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Physical Sciences and Mathematics

LSU Doctoral Dissertations

Combustion

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Environmentally Persistent Free Radicals (Epfrs) In Pm₂.₅ : Their Contribution To Hydroxyl Radical Formation And Atmospheric Transformation, William Micheal Gehling, Jr. Jan 2013

Environmentally Persistent Free Radicals (Epfrs) In Pm₂.₅ : Their Contribution To Hydroxyl Radical Formation And Atmospheric Transformation, William Micheal Gehling, Jr.

LSU Doctoral Dissertations

Previous research demonstrated environmentally persistent free radicals (EPFRs) will form on particulate surfaces under combustion conditions (temperature range of 150-400 °C) from reactions of organic precursors with redox-active transition metals. With an understanding of how these EPFRs form, it is necessary to determine how they behave in a natural environment after emission. To better understand this, the nature of EPFRs in ambient PM2.5 under simulated atmospheric conditions was investigated. Ambient PM2.5 samples were collected at a roadside ambient monitoring site near heavy interstate traffic and major industrial activity. The EPFR concentration and general radical structure were determined with EPR spectroscopy. …


Formation And Stabilization Of Combustion-Generated Environmentally Persistent Free Radicals On Transition Metal Oxides Supported On Silica, Eric Warren Pimentel Vejerano Jan 2011

Formation And Stabilization Of Combustion-Generated Environmentally Persistent Free Radicals On Transition Metal Oxides Supported On Silica, Eric Warren Pimentel Vejerano

LSU Doctoral Dissertations

The formation of environmentally persistent free radicals in combustion system was investigated from chemisorptions of chlorine- and hydroxy-substituted benzenes on transition metal oxide surface under post-combustion conditions. This manuscript reports the formation of EPFRs on silica particles containing 5% Fe(III)2O3, Ni(II)O, and Zn(II)O. The EPFRs are formed by the chemisorption of substituted aromatic molecular adsorbates on the metal cation center followed by electron transfer from the adsorbate to the metal ion at temperatures from 150 to 400 oC. Depending on the nature of the adsorbate and the temperature, two organic EPFRs were formed: a phenoxyl-type radical, which has a lower …


Gas-Phase Formation Of Environmentally Persistent Free Radicals From Thermal Degradation Of Catechol, Hydroquinone, Phenols And Tobacco, Julien Gnonlonfoun Adounkpe Jan 2008

Gas-Phase Formation Of Environmentally Persistent Free Radicals From Thermal Degradation Of Catechol, Hydroquinone, Phenols And Tobacco, Julien Gnonlonfoun Adounkpe

LSU Doctoral Dissertations

Catechol, hydroquinone and Phenol are major constituents of the mainstream tobacco smoke. The toxicity of tobacco has been attributed to the ability of catechol and hydroquinone to undergo endogenous or exogenous redox cycling to form semiquinone type radicals responsible of Reactive Oxygen Species (ROS) formation. ROS such as hydroxyl radicals can cause severe oxidative stress on biological tissues and can provoke severe signaling pathways leading to cardiovascular and pulmonary dysfunctions and carcinogenesis. Given that semiquinone type radicals are organic radicals, characterized by their high instability and reactivity; it is somewhat surprising that they can live long enough mostly when associated …


Comparison Studies Of The Mechanistic Formation Of Polyhalogentaed Dibenzo-P-Dioxins And Furans From The Thermal Degradation Of 2-Bromophenol And 2-Chlorophenol, Catherine Spearing Evans Jan 2004

Comparison Studies Of The Mechanistic Formation Of Polyhalogentaed Dibenzo-P-Dioxins And Furans From The Thermal Degradation Of 2-Bromophenol And 2-Chlorophenol, Catherine Spearing Evans

LSU Doctoral Dissertations

Emissions of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) and polybrominated dibenzo-p-dioxins and furans (PBDD/Fs) from hazardous waste incinerators, and many other sources for combustion have been considered environmentally hazardous and a major health threat. Recently, a growing number of materials containing brominated hydrocarbons, commonly used flame retardants, have been disposed in municipal and hazardous waste incinerators. This results in the increased potential for formation of PBDD/Fs and other hazardous combustion by-products. In contrast to chlorinated hydrocarbons, the reactions of brominated hydrocarbons have been studied only minimally. In fact, studies have shown that brominated phenols form higher yields of PBDD/Fs than the …