemical cycling, many ecosystems across the United States are at risk of exceeding the critical nitrogen deposition load. While nitrogen oxides are routinely measured in urban …

Depletion Of Ozone And Reservoir Species Of Chlorine And Nitrogen Oxide In The Lower Antarctic Polar Vortex Measured From Aircraft, T. Jurkat, C. Voigt, S. Kaufmann, J.-U. Grooß, H. Ziereis, A. Dörnbrack, P. Hoor, H. Bozem, A. Engel, H. Bönisch, P. F. Bernath

Chemistry & Biochemistry Faculty Publications

Novel airborne in situ measurements of inorganic chlorine, nitrogen oxide species, and ozone were performed inside the lower Antarctic polar vortex and at its edge in September 2012. We focus on one flight during the Transport and Composition of the LMS/Earth System Model Validation (TACTS/ESMVal) campaign with the German research aircraft HALO (High-Altitude LOng range research aircraft), reaching latitudes of 65°S and potential temperatures up to 405 K. Using the early winter correlations of reactive trace gases with N₂O from the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS), we find high depletion of chlorine reservoir gases up to ∼40% …

Unraveling The Fingerprints Of Nox Using Stable Isotopes: Implications For Nox Source Partitioning And Oxidation Chemistry, Wendell William Walters

Open Access Dissertations

The nitrogen (N) and oxygen (O) stable isotope composition (δ15N & δ18O) of nitrogen oxides (NOx )may be a useful tool for constraining NOx emission sources as well as for understanding the atmospheric oxidation pathways responsible for its removal if various NOx sources and sink processes exhibit characteristic isotopic compositions (“fingerprints”). However, this requires (1) an accurate and complete inventory of δ15N(NOx) values from major emission sources, (2) an assessment of the kinetic and equilibrium isotope effects that can impact δ15N and δ18O values of NOx, (3) and test these assumptions by conducting accurate in situ δ15N and δ18O measurements …

Variability Of No And No2 Above The Snowpack At Summit, Greenland, Zhixin Wang

Dissertations, Master's Theses and Master's Reports - Open

Nitric oxide (NO) and nitrogen dioxide (NO₂) were measured at levels of approximately 7.5 m, 3 m, and 0.5 m above the surface snowpack at Summit, Greenland from July 2008 to July 2010, respectively, with two sets of instrument systems. Instrument I measured NO and NO₂ at levels of 3 m and 0.5 m with two inlets, and instrument II measured NO and NO₂ at a level of 7.5 m plus total reactive nitrogen oxides (NO_y) at the same level with one inlet. Compared to previous measurements, the data provided the first year-round simultaneous …

Distributions And Formations Of Hono In The Troposphere, Dennis Pu

Legacy Theses & Dissertations (2009 - 2024)

Nitrous acid (HONO) is an important reactive nitrogen species and a precursor to the hydroxyl radical. It plays important roles in reactive nitrogen recycling and in photo-oxidant formation in the troposphere. However, much is still unknown about its formation mechanisms and distributions in the troposphere. This research is part of NOMADSS (Nitrogen, Oxidants, Mercury, and Aerosol Distributions, Sources and Sinks) field study contributed by over 10 research groups in the United States to investigate the tropospheric chemistry of reactive nitrogen, mercury, oxidant and aerosols. One of the goals was to study the HONO distribution and formation mechanisms in the troposphere. …

Slides: What We Know (And Don't Know) About Air Quality Impacts Of Oil And Gas Development, Anna Karion

Water and Air Quality Issues in Oil and Gas Development: The Evolving Framework of Regulation and Management (Martz Summer Conference, June 5-6)

Presenter: Anna Karion, NOAA/ESRL, University of Colorado/CIRES

35 slides

Acetyl Radical In Tobacco Smoke: Detection, Quantification And Simulation, Na Hu

Dissertations, Master's Theses and Master's Reports - Open

Free radicals are present in cigarette smoke and can have a negative effect on human health by attacking lipids, nucleic acids, proteins and other biologically important species. However, because of the complexity of the tobacco smoke system and the dynamic nature of radicals, little is known about the identity of the radicals, and debate continues on the mechanisms by which those radicals are produced. In this study, acetyl radicals were trapped from the gas phase using 3-amino-2, 2, 5, 5- tetramethyl-proxyl (3AP) on solid support to form stable 3AP adducts for later analysis by high performance liquid chromatography (HPLC), mass …

Atmospheric Effects Of Energetic Particle Precipitation In The Arctic Winter 1978-1979 Revisted, L. A. Holt, C. E. Randall, V. L. Harvey, E. E. Remsberg, G. P. Stiller, B. Funke, P. F. Bernath, K. A. Walker

Chemistry & Biochemistry Faculty Publications

[1] The Limb Infrared Monitor of the Stratosphere (LIMS) measured polar stratospheric enhancements of NO₂ mixing ratios due to energetic particle precipitation (EPP) in the Arctic winter of 1978–1979. Recently reprocessed LIMS data are compared to more recent measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) and the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) to place the LIMS measurements in the context of current observations. The amount of NO_x (NO + NO₂) entering the stratosphere that has been created by EPP in the mesosphere and lower thermosphere (EPP-NO_x) has been quantified …

Slides: Environmentally Friendly Drilling Systems Program (Efd), Rich Haut

Best Practices for Community and Environmental Protection (October 14)

Presenter: Rich Haut, Houston Advanced Research Center

23 slides

Theoretical Study On The Mechanism Of Removing Nitrogen Oxides Using Isocyanic Acid., Taraneh Nowroozi-Isfahani

Electronic Theses and Dissertations

The mechanism of RAPRENO_x reactions - RAPid REduction of Nitrogen Oxides using Isocyanic acid - proposed by Robert A. Perry¹ in an attempt to help control the emission of nitrogen oxides pollutant into the atmosphere, has been re-investigated theoretically. The study of reaction mechanisms was carried out using Chemist software². All mathematically possible elementary steps have been evaluated and the chemically reasonable ones have been considered to propose new sets of reaction mechanisms. Density Functional Theory (B3LYP/6-31 G**) calculations using Gaussian 98³ were made in order to study the relative energies of all species and …

Collisional Broadening Of Spectral Lines In The X → B System Of O2 And The First Vibrational Band Of No By The Noble Gases, John J. Cornicelli

Theses and Dissertations

Collisional broadening of the rotational spectral lines of the X to b system of O₂ and the first vibrational band of NO by the noble gases is examined by Fourier transform spectroscopy. Peaks of the individual rotational lines are modeled with a Voigt function, from which Lorentzian half widths are extracted. Lorentzian widths are plotted vs. pressure of foreign gas, from which the pressure broadening coefficients and pressure broadening cross sections are calculated. The pressure broadening coefficients are compared to theoretical values determined by past research for O₂. NO coefficients are compared to similar research using N …

Selective No Absorption From Gas Streams With Tertiary Organic Hydroperoxide Solutions, Huihong Ao

Theses

The selective removal of nitric oxide from gas streams was investigated using 3,6-dimethyl-3-octyl hydroperoxide, p-menthane hydroperoxide, pinane hydroperoxide, and cumene hydroperoxide in solutions of n-hexadecane (cetane). The influence of different parameters such as temperature, gas stream flow rate (or residence time), and concentration of hydroperoxide compounds on efficiency of NO removal was evaluated. The basis of this research was to duplicate atmospheric reactions between hydroperoxides and NO in order to produce NO₂. We succeeded in removing NO from gas streams, but failed to produce NO₂. NO reacted with the hydroperoxides to produce nitrates. These nitrates are …

Motor Vehicle Air Pollution Control: The Remaining Issues, Michael P. Walsh

Air Quality Protection in the West (November 27-28)

26 pages (includes illustrations).

Contains references.